European Union Risk Assessment Report COPPER_ COPPER II .rtf by shenreng9qgrg132

VIEWS: 16 PAGES: 125

									 EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
       DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]




                      European Union Risk Assessment Report
       COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE,
          COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE


                CAS No: 7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6
             EINECS No: 231–159–6, 231–847–6, 215-270-7, 215–269–1, 215-572-9


                               VOLUNTARY RISK ASSESSMENT
                                  European Copper Institute




RAPPORTEUR [ITALY]                               I                    VRAR_CU_0706_HH_EXPOSURE
DISTRIBUTION DATE: 1 JUNE 07
 EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
       DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]

                                       LEGAL NOTICE

                   Neither the European Commission nor any person
        acting on behalf of the Commission is responsible for the use which might
                           be made of the following information



                 A great deal of additional information on the European Union
                                  is available on the Internet.
                        It can be accessed through the Europa Server
                                      (http://europa.eu.int).




                  Cataloguing data can be found at the end of this publication


   Luxembourg: Office for Official Publications of the European Communities, [ECB:
                                          year]
                           ISBN [ECB: insert number here]


                    © European Communities, [ECB: insert year here]
              Reproduction is authorised provided the source is acknowledged.




RAPPORTEUR [ITALY]                               II                   VRAR_CU_0706_HH_EXPOSURE
DISTRIBUTION DATE: 1 JUNE 07
 EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
       DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]

Foreword
In response to a request from the European Commission to “start preparing the initial
assessments for substances on the EU working list as these were considered as Community
priorities in the context of the industry voluntary initiatives for high production volume
chemicals” the copper industry committed to undertake a Voluntary Risk Assessment (VRA)
for copper and the copper compounds on the EU working list: Cu, CuO, Cu 2O, CuSO4 and
Cu2Cl(OH)3. This initiative was endorsed by the EU CAs in 2001. Yearly summaries on
progress have been presented at the CA meeting.
This comprehensive VRA dossier has taken four years to complete, with the whole process
managed by the European Copper Institute. It was compiled in co-operation with expert
consultants from the Institute of Occupational and Environmental Medicine (University of
Birmingham) and ICON for human health – toxicity, BR. Stern and Associates for human
health deficiency and from Euras/Ecolas for the environment. It is based on the principles of
Regulation 793/93, 1488/94 and the detailed methodology laid down in the revised Technical
Guidance Document on Risk Assessment for New and Existing Substances. Methodological
experiences gained through other metal Risk Assessments, e.g. the incorporation of
bioavailability for zinc, were incorporated as appropriate. Additional up to date scientific
information was integrated into the assessment where scientifically relevant (i.e. the use of
bioavailability models for water, sediment and soil, plus information on copper as an essential
nutrient). A broad cross section of the European copper industry has been fully involved in
the process and has submitted a significant amount of proprietary data.
To ensure the transparency and quality of the dossier, the initial draft RA reports have been
refined by incorporating inputs from the Review Country (Italy – Istituto Superiori di Sanità)
and the independent peer review panels.
For several of the substances under consideration, targeted risk assessments are required
under the Biocidal Product Directive (98/8/EC) and the Plant Protection Products Directive
(91/414). These dossiers, which have been/will be provided to the competent authorities
(France) by the respective end user industry groups, contain confidential information not
available to ECI. However, ECI has worked closely with both of these groups in incorporating
relevant information to ensure consistency to the extent possible.
A single dossier covers the assessments for copper metal and the copper compounds, with
substance specific aspects provided where relevant. For the base data compilation, extensive
literature searches were performed for each substance. Data gaps were filled with analogous
data, where relevant, or by additional testing where possible. Where the information was
either unnecessary for the copper risk assessment, or impossible to obtain, waiving for testing
and/or justification to support derogation is discussed. Some remaining data gaps (eg. a
marine risk assessment) were identified and will be tackled as a follow-up to this report.
Since its submission on 15 May 2005, the dossier has been reviewed and discussed by
TCNES at its meetings in 2005, 2006 and 2007. The current version is based on the draft
distributed 15 May 2005 and takes into account the comments made by TCNES the Review
Country (Italy – Istituto Superiori di Sanità) and the independent peer review panel.

This Draft Risk Assessment Report is the responsibility of the European Copper Insitute
(ECI) on behalf of the copper industry consortium




RAPPORTEUR [ITALY]                              III                   VRAR_CU_0706_HH_EXPOSURE
DISTRIBUTION DATE: 1 JUNE 07
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8,
                                                            1317-39-1, 1317–38–0, 1332-65-6]

Ownership
This RA was conducted on behalf of the copper industry consortium. In order to avoid possible misinterpretations or misuse of the findings in
this draft, anyone wishing to cite or quote this report is advised to contact the ECI beforehand.
Contact Details of the responsible: Katrien Delbeke, European Copper Insitute, Tervurenlaan 168, B-1150 Brussels, Belgium. Tel : +32 2 7777083, e-mail : kmd
@eurocopper.org

The industry companies that are part of the industry consortium are listed below
                                        COPPER VOLUNTARY RISK ASSESSMENT - COMPANY MEMBERS IN INDUSTRY CONSORTIUM


 SITE                                                          ADDRESS                                             CITY                    COUNTRY
 ALCHEMA                                East Ord Industrial Estate                         Berwick Upon Tweed TD15 2XF           UK
 ANGLO AMERICAN BASE METALS             20 Carlton House Terrace                           London SW1Y 5AN                       UK
 ANTOFAGASTA MINERALS S.A.              Ahumada 11 - Piso 6                                Santiago                              CHILE
 Atlantic Copper - Cordoba              Barriada Electromecanica, s/n                      E-14005 CORDOBA                       SPAIN
 Atlantic Copper Barcelona              Ctra. Palaudaries, Km 0.4                          E-08185 Llica de Vall                 SPAIN
 ATLANTIC COPPER HOLDING S.A. -Huelva   Avda Francisco Montenegro, s/n                     E-21001 HUELVA                        SPAIN
 B. MASON & SONS LTD.                   WHARF STREET, ASTON                                BIRMINGHAM B6 5SA                     UK
 BHP Billiton Plc                       Avenida Americo Sur Nr. 100 - 8th Floor            Santiago                              CHILE
 BOLIDEN AB.                            Smaltverket                                        S-93281 Skelleftehamm                 SWEDEN
 BOLIDEN CUIVRE ET ZINC                 RUE DU FOURNEAU, 43                                B-4030 GRIVEGNEE (LIEGE)              BELGIUM
 BOLIDEN LDM NEDERLAND B.V.             P.O. BOX 42 - LIPSSTRAAT 44                        NL-5150 AA DRUNEN                     NETHERLANDS
 BOLIDEN MINERAL AB                     Klarabergsviadukten 90                             SE - 101 20 Stockholm                 SWEDEN
 BRAZE TEC GmbH                         Rodenbacher Chaussee 4                             D-63457 Hanau-Wolfgang                GERMANY
 BUNTMETALL AMSTETTEN GES.M.B.H.        FABRIKSTRASSE 4                                    A-3300 AMSTETTEN                      AUSTRIA
 CODELCO-Chile                          Huerfanos 1270, piso 11                            650-0544 Santiago                     CHILE
 Compañia Minera Doña Ines Collahuasi   Av. Andres Bello 2687 Piso 11                      Las Condes, Santiago 6760276          CHILE
 Compañia Mineraria Zaldívar            1125 Seventeenth Street, Suite 2310                Denver, Colorado 80202                USA
 CUMERIO (was Umicore Copper)           Watertorenstraat 33                                B-2250 OLEN                           BELGIUM
 DEUTSCHE GIESSDRAHT GmbH               Kupferstraße 5                                     D-46446 EMMERICH                      GERMANY
 ELMET S.L.                             Barrio Arene 20                                    E-48640 BERANGO (Vizcaya)             SPAIN
 ENZESFELD-CARO METALLWERKE AG          Postfach 1, FABRIKSTRASSE 2                        A-2551 ENZESFELD/TRIESTING            AUSTRIA
 Erachem Comilog SA                     Rue du Bois                                        B-7334 Saint-Ghislain                 BELGIUM




RAPPORTEUR [ITALY]                                 IV                         VRAR_CU_0706_HH_EXPOSURE
DISTRIBUTION DATE: 1 JUNE 07
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8,
                                                            1317-39-1, 1317–38–0, 1332-65-6]

 EUROPA METALLI S.P.A Fornaci           Via della Repubblica, 257                           I-55052 Fornaci di Barga (Lucca)            ITALY
 EUROPA METALLI S.P.A. Serravalle       Via Cassano 113                                     I-15069 Serravalle Scrivia (Alessaandria)   ITALY
 EUROPA METALLI SpA Campo Tizzoro       Viale L. Orlando 325                                I-51023 Campo Tizzoro (Pistoia)             ITALY
 HALCOR METAL WORKS S.A.                16 Himaras Str.                                     Maroussi , GR 151 25                        GREECE
 HALCOR METAL WORKS S.A. casting
 shapes                                 Foundry, Oinofyta (55th km)                         GR                                          GREECE
 HALCOR METAL WORKS S.A. rolling mill   Rolling Mill, 252 PIRAEUS STREET                    GR-17778 ATHENS                             GREECE
 HALCOR METAL WORKS S.A. tube           Copper Tube Mill, Oinofyta (57th km)                GR                                          GREECE
 HÜTTENWERKE KAYSER AG.                 Postfach 15 60, Kupferstraße 23                     D-44505 LÜNEN                               GERMANY
 IBP Group Services Limited             Whitehall Road                                      Tipton, West Midland DY4 7JU                UK
 ISAGRO (ex Caffaro)                    Via Caldera, 21                                     20153 Milano                                ITALY
 KGHM Polska Miedz SA                   ul. Sklodowsklej-Curie 48                           59-301 Lubin                                POLAND
 KM EUROPA METAL AG                     POSTFACH 3320, Klosterstraße 29                     D-49023 OSNABRUECK                          GERMANY
 KME - Berlin                           Miraustraße 10-14                                   D-13509 Berlin                              GERMANY
 KME - Menden                           Carl-Benz-Straße 13                                 D-58706 Menden                              GERMANY
 KME Group                              P.O. Box 33 20 Klosterstrasse                       D-49074 Osnabruck                           GERMANY
                                                                                            E-08509 LES MASIES DE VOLTREGA
 LA FARGA LACAMBRA, SA                  Ctra C-17, Km 73,5 COLONIA LACAMBRA                 (BARCELONA)                                 SPAIN
 MANICA                                 Via all'Adige,4                                     38068 ROVERETO (Trento)                     ITALY
 Méxicana de Cobre, S.A. de C.V.        Baja California No. 200 Sixth Floor                 Mexico City 06760                           MEXICO D.F.
 Minera Escondida Limitada              Avenida Americo Vespucio Sur Nr. 100 - 9th Floor    La Condes, Santiago                         CHILE
                                        20F OtemachiFirst Square West, 1-5-1, Ohtemachi,
 Mitsubishi Materials Corporation       Chiyoda-KU                                          100-8117 Tokyo                              JAPAN
 MKM MANSFELDER KUPFER UND
 MESSING GMBH                           POSTFACH 1254, Lichtlöcherberg 40                   D-06323 HETTSTEDT, D-0ß6333 Hettstedt       GERMANY
 MUELLER INDUSTRIES, Inc.               8285 Tournament Drive, Suite 150                    Memphis, TN 38125                           USA
 NEXANS                                 4-10, rue Mozart                                    92587 Clichy Cedex                          FRANCE
 NEXANS BOURG EN BRESSE                 PO Box 101                                          F-01003 Bourg en Bresse                     FRANCE
 Nexans IKO Sweden AB                                                                       S-514 81 Grimsas                            SWEDEN
 NEXANS MEHUN SUR YEVRE                                                                     F-18500 Mehun Sur Yevre                     FRANCE
 NEXANS WIRES CHAUNY                    128, avenue Jean Jaures, BP30                       F-02301 Chauny                              FRANCE
 NEXANS WIRES MÂCON                     Rue du Port                                         F-71000 Macon                               FRANCE
 Nippon Mining & Metals Co., Ltd        Toranomon 2-chome, Minato, Ku                       105-0001 Tokyo                              JAPAN
 NORANDA Inc.                           Avda Andrés Bello 2777 Oficina 801                  Las Condes, Santiago 6760276                CHILE
 NORDDEUTSCHE AFFINERIE AG.             Postfach 10 48 40, Hovestraße 50                    D-20033 HAMBURG, D-20539 Hamburg            GERMANY
 NORDIC BRASS AB                        Box 524                                             S-721 09 Västeras                           SWEDEN




RAPPORTEUR [ITALY]                                  V                          VRAR_CU_0706_HH_EXPOSURE
DISTRIBUTION DATE: 1 JUNE 07
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8,
                                                            1317-39-1, 1317–38–0, 1332-65-6]

 Nordox Industries AS                     Ostensjovn. 13, PB 6639 Etterstad                    N-0607 Oslo                             NORWAY
 OK Tedi Mining Limited                   P.O. Box 1, Dakon Road, Tabubil                      Western Province, Papua                 NEW GUINEA
 OUTOKUMPU American Brass                 70 Sayre Street, P.O. Box 981                        Buffalo, NY 14240                       USA
 OUTOKUMPU COPPER Products AB             Box 510, Metallverksgatan 5                          S-721 88 VAESTERAS, S-721 09 Västeras   SWEDEN
 OUTOKUMPU Copper Products Oyj            Riihitontuntie 7 A, P.O. Box 144                     Espoo FIN-02201                         FINLAND
 OUTOKUMPU COPPER STRIP AB                Metallverksgatan 20-22                               S-721 88 VAESTERAS, S-721 10 Västeras   SWEDEN
 Outokumpu Copper Strip AB- Finspang                                                           S-612 81 Finspang                       SWEDEN
 OUTOKUMPU COPPER TUBES S.A.              Bº ARKOTXA S/N                                       E-48480 ZARATAMO                        SPAIN
 OUTOKUMPU HARJAVALTA METALS OY           P.O.Box 89                                           FIN-29200 Harjavalta                    FINLAND
 OUTOKUMPU MKM LTD. (ex Boliden MKM)      MIDDLEMORE LANE - ALDRIDGE                           WALSALL, West Midlands WS9 8DN          UK
 Outokumpu Nordic Brass AB (was BOLIDEN
 GUSUM AB)                                Gräsdalens Industrial site                           S-610 40 GUSUM                          SWEDEN
 OUTOKUMPU PORICOPPER OY                  P.O. Box 60                                          FIN-28101 Pori                          FINLAND
 P.T. Freeport Indonesia Inc.             1615 Poydras Street P.O. Box 51777                   New Orleans, Louisiana 70112            USA
 PALABORA Mining Company                  P.O. Box 65 Phalaborwa, 1390                         Limpopo Province                        SOUTH AFRICA
 Phelps Dodge Corporation                 One North Central Avenue                             Phoenix, AZ 85004                       USA
 PRYMETALL GMBH & CO. KG                  Zweifaller Strasse 150                               D-52224 Stolberg                        GERMANY
 Revere Copper Products Inc.              One Revere Park                                      Rome, NY 13440-5561                     USA
 RIO TINTO Plc                            6 St. James' Square                                  London SW1Y 4LD                         UK
 Sahna Kaimer GmbH/KG                     Im Teelbruch 80                                      D-45219 Essen-Kettwig                   GERMANY
 SCHWERMETALL HALBZEUGWERK GMBH           POSTFACH 6264, Breiniger Berg 165                    D-52211 STOLBERG, D-52223 STOLBERG      GERMANY
 SOCIETE DE COULEE CONTINUE DE
 CUIVRE                                   42 RUE FERDINAND-BUISSON - B.P. 105                  F-02301 CHAUNY CEDEX                    FRANCE
 SOCIETE LENSOISE DU CUIVRE               Boulevard du Marais                                  F-62300 LENS CEDEX                      FRANCE
 SPIESS URANIA                            Heidenkampsweg 77                                    D-20097 Hamburg                         GERMANY
 STOLBERGER METALLWERKE GMBH &
 CO. KG                                   POSTFACH 1929, Frankentalstraße 5                    D-52206 STOLBERG, D-52222 Stolberg      GERMANY
 SUMITOMO Metal Mining Co., Ltd           1 1-3, Shimbasi 5-Chome, Minato-KU                   105-871 6 Tokyo                         JAPAN
 Thyssen Krupp VDM                        Plettenberger Strsse 2                               D-58791 Werdohl                         GERMANY
 TREFILERIES ET LAMINOIRS DE LA
 MEDITERRANEE                             35 RUE LE CHATELIER                                  F-13015 MARSEILLE CEDEX 15              FRANCE
 TREFIMETAUX - Givet Plant                Rue des Vieilles Forges                              F-08600 Fromelennes                     FRANCE
 TREFIMETAUX - Niederbruck                31, Rue Joseph Vogt                                  F-68290 Niederbruck                     FRANCE
 TREFIMETAUX - Serifontaine               Rue M. Thorez, BP3                                   F-60590 Serifontaine                    FRANCE
 TREFIMETAUX --usine de Boisthorel                                                             F-61270 Rai                             FRANCE
 UMICORE ITALIA SRL                       nucleo industriale di Pianodardine (Avellino)        I-AVELLINO                              ITALY




RAPPORTEUR [ITALY]                                   VI                           VRAR_CU_0706_HH_EXPOSURE
DISTRIBUTION DATE: 1 JUNE 07
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8,
                                                            1317-39-1, 1317–38–0, 1332-65-6]

 WEDNESBURY TUBE & FITTINGS -
 MUELLER EUROPE                              OXFORD STREET                                       GB- BILSTON WEST MIDLANDS WV14 7DS      UK
 WIELAND-WERKE AG Ulm Vöhringen              POSTFACH 42 40, Graf-Arco-Straße 36                 D-89070 ULM, D-89079 ULM                GERMANY
 WIELAND-WERKE AG, WERK
 LANGENBERG                                  POSTFACH 110269, Ziegeleiweg 20                     D-42530 VELBERT, D-42555 VELBERT        GERMANY
                                                                                                 D-78007 VILLINGEN, D-78050 VILLINGEN-
 WIELAND-WERKE AG, WERK VILLINGEN            POSTFACH 1780, Lantwattenstr 11                     SCHWENNINGEN                            GERMANY
 WILLIAM BLYTHE LIMITED                      Church, Accrington                                  Lancashire, BB5 4PD                     UK
 WMC Copper uranium/WMC Resources
 Limited                                     IBM Tower 60 City Road                              Southbank Vic 3006                      AUSTRALIA
 Wolstenholme International                  Springfield House, Lower Ecclesfield Road, Darwen   Lancashire BB3 0RP                      UK
 XSTRATA Copper                              Level 9, Riverside Centre, 123 Eagle Street         Brisbane Q 4000                         AUSTRALIA
 YORKSHIRE COPPER TUBE LTD. (KME)            East Lancashire Road, Kirby                         LIVERPOOL L33 7TU                       UK
 YORKSHIRE Fittings Ltd                      P.O. Box 166                                        Leeds, LS10 1NA                         UK


 European Copper Institute - May 12th 2005




RAPPORTEUR [ITALY]                                     VII                          VRAR_CU_0706_HH_EXPOSURE
DISTRIBUTION DATE: 1 JUNE 07
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]




      COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE,
         COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE


                 CAS No: 7440-50-8, 7758-99-8, 1317-3-1, 1317–38–0, 1332-65-6
            EINECS No: 231–159–6, 231–847–6, 215-270-7, 215–269–1, 215-572-9


                         VOLUNTARY RISK ASSESSMENT
    CHAPTER 4.1.1 – HUMAN HEALTH – EXPOSURE ASSESSMENT
               A.Wheatley, S.Sadhra, I.Schoeters, K.Delbeke, R.Gaunt


                                     Draft of 1 June 2007

Ownership of this risk assessment: European Copper Institute (ECI)

Lead contact person for this section:
Ilse Schoeters, European Copper Institute, Brussels, Belgium.
E-mail: isc@eurocopper.org

Other contact persons:
Dr.Katrien Delbeke, European Copper Institute, Brussels, Belgium.
E-mail: kmd@eurocopper.org

Thierry Gerschel, European Copper Institute, Brussels, Belgium.
E-mail: teg@eurocopper.org

Review Country for this risk assessment of Copper and Copper compounds is Italy
Contact person:
Dr. Roberto Binetti , Istituto Superiore di Sanità, Rome, Italy.
Email: binetti@iss.it


Date of Last Literature Search :                             2004
Review of report by MS Technical Experts finalised:          [insert month and year]
Final report:                                                [insert year]




RAPPORTEUR [ITALY]                             1                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                            CONTENTS

4 HUMAN HEALTH ..................................................................................................................................... 5

    4.1 HUMAN HEALTH (TOXICITY) ...................................................................................................... 5
        4.1.1 Exposure assessment ............................................................................................................... 5
              4.1.1.1 General discussion ..................................................................................................... 5
              4.1.1.2 Occupational exposure............................................................................................... 5
                      4.1.1.2.1 Introduction............................................................................................... 5
                      4.1.1.2.2 Data coverage and representativeness ....................................................... 15
                      4.1.1.2.3 Production of copper massive ................................................................... 19
                      4.1.1.2.4 Melting and casting ................................................................................... 34
                      4.1.1.2.5 Downstream use: Further processing ........................................................ 40
                      4.1.1.2.6 Production of Copper powders ................................................................. 42
                      4.1.1.2.7 Production of Copper compounds ............................................................ 49
                      4.1.1.2.8 Formulation of Copper compounds .......................................................... 58
                      4.1.1.2.9 Professional exposure to coins .................................................................. 58
                      4.1.1.2.10 Particle size distributions .......................................................................... 58
                      4.1.1.2.11 Summary of occupational exposure and data gaps ................................... 66
              4.1.1.3 Consumer exposure ................................................................................................... 70
                      4.1.1.3.1 Sources of exposures ................................................................................ 70
                      4.1.1.3.2 Summary of consumer exposure ............................................................... 75
              4.1.1.4 Humans exposed via the environment - local environment ....................................... 77
                      4.1.1.4.1 Background and scope .............................................................................. 77
                      4.1.1.4.2 Information gathering ............................................................................... 77
                      4.1.1.4.3 Inhalation exposure ................................................................................... 77
                      4.1.1.4.4 Drinking water .......................................................................................... 80
                      4.1.1.4.5 Ingestion of dust ....................................................................................... 80
                      4.1.1.4.6 Copper levels in soil ................................................................................. 80
                      4.1.1.4.7 Copper levels in food ................................................................................ 81
                      4.1.1.4.8 Values taken forward for risk characterisation ......................................... 89
              4.1.1.5 Humans exposed via the environment - regional environment .................................. 91
                      4.1.1.5.1 Exposure via air ........................................................................................ 91
                      4.1.1.5.2 Exposure via food and water..................................................................... 91
                      4.1.1.5.3 Copper levels in drinking water ................................................................ 105
                      4.1.1.5.4 Exposure carried forward for risk characterisation ................................... 111
              4.1.1.6 Combined exposure ................................................................................................... 115


FIGURES
Figure 4-1 CEN and ISO particulate deposition curves ................................................................................. 9
Figure 4-2 Primary smelter schematic ........................................................................................................... 20
Figure 4-3 Secondary smelter schematic ....................................................................................................... 20
Figure 4-4 Typical personal exposure to copper for smelting furnaces ......................................................... 26
Figure 4-5 Typical personal exposure to copper for converters ..................................................................... 27
Figure 4-6 Typical personal exposure to copper for anode furnaces.............................................................. 28
Figure 4-7 Indicative dust levels for anode furnace tapping (ECI-07). .......................................................... 28
Figure 4-8 Parallel Casella Microdust and Respicon sampling data (mg/m3) during routine operations in
smelting with intermittent generation of dust from handling of dry slag. ......................................................... 30
Figure 4-9 Indicative dust exposure during finishing of billets. .................................................................... 38
Figure 4-10 Indicative exposure to dust during furnace operation in production of copper powder. ............. 44
Figure 4-11 Indicative exposure to dust during bagging of copper oxychloride. ............................................. 55
Figure 4-12 Particle size distributions during melting and casting operations, arithmetic means of all available
values for each stage/task .................................................................................................................................. 62
Figure 4-13 Physical particle size of copper compounds (determined by dry dispersion and laser diffraction) 63
Figure 4-14 Particle size (aerodynamic diameter) distribution of copper compounds (Heubach method) ..... 64
Figure 4-15 Particle size density function of copper compounds ................................................................... 65
Figure 4-16 Copper exposure from cigarette smoking ..................................................................................... 71
Figure 4-17 Copper in edible part of lettuce from “greenhouse” experiments. ................................................ 85
Figure 4-18 Copper in edible part of tomatoes from “greenhouse” experiments. ............................................ 85




RAPPORTEUR [ITALY]                                                            2                                   VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                                      CONTENTS
Figure 4-19 Copper in edible part of onions from “greenhouse” experiments. ................................................ 86
Figure 4-20 Copper uptake by food group ....................................................................................................... 93
Figure 4-21 Copper concentration versus stagnation time in a copper pipe ..................................................... 106

TABLES
Table 4-1 Process codes for industry questionnaire ....................................................................................... 5
Table 4-2 Performance of sampling heads mounted on manikins in wind tunnel experiments ...................... 10
Table 4-3 Parallel sampling using IOM and open-face 37mm samplers in field conditions at dust levels of
approximately 3-9 mg/m3 .................................................................................................................................. 11
Table 4-4 Occupational exposure limits in EU countries ............................................................................... 12
Table 4-5 Total dataset for ECI companies .................................................................................................... 15
Table 4-6 Evaluation of sampling methods and determination of sampler bias for occupational exposure
assessment. ........................................................................................................................................................ 17
Table 4-7 Results for personal and static copper measurements for primary (PC3) and secondary (PC4)
smelting ............................................................................................................................................................. 22
Table 4-8 Job exposure matrix by company (personal samples mg/m³) ........................................................ 23
Table 4-9 Summary exposure data for smelting ............................................................................................ 25
Table 4-10 Comparison of selected physico-chemical properties of zinc and copper compounds ................ 32
Table 4-11 Dermal exposure to zinc in a zinc refinery [μg zinc / cm² skin] .................................................. 33
Table 4-12 Extrapolated dermal exposure to copper in the production of copper massive ............................ 33
Table 4-13 Personal exposure melting and casting (mg/m3) .......................................................................... 36
Table 4-14 Estimated 8 hour TWA exposures (mg/m3) for melting and casting (ECI-10) incorporating furnace
cleaning operations ........................................................................................................................................... 37
Table 4-15 Melting and casting: indicative dust levels by operation (mg/m3) .............................................. 37
Table 4-16 Inhalation data carried forward for risk characterisation for melting and casting........................ 39
Table 4-17 Personal exposures for further processing .................................................................................... 41
Table 4-18 Inhalation data carried forward for risk characterisation for further processing ........................... 41
Table 4-19 Personal exposure to copper and copper alloy powders ............................................................... 43
Table 4-20 Job exposure matrix by company, copper and copper alloy powders. .......................................... 44
Table 4-21 Copper fraction of inhalable dust in manufacture of copper powders .......................................... 45
Table 4-22 EASE predictions and measured exposure data (mg/m³) .............................................................. 45
Table 4-23 Inhalation data carried forward for risk characterisation for copper powders. ............................. 46
Table 4-24 Measured cumulative dermal exposure to “zinc”, production of zinc dust, powder and compounds
[μg/cm² skin] ..................................................................................................................................................... 47
Table 4-25 Measured corrected dermal exposure to “zinc”, production of of zinc dust, powder and zinc
compounds [μg/cm² skin] .................................................................................................................................. 48
Table 4-26 Measured corrected cumulative dermal exposure recalculated to “zinc oxide“, production of zinc
dust, powders and zinc compounds [μg/cm²] .................................................................................................... 48
Table 4-27 Extrapolated shift corrected cumulative dermal exposure to copper in the production of copper
powders. ............................................................................................................................................................ 48
Table 4-28 Dermal exposure assessment copper powder* – EASE calculations ............................................ 49
Table 4-29 Copper compounds: Personal exposure by company .................................................................... 51
Table 4-30 Copper compounds: Personal exposure by operation ................................................................... 51
Table 4-31 Copper compounds, bagging of Cu(I)O: indicative dust levels (mg/m 3) ...................................... 52
Table 4-32 Copper fraction of inhalable dust in manufacture of copper compounds ..................................... 53
Table 4-33 EASE predictions and measured data ........................................................................................... 54
Table 4-34 Inhalation data carried forward for risk characterisation for copper compounds. ........................ 54
Table 4-35 Copper content of several copper compounds ............................................................................. 56
Table 4-36 Extrapolated shift corrected cumulative dermal exposure to copper compounds [μg substance / cm²
skin] .................................................................................................................................................................. 56
Table 4-37 Extrapolated dermal exposure to copper compounds [mg copper / day] ..................................... 56
Table 4-38 Dermal exposure assessment to copper compounds* – EASE calculations ................................. 57
Table 4-39 Copper in inhalable and respirable dust ........................................................................................ 59
Table 4-40 Particle size distribution of airborne copper ................................................................................. 59
Table 4-41 Composition, melt, and pour temperatures of material handled ................................................... 60
Table 4-42 Summary of air sampling data as a percentage of mass analysed on each filter stage, Cohen &
Powers (2000) ................................................................................................................................................... 61
Table 4-43 Results of regession analysis ........................................................................................................ 62
Table 4-44 Dustiness and particle size information of copper and copper compounds .................................. 65




RAPPORTEUR [ITALY]                                                                   3                                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                                                                  CONTENTS
Table 4-45 Inhalation data carried forward for risk characterisation for primary and secondary smelting. .... 67
Table 4-46 Inhalation data carried forward for risk characterisation for melting and casting ........................ 67
Table 4-47 Inhalation data carried forward for risk characterisation for further processing ........................... 67
Table 4-48 Inhalation data carried forward for risk characterisation for copper powders. ............................. 68
Table 4-49 Inhalation data carried forward for risk characterisation for copper compounds. ........................ 68
Table 4-50 Particle size distribution of airborne copper to predict the fractional deposition in the respiratory
tract ................................................................................................................................................................... 68
Table 4-51 Dermal exposure data carried forward for risk characterisation for all main scenarios. ............... 68
Table 4-52 Summary of population exposure estimates for consumer exposure. ........................................... 76
Table 4-53 Measured and derived copper levels in environmental compartments relevant for indirect local
exposure assessment ......................................................................................................................................... 79
Table 4-54 External inhalation exposure (mg/day) by sector (Table 4-53)..................................................... 80
Table 4-55 Copper in soil and copper uptake by plants in the vicinity of a copper smelter............................ 82
Table 4-56 Mean biotransfer factors (BTF)1 for food crops impacted by aerial deposition from a copper smelter.
 .......................................................................................................................................................................... 83
Table 4-57 Copper in lettuce ........................................................................................................................... 87
Table 4-58 Copper in tomatoes ....................................................................................................................... 87
Table 4-59 Copper in onions ........................................................................................................................... 88
Table 4-60 Copper in lettuce at lower end of soil copper concentration ......................................................... 88
Table 4-61 Summary of values for the local environment taken forward for risk characterisation ................ 90
Table 4-62 Summary of typical and RWC dietary exposure data (mg/day) ................................................... 99
Table 4-63 Dust and copper ingestion by children .......................................................................................... 100
Table 4-64 Summary of dietary exposure to copper for adults (mg/day)........................................................ 102
Table 4-65 Estimated population averages for mean dietary intake of copper ............................................... 104
Table 4-66 Summary of copper concentrations in standing water and assessment of acute exposure ............ 108
Table 4-67 Mean dietary intake of copper: influence of beverages. (Summarised from Table 4-64) ............. 110
Table 4-68 Estimate of copper exposure in drinking water for adults applicable for chronic effects ............. 111
Table 4-69 Estimates of total oral exposure to copper (mg/day) .................................................................... 113
Table 4-70 Estimated typical oral copper intake for children and adolescents ............................................... 113
Table 4-71 Estimated 10P-RWC oral copper intake for children and adolescents ......................................... 114
Table 4-72 Estimated 90P-RWC oral copper intake for children and adolescents ......................................... 114
Table 4-73 Combined exposure data carried forward for risk characterisation for workers - Typical scenarios
 .......................................................................................................................................................................... 115
Table 4-74 Combined exposure data carried forward for risk characterisation for workers – RWC scenarios 116
Table 4-75 Combined exposure data carried forward for risk characterisation for the general population –
Typical scenarios............................................................................................................................................... 117
Table 4-76 Combined exposure data carried forward for risk characterisation for the general population –
RWC scenarios.................................................................................................................................................. 118




RAPPORTEUR [ITALY]                                                                    4                                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
4                        HUMAN HEALTH


4.1                      HUMAN HEALTH (TOXICITY)


4.1.1                    Exposure assessment


4.1.1.1                  General discussion


4.1.1.2                  Occupational exposure


4.1.1.2.1                Introduction

Data collection and analysis
Twelve processes were defined at the outset of the data collection process in order to span the
full range of activities within the industry. A process code was assigned to each for purposes
of data collection. These are shown in Table 4-1. The overall aim was to determine the
volume and quality of exposure data and to derive scenarios from the process categorisations.

Table 4-1 Process codes for industry questionnaire

    Process code                                                       Description
         1           Production of copper concentrates
         2           Raw material handling (unloading, weighing, sampling, storage and in house transportation)
         3           Copper smelting (primary)
         4           Copper smelting (secondary)
         5           Copper refining
         6           Melting and casting for production of copper and copper alloys, billets plates and ingots.
         7           Melting and casting for production of sand and die castings
         8           Melting and casting for production of copper wire rod
         9           Further processing (rolling, drawing and extrusion) of billets, plates and ingots for the production of copper &
                     copper alloy semis: wire, bars, rods, profiles, plates, sheet, strip and tubes
        10           Production of copper and copper alloy powders
        11           Production of copper chemical compounds (please specify copper compounds produced)
        12           Other copper production/manufacturing processes – please specify



The following exposure scenarios were derived by consideration of the process descriptions,
visits to typical sites and review of the monitoring data. These exposure scenarios are
regarded as relevant for occupational exposure assessment:




RAPPORTEUR [ITALY]                                               5                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Production of copper massive incorporates primary smelting (PC3) and secondary smelting
(PC4). These operations may be entirely discrete or merged to some extent. Ancillary
operations include raw material handling and sampling plant operation where scrap is tested
and graded in secondary smelters.
Production of copper powders by melting and atomisation of copper or copper alloys
followed by drying, sizing and packing.
Production of copper compounds, usually by wet reaction processes followed by drying and
packing. Copper compounds considered in this risk assessment are copper(I)oxide,
copper(II)oxide, copper sulphate pentahydrate and copper oxychloride.
Downstream users are included as follows:
Melting and Casting is subdivided, according to the end use of the product, into melting and
casting of billets (PC6), melting and casting for sand and die casting (PC7) and melting and
casting for wirerod (PC8). These processes are essentially similar and distinguished mainly by
the final manipulation of the product.
Further processing entails the melting of copper followed by mechanical processing
(extrusion, drawing etc) to form semis, items destined for a specific application, e.g. tubes
sheets etc.
The use of copper compounds in biocides and pesticides is being dealt with in the respective
biocides and pesticides dossiers.
Detailed descriptions of these processes in the production of copper and the manufacture
products may be found in the chapter on general exposure (chapter 2). Extensive descriptions
of metallurgical processes are given elsewhere (European Commission, 2000). Brief process
descriptions, with particular reference to exposure generation, are given in the discussion of
exposure by process code further in this section.
The aim of the exposure assessment is to determine typical and reasonable worst case (RWC)
exposures for a range of scenarios the derivation of which are described below. This is done
for the inhalation and dermal routes. (It is considered, both in the TGD and more generally,
that ingestion is an insignificant route in occupational exposure). For the purpose of the RA,
typical and RWC exposures are defined as the median and 90th percentile values respectively
(revised TGD sections 2.2.7.7 and 2.2.7.6). It is further specified that small datasets should be
carefully evaluated in order that isolated high values do not introduce unreasonable bias in
RWC estimates. Also, RWC estimates should specifically exclude gross worst case exposures
arising from wilful misuse etc. Given the large datasets it is inevitable that occasional high
values will be produced. Typical and RWC values have been derived as described in the TGD
and will be taken forward to risk characterisation.
Exposure data was collected for the period 1998-2006 inclusive. This is consistent with the
TGD recommendation to use only the most recent data. This timeframe was chosen in the
expectation that it would strike a balance allowing the collection of an adequate dataset,
allowing the determination of typical and reasonable worst-case exposures, without incurring
bias from potentially high historical exposures. Also datasets with a minimum of 12 samples
in accordance with the TGD were preferred, smaller datasets were included and interpreted
with suitable caution, again as recommended by the TGD. Personal and background (static)
copper exposure levels, as well as total inhalable dust exposure data, were requested.




RAPPORTEUR [ITALY]                               6                      VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
An initial questionnaire (questionnaire 1) was sent to ECI members in 2001 in order to
determine which companies had collected occupational exposure data within the last three
years. An outline of the scope of data collection was also requested. A more detailed second
questionnaire was then sent to companies that had provided an affirmative response.
Questionnaire 2 was designed by the IOEM, in conjunction with the ECI’s environmental
consultants, to encompass both the results of exposure measurements and, as far as possible,
the full range of supporting information detailed in the TGD. A summary of the information
requested in questionnaire 2 is shown in Appendix HH-1.
The terminology employed in this report uses three terms to describe operations in the copper
industry; process code, exposure scenario and sector. The process codes were used to gather
information in order to determine exposure scenarios required for the RA. The derivation of
exposure scenarios forms the basis of the exposure assessment and requires special
consideration. The TGD (section 2.2.2.4) indicates that scenarios are “based on the most
important characteristics of the substance in the view of occupational exposure” taking into
account the properties of the substance and process etc.
This concept is elaborated in authoritative guidance on retrospective employee grouping
published by the British Occupational Hygiene Society (BOHS, 1993). Grouping is based on
establishing homogeneous, or “monomorphic” exposure groups through a process of
stratification. Advanced methodologies involve the determination of within and between-
worker variance. Simplified methods still require the determination of the mean exposures for
individual workers (Rappaport, 1991; HSE 1989). This was not possible within the
framework of this data collection exercise In any case, it is clear that the demanding criteria
for defining monomorphic exposure groups required by these methodologies was unlikely to
be met in this assessment. In this case it is necessary to apply stratification pragmatically: too
little stratification may yield a few highly non-homogeneous groups while too dense
stratification may produce innumerable groups of small sample size. Such a pragmatic
approach is adopted based on exposure data by company, process code and secondary process
code. Secondary process codes correspond to specific operations within each company which
may be common to other companies and therefore may allow horizontal, industry-wide
analysis.
Sector is a term related to the end product rather than specific activities (e.g. melting, routine
maintenance) some of which may be common to different sectors. Similarly some companies
are active in different sectors. Since the available data on company output are sector-based,
this term provides a useful means of evaluating data coverage of the industry hence its
inclusion.

Inhalation data

Site surveys
In addition to the exposure data collected by the individual companies, a range of sites
covering all process codes were visited in order to; a) investigate sources of exposure and
exposure variability and b) determine the particle size distribution of inhalable dust in selected
cases.
Instrumentation used was as follows. Real-time dust measurements were obtained using an
infrared forward scattering (12-20 ) optical detector with integral data logger (Casella
Microdust Pro, Casella CEL, Bedford UK). This instrument exhibits maximum sensitivity
within the respirable range (aerodynamic diameter ≤7 μm) with a cut off of approximately 10



RAPPORTEUR [ITALY]                               7                      VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
μm. It is factory calibrated to Arizona Road dust. Response is heavily dependent on the
particle size distribution and the optical properties of the dust under investigation. Results are
therefore considered as indicative to semi-quantitative. The primary purpose of the use of this
instrument in the present context is as a qualitative tool for the determination of relative
exposure levels as indicated above. Levels indicated graphically in the discussion of exposure
levels below show real-time integrated readings (integration time 5 secs). Summary
“statistics” indicated alongside graphic refer to instantaneously recorded levels and hence may
be higher.
Particle size distributions for selected operations were determined using a Respicon 3-stage
virtual impactor (Hund, Wetzlar, Germany). The aerodynamic particle cut sizes of the 3
stages are respectively 4 µm, 10µm and 100µm.The Respicon sampler was calibrated at 3.1
l/min ±2% and dust was collected on 37mm diameter glass fibre filters (TSI, St Paul Minn,
USA). Sample and blank filters were analysed by atomic absorption spectrometry for copper
and other metals. Three independent size fractions were measured; pulmonary,
tracheobronchial and extrathoracic. Inhalable dust was measured as a function of the total
sample collected. The favourable performance of this instrument as an inhalable dust sampler,
and it’s operation as a virtual impactor, are described in detail elsewhere ( Li et. al., 2000;
Koch et. al., 2002; Tatum et. al., 2002). The version used incorporates optical detectors in
each stage which continuously monitor each fraction. Data was downloaded to a Hund,
Wetzlar data logger. The real-time output was calibrated quantitatively for copper by entering
the analytical results via the instrument’s software transforming data from signal to
concentration values (i.e., mV to mV/mg/m3 to mg/m3). The assumption is made that the
concentration of copper in each fraction remains reasonably consistent.

Monitoring overview and evaluation of sampler performance for exposure assessment
Measured data from questionnaire responses refer exclusively to inhalation exposure. No
measured dermal exposure data are available. A brief description of the monitoring process is
given as follows. In order to monitor inhalation exposure, a dust sample must first be
collected on a filter. For personal sampling the sampling head is located close to the worker’s
breathing zone. On completion of sampling, the dust exposure level (in mg/m 3) can be
determined gravimetrically. In most, but not all cases, gravimetric analysis was not performed
for the data presented here which mostly refer to copper concentration only. The filter is
analysed for copper after gravimetric analysis where applicable.
A common definition of health related particle size distributions (inhalable, thoracic and
respirable) has now been agreed by the European Committee for Standardisation. This is
published as CEN:EN 481 (CEN, 1993) and is shown in Figure 4-1. As is normal practice in
the assessment of occupational exposure, data for copper in inhalable and respirable dust were
submitted by ECI companies:
The inhalable fraction “approximates to the fraction of airborne material that enters the nose
and mouth during breathing, and is therefore available for deposition in the respiratory tract”.
(HSE, 2000). According the CEN convention, 50% of particles with an aerodynamic diameter
of 100 μm are included in the inhalable fraction. The fate of larger particles is not specified in
the convention.
The respirable fraction “approximates to the fraction of airborne material that penetrates to the
gas exchange region of the lung” (HSE, 2000). According the CEN convention, 50% of
particles with an aerodynamic diameter of 4 μm are included in the respirable fraction. A




RAPPORTEUR [ITALY]                               8                      VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
proportion of inhaled respirable dust may be deposited in the upper part of the respiratory
tract (Schroter and Lever, 1980).
A few data for copper in “fume” were also submitted:
Fume is “fine particles formed from solid materials by evaporation, condensation, and by gas
phase molecular reactions. When heated materials such as lead produce a vapour that
condenses in the atmosphere to form metallic particles that oxidize, e.g. to lead oxide. These
particles range in size from 1.0 to 0.0001 μm” (ACGIH). Although within this size range
when first formed, particles continue to condense and agglomerate.
In addition to the fractions described above, the CEN convention also defines the thoracic
fraction. Fifty percent of particles with an aerodynamic diameter of 10 μm are included in the
thoracic fraction which corresponds approximately to the PM10 fraction, widely used in
environmental sampling but little used for personal sampling in the EU.
The ISO “inspirable” convention is also shown. Sampling devices should be selected so that
their sampling efficiency (E) at a given aerodynamic diameter matches that of EN 481.

Figure 4-1 CEN and ISO particulate deposition curves


                         100
                                                       EN 481 - inhalable
                                                       ISO 7708 - "inspirable"
    percent deposition




                          80

                          60

                          40

                          20

                           0
                               0   20     40           60          80            100
                                    aerodynamic diameter (m)


In the risk assessment an estimate of total systemic absorption is required and measurement of
inhalable dust is therefore necessary. Historically, there has been little consensus on what
constitutes the inhalable or “inspirable” fraction and different measurement methods and
sampling devices are in use across the EU. Numerous studies have been conducted to
determine the performance of widely used sampling heads in relation to EN 481. While
samplers in industrial practice generally comply with the CEN convention, dust particles
bigger than 100 µm are collected. The most relevant and wide-ranging study investigated the
performance of several samplers in collecting near-monodisperse particles while mounted on
a manikin in a large scale wind tunnel (Kenny et. al., 1997). In agreement with similar
studies, large errors were found for all samplers at high windspeeds (>1.0 m.sec-1) at higher
aerodynamic diameters (20-30 µm). Better performance at lower particle sizes was observed
for several samplers. Suggested correction factors for performance in field conditions for each



RAPPORTEUR [ITALY]                                      9                        VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
sampler were presented. Correction factors for selected samplers in use in the copper industry
at a windspeed of 1.0 m/sec are shown in Table 4-2.

Table 4-2 Performance of sampling heads mounted on manikins in wind tunnel experiments    (Kenny et al, 1997)

     Sampling head             Flow rate (l/min)       Suggested correction factor relative to CEN:EN 481
                                                             0.5 m./sec                  1.0 m/sec
          IOM                        2.0                         1.0                        1.0
    Seven-hole head                  2.0                         1.0                        1.2
          GSP                        3.5                         1.0                        1.0
         PAS-6                       2.0                         1.0                        1.25
    37mm open face                   2.0                        1.15                        1.15
    37mm closed face                 2.0                         1.0                        1.2



The open and closed-face 37mm samplers indicated in Table 4-2 were not designed
specifically for size selective sampling and have been adapted from other applications. They
are used in methods for “total” dust in the US including total nuisance dust (NIOSH 0500)
collected at 1-2 l/min, and for metals in total dust (NIOSH 7300) collected at 1-4 l/min. They
are also widely used in Scandinavian countries. Inaccuracies in their use as inhalable samplers
occur partly due to aspiration efficiency, arising from inlet geometry/flow rate, and also from
electrostatic effects from the non-conductive plastic construction.
Studies employing unmodified open-face 37mm samplers for personal sampling in field
conditions indicate much greater deviation from the performance of more accurate
alternatives such as the IOM sampler. Data from a wide range of industries are shown in
Table 4-3 (Liden et al., 2000). Kenny and co-workers acknowledged earlier work showing
the disparity between the performance of these samplers in field and laboratory conditions.
They refer to a differential of 2-3, broadly consistent with the later findings of Liden et al
(1.5-5) shown in Table 4-3 suggesting undersampling in laboratory studies. Several reasons
may explain these differences. In the work of Kenny and co-workers, the cassette body was
coated with conducting paint in order to minimise electrostatic effects and the study design
may therefore have underestimated negative bias in respect of these samplers. Open-faced
37mm samplers used as purchased do indeed appear to show lower collection efficiencies for
particles >10 µm when similarly tested on manikins in wind tunnel experiments (Buchan et.
al., 1986). In addition, localised air currents in workplace settings may create conditions
which are not replicated in wind tunnel experiments and which may exacerbate bias arising
from inertial factors. Conversely, the IOM sampler moderately oversamples particles of all
sizes at a windspeed of 0.5 m/sec (Kenny et al., 1997) which is considered most
representative of actual windspeeds in workplace conditions. Hence the deviation of the
37mm sampler from the CEN convention may be less marked than comparison with the IOM
sampler may suggest.
In conclusion, the open-faced 37mm sampler is assumed to undersample in field conditions
by a factor of two. The correction factor of two is based on an approximately median estimate
of performance in the field. This correction factor is applied to exposure data submitted for
these samplers. This adjustment is considered moderately conservative. Correction factors
applied to other samplers are as shown in Table 4-2. In order to avoid negative bias in the
assessment of exposure, a correction factor of two is also applied to data acquired using



RAPPORTEUR [ITALY]                                      10                        VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
samplers which are not clearly defined or are not listed in Table 4-2. The data used in the
exposure assessment are therefore in compliance with the CEN convention or, where
adjustment of the measured values is required, a best approximation of compliant.

Table 4-3 Parallel sampling using IOM and open-face 37mm samplers in field conditions at dust       (Liden et al, 2000)
levels of approximately 3-9 mg/m3

                                                                             Approximate relative
                                 Industry                                        efficiency (E)
                                                                                 (EIOM/ E37mm)
                           Thermosetting plastics                                      3
                                 Wood dust                                            2-3
                                Poultry dust                                        1.5-2.5
                                 Paper dust                                         2.5-3.0
                                 Flour dust                                           2-5




RAPPORTEUR [ITALY]                                        11                         VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH
Occupational exposure limits

There are a number of countries with exposure limits for copper and these are shown in Table 4-4.
Table 4-4 Occupational exposure limits in EU countries

      Country                 Substance                        Standard        Date                  Document and Online document reference
       Austria              Dust (inhalable)               MAK 1 mg/m3       Jan, 1999   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       Austria             Fume (respirable)               MAK 0.1 mg/m3     Jan, 1999   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
      Belgium               Dust (inhalable)               TWA 1 mg/m3       Jan, 1993   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
      Belgium              Fume (respirable)               TWA 0.2 mg/m3     Jan, 1993   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
      Denmark               Dust (total dust)              TWA 1 mg/m3         1991      International Labour Organization ILO. 1991. Occupational Safety
                                                                                         and Health Series, No. 37. Occupational Exposure Limits for Airborne
                                                                                         Toxic Substances: Values of Selected Countries. Prepared from the
                                                                                         ILO-CIS Data Base of Exposure Limits, Third Edition. International
                                                                                         Labour Office; Geneva, Switzerland. 455 pp.
      Denmark              Fume (respirable)               TWA 0.1 mg/m3     Jan, 1999   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
  The Netherlands           Dust (inhalable)             MAC-TGG 1 mg/m3       2003      http://www.cdc.gov/niosh/rtecs/gl5140c8.html
  The Netherlands          Fume (respirable)             MAC-TGG 0.2 mg/m3     2003      http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       Finland              Dust (total dust)              TWA 1 mg/m3       Jan, 1999   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       Finland             Fume (respirable)               TWA 0.2 mg/m3       1991      International Labour Organization ILO. 1991. Occupational Safety
                                                                                         and Health Series, No. 37. Occupational Exposure Limits for Airborne
                                                                                         Toxic Substances: Values of Selected Countries. Prepared from the
                                                                                         ILO-CIS Data Base of Exposure Limits, Third Edition. International
                                                                                         Labour Office; Geneva, Switzerland. 455 pp.
       France               Dust (inhalable)               VME 1 mg/m3       Jan, 1999   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       France              Fume (respirable)               VME 0.2 mg/m3     Jan, 1999   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       France               Dust (inhalable)                VLE 2 mg/m3      Jan, 1993   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
      Germany               Dust (inhalable)               MAK 1 mg/m3       Jan, 1999   http://www.cdc.gov/niosh/rtecs/gl5140c8.html
      Germany              Fume (respirable)               MAK 0.1 mg/m3     Jan, 1999   http://www.cdc.gov/niosh/rtecs/gl5140c8.html




RAPPORTEUR [ITALY]                                        12                 VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH
      Country               Substance                     Standard           Date                   Document and Online document reference
      Hungary             Dust (respirable)           TWA 0.2 mg/m3        Jan, 1993    http://www.cdc.gov/niosh/rtecs/gl5140c8.html
      Hungary             Dust (respirable)          STEL 0.4 mg/m3        Jan, 1993    http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       Ireland       Dusts and mists (inhalable)    OEL (8hr) 1 mg/m3        2002       http://www.niso.ie/documents/COPChemAgents.pdf
       Ireland           Fume (respirable)          OEL (8hr) 0.2 mg/m3      2002       http://www.niso.ie/documents/COPChemAgents.pdf
       Ireland       Dusts and mists (inhalable)   OEL (15min) 2 mg/m3       2002       http://www.niso.ie/documents/COPChemAgents.pdf
       Poland             Dust (inhalable)          MAC (TWA) 1 mg/m3      Jan, 1999    http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       Poland             Dust (inhalable)         MAC (STEL) 2 mg/m3      Jan, 1999    http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       Poland            Fume (respirable)         MAC (TWA) 0.1 mg/m3     Jan, 1999    http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       Poland            Fume (respirable)         MAC (STEL) 0.3 mg/m3    Jan, 1999    http://www.cdc.gov/niosh/rtecs/gl5140c8.html
       Spain            Dust and mist, as Cu         VLA-ED 1 mg/m3          2005       http://www.mtas.es/insht/en/practice/vla2_en.htm
                             (inhalable)
       Spain             Fume (respirable)          VLA-ED 0.2 mg/m3         2005       http://www.mtas.es/insht/en/practice/vla2_en.htm
      Sweden              Dust (total dust)               CLV 1ppm        March, 2000   http://www.av.se/english/legislation/afs/eng0003.pdf
      Sweden              Respirable dust             LLV 0.2 mg/m3       March, 2000   http://www.av.se/english/legislation/afs/eng0003.pdf
   United Kingdom     Dusts and mists (as Cu)       TWA (8hr) 1 mg/m3     2002, 2004    http://www.uwe.ac.uk/estates/Official%20Documentation/COSHH/
                            (inhalable)                                                 EH%2040%202002%20-
                                                                                        %20Occupational%20Exposure%20Limits%202002%20To%20be
                                                                                        %20read%20with%202000%20and%202001%20Ed.pdf

                                                                                        http://www.shef.ac.uk/safety/guidance/OES2004.pdf

   United Kingdom     Dusts and mists (as Cu)      STEL (15min) 2 mg/m3   2002, 2004    http://www.uwe.ac.uk/estates/Official%20Documentation/COSHH/
                            (inhalable)                                                 EH%2040%202002%20-
                                                                                        %20Occupational%20Exposure%20Limits%202002%20To%20be
                                                                                        %20read%20with%202000%20and%202001%20Ed.pdf

                                                                                        http://www.shef.ac.uk/safety/guidance/OES2004.pdf




RAPPORTEUR [ITALY]                                   13                   VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH
      Country               Substance                      Standard                 Date                 Document and Online document reference
   United Kingdom        Fume (respirable)           TWA (8hr) 0.2 mg/m3         2002, 2004   http://www.uwe.ac.uk/estates/Official%20Documentation/COSHH/
                                                                                              EH%2040%202002%20-
                                                                                              %20Occupational%20Exposure%20Limits%202002%20To%20be
                                                                                              %20read%20with%202000%20and%202001%20Ed.pdf

                                                                                              http://www.shef.ac.uk/safety/guidance/OES2004.pdf

 VLA -ED             Daily Exposure Value
 VLA-EC              Short Exposure Value
 TWA                 Time Weighted Average
 STEL                Short Term Exposure Limit
 TLV                 Threshold Limit Value
 LLV                 Level Limit Value
 CLV                 Ceiling Limit Value
 VME                 Valeur Moyenne d'Exposition (INRS value; equivalent to OSHA PEL)
 VLE                 Valeur Limite d'Exposition (INRS value; equivalent to OSHA STEL)
 PEL                 Permissable Exposure Limit (OSHA value)
 REL                 Recommended Exposure Limit (NIOSH value)




RAPPORTEUR [ITALY]                                    14                        VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH


4.1.1.2.2                 Data coverage and representativeness
An overview of the data coverage of EU copper producing and processing plants in the EU is
given in the exposure scenarios.
For an overview of the regional distribution of individual sites in the EU, reference is made to
chapter General information on exposure – Production and Processing.

Overview of data
Most personal exposure inhalation data were described as “typical of routine exposure” and
therefore admissible in the exposure assessment. The duration of exposures for which results
were included ranged from >2-8 hours and these are referred to as time weighted average
(TWA) estimates in the following discussion. Short term samples of duration less than 2 hours
were excluded regardless of apparent representativeness.
Data analysis was broken down by process code, company and by specific activities where
possible. Where very high values were reported, these were examined as possible outliers.
Individual worker codes were not provided by companies hence it was impossible to
determine mean exposures for individual workers. It was therefore not possible to determine
monomorphic exposure groups according to recognised criteria as discussed in section Data
collection and analysis.
The dataset broken down by process code is shown in Table 4-5. There are relatively few data
for exposure to copper powders and copper compounds. This is partly due to the fact that
relatively few companies and workers are engaged in these processes. PC1, mining, was
excluded from the RA prior to data collection as this is outside the scope of the regulation.

Table 4-5 Total dataset for ECI companies

        Process code          Number of     Total number of personal   Number of      Total number of
       (process name)         companies             samples            companies       static samples
      3 (primary smelting)        3                   229                  3               403
    4 (secondary smelting)        4                   196                  3                96
     6 (melting & casting)       12                   240                  9               114
        7 (sand and die           1                    8                   0                 -
            casting)
    8 (wire rod production)       2                   34                   1                1
     9 (further processing)       7                   103                  3                23
      10 (copper powder)          3                   76                   1                6
          11 (copper              4                   67                   1                11
         compounds)
             Total                                    953                                  654



Analysis of personal and static samples by process indicated that static samples generally
underestimate personal exposure with the exception of smelting where the results are




RAPPORTEUR [ITALY]                                     15                      VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
ambiguous. Personal samples only are therefore used for the assessment for risk
characterisation.
No dermal exposure data were available. The derivation of exposure estimates is described
below by process code.

Review of sampling methods and evaluation for exposure assessment
Based on the discussion of sampler efficiency in section 4.1.1.1, details received from
companies were evaluated for sampler selection and use. Correction factors were assigned to
these data accordingly. These are shown in Table 4-6. For all samplers, except the 37mm
open-face cassette, these factors were derived from sampler performance at a windspeed of
1.0 m/sec as shown in Table 4-2. Performance is heavily dependent on windspeed (windspeed
↑, efficiency ↓) with workplace windspeeds expected to be predominantly below 1.0 m/sec.
The correction factor of 2 for the 37-mm open-face cassette is based on an approximately
median estimate of performance in the field. The derived correction factors are therefore
considered to be broadly, but not excessively, conservative.

Process changes
Questionnaires submitted by each company were examined for evidence of process changes
occurring within the data collection period. This examination was designed to identify any
data that were now effectively obsolete, again consistent with the TGD guidance to use only
the most recent data in the RA. One company (ECI-7) engaged in smelting (PC4) reported the
installation of an LEV system in 2000 that resulted in a considerable reduction in exposure.
An approximate eightfold reduction in median personal exposures occurred (Mann Whitney
test, p<0.005). These results were closely reflected by corresponding reductions in static
measurements. Data collected before the introduction of the LEV system were therefore
excluded from further analysis. (This observation also demonstrates the bias that may arise
using historical occupational exposures in the RA).




RAPPORTEUR [ITALY]                               16                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH

Table 4-6 Evaluation of sampling methods and determination of sampler bias for occupational exposure assessment.

ECI code       PC        Number of      Sampling head         Flow rate          Method reference                                Comments                              Correction factor
                          personal                             (l/min)                                                                                                    applied to
                          samples                                                                                                                                        occupational
                                                                                                                                                                        exposure data
    1           3            48        37mm open-face            1-2             ISO/TR 7708:1983                   Sampling described as for “total” dust.                   2
                                          cassette
                                                                                 MTA/MA-025/A92             ISO 7708 defined as ”inspirable” with finer distribution
                                                                                                                               than EN:481
                                                                           (NIOSH method 7300), NIOSH,
                                                                                      2003
    7           4            33              GSP                 3.5            BIA 1989; HSE 2000                        Complies well with EN:481                           1
   10          6/9           39              GSP                 3.5            BIA 1989; HSE 2000                        Complies well with EN:481                           1
   12           9            18              IOM                 2.0                 HSE 2000                             Complies well with EN:481                           1
   17           8            10              IOM                 2.0                 HSE 2000                             Complies well with EN:481                           1
   18           6            88              IOM                 2.0                 HSE 2000                             Complies well with EN:481                           1
   20           9            10              IOM                 2.0                 HSE 2000                             Complies well with EN:481                           1
   21           6            14              IOM                 2.0                 HSE 2000                             Complies well with EN:481                           1
   27           6            36               n/a                2.1                    n/a                  Copper in “total” dust. Sampling method not clearly              2
                                                                                                                                   specified
   28           6            9                n/a                2.1                    n/a                  Copper in “total” dust. Sampling method not clearly              2
                                                                                                                                   specified
   32           6            3         37mm open face            2.0               “BIA” cassette             Copper in “total” dust. Sampling method not clearly             2
                                                                                                            specified but appears to correspond to NIOSH method
                                                                            (NIOSH method 7300, NIOSH
                                                                                      2003)
   46           9            10              IOM                 2.0                 HSE 2000                             Complies well with EN:481                           1
   48           6            38              7HS                 2.0                 HSE 2000                        Reasonable agreement with EN:481                         1.2
   53           9            38              IOM                 2.0                 HSE 2000                             Complies well with EN:481                           1
   54           4           112              GSP                 3.5            BIA 1989; HSE 2000                        Complies well with EN:481                           1




RAPPORTEUR [ITALY]                                       17                         VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH
ECI code       PC     Number of   Sampling head         Flow rate        Method reference                             Comments                           Correction factor
                       personal                          (l/min)                                                                                            applied to
                       samples                                                                                                                             occupational
                                                                                                                                                          exposure data
   55         3/4/6      47            GSP                 3.5          BIA 1989; HSE 2000                    Complies well with EN:481                         1
   67          3/4       198      37mm open-face           1.8      (NIOSH method 7300), NIOSH,     Sampling described as for “total” dust. Sampling            2
                                                                               2003                    method corresponds to NIOSH method
   68          6          4           PAS-6                2.0                  n/a                       Reasonable agreement with EN:481                     1.25
   70          9          9            IOM                 2.0               HSE 2000                         Complies well with EN:481                         1
   76          8         24            n/a                 n/a                  n/a                                        -
   79          6          6            GSP                 3.5          BIA 1989; HSE 2000                    Complies well with EN:481                         1
   81          6          8            n/a                 2.0                  n/a                                        -
   91          11         8       37mm open face           n/a      (NIOSH method 7300), NIOSH,   Sampling method not clearly specified but appears to          2
                                     cassette                                  2003                         correspond to NIOSH method
   93          11        31            GSP                 3.5          BIA 1989; HSE 2000                    Complies well with EN:481                         1
   95          6/7        8            n/a                 n/a                  n/a                                   “inhalable”                               2
   97          10        36            GSP                 3.5          BIA 1989; HSE 2000                    Complies well with EN:481                         1
   105         10        10            IOM                 2.0               HSE 2000                         Complies well with EN:481                         1
   106         10        30            IOM                 2.0               HSE 2000                         Complies well with EN:481                         1
   110         11        12            IOM                 2.0               HSE 2000                         Complies well with EN:481                         1
   112         11        16            IOM                 2.0               HSE 2000                         Complies well with EN:481                         1




RAPPORTEUR [ITALY]                                 18                       VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Use of RPE
The questionnaires were also examined for responses concerning RPE usage. RPE was
factored into the exposure assessment where its use was effectively continuous during the
monitoring period. Hence it was assumed that this period encompassed the periods of
significant exposure. Where ambiguities in the response occurred, for example where it was
reported that RPE was used by “some workers” or by all workers “some of the time”, its use
was discounted for the purpose of the exposure assessment. Specific responses on the class of
RPE worn were used to assign Actual Protection Factors (APFs) in order to provide a realistic
estimate of the resulting attenuation of exposure. Type Approval classes and their associated
APFs are shown in Appendix HH-2. The Nominal Protection Factors (NPFs), now
superseded by APFs, are also shown.


4.1.1.2.3            Production of copper massive

Process description
A schematic of primary and secondary smelter operation is shown in Figure 4-2 and Figure
4-3 respectively. Although furnace configuration varies from plant to plant, smelter operation
can be depicted as a flow chart in which copper concentrate and/or scrap is melted and
progressively purified to produce anodes or blister. In primary smelting, the feed material is
copper concentrate derived from ore, usually loaded automatically via a conveyer. The
furnace configuration may differ from that shown. In secondary smelting the feed material is
scrap either loaded into a smelting furnace, for example loaded through a vertical shaft into a
blast furnace below, or, if sufficiently pure, loaded directly into a converter or anode furnace.
Primary smelting is usually supplemented with the addition of scrap.
The release of molten matte or slag from furnaces may be automated using tipping furnaces.
Alternatively, the transfer is carried out manually, a process known as “tapping”. Using a long
pole, a worker breaches the sand or ceramic material holding the molten metal which then
flows out through a permanent channel. Vigorous agitation of the stream may be necessary to
maintain flow. Transfer of matte or slag between furnaces is performed using large tubs
transported by an overhead crane. Solidified slag arising from various stages of the process,
such as solidified residue emptied from the tubs, is regularly collected by a tipper truck and
loaded into large skips. The skip loads are then recycled into a furnace or converter by the
crane driver.
The final stage of purification is the oxidation of the remaining sulphur in the converter by
blasting the molten metal with air. The 99% copper matte from the converter is then removed
to the anode furnace and cast into anodes on a casting wheel. These are then further purified
electrolytically in the refinery.
However, at large smelters, primary and secondary smelting may be combined within the
same building with separate and/or combined smelting furnaces feeding into a common
converter and anode furnace system. This applies to the data for ECI-67 discussed below.




RAPPORTEUR [ITALY]                               19                     VRAR_CU_0706_HH_EXPOSURE
                    EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
                    DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                  CHAPTER 4. HUMAN HEALTH

                    Figure 4-2 Primary smelter schematic

                                           Concentrates


                                   Raw Material Reception,
                                     Storage & Blending



                                     Feed Material Drying


                                              Feed Mix


                                   Flash Smelting Furnace


                                                Matte


                                          P.S. Converters


                                           Blister Copper

                                         Anode Furnaces
                                         & Casting Wheels

                                         Copper Anodes


                                             Tankhouse



                                         Copper Cathodes




                    Figure 4-3 Secondary smelter schematic

                                         Feed Materials
                                   (scraps, slags, sludges etc)



                                           Shaft Furnace
 Metal oxide dust


                                            Black Copper
    Slag Products


                                              Converter
Mixed Metal oxide


                                               Copper



                                           Anode Furnace



                                               Anodes



                                         Electrolytic Refinery




                                              Cathodes




                    RAPPORTEUR [ITALY]                               20                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH



Inhalation exposure - measured data
All exposure data are adjusted values calculated according to the evaluation of sampling
methods as shown in Table 4-6 . Personal exposure data to copper were provided by 5
companies and the same number of companies submitted static exposure data to copper.
Personal and static exposure to copper by company is shown in Table 4-7 in conjunction with
Table 4-8. Typical personal exposures for primary smelters range from 0.11-0.15 mg/m3. For
secondary smelters the range is 0.02-0.27 mg/m3. Therefore, no straightforward distinction in
exposure levels between primary and secondary smelters can be made. It can be seen that
ECI-55 and ECI-67 have both primary and secondary smelters. In this case, the secondary
smelter represents a minor part of total capacity and operation is less intensive hence
relatively low typical exposures (0.02-0.03 mg/m3) compared to the corresponding results for
their primary smelters (0.11-0.15 mg/m3). There is no clear trend between personal and static
samples. For primary smelting static samples are higher than corresponding personal samples
while this is not the case for secondary smelting. Data for ECI-07 indicate that static samples
heavily underestimate the relatively high RWC exposure.
Other data are broadly in agreement with the lower end of the range of exposure levels
reported above. A small number of static samples (n=4) for the primary smelter of ECI-501
(0.06-0.08 mg/m3) are comparable to personal exposures elsewhere taking into account a
possible underestimate from static samples. ECI-53, another primary smelter, report personal
exposures to copper from 1992 with typical and RWC values of 0.07 and 0.25 mg/m 3
respectively2, in good agreement with the lower range of more recent personal exposures for
primary smelters shown in Table 4-7. The median for static samples taken during this period
was 0.11 mg/m3. Copper exposure monitoring was discontinued at this time, presumably
because the results did not warrant continued monitoring from a regulatory perspective.




1   ECI-50: This company has been closed recently.
2   Data not shown in Table 4.7 because they fall beyond the period 1998-2006



RAPPORTEUR [ITALY]                                     21                       VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH



Table 4-7 Results for personal and static copper measurements for primary (PC3) and secondary (PC4) smelting

                                              primary smelting                                                                     secondary smelting
                               Personal                                    static                                     personal                                    static
                                    mg/m3                                      mg/m3                                       mg/m3                                      mg/m3
             n       typical        RWC     Range         n      typical     RWC        Range       n      typical        RWC       Range        n      typical       RWC      Range
                                            SD                                            SD                                          SD                                         SD
ECI-01      48        0.13          0.46    0.01-9.86     45      0.16       0.25      0.006-0.35
                                                 0.7                                      0.1
ECI-07                                                                                              33         0.27       1.53      0.02-3.5     45      0.06          0.35   0.003-1.4
                                                                                                                                      0.8                                        0.3
ECI-50                                                    4       0.06       0.08      0.04-0.08                                                 11      0.06          0.18   0.04-0.31
                                                                                                                                                                                0.08
ECI-54                                                                                              112        0.14       0.46     0.005-1.19
                                                                                                                                      0.2
ECI-55      21        0.15          0.43    0.005-0.74                                              13         0.03       0.06     0.003-0.08
                                                 0.2                                                                                 0.02
ECI-67      160       0.11          0.88      0.008-     145      0.30       1.72      0.01-75.18   38         0.02       0.18     0.004-1.3    252      0.02          0.91    0.002-
                                              19.10                                                                                                                            107.84
                                                                                          6.6                                        0.01
                                                 1.1                                                                                                                             8.4




RAPPORTEUR [ITALY]                                        22                           VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH

Table 4-8 Job exposure matrix by company (personal samples mg/m³)
Where applicable, exposures incorporating use of RPE in parentheses
                                   smelting        converter            anode       sampling     raw material     other           all
                                                                       furnace
                                   furnaces                                           plant
   ECI-01              n              27              19                                                            2             48
                     Typical      0.13 (0.01)     0.13 (0.01)                                                   4.90 (0.85)   0.13 (0.01)
                     RWC          0.44 (0.02)     0.44 (0.02)                                                   9.86 (0.49)   0.46 (0.02)
                      SD              0.4             0.2                                                                         0.7
                     Range        0.024-1.98       0.012-0.7                                                                   0.01-9.86
                                  (0.001-0.1)     (0.001-0.04)                                                                (0.001-0.49)


   ECI-07              n              16                                  17                                                      33
                     typical      0.17 (0.02)                         0.85 (0.09)                                             0.27 (0.03)
                     RWC          0.89 (0.09)                         1.55 (0.15)                                             1.53 (0.15)
                      SD              0.7                                0.8                                                      0.8
                     Range         0.02-2.78                           0.02-3.5                                                0.02-3.5
                                 (0.002-0.28)                       (0.002-0.35)                                              (0.002-0.35)


   ECI-54              n              35                                  10           42            19             6             112
                     typical         0.11                                0.15         0.32           0.02          0.10          0.14
                     RWC             0.18                                0.20         0.60           0.07          0.52          0.46
                      SD              0.1                                0.1           0.2           0.1           0.2            0.2
                     Range        0.005-0.28                          0.031-0.31    0.033-1.19    0.005-0.28    0.02-0.52     0.005-1.19




RAPPORTEUR [ITALY]                                             23                        VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH
   ECI-55              n           14           10               8                        2                        34
                     typical      0.03         0.16             0.07                    0.16                      0.06
                     RWC          0.17         0.46              0.2                    0.54                      0.31
                      SD           0.1          0.2              0.1                                               0.2
                     Range     0.003-0.24    0.02-0.74        0.03-0.31               0.03-0.54                0.003-0.74


   ECI-67              n           71           42               41          32          12                       198
                     typical      0.23         0.05             0.08        0.04        0.02                      0.10
                     RWC          1.28         0.53             0.40        0.19        1.03                      0.74
                      SD           3.3          0.5              0.4         0.3         0.4                       2.2
                     Range     0.022-19.14   0.008-2.19       0.02-2.58   0.004-1.3   0.006-1.21               0.004-19.14


     all               n          163           71               76          74          33           8           425
                     typical      0.13         0.09             0.12        0.19        0.02         0.10         0.12
                     RWC          0.66         0.47             0.95        0.55        0.29         3.32         0.68
                      SD           2.2          0.4              0.6         0.3         0.3          3.4          1.5
                     Range     0.003-19.14   0.008-2.19       0.02-3.5    0.004-1.3   0.005-1.21   0.02-9.86   0.003-19.14




RAPPORTEUR [ITALY]                                       24                   VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
A job exposure matrix for major smelting TWA exposures is shown in Table 4-8. These
results are also shown in summary form in Table 4-9.
Smelting furnaces are defined as those principally employed at the earlier stages of smelting
and the various designs of smelting furnaces are therefore considered as a generic scenario.
Typical exposures for smelting furnaces are also shown in Figure 4-4 . These range from
0.03-0.23 mg/m3. With the exception of ECI-67, RWC exposures range from 0.17-0.89
mg/m3. RWC exposure for ECI-67 is 1.28 mg/m3. This is due to a small number of unusually
high exposures for flash furnace workers with adjusted values ranging from 10.7-19.14 mg/m3
(n=3). If these points are excluded, typical and RWC estimates are 0.21 and 0.84 mg/m3
respectively indicating the leverage exerted by these few data points. These high exposures
arose from occasional failures in filters/seals etc which are promptly remedied. When these
points are excluded, data across the sector are in good agreement as shown in Table 4-9.
Recent information from ECI 67 states “these problems have been resolved due to a better
exhaust hood and due to the implementation of a new routine to handle equipment.” The
higher exposures should no longer apply.
The pooled data for smelting furnaces are presented in Table 4.9. These show a typical
exposure of 0.13 and RWC of 0.66 mg/m³ including the high exposure values of ECI-67.
Excluding these values, the typical and RWC values are 0.13 and 0.63 mg/m³ respectively.

Table 4-9 Summary exposure data for smelting                (from Table 4-8)

                                               Range of results by company          Pooled data
                                                         (mg/m3)
                                                Typical             RWC        Typical       RWC


         Smelting furnaces, all data            0.03-0.23         0.17-1.28     0.13          0.66


  Results with high leverage points (ECI-67)    0.03-0.21         0.17-0.84     0.13          0.63
                   excluded
                 Converters                     0.05-0.16         0.44-0.53     0.09          0.47
           Anode furnace, all data                                              0.12          0.95
 Automated furnace operation (w/out tapping)    0.07-0.15         0.20-0.40


   Manual furnace operation (with tapping)        0.85              1.55
               Sampling plant                   0.04-0.32         0.19-0.60     0.19          0.55
           Raw material handling                0.02-0.16         0.07-1.03     0.02          0.29




RAPPORTEUR [ITALY]                                        25                   VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Figure 4-4 Typical personal exposure to copper for smelting furnaces                    (a) high scale showing points of high leverage
                                                                                        (ECI-67), (b) low scale showing typical spread
                                                                                        of data.
a)
                    copper mg/m3


                                    20
                     Cu (corr)




                                    10




                                         0

                                                 1       7           54            55            67

                                                             Company code
b)
                 copper mg/m3


                                             2
                             Cu (corr)




                                             1




                                             0
                                                     1       7         54            55            67
                                                         Company code

Horizontal bars indicate median values; boxes indicate the interquartile range; whiskers indicate the range of points within one
interquartile range of the box; asterisks indicate points outside this range but are not necessarily outliers.


Data for converter operation are also shown in Figure 4-5. Data are generally in good
agreement with some higher values for ECI-67. Typical and RWC exposures range from 0.05-
0.16 mg/m3 and 0.44-0.53 mg/m3 respectively. The corresponding pooled data for typical and
RWC exposure are 0.09 and 0.47 mg/m3.




RAPPORTEUR [ITALY]                                                  26                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Figure 4-5 Typical personal exposure to copper for converters



                               2


   copper mg/m3
                   Cu (corr)




                               1




                               0
                                          1                      55                      67

                                                          ECI company code

Horizontal bars indicate median values; boxes indicate the interquartile range; whiskers indicate the range of points within one
interquartile range of the box; asterisks indicate points outside this range but are not necessarily outliers.


Typical anode furnace exposures are shown in Figure 4-6 . With the exception of ECI-07,
exposures for anode furnace workers are in good agreement with typical and RWC exposures
range from 0.07-0.15 mg/m3 and 0.20-0.40 mg/m3 respectively. ECI-54 and ECI-55 employ
two tipping anode furnaces therefore no direct worker contact is required during pouring of
molten metal. The corresponding exposures for ECI-07 are 0.85 and 1.55 mg/m3. These
results are due mainly to manual tapping. RPE is used by all continuously exposed workers at
this company. Corresponding exposures taking use of RPE into account are 0.09 and 0.15
mg/m3.
As a result of such differences between companies arising from process variables, pooled data
for anode furnace operation are not representative of real exposures. The pooled estimate of
typical exposure (0.12 mg/m3) is a considerable understimate of data for ECI-07 (0.85
mg/m3). The pooled RWC estimate (0.95 mg/m3) also heavily underestimates exposure for
ECI-07 (1.55 mg/m3) and overestimates exposures for other companies (0.20-0.40 mg/m3).
Indicative dust exposures during tapping at ECI-07 are shown in Figure 4-7. Peaks arise
when the worker starts the flow or vigorously agitates the molten metal. Time weighted
results for this monitoring indicate levels of 3.4-4.7 mg dust/m3 in contrast with equivalent
data for other activities at this plant ranging from 0.9-1.7 mg dust/m3. It is noted that
comparable indicative dust results (3.4 mg dust/m3) were recorded during tapping of slag at
the melting furnace at ECI-55. However, the latter material, slag from first-stage smelting, is
low in copper while anode furnace matte for casting is 99% pure copper. These differences in
composition are not reflected in the Microdust results.




RAPPORTEUR [ITALY]                                                  27                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Figure 4-6 Typical personal exposure to copper for anode furnaces



              copper mg/m3
                                      2


                          Cu (corr)



                                      1




                                      0
                                          1           7          54          55          67

                                                      ECI company code
Horizontal bars indicate median values; boxes indicate the interquartile range; whiskers indicate the range of points within one
interquartile range of the box; asterisks indicate points outside this range but are not necessarily outliers.

Figure 4-7 Indicative dust levels for anode furnace tapping (ECI-07).          Real-time indicative dust levels (y-axis) as a
                                                                               function of time in minutes (x-axis)




                                                                                                                        Time (min)




                                                                                                                          Time (min)


RAPPORTEUR [ITALY]                                               28                            VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Exposures from the sampling plant are available for ECI-54 and ECI-67. Sampling plants are
small units attached to secondary smelters where small amounts of scrap are tested and
smelted to determine the copper content and physical properties. Some activities, such as
milling and crushing, may generate dust. Typical and RWC exposure are 0.04-0.32 and 0.19-
0.60 mg/m3 respectively. The pooled data for typical and RWC exposure are 0.19 and 0.55
mg/m3 reflecting the homogeneity in results for the two companies for which data are
available.
Limited exposure data are available for raw material handling. In some cases raw material
handling is indistinguishable from furnace operation, for example, loading a secondary anode
furnace with high purity scrap. In these cases, exposures are classified as furnace operation.
Exposures are classified as raw material handling where this activity comprises all or most of
a worker’s exposure, hence the small number of samples. Typical and RWC estimates range
from 0.02-0.16 mg/m³ and 0.07-1.03 mg/m3 respectively. Data for ECI-67 are higher with a
RWC of 1.03 mg/m3. This arises due to two datapoints taken during an operation of a loading
vehicle presumably without cabin filtration. If these points are excluded, typical and RWC
estimates for ECI-67 are 0.02 and 0.17 mg/m3 respectively indicating the leverage exerted by
these two data points. The pooled data for typical and RWC exposure are 0.02 and 0.29
mg/m3.
The analysis of the company data in Table 4-8 indicates that much of the variability can be
explained by operational variables. SD values are generally lower when this stratification is
performed relative to the pooled values for individual companies or sector-wide analysis.
Conclusion
It can be concluded that for copper smelters and refineries (primary, secondary smelting and
refining) the data collected cover 79% of the tonnage produced in Europe. Nine out of 10
companies provided personal or static exposure data of which 5 companies provided recent
personal exposure data and a sixth company provided older data. The personal data collected
cover about 64% of the workers exposed. In respect of plant size and smelter types, the
coverage is considered reasonably representative. Application of these data to other
companies assumes an equivalent level of control measures, specifically effective hoods at
furnaces.

Personal sampling data are available for five smelters covering the primary and secondary
sectors. Most data are for furnace activity with more limited data for ancillary operations,
mainly sampling plant and raw material handling. Some supporting data arising before the
beginning of data collection for the risk assessment are also available. Exposure data across
the smelting sector are generally similar with some higher exposures attributable to specific
operational variables. With the exception of manual furnace operation, exposure data from all
furnace operations will be pooled for risk characterisation. The following operations will be
distinguished:
-Furnace operations (all smelting, converter, automated anode furnace operations)
-Manual anode furnace operations
-Sampling plant
-Raw material handling
These are summarised in Table 4-45.




RAPPORTEUR [ITALY]                               29                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Inhalation exposure – modelled data

Application of the EASE model is inapplicable to processes (such as hot metal processes) for
which there is no related EASE scenario.

Acute inhalation exposure
Process observation indicates that task specific exposures in smelting likely to produce the
highest acute exposures are the mechanical handling of solid slag/waste for disposal or
recycling within the smelting operation and manual furnace tapping.
The mechanical handling of solid slag can produce high peak copper concentrations as shown
in Figure 4-8. The data shown are for parallel Respicon and Microdust static measurements
taken at the furnace operator’s normal position. Exposure estimates that follow assume he
remains at this position. Further analysis of the data in Figure 4-8 indicate peak exposures of
copper ranging from approximately 12-65 mg/m3. These are typically less than one minute
and can be as short as 5 seconds in duration. Event based copper exposures, defined as
exposure for the duration of the peaks in Figure 4-8, are typically of three minutes duration.
These range from 2.4-21.0 mg/m3. Estimated 15 minute exposures (relevant for compliance
with national regulatory STELs), range from 1.9-5.1 mg/m3.

Figure 4-8 Parallel Casella Microdust and Respicon sampling data (mg/m3) during routine operations in smelting with
intermittent generation of dust from handling of dry slag.



                                                                                70
                                                                                           microdust
          Casella Microdust: indicative dust level (mg/m3). Respicon sampler:




                                                                                           Respicon (copper in
                                                                                60         inhalable dust)



                                                                                50



                                                                                40



                                                                                30
          copper in inhalable dust (mg/m3).




                                                                                20



                                                                                10



                                                                                 0
                                                                                     0.0   20.0        40.0      60.0    80.0   100.0   120.0   140.0   160.0

                                                                                                                                                    Time (min)




RAPPORTEUR [ITALY]                                                                                                  30                    VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
These estimates are subject to a number of uncertainties. The operator may not remain at this
position throughout the event if his presence is not required, nor is it known how
representative this plant is of acute exposures throughout the sector. The major uncertainty
with the sampling method is the assumption that the copper fraction of inhalable dust remains
constant during the sampling period.
Figure 4-8 indicates that the Casella Microdust performs reasonably well as a surrogate for
real-time copper measurements during the activity monitored. The indicative reading is
typically 50-100% of the corresponding value for the Respicon sampler. The closest
agreement is found at lower concentrations (~100%) while the instrument underestimates by
up to 50% at peak levels. Further analysis of the Respicon data for the inhalable and
respirable fractions indicates that the peak exposures from dry slag handling have a higher
proportion of inhalable dust than that found in “background” levels between these events.
This observation is consistent with the good agreement with the Microdust at low levels given
that the sensitivity of the Microdust tapers off outside the respirable range.
The second activity which can produce high peak copper concentrations is manual anode
furnace tapping. It is possible to derive an approximate estimate for acute copper exposure
during manual anode furnace tapping shown in Figure 4-7. In broad terms, task specific
exposure to copper over a 15 minute (or longer) period is expected to be in the range 3-5
mg/m3 based on the mean values in Figure 4-7 and assuming the activity is extended to 15
minutes. Peak based exposures in Figure 4-7 over a minute or less are in the range 10-15
mg/m3. These values are in broad agreement with the data above for peak exposures in
smelter operation. These estimates are specific to manual anode furnace tapping for one
company. As indicated above, automated tipping furnaces remove the need for tapping.
Tapping of other furnaces also produces high indicative dust levels but less copper exposure
due to the lower copper fraction of the matte or slag. This is evident from the long term
personal sampling data in Table 4-8.

Conclusion – Acute inhalation exposure
Acute exposures are conventionally assessed against a 15 minute TWA. Many regulatory
authorities use a STEL (15 minute limit) to protect against acute effects. RWC acute exposure
to copper is therefore estimated at 2-5 mg/m3, Using optical based sampling devices shorter
term event-based exposures have been investigated. Event based exposures of three minutes
or less of 2.5-20 mg/m3 and 5-seconds exposures of up to 65 mg/m³ have been found.
However, based on many observations during the sampling exercises, it is considered that
exposures of this magnitude are infrequent on a sector-wide basis. In the absence of irritant
effects, acute exposures are assessed against 15-minute limits.

Dermal exposure – measured data
No dermal exposure data are available for the copper industry. However, dermal exposure
data for a comparable type of production are available from Hughson et al (2005) in various
zinc industries. In these studies, measurements of dermal zinc exposures at the workplace
were collected for an industry-wide risk assessment and also compared with the levels
predicted by EASE. Measurements were obtained from subjects in seven different workplaces
that were producing or working with zinc metal or zinc compounds. Further to the cited paper,
the original raw data were made available by the authors (Hughson, 2005). The production of
zinc involves amongst others raw material handling, smelting and refining, similar steps as
those involved in the production of copper. Similarly, the production of Cu-powders and Cu-




RAPPORTEUR [ITALY]                               31                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
compounds largely involves the same basic process steps as in the production of Zn-powder
and Zn-compounds. Hughson et al. (2005) analysed data from a survey consisting of 3 phases.
However, data from the first phase are not considered here due to methodological differences
between these phases (i.e. whereas palms and backs of the hands were examined in the second
phase, only the backs of the hands were sampled in the first phase). Selected data potentially
relevant for justification of the extrapolation form zinc data to copper such as particle size,
dustiness and relative density have been summarised in Table 4-10 below, in comparison to
the corresponding zinc compounds:

Table 4-10 Comparison of selected physico-chemical properties of zinc and copper compounds

   Property of     Copper        Copper        Copper (II)        Dicopper      Copper        Zinc          Zinc         Zinc
   compound        (I)oxide      (II)oxide     Sulphate           chloride      powder        powder        dust         oxide
                                               pentahydrate       trioxide
         rel.         5.87          6.32             2.29             3.64          8.9          7.14          7.14        5.6(2)
    density(1)
      [g/cm³]
    d50(3)[μm]         3.3          32.5            220.4             2.3          129.0        ~200(2)       ~4(2)         ~1(4)
        total           7           363              49               33            46             1            2           30(6)
   dustiness(5)
      [mg/g]
Sources: (1) producer data; (2) Zinc RAR (2004); (3) Franke, 2004a-e; (4) company data; (5) Selck, 2004; (6) Armbruster, 2000


Despite the fact that the use of dustiness and particle size distribution data in the assessment
of occupational inhalation exposure is far from standardised, use of these parameters has
previously been made in the EU Risk Assessment Reports on Zinc and Zinc compounds for
the purpose of extrapolation between compounds. Using the same approach, the following
tentative conclusion may be drawn with reference to the possibility of extrapolating from
occupational exposure data collected for zinc oxide: Copper sulphate, Copper oxychloride,
Copper (I) oxide and Copper powder have total dustiness values of a similar order of
magnitude as zinc oxide. Given that the perception of potential health hazards for both metals
that influence the design of exposure control measures are similar, then it would appear
reasonable to extrapolate from zinc oxide to these for the assessment of dermal exposure
during handling of finished products. Since the dustiness of Copper (II) oxide is somewhat
higher, extrapolation from zinc oxide to this compound could at first sight be considered as
somewhat limited, and to potentially represent an underestimate. However, the occupational
inhalation exposure data for Copper (II) oxide are similar to those of the other Copper
compounds, indicating that exposure controls are similar between all Copper compounds.
The production of copper metal largely precludes direct contact either with the input materials
or the interim and /or finished product. This is also the case for the scenarios "melting and
casting" and “further processing”, which is why these are dealt with together in view of the
anticipated common exposure characteristics.
Dermal exposure data specifically for the scenarios production of copper metal, melting and
casting and further processing are not available. For this reason, the “analogous substance”
approach (HERAG, 2006) was taken, by extrapolating from data collected in the zinc
industry. The production of zinc metal involves among others processes such as raw material
handling, smelting, refining and casting, which are very similar to those involved in the
production of copper.




RAPPORTEUR [ITALY]                                               32                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
The collection of the analogous zinc data (Hughson & Cherrie, 2005) can be summarised as
follows:
In the zinc refinery, tasks involving the greatest potential for exposure were selected. This
included workers who were involved with the transfer of raw materials, workers in the
smelting and molten metal refining areas, and those involved with packing of the final
product. Samples were collected using wet wipes, and sampled areas included the hands (back
and palms), forearms, forehead, neck and chest. Three consecutive wipes were collected from
the same area of skin each time of sampling, and pooled for a cumulative analysis in an effort
to limit the number of separate samples to be analysed. The method validation included
efficiency of recovery, field blank samples and control samples from non-occupationally
exposed individuals. It is explicitly noted that this zinc survey was conducted in two phases.
Only the data from phase 2 were considered here, because in phase 1 only the backs of the
hands were sampled, whereas in phase 2 also the palms were included, which showed a clear
trend to higher levels of exposure. Dermal loading rates and maximum skin loading levels as
investigated in phase III of these surveys are not considered here in view of the overall low
exposure levels which are very distant from saturation levels. The measured dermal exposure
data (hands and forearms only) available for "zinc refineries" used for this extrapolation are
presented in a summarized form in Table 4-11 below (the individual raw data used for these
calculations are presented in Appendix HH-4):

Table 4-11 Dermal exposure to zinc in a zinc refinery [μg zinc / cm² skin]

  Exposure to                Max              90th percentile           Median                   Min                 Counts


      Zinc                    123                    34                    24                      8                    14
   Zinc oxide*                153                    43                    30                     10                    14
*The dermal exposure against zinc oxide was estimated by multiplying the exposure values for "zinc” with the reciprocal value of the zinc
content in zinc oxide (1.245), in analogy to HERAG (2006).


It is assumed that occupational dermal exposure in the processes summarised under this
scenario occurs primarily to copper and copper oxide, the ratio of which under occupational
circumstances is however not known. Given the fact that the relative copper content between
“pure” copper and the two oxides varies at most between 80-100%, the conservative
assumption is made that exposure occurs to the metal itself, and no correction was made when
extrapolating from zinc dermal loading to copper. Given that zinc under these industrial
circumstances is always coated with a passivated zinc oxide layer, zinc refinery dermal
exposure levels were assumed to represent exposure to “zinc oxide”. Thus, these dermal
loading rates were converted to “copper” without any correction factor, assuming for
simplification that equal mass loading occurs in both industries, with some inherent
conservatism given by this approach. The extrapolation from zinc/zinc oxide data to copper
and copper oxide is also considered justified in view of the similarly low dustiness of zinc
powder, zinc dust and zinc oxide in comparison to copper (powder), which all fall within the
dustiness range 0-50 mg/g.

Table 4-12 Extrapolated dermal exposure to copper in the production of copper massive
  Exposure to                Max              90th percentile           Median                   Min
     Copper                  153                    43                    30                     10
  concentration
    [μg/cm²]




RAPPORTEUR [ITALY]                                                 33                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
  Copper mass        303            85                 60                 21
   [mg/day]*
*full-shift dermal exposure in [mg/day] based on an assumed exposed surface of 1980 cm² (hands and forearms)
In conclusion, the occupational dermal exposure (full shift) to copper in the scenarios
“production of copper massive”, “melting and casting” and “further processing” by way of
extrapolation from “analogous” data on zinc yields estimated values of 60 mg/day (typical
exposure) and 85 mg/day (worst-case), respectively.
Dermal exposure - modelled data (EASE 2.0)

Application of the EASE model is inapplicable to hot metal processes for which there is no
related EASE scenario.

Conclusion – dermal exposure
The estimated typical and reasonable worst case exposure levels for hands and forearms
during the production of copper are respectively 60 mg Cu/day and 85 mg Cu/day.


4.1.1.2.4                 Melting and casting

Process description
Process codes 6 (melting and casting of billets and ingots), 7 (sand and die castings) and 8
(melting and casting for the production of wire rod) cover the production of semi-finished
products through melting and casting operations. The production process includes the
following operations:
-melting refined copper cathodes or high purity scrap in a melting furnace,
-casting of shapes
-finishing
Scrap may first need to be sorted manually and bundled. Casting is usually continuous or
semi-continuous depending on the plant and the application. Billets and wire rod are formed
from continuous casting by cutting the cooled copper with a saw, while ingots may be cast
discretely in moulds. Routine operation performed by workers include furnace loading,
furnace operation and supervision, process control and inspection. Finishing by sawing,
blasting or manually finishing with power tools may be carried out.
Routine maintenance includes furnace cleaning. This entails cooling the furnace, deslagging
using hand or power tools and removal of waste material. Other maintenance tasks include
maintenance of dust extraction systems.
Since exposures are very similar across companies and tasks in melting and casting,
exposures were pooled.

Inhalation exposure – measured data
Data are available for 15 companies in melting and casting and cover 30% of the tonnage
produced. The personal data collected cover about 30% of the workers exposed.
Routine production operations



RAPPORTEUR [ITALY]                                              34                           VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Based on the job descriptions above, exposures in routine production operations are
associated with low exposures as shown in Table 4-13. Typical exposures across a range of
companies in melting and casting for billets (PC6) sand and die castings (PC7) and wire rod
production (PC8) are in good agreement 0.06-0.15 mg/m3.
RWC exposures during production across a range of companies in melting and casting for
billets (PC6), sand and die castings (PC7) and wire rod production range from 0.11 to 0.64
mg/m3.
Routine furnace cleaning forms part of the operators’ normal workload. These exposures are
therefore within the scope of the TGD. The frequency of this operation is reported typically as
30 minutes once per week. Estimates of task specific exposures for furnace cleaning (ECI-10)
are based on one task specific measurement (0.68 mg/m3) at ECI-10 and one task specific
estimate of 11.5 mg/m³ from a longer term (3 hr) sample of 2 mg/m³. Both values are used to
estimate daily, and weekly average, 8 hour TWA exposures incorporating furnace cleaning.
These calculations are based on the measured furnace cleaning exposures of 0.68 and 11.5
mg/m³ (30 minutes), with the remainder of the shift estimated at the median exposure for ECI-
10 (0.11 mg/m3). The results are shown in Table 4-14. Even when the higher value of 11.5
mg/m3 is used, the weekly average 8 hour TWA exposure without RPE (0.25 mg/m3) is close
to the range for exposures during routine operations (0.06-0.15 mg/m³) as shown in Table
4-13. RPE is always used during furnace cleaning at this company resulting in a weekly
average exposure estimate of 0.12 mg/m3, effectively unchanged from the median value in the
absence of furnace cleaning.




RAPPORTEUR [ITALY]                               35                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH

Table 4-13 Personal exposure melting and casting (mg/m3)

                                                             Billets (PC6)1                                 Sand and die castings (PC7) 2                     Wirerod (PC8) 3
                                              n           Typical      RWC          Range            n           Typical       RWC          Range     n      Typical      RWC     Range
                                                                                      SD                                                     SD                                     SD
Routine operations                         187 (12)        0.14         0.64      0.002-10.82       8 (1)          0.15        0.24     0.03-0.29   30 (2)    0.06        0.37    0.004-
                                                                                                                                                                                   17.4
                                                                                      1.0                                                    0.1
                                                                                                                                                                                    3.1
Routine operations including furnace                         0.25 (0.12)                            n/a            n/a          n/a          n/a     n/a       n/a         n/a      n/a
cleaning. Estimate of weekly average
    with RPE (in parentheses) and
 without. See text and Table 4-11 for
                details
            Alloy operations                24 (2)         0.03         0.30      0.008-1.04        n/a            n/a          n/a          n/a     n/a       n/a         n/a      n/a
                                                                                      0.2
             Finishing ops                  17 (4)         0.07         0.33       0.02-0.74        n/a            n/a          n/a          n/a     n/a       n/a         n/a      n/a
                                                                                      0.2
             Raw material                   22 (2)         0.24         1.24       0.02-3.6         n/a            n/a          n/a          n/a    4 (1)     0.18        0.23   0.02-0.23
                                                                                      0.8

n/a not available
n=sample size, (number of companies providing data in parentheses)
1: ECI-10, ECI-18, ECI-21, ECI-27, ECI-28, ECI-32, ECI-48, ECI-53, ECI-55, ECI-68, ECI-73, ECI-81
2:ECI-95
3: ECI-17, ECI-76”




RAPPORTEUR [ITALY]                                             36                              VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Table 4-14 Estimated 8 hour TWA exposures (mg/m3) for melting and casting (ECI-10) incorporating                         (1)
furnace cleaning operations



                                   8 hour TWA exposure (mg/m³)              Weekly average 8 hour TWA exposure (2)
                                                                                           (mg/m³)


   Task specific                Without RPE          With RPE (P2)                Without RPE           With RPE (P2)
   exposures for                                     during furnace                                     during furnace
 furnace cleaning                                     cleaning only                                      cleaning only
       0.68 (3)                      0.15                  0.11                      0.12                      0.11
       11.5 (4)                    0.82 (5)                0.18                     0.25 (6)                   0.12

(1) Basis: TWA exposures are calculated using task specific exposures shown with a “background” exposure of 0.11 mg/m3 (median
exposure for ECI-10)
(2) Basis: one 30 minute furnace cleaning operation per 40-hour week
(3) Single measured task specific exposure
(4) Calculated task specific exposure based on 3 hour sample (2.0 mg/m3) with 30 minutes furnace cleaning.
(5) 0.82 = (0,11*7,5+11,5*0.5)/8
(6) 0.25 = (0,11*39.5+11,5*0.5)/40


A number (n=10) of anomalously high exposure values are reported at two companies. These
findings are due to operations to remove molten slag from the holding furnace using a piece
of timber. During the industrial hygiene sampling operations at one of the companies, one
operator did this job regularly during the shift. Of the 4 shifts sampled, three operators had
measured copper exposures of less than 2 mg/m³ whereas the fourth had a result of 17.4
mg/m³. The disturbance of the molten metal and the thermal degradation of the timber during
this action produces high transient exposures. RPE is not used. Such exposures are surprising
and do not appear to occur elsewhere.
Indicative dust levels from industrial hygiene investigations using the Casella Microdust
sampler for melting and casting for billets are shown in Table 4-15. These support the data in
Table 4-13 with mean dust levels around the casting line and melting furnace of ≤0.1 mg
dust/m³. An exception to this is the long-term dust measurement for which a maximum value
of 5.8 mg dust/m³ was recorded. Observation of the process and inspection of nearby surfaces
indicated that this was due to the periodic addition of powdered charcoal to prevent oxidation
of copper which did not increase exposure to copper.

Table 4-15 Melting and casting: indicative dust levels by operation (mg/m3)

                     location                         t       mean         max                               comments
 casting                                            L/T           0.4       5.8        dust caused by addition of carbon black
 casting                                            S/T           0.1       0.3        no carbon black added
 melting furnace                                    S/T           0.1       0.3
 "channel" between casting furnace and              S/T        <0.1         0.2
 casting
 hand finishing billets of (during and after)       S/T           0.5       4.2        Performed outside. No exposure when not finishing




RAPPORTEUR [ITALY]                                                 37                           VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
The Casella microdust sampler makes it possible to obtain instantaneous (1 seconds) dust
level measurements and also to graph exposure averages over a 5 second period. In Table
4-15, the maximum instantaneous reading for hand finishing of billets is 4.2 mg/m³. The
maximum 5 second reading is 2.6 mg/m³(Figure 4-9). The dust exposure averaged over the
cleaning of 1 billet (2 minutes) is approximately 1.5 to 2 mg/m³. All these exposures were
measured close to the workers breathing zone. However, the two available samples for copper
exposure during hand finishing of billets (for another company) are both <0.10mg/m³. Clearly
the time spent on this task is limited hence the modest measured 8 hr TWA exposure to
copper.

Copper alloys
Results for melting and casting of copper alloys are lower with typical and RWC exposures of
0.03 and 0.30 mg/m³. These findings are consistent with recent data for alloy foundries in the
US (n=22) where reported median values for personal exposure were 0.04 mg/m3 with a 90th
percentile of 0.18 mg/m³. (Cohen and Powers, 2000).

Raw material handling
Raw material handling exposures are very similar for the two companies for which data are
available, ECI-21 and ECI-18. The typical and RWC for this operation are 0.24 and 1.24
mg/m³. The RWC value is highly influenced by an unusual high exposure value. If this point
is excluded, typical and RWC estimates are 0.23 and 0.60 mg/m3 respectively.

Figure 4-9 Indicative dust exposure during finishing of billets.   Real-time indicative dust levels (y-axis) as a function of
                                                                   time in minutes (x-axis)




Inhalation exposure – modelled data
Application of the EASE model is inapplicable to processes (such as hot metal processes) for
which there is no related EASE scenario.




RAPPORTEUR [ITALY]                                           38                          VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Conclusion – inhalation exposure
For the melting & casting activities (including casting of billets, plates, wirerod, ingots and
sand and die casting), 30% of the tonnage produced is covered by the data obtained. The
personal data collected cover about 30% of the workers exposed.
Melting and casting operations considered here employ largely homogeneous production
methods, i.e. continuous or semi-continuous casting. Exposure from routine maintenance i.e.
furnace cleaning is generally well controlled using RPE. Provided that inappropriate practises
for furnace de-slagging are avoided the data are considered reasonably applicable to the
sector.
In all, data are available for 15 companies in melting and casting. Exposure levels are
generally in good agreement. Therefore data for all companies will be considered as a single
scenario in risk characterisation. The data carried forward for risk characterisation are
summarised below in Table 4-16.

Table 4-16 Inhalation data carried forward for risk    Data from Table 4-13.
characterisation for melting and casting

Risk characterisation                                      Typical             RWC
                                                       Cu(mg/m³)          Cu(mg/m³)
PRODUCTION OF BILLETS (PC6), SAND AND DIE CASTINGS (PC7), WIREROD (PC8)
All operations (site specific data)                        0.03-0.24       0.23-1.24
Pooled data                                                  0.12              0.6



Acute inhalation exposure
Acute exposures for melting and casting are considered to arise mainly from periodic furnace
cleaning, as described above, and from manual deslagging operations. Estimates of copper
exposure for furnace cleaning over a 30 minute period are shown in Table 4-14 and range
from 0.68-11.5 mg/m3 without RPE. Use of RPE is however mandatory during furnance
cleaning and acute exposure values range between 0.34 and 0.58 mg/m³ taking into account
their use. The corresponding 15 minute and peak event based exposures are unknown. These
data are therefore used as an approximation for the 15 minute acute exposure although they
may be underestimates.
Conclusion – acute inhalation exposure
RWC acute exposure for furnace cleaning without RPE is taken as 11.5 mg/m3.
RWC acute exposure for furnace cleaning with RPE is taken as 0.58 mg/m3.

Dermal exposure – measured data

No dermal exposure data are available for the copper industry. However, dermal exposure
data for a comparable type of production are available from Hughson et al (2005) in various
zinc industries. In these studies, measurements of dermal zinc exposures at the workplace
were collected for an industry-wide risk assessment and also compared with the levels
predicted by EASE. Measurements were obtained from subjects in seven different workplaces




RAPPORTEUR [ITALY]                                    39                       VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
that were producing or working with zinc metal or zinc compounds. Appendix HH-4 to this
document describes the zinc dermal exposure data. Chapter Production of copper massive -
Dermal exposure – measured data describes the rationale for the extrapolation from zinc
data to copper and the proposed dermal exposure values for copper. The data for the
production of massive copper (Table 4-12) are used here on the basis that dermal exposure
for melting and casting is expected to be similar as similar hot process are involved.
Typical and RWC dermal exposure estimates are 60 and 85 mg/day based on exposure to
hands and forearms only in accordance with the TGD.
Dermal exposure - modelled data (EASE 2.0)

Application of the EASE model is inapplicable to hot metal processes for which there is no
related EASE scenario.

Conclusion – dermal exposure
The estimated typical and reasonable worst case exposure levels for hands and forearms
during melting and casting are respectively 60 mg Cu/day and 85 mg Cu/day.


4.1.1.2.5            Downstream use: Further processing

Process description
Semi-finished products are further processed through mechanical processes (rolling, extrusion
and drawing) to a variety of copper and copper alloy industrial and consumer products as
wires, cables, sheets, profiles and strips. Little dust is generated and further processing is
therefore rather different to other processes considered in the RA although some other
activities are also carried out (e.g. sorting of scrap and other raw material handling).
It should be noted that polishing of copper plates, the activity described in the paper by
Gleason (1968), has not been used for many years in Europe. Also the grinding activity
described by Suciu et al. (1981) has not been used in Europe for many years. The endproduct
is obtained through improved technologies and the selection of specific alloys.

Inhalation exposure data – measured data
The total number of responses received covers 68% of the tonnage. Many of the data provided
were however from static samples, which have not been further used. Personal exposure data
were provided by six companies and cover 20% of the tonnage processed and about 20% of
the workers exposed.
Personal exposure data are shown in Table 4-17. Exposures during routine operations are low
with typical and RWC exposures of 0.03 mg/m3 and 0.2 mg/m3 respectively. No indicative
dust data are available but, given that operations similar to those in melting and casting
(Table 4-13) may occur, the low exposures reported here are plausible.
Exposure during raw material handling is typically low (0.1 mg/m³) but high exposure may
occur. The use of RPE is however mandatory and reduces the RWC from 2.45 mg/m³ to 0.13
mg/m³. Typical and RWC of all pooled data (without RPE) are 0.04 and 0.3 mg/m³
respectively and -considering the use of RPE- reflects well the exposure of the workers during




RAPPORTEUR [ITALY]                               40                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
further processing activities. These values will be taken forward to the risk characterisation
chapter.

Table 4-17 Personal exposures for further processing

                                                                         Cu (mg/m³)
                                               n          typical           RWC        Range
                                                                                         SD
 routine ops                                81 (6)          0.03               0.2    0.001-0.78
                                                                                         0.1
 raw material –without RPE                  12 (3)          0.1                2.45    0.01-19
 (with RPE)                                                (0.05)           (0.13)       5.2
                                                                                       (0.003-
                                                                                        0.95)
 All data                                   93 (6)          0.04               0.3    0.001-19
                                                                                         2.0

n=sample size, (number of companies providing data in parentheses)


Inhalation exposure - modelled data (EASE 2.0)

Application of the EASE model is inapplicable as there is no related EASE scenario.
Conclusion
With respect to mechanical processing activities (extrusion, rolling, drawing), the personal
exposure data provided covers 20% of the tonnage processed. The personal data collected
cover about 20% of the workers exposed.
Personal exposure data are available for nine companies indicating generally low exposures.
Processes are similar across the sector and are assessed as not likely to lead to significant
exposures for the sector. Therefore these data will be considered as a generic scenario in risk
characterisation as shown in Table 4-18.

Table 4-18 Inhalation data carried forward for risk characterisation for further processing

Risk characterisation                                                 Typical              RWC
                                                                     Cu(mg/m³)          Cu(mg/m³)
All operations (Table 4-17 )                                            0.04                0.3
Task specific (using RPE)                                          0.03-0.1 (0.05)    0.2-2.45 (0.13)

Acute inhalation exposure
No data are available for acute exposure which is considered to be negligible

Dermal exposure – measured data

No dermal exposure data are available for the copper industry. However, dermal exposure
data for a comparable type of production are available from Hughson et al (2005) in various



RAPPORTEUR [ITALY]                                             41                              VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
zinc industries. In these studies, measurements of dermal zinc exposures at the workplace
were collected for an industry-wide risk assessment and also compared with the levels
predicted by EASE. Measurements were obtained from subjects in seven different workplaces
that were producing or working with zinc metal or zinc compounds. Appendix HH-4 to this
document describes the zinc dermal exposure data. Chapter Production of copper massive -
Dermal exposure – measured data describes the rationale for the extrapolation from zinc
data to copper and the proposed dermal exposure values for copper. The data for the
production of massive copper (Table 4-12) are used here on the basis that dermal exposure
for further processing is expected to be similar.

Typical and RWC dermal exposure estimates are 60 and 85 mg/day based on exposure to
hands and forearms only in accordance with the TGD.

Dermal exposure - modelled data (EASE 2.0)

Application of the EASE model is inapplicable as there is no related EASE scenario.

Conclusion – dermal exposure
The estimated typical and reasonable worst case exposure levels for hands and forearms
during the production of copper are respectively 60 mg Cu/day and 85 mg Cu/day.


4.1.1.2.6            Production of Copper powders

Process description
There are several stages in the manufacture of copper powders. Firstly copper, usually high
purity scrap, is melted in a melting furnace. The molten copper is poured in a thin stream and
atomized by a jet of water (see chapter “General exposure information” for further details).
The furnace operator has to check the furnace, which may entail his presence between the
furnace and the hood above (if present), heat the runoff channel and perform some
maintenance although he is not directly exposed to the atomization stage. The copper powder
formed during atomisation is then dried, usually on a belt/vacuum dryer. The dried product
may be sieved or milled and blended. After storage in a silo if required, the powder is then
dispensed into drums or bags. Stages of exposure can therefore be classified as furnace
operation, process operation (e.g. drying and milling) and bagging.
A variety of methods may be used for bagging and this may influence exposure. Bagging is
potentially the dustiest part of the production process. The most effective form of dust control
is provided by a fully fitted and enclosed unit onto which the receiving drum/bag is attached.
Suction is applied by a vacuum line attached to the unit which continuously extracts dusty air
during filling. The slight vacuum created also assists in the free flow of the material (ACGIH,
1992). During the filling operation itself this arrangement should almost entirely prevent the
escape of dust. However, exposure may occur during removal and changing of bags/drums or
during any intervention that is necessary if a malfunction occurs. Data are available for one
company (ECI-97) where a similar system is in use.
Alternatively, the filling operation may entail the vertical dropping of powders in a relatively,
or wholly, uncontrolled manner. Copious amounts of airborne dust may be generated
depending on the availability and efficiency of other control measures, the amount and



RAPPORTEUR [ITALY]                               42                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
velocity of the falling powder and also its dustiness. Data are available for two companies
(ECI-105, ECI-106) where relatively uncontrolled filling and tipping occur.

Inhalation exposure – measured data
Personal exposure data were collected at 3 sites. The dataset covers fourty-three percent of the
sites. The personal data collected cover about 40% of the workers exposed and 40% of the
tonnage produced in Europe.
TWA personal exposure for copper powders by company is shown in Table 4-19. It is clear
that exposures are much higher than those reported for other processes. Typical and RWC
exposures for ECI-97 are 0.42 and 0.92 mg/m3. For ECI-105 and ECI-106 the corresponding
ranges are 2.6-5.59 mg/m3 and 11.26-19.0 mg/m3. A job exposure matrix by company is
shown in Table 4-20. With the exception of ECI-97, the highest exposures are for bag/drum
filling. Typical and RWC exposures for ECI-105 and ECI-106 are 6.90-9.70 mg/m3 and 10.2-
16.0 mg/m3. The corresponding results for ECI-97 are 0.34 and 0.85 mg/m3. Exposures for
process operation are also elevated, particularly for ECI-105 with typical and RWC estimates
of 1.95 and 98.2 mg/m3, although the latter result may be exceptional and also reflect the
small dataset or possibly contamination. At this company, the tipping of material is not
confined to bagging but also occurs during the transfer and blending of materials. The limited
control measures available appear ineffective and the typical exposures indicated appear
plausible in this context.
It should be noted that use of the IOM-sampling head may result in a moderate overestimate
of exposures. However this will only account for a very marginal proportion of the results
presented.
RPE is worn by all exposed workers at ECI-106 but, even taking continuous use of RPE into
account, typical and RWC received exposures for bagging range from 0.83-1.60 mg/m3. The
results are shown in parentheses in Table 4-20.
Exposures from furnace operation shown in Table 4-20 are clearly higher than furnace
operation in melting and casting (PC6) or further processing (PC9). Much closer operator
contact is required for small scale melting for atomization which, in some ways, is more
analogous to manual tapping than other types of furnace operation. Indicative dust results for
furnace operation are shown in Figure 4-10. Measurements were made approximately 4m
from the operator’s position. A clear trend is observed where increasing exposure results from
channel heating and pouring rising to 1.5-2.0 mg/m3 during these stages.

Table 4-19 Personal exposure to copper and copper alloy powders

                                                            without RPE (mg/m³)                         with RPE (mg/m³)
                                         n         typical         RWC            Range       typical        RWC           Range
                                                                                   SD
ECI-97                                   36          0.42          0.92           0.02-2
                                                                                   0.4
ECI-105                                  10          5.59          19.0       0.9-98.2
                                                                                  28.2
ECI-106                                  30          2.6           11.26      0.1-27.5         0.22           1.13         0.01-2.8
                                                                                   6.0




RAPPORTEUR [ITALY]                                      43                               VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
 all                                             76       0.90              10.1           0.02-98.2
                                                                                               11.8




Table 4-20 Job exposure matrix by company, copper and copper alloy powders.                   Results incorporating RPE use (where
                                                                                              applicable) shown in parentheses
                                ECI-97                              ECI-105                                      ECI-106
                                  mg/m3                                mg/m3                                        mg/m3
               n      typical    RWC      Range       n   typical     RWC          Range          n    typical    RWC       Range
                                          SD                                       SD                                       SD
bag/drum       13     0.34       0.85     0.11-1.18   5   6.90        10.2         2.14-10.2      12   9.70       16.0      1.43-27.53
filling                                                                                                           (1.6)
                                          0.3                                      2.9                 (0.83)               6.7
process op     11     0.43       0.82     0.02-1.08   5   1.95        98.2         0.9-98.2       12   0.77       3.69      0.1-5.08
                                                                                                       (0.06)     (0.22)
                                          0.3                                      38.3                                     1.5
furnace op     12     0.59       0.97     0.22-1.98       n/a         n/a          n/a            6    2.33       11.16     0.81-11.16
                                                                                                       (0.23)
                                          0.5                                                                     (1.12)    3.5
Estimates incorporating RPE are in parenthesis



Figure 4-10 Indicative exposure to dust during furnace operation in         Real-time indicative dust levels (y-axis) as a function
production of copper powder.                                                of time in minutes (x-axis)




Inhalation exposure – modelled data
The EASE model was used to derive estimates of inhalation exposure. Operational variables
in the manufacture of copper powders do not necessarily correspond to key parameters in the
EASE model and a range of estimates was derived as shown in Appendix HH-3. The results
are shown in Table 4-22 with upper and lower estimates according to the presence of




RAPPORTEUR [ITALY]                                           44                                   VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
“effective” LEV. The copper fraction of the dust was estimated from the available data for
manufacturing of copper powder. This is shown in Table 4-21.
The lower EASE estimates (0-2.3 mg/m3) exceed the span of the measured data for ECI-97 in
Table 4-20. Effective control technology clearly precludes application of the higher EASE
estimates in this case. The higher EASE estimates (0-22.5 mg/m3) exceed the range of results
for ECI-106 while RWC exposures for ECI-105 may exceed the upper EASE estimate.
It is noted that the EASE output is heavily dependent on the selected inputs which may not
accurately represent actual conditions at the workplace. These estimates therefore serve little
purpose when reasonably reliable measured exposure data are available.

Table 4-21 Copper fraction of inhalable dust in manufacture of copper powders

                                            n          median (%)
 ECI-97                                     20               37
 ECI-105                                    10               56
 ECI-106                                    29               41
 combined                                   59               45

Table 4-22 EASE predictions and measured exposure data (mg/m³)
                        Lower           Typical     Upper           RWC

Measured data

Bagging                                 0.34-9.70                   0.85-16.9

Process op                              0.43-2.0                    0.82-98.2

Modelled data

EASE (1)                0-2.3                       0-22.5

(1) Lower and upper range with and without LEV



Conclusion – inhalation exposure
Personal exposure data were collected at 3 companies out of the 5 producing companies in
Europe. One of the companies produces copper powder at 3 different sites. The data provided
by the company were collected at one of the 3 sites. The dataset covers thus fourty-three
percent of the sites. The personal data collected cover about 40% of the workers exposed and
40% of the tonnage produced in Europe.
The magnitude and variability is considerable relative to data for other process codes. This
variability arises mainly due to the range of operating practices. Therefore site-specific
exposures are carried forward for these three sites with exposure data. These are summarised
in Table 4-23. Because of the variability these data can not be used for other sites in this
sector.




RAPPORTEUR [ITALY]                                          45                  VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Table 4-23 Inhalation data carried forward for risk characterisation     Data from Table 4-20. Range of exposures for
for copper powders.                                                      bagging, process opn and furnace opn. Exposures
                                                                         incorporating RPE in parentheses
Risk characterisation                                  Typical                    RWC
                                                      Cu(mg/m³)                Cu(mg/m³)
ECI-97 – operation specific                           0.34-0.59                 0.82-0.97
       -pooled                                           0.42                      0.92
ECI-105– operation specific                            1.95-6.9                 10.2-98.2
       -pooled                                           5.59                      19.0
ECI-106– operation specific                      0.77-9.70 (0.06-0.83)     3.69-11.16 (0.22-1.6)
       -pooled                                        2.6 (0.22)               11.26 (1.13)



Acute inhalation exposure
No data are available for acute inhalation exposure. Given the long term exposure data shown
in Table 4-20, very high acute exposures are considered inevitable for companies ECI-105
and ECI-106. For these companies the RWC long term exposures (98.2 and 11.26 mg/m³)
indicate a minimum acute exposure. Actual acute exposures are likely to be significantly in
excess of these values.
Operation in copper powder production have some similarity to smelting, i.e. furnace
operation and the manipulation of powdered or highly friable material. The range of estimates
for acute exposure for smelting exceed the corresponding RWC long term exposure by a
factor of approximately 2-20. Applying the lower end of this range to copper powders gives a
minimum acute exposure to copper ranging from 200 down to 30 mg/m³ before the effect of
RPE is considered.
Acute exposure for ECI-97 is likely to be considerably lower than these estimates due to the
more effective control technology employed. Similarly applying a minimum factor of two to
RWC long term exposures suggests acute exposures of 1.6-2.0 mg/m³.
While the derivation of these estimates is (necessarily) rather arbitrary, the minimum
predicted acute exposures are considered plausible as are values in excess of these.

Dermal Exposure

Measured data
No dermal exposure data are available for copper powders. However, dermal exposure data
for a comparable type of production are available from Hughson et al (2005) in various zinc
industries. In these studies, measurements of dermal zinc exposures at the workplace were
collected for an industry-wide risk assessment and also compared with the levels predicted by
EASE. Measurements were obtained from subjects in seven different workplaces that were
producing or working with zinc metal or zinc compounds. The original raw data were made
available by the authors (Hughson, 2005). Appendix HH-4 to this document describes the
zinc dermal exposure data. Chapter Production of copper massive - Dermal exposure –
measured data describes the rationale for the extrapolation from zinc data to copper powder.




RAPPORTEUR [ITALY]                                           46                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
The production of copper powders usually starts from high purity metal, and further includes
the processes of melting, „atomisation“ by a jet of air or „atomisation“ by a jet of water,
drying, sieving, milling, blending and finally dispensing into drums or bags. Whereas a
variety of methods may be used for bagging, this is nevertheless considered the dustiest part
of the production process when operated predominantly manually. Dermal exposure data
specifically for the scenario “production of copper powders” are not available. For this reason,
the “analogous substance” approach (HERAG, 2006) was taken, by extrapolating from data
collected in the zinc industry (Hughson & Cherrie, 2005). The production of zinc oxide and
zinc dust involves similar processes such as loading of raw material, melting, blending and
bagging, which are reasonably similar to those involved in the production of copper powders.
For copper powder, extrapolation from dermal exposure data generated in the production of
zinc oxide (including data on zinc dust production) to copper powder was performed.
Assuming that dermal exposure to copper is almost exclusively to “pure” copper, no
correction factor was applied to the extrapolation from zinc/zinc oxide data. This is
considered justified in view of the qualitatively similarly low dustiness of zinc powder, zinc
dust and zinc oxide in comparison to copper powder, which all fall in the dustiness range 0-
50 mg/g, and in view of the similarities of the processes involved. The available measured
data (hands and forearms only) obtained for zinc dust, powder, and oxide are summarised in
Table 4-24 (the individual raw data used for these calculations are presented in Appendix
HH-4):

Table 4-24 Measured cumulative dermal exposure to “zinc”, production of zinc dust, powder and compounds [μg/cm² skin]
   Plant producing          Max           90th percentile        Median               Min              Counts
         ZnO               1060                921                208                 59                 11
     ZnO, Zn dust           494                414                297                 70                 10
   ZnO, Zn dust, Zn        1317                1055               565                 155                 8
       powder
     All scenarios         1317                926                251                 59                 29
       (pooled)
A comparison of these cumulated (i.e., obtained from three consecutive samples that were
pooled into one analysis) data with the average maximum (saturation) level of 730 μg/cm²
obtained in human volunteer tests (Hughson & Cherrie, 2005; for details, see Appendix HH-
4) shows that the sampling methodology suffers from a major drawback: in the zinc
monitoring surveys, samples were taken before breaks (morning and lunch) and at end-of-
shift, so that in reality dermal exposure at each break would be reduced to zero by washing of
hands. The assessment of dermal exposure by the cumulative analysed value alone is
therefore associated with a potential over-sampling. Experimental verification of this was
further established in a subsequent phase III survey (Hughson & Cherrie, 2005). For this
reason, a correction factor needs to be applied on the cumulative zinc dermal exposure data.
In absence of individual sample data for zinc, a correction factor was derived from the dermal
exposure data available for a number of other metals and compounds. Individual and pooled
dermal exposure data are available for Sb2O3, Pb and Pb-compounds, Ni and Ni-compounds.
For each metal and scenario the 90th percentile of the individual samples and of the
cumulative data was calculated and a correction factor was derived as the ratio of the 90 th-
percentile of the cumulative data over the 90th-percentile of the individual sample data.
Twelve correction factors were derived ranging between 2.2 and 8.8. There was no specific
influence of the type of metal or scenario. As a conservative estimate of the correction factor
to be applied on the cumulative zinc dermal exposure data, the 10th-percentile of the range,




RAPPORTEUR [ITALY]                                          47                      VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
this is 2.4 will be used. The details of this analysis are described in Appendix HH-4. The
corrected zinc dermal exposure data are summarised in Table 4-25.

Table 4-25 Measured corrected dermal exposure to “zinc”, production of of zinc dust, powder and zinc compounds [μg/cm²
skin]
   Plant producing             Max             90th percentile          Median                  Min                Counts
          ZnO                  442                   384                   87                    25                   11
     ZnO, Zn dust              206                   172                  124                    29                   10
   ZnO, Zn dust, Zn            549                   440                  235                    65                    8
       powder
     All scenarios             549                   386                  105                    25                   29
       (pooled)
Given that under the industrial circumstances assessed above, any zinc present can be
assumed to be coated with a passivated zinc oxide layer, so that the dermal exposure levels
(all scenarios pooled) analysed and reported as mass of “zinc” per surface area unit were
assumed to represent exposure to “zinc oxide”, and were thus required recalculation to a zinc
oxide value by multiplication with a factor derived for the relative content of zinc in the
oxide, yielding following values summarised in Table 4-26.

Table 4-26 Measured corrected cumulative dermal exposure recalculated to “zinc oxide“, production of zinc dust, powders
and zinc compounds [μg/cm²]
     Exposure to               Max             90th percentile          Median                  Min                Counts
          Zinc                 549                   386                  105                    25                   29
      Zinc Oxide*              684                   481                  131                    31                   29
*Dermal exposure to zinc oxide was estimated by multiplying the exposure values for "pure" zinc with the reciprocal value of the
zinc content in zinc oxide (1.245), in analogy to HERAG (2006).
Finally, the dermal exposure to zinc oxide was extrapolated to copper powder assuming equal
mass loading, 100% copper present, and a total exposed area of 1980 cm² (hands and
forearms), as given in the table below:

Table 4-27 Extrapolated shift corrected cumulative dermal exposure to copper in the production of copper powders.
     Exposure to               Max             90th percentile          Median                  Min                Counts
        Copper                 684                   481                  131                    31                   29
     concentration
       (µg/cm²)
     Copper mass               1353                  952                  259                    62                   29
      (mg/day)
In conclusion, the occupational dermal exposure (full shift) to copper in the scenario
“production of copper powder” by way of extrapolation from “analogous” data on zinc yields
estimated values of 259 mg/day (typical exposure) and 952 mg/day (worst-case), respectively.
Dermal exposure - modelled data (EASE 2.0)
The EASE model was also used to predict dermal exposures. EASE estimations have been
further corrected for the copper fraction in inhalable dust as shown in Table 4-21. In fact, the
dust may be a mixture arising from airborne deposition and direct contact so the accuracy of
this estimate is unknown.




RAPPORTEUR [ITALY]                                               48                           VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
The varied work practices carried out are not readily classifiable in the EASE input menu. A
range of calculations were therefore performed to test the sensitivity of the output to the
selected inputs. The applied pattern of control ranged from not-direct to direct handling and
the contact level from incidental to extensive. The results are shown in Table 4-28.

Table 4-28 Dermal exposure assessment copper powder* – EASE calculations
                         Scenario A           Scenario B         Scenario C             Scenario D
Temperature              20°C                 20°C               20°C                   20°C
Physical-state           Solid                Solid              Solid                  Solid
Dust-inhalation          Mobile               Mobile             Mobile                 Mobile
Vapour pressure          no                   no                 no                     no
Use-pattern              Non-dispersive       Non-dispersive     Non-dispersive         Non-dispersive
Pattern-of-control       Not direct           Direct handling    Direct handling        Direct handling
Contact-level            /                    Incidental         Intermittent           Extensive
Predicted dermal         very low             0-0.1 mg/cm2/day   0.1-1 mg/cm2/day       1-5 mg/cm2/day
exposure
                                              or                 or                     or
                                              0-198 mg/day       198-1980 mg/day        1980-9900 mg/day
*Exposed surface area: 1980 cm² (TGD, 2003)


Applying to the results of scenarios B and C a modifying factor of 0.45 for the median copper
fraction in inhalable dust for copper powders (Table 4-21), the results indicate that dermal
exposure to copper ranges from zero to 890 mg/day. However, the possibility of predicted
exposures outside this range cannot be excluded.

Conclusion
The level of dermal exposure was estimated by two approaches, (i) using the measured data
for zinc and (ii) by modelling. As copper exposure data were absent, zinc dermal exposure
data were considered relevant as the production of zinc powder is broadly analogous to the
production of copper powder. The measured dermal exposures were similar as the predicted
values generated by the EASE model. The measured data were obtained at conditions typical
of normal production, so the measured exposures can be considered representative of normal
production conditions (Hughson, 2005) and are taken forward to the risk characterization. The
estimated typical and reasonable worst-case exposure levels for hands and forearms are
respectively 259 mg Cu/day and 952 mg Cu/day.


4.1.1.2.7                Production of Copper compounds

Process description
Copper compounds are mostly produced by wet processes although one company employs a
furnace operation for atomisation. An example, production of copper(I)oxide, is discussed
below along with exposure data. The stages in production typically involve loading a reaction
vessel, pumping the wet reaction product to dryers, storage in silos and finally bagging.
Similarly to copper powders, bagging is potentially the greatest source of exposure.




RAPPORTEUR [ITALY]                                         49                   VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Inhalation exposure – measured data
Currently, personal exposure data are available for four companies engaged mainly in the
manufacture of copper(I)oxide, copper(II)oxide, copper oxychloride and copper sulphate.
The tonnage based coverage for copper chemical production is 40%. The number of sites
based coverage is 33.3%. The personal data collected cover about 30% of the workers
exposed.
For some samples the compound is not specified. In such cases, workers may be exposed to
more than one copper compound. Results by company are shown in Table 4-29. Similarly to
copper powder, results are clearly higher than those for smelting and melting and casting with
typically very similar data reported for ECI-93, ECI-110 and ECI-112 (0.1-0.3 mg/m³). The
typical value of ECI-91 is higher (0.68 mg/m³) and could be due to the higher copper-content
of Cu20 produced at this site. The typical value for ECI-110 (0.10 mg/m³) is lower than for
other companies. This is due to the fact that this company manufactures copper compounds
amongst a range of unrelated compounds with much multitasking by workers.
RWC values for all four companies range from 0.31 to 1.43 mg/m³ with the lowest value for
ECI-112 and the highest value for ECI-91, reflecting the copper content of the compound
produced at each site (CuSO4.5H20 – 25%Cu at ECI-112 and Cu20 – 80% Cu at ECI-91).
Exposures for copper compounds by operation are shown in Table 4-30. The highest
exposures are for furnace operation with typical and RWC exposures of 0.59 mg/m³ and 0.70
mg/m³ and for bagging operations with typical and RWC exposures of 0.31 mg/m³ and 0.90
mg/m³. Lower exposures are reported for process operation and formulation of the wet
product. There are only a small number of samples for furnace operation. However, most
copper compounds are manufactured by wet processes and furnace operation is believed to be
rare.
Compound specific exposure estimates are not presented in Table 4-30. Such estimates are
problematical for a number of reasons. In some cases the available supporting information is
limited. Typically, several copper compounds are manufactured in the same plant with
reaction vessels, drying plant and bagging operations located side-by-side. This may result in
co-exposure to copper compounds some of which (e.g. copper hydroxide) are not relevant to
the risk assessment.
The manufacture of copper(I)oxide, copper oxychloride and copper sulphate, each on a single
site, are discussed in more detail. In the discussion that follows, mean indicative dust
measurements are indicated in parentheses.
The entire copper(I)oxide plant is operated by three workers per shift. From the reaction
vessel, copper(I)oxide is pumped under pressure as a slurry to a press dryer which was not in
use when measurements were made (0.18 mg/m³). The product is retained in the press filters
as the slurry passes through and thereby separated from the water. The copper(I)oxide is
precipitated by pulsing. Manual finishing in the form of agitating the filters with a hand tool is
required. Deposits of powdered copper(I)oxide were observed on the floor arising from
splashes of slurry. The potential for exposure from this operation is unknown. The product is
further dried in a spray drier (0.11 mg/m³). Workers are rarely present on the drier plant. The
dried product is then routed to a silo and from there to the bagging plant.




RAPPORTEUR [ITALY]                               50                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Table 4-29 Copper compounds: Personal exposure by company
 ECI code     Copper compound                                copper mg/m3

                                           n       median        RWC          Range
                                                                               SD
    91               Cu2O                  8        0.68         1.43        0.44-1.64
                                                                                0.4
    93        Cu2Cl(OH)3, Cu2O,            31       0.30         0.80        0.06-1.37
               co-exposure to
                                                                                0.3
                  Cu(OH)2

    110           CuO and                  12       0.10         0.76        0.01_2.65
                 Cu2Cl(OH)3
                                                                                0.7
    112         CuSO4.5H20                 16       0.12         0.31        0.06-0.41
                                                                                0.1
    All                                    67       0.23         0.82        0.01-2.65
                                                                                0.4



Indicative dust measurements at locations reflecting the passage of the product through the
bagging plant are also shown in Table 4-31. Bag filling (25 kg) and sealing operations are
automated and are located inside an enclosure extracted with LEV. It is apparent from Table
4-31 that mean dust levels are very low throughout (0.2-0.3 mg dust/m³). This is reflected by
the fact that a measurement taken in the worker’s breathing zone while smoking a cigarette
(mean=1.1 mg dust/m³) was considerably higher than those attributable to process operation
(although it is noted this instrument is highly sensitive to particles in this range).

Table 4-30 Copper compounds: Personal exposure by operation

                                                           copper mg/m3
                                    n           typical       RWC           Range
                                                                              SD
Bagging                           40 (4)         0.31          0.90       0.01-2.65
                                                                              0.5
process op                        19 (3)         0.12          0.54       0.01-1.37
                                                                              0.3
furnace op                        4 (1)          0.59          0.70         0.44-0.7
                                                                              0.1
Formulation                       4 (1)          0.16          0.22       0.08-0.22
                                                                             0.05



However, malfunctions in the bag filling enclosure required the frequent intervention of the
operator obliging him to enter the enclosure. It was not possible to take measurements inside
the enclosure but it can reasonably be assumed that dust and copper levels inside were highly
elevated relative to those outside. It is therefore assumed that these interventions contributed




RAPPORTEUR [ITALY]                                          51                           VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
significantly to his personal exposure. After attending to these problems he also left the access
doors open for extended periods possibly resulting in additional egress of dust from the
enclosure as suggested in Table 4-31. Another possible source of exposure is the escape of
the product while lifting the 25 kg bags close to the chest when they are loaded onto pallets.
Manufacture of copper oxychloride consists of similar wet and drier plant although no filter
press operations. From the drier, the product is conveyed by gravity to a filter. A fan located
at the exit from the filter then conveys the copper oxychloride vertically upwards some 20m
to the entry to the silo. It is assumed that the dimensions of the building dictate this
configuration. The copper oxychloride is then released from the silo to the bagging machine
by gravity as required. Bag filling (25 kg) and sealing is performed manually at a filling
machine with integral LEV.
During the survey, blockage of the ducting at the bottom of the vertical section described
above necessitated the suspension of bagging in order to free the blockage. This was achieved
by disconnecting the ducting and applying forceful blows to the section of duct containing the
dust deposit resulting in the generation of a considerable dust cloud. This exercise was
repeated before satisfactory flow of product was resumed.

Table 4-31 Copper compounds, bagging of Cu(I)O: indicative dust levels (mg/m3)

                   location                    t      mean        max                          comments
 operator breathing zone                      S/T       0.2        0.5     bagging position
 operator breathing zone                      S/T       1.1        8.7     smoking cigarette
 above pallet                                 S/T       0.2        1.1     during loading
 bagging station                              S/T       0.2        0.9     door closed
 bagging station                              S/T       0.3        3.4     door open
 outside bldg                                 S/T       0.1        0.4



In conclusion, while bagging of copper compounds may be expected to contribute
significantly to exposure during their manufacture, exposure appears to be generally well
controlled when no operational difficulties are experienced. However, where such difficulties
do occur, exposure levels may be highly elevated. During manual bag filling operations,
subjective observations suggest that the efficacy of the LEV is variable.
The manufacturing of copper sulphate pentahydrate also involves 3 or 4 employees per day
and they are employed on a variety of tasks during the working day. Copper scrap is loaded
into a reaction tower. At the top of the tower sulphuric acid and warm (70°C) exhausted
copper sulphate solution (70 g/l of Cu approximately) are added. From the bottom air or O 2
are supplied. The resulting hot copper sulphate solution is transferred to a crystallization
system that maintains the solution by mixing and cools the solution to room temperature. The
copper sulphate pentahydrate produced is then centrifuged, dried and transferred to a storage
silo where it is packed into 10 or 25 kg bags or in 500-1000 kg bags. The bagging machine
used is automatic and the operator is not in contact with the product. An adequate filtration
system prevents the release of powder. The bags are then placed automatically on pallets
(10000 – 15000 Kg).
For the production of formulations, the active ingredient stored in silos in the form of powder
(technical Bordeaux mixture or technical copper oxychloride), is transferred through a closed



RAPPORTEUR [ITALY]                                       52                         VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
system to an industrial balance. The additives needed for the formulation are added, manually
into the balance. A proper extractor system and a filter prevent emission of powder. After
weighing the products are transferred into a mixer to homogenise the product. The resulting
product is transferred into adequate storage silos for packaging.

Inhalation exposure – dustiness testing
The particle size distribution and relative dustiness of copper compounds generated from bulk
materials was determined in a supplementary study initiated by ECI. A summary report
containing the methodology and the results is given in Appendix HH-5. Relative dustiness is
measured as the mass of airborne substance generated from unit mass of the bulk material
under laboratory conditions (mg/g). Results for compounds of interest are summarised as
follows: the least dusty compound was copper(I)oxide (7.1 mg/g) while copper oxychloride
and copper sulphate pentahydrate were of similar dustiness (33.4 and 48.8 mg/g respectively).
The dustiness of copper(II)oxide was found to be of a different order (363.7 mg/g).
The exposure data in Table 4-30 do not reflect these findings with the lowest exposure for
ECI-110 engaged in the manufacture of the dustiest compound copper(II)oxide. However, this
is explained by the less intensive production at this site. It is a reasonable assumption that, if
process variables and the intensity of production are similar to those for the other companies
cited, copper (II)oxide production could well result in higher exposures than those measured
at these sites for copper(I)oxide and copper oxychloride. Clearly, inhalation exposures are
highly sensitive to process variables and these may override relative dustiness as a
determinant of inhalation exposure.

Inhalation exposure – modelled data
The EASE model was used to derive estimates of inhalation exposure. Operational variables
in the manufacture of copper compounds do not necessarily correspond to key parameters in
the EASE model and a range of estimates was derived as shown in Appendix HH-3. The
results are shown in Table 4-33 with upper and lower estimates according to the presence of
“effective” LEV. The copper fraction of the dust was estimated from the available data for the
copper fraction of inhalable dust. This is shown in Table 4-39.
The lower EASE estimates (0-1 mg/m³) cover the entire range of the typical and RWC
measured exposures shown in Table 4-29 and Table 4-30. The higher EASE estimates (0-10
mg/m³) are clearly overestimates of exposure for companies for which measured data are
available.
It is noted that the EASE output is heavily dependent on the selected inputs which may not
accurately represent actual conditions at the workplace. These estimates therefore serve little
purpose when reasonably reliable measured exposure data are available.

Table 4-32 Copper fraction of inhalable dust in manufacture of copper compounds

                                        n             median (%)
 ECI-93                                 20                22
 ECI-110                                12                19
 combined                               32                20




RAPPORTEUR [ITALY]                                       53                       VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Table 4-33 EASE predictions and measured data
                          Lower           Typical         Upper          RWC

Measured data

Bagging                                    0.32                          0.82

Process op                                 0.15                          0.59

Modelled data

EASE                        0-1                            0-10

Conclusion – inhalation exposure
The tonnage based coverage for copper chemical production is 40%. The number of sites
based coverage is 33.3%. The personal data collected cover about 30% of the workers
exposed.
Personal exposure data are available for four companies. Data for two companies are in good
agreement, one company reported higher exposure values and the fourth company lower
exposure values.
In this sector exposure can be highly sensitive to production and process variables and it may
therefore not be appropriate to apply these data to non-responding companies. However, data
supplied are overall consistent. Typical and RWC values of the pooled data are 0.23 and 0.82
mg/m³ respectively and reflect the range of the data collected.

Both site-specific and pooled exposure data are carried forward to risk characterisation. These
are summarised in Table 4-34.

Table 4-34 Inhalation data carried forward for risk characterisation   Data from Table 4-29. Range of exposures for
for copper compounds.                                                  bagging, process opn and furnace opn.

                                                       Typical                  RWC
                                                      Cu(mg/m³)             Cu(mg/m³)
ECI-91                                                   0.68                   1.43
ECI-93                                                   0.30                   0.80
ECI-110                                                  0.10                   0.76
ECI-112                                                  0.12                   0.31
All data (pooled)                                        0.23                   0.82



Acute inhalation exposure
No data are available for acute inhalation exposure. One source of acute exposure is the
entrainment of copper compounds in displaced air during manual bag filling. Although it is
usual for LEV to be provided at this operation, the LEV may not adequately control exposure,
particularly if sealing the 25kg bag is performed remotely from the LEV. Indicative dust data
measured in the worker’s breathing zone during such an operation are shown in Figure 4-11.
(No personal sampling data are available for this company). A burst of dust is generated each
time a bag is sealed resulting in the cyclical exposure profile shown.




RAPPORTEUR [ITALY]                                           54                         VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Figure 4-11 Indicative exposure to dust during bagging of copper oxychloride.   Realtime indicative dust levels (y-axis) as
                                                                                a function of time in minutes (x-axis)




Indicative dust measurements indicate a mean value of 17 mg/m³ with transient peak
exposures of 40-70 mg/m3. Estimation of copper exposure from these results is problematical
as it would be necessary to interpret the response of the instrument from a wholly different
matrix, i.e. particulate from a smelter. Variation in the particle size distribution and optical
properties of copper oxychloride relative to copper metal render such an estimate uncertain.
However, these data do show the potential for high 15 minute or event based exposures. In
addition, any estimate is considered conservative as a generalisation across the sector as the
adequacy of control is rather poor at this plant relative to some others, particularly those
plants where this operation is automated and enclosed.
Process interventions (e.g. freeing blocked ducts, plant malfunctions) can also cause elevated
acute exposures as described above. However, no data are available.
Dermal Exposure – measured data

No dermal exposure data are available for the copper compounds. However, dermal exposure
data for a comparable type of production are available from Hughson et al (2005) in various
zinc industries. In these studies, measurements of dermal zinc exposures at the workplace
were collected for an industry-wide risk assessment and also compared with the levels
predicted by EASE. Measurements were obtained from subjects in seven different workplaces
that were producing or working with zinc metal or zinc compounds. Appendix HH-4 to this
document describes the zinc dermal exposure data. The original raw data were made available
by the authors (Hughson, 2005). Chapter Production of copper massive - Dermal exposure
– measured data describes the rationale for the extrapolation from zinc data to copper
compounds.
Copper compounds are mostly produced by wet processes. The various process stages
typically involve loading a reaction vessel, pumping the wet reaction product to dryers,
storage in silos and final bagging. Similar to copper powders, bagging is considered to have
the greatest potential for dermal exposure when operated predominantly manually. For copper
chemicals, the relative copper content varies between compounds between 25-89%.




RAPPORTEUR [ITALY]                                         55                        VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Therefore, when extrapolating from zinc oxide/zinc dust data to these copper chemicals, a
correction factor was applied as given Table 4-35.

Table 4-35 Copper content of several copper compounds
  Compound              Cu metal         Copper(II)       Cuprous(I) oxide   Copper(II) oxide        Copper
                                          sulphate                                                 oxychloride
                                        pentahydrate
Molecular formula         Cu            CuSO45H2O             Cu2O                CuO             Cu2Cl(OH)3
   Relative Cu           100%               25.5%              88.8%              79.9%               59.5%
    content
The extrapolation from the zinc/zinc oxide data to the various copper compounds is
considered justified in view of the qualitatively similarly dustiness of zinc (powder, dust and
oxide) in comparison to copper powder, copper (I) oxide, copper (II) sulphate pentahydrate
and dicopper chloride trioxide, which all fall in the dustiness range 0-50 mg/g, and in view of
the fact that in all cases, bagging as the final process step is the decisive driver for the
resulting high dermal loading levels. Whereas in the case of copper (II) oxide, the dustiness is
somewhat higher than that of the zinc compounds, given the lack of a precise quantitative
relationship between dustiness and dermal exposure, the assumption that exposure controls
will be more influential, the similarity of inhalation exposure levels between the various
Copper compounds that indicate similar levels of control, and that in reality mixed exposures
due to simultaneous production of several copper compounds will prevail, a correction for this
parameter was not applied.
Adopting the same reasoning for the treatment of cumulated sampling data as in scenario 2
above, extrapolation from shift corrected cumulative zinc oxide data to copper compounds
assuming equal mass loading but including a reflection of the relative copper content of each
particular copper compound was performed as summarised Table 4-36.

Table 4-36 Extrapolated shift corrected cumulative dermal exposure to copper compounds [μg substance / cm² skin]

   Substance         Copper content         Max            90th percentile        Median               Min
   Zinc oxide             n.a.               684                481                131                 31
   Copper(II)            25.5%               174                123                 33                  8
    sulphate
  pentahydrate
 Copper(I) oxide         88.8%               607                427                116                 28
Copper(II) oxide         79.9%               546                384                104                 25
Dicopper chloride        59.5%               407                286                 78                 19
   trihydroxide
Given a total exposed area of 1980 cm² (hands and forearms), Table 4-37 shows the resulting
prediction of total mass per day of copper on the skin, depending on the individual compound.

Table 4-37 Extrapolated dermal exposure to copper compounds [mg copper / day]

   Substance         Copper content         Max            90th percentile        Median               Min
   Copper(II)            25.5%               345                243                 66                 16
    sulphate
  pentahydrate
 Copper(I) oxide         88.8%              1202                845                230                 55




RAPPORTEUR [ITALY]                                       56                         VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
 Copper(II) oxide         79.9%               1081                    760                  207              49
Dicopper chloride         59.5%               805                     566                  154              37
   trihydroxide
In conclusion, the occupational dermal exposure (full shift) to copper in the scenario
“production of copper compounds” by way of extrapolation from “analogous” data on zinc
yields estimated values of:
- for copper (I) oxide, 230 mg/day (typical exposure) and 845 mg/day (worst-case),
respectively
- for copper (II) oxide, 207 mg/day (typical exposure) and 760 mg/day (worst-case),
respectively
- for copper chloride trihydroxide, 154 mg/day (typical exposure) and 566 mg/day (worst-
case), respectively
- for copper sulphate pentahydrate, 66 mg/day (typical exposure) and 243 mg/day (worst-
case), respectively.

Dermal exposure - modelled data (EASE 2.0)
The EASE model was also used to predict dermal exposures. EASE estimations have been
further corrected for the copper fraction in inhalable dust as shown in Table 4-32. In fact, the
dust may be a mixture arising from airborne deposition and direct contact so the accuracy of
this estimate is unknown.
The varied work practices carried out are not readily classifiable in the EASE input menu. A
range of calculations were therefore performed to test the sensitivity of the output to the
selected inputs. The applied pattern of control ranged from not-direct to direct handling and
the contact level from incidental to extensive. The results are shown in Table 4-38.

Table 4-38 Dermal exposure assessment to copper compounds* – EASE calculations

                         Scenario A                 Scenario B              Scenario C             Scenario D
Temperature              20°C                       20°C                    20°C                   20°C
Physical-state           Solid                      Solid                   Solid                  Solid
Dust-inhalation          Mobile                     Mobile                  Mobile                 Mobile
Vapour pressure          no                         no                      no                     no
Use-pattern              Non-dispersive             Non-dispersive          Non-dispersive         Non-dispersive
Pattern-of-control       Not direct                 Direct handling         Direct handling        Direct handling
Contact-level            /                          Incidental              Intermittent           Extensive
Predicted dermal         very low                   0-0.1 mg/cm2/day        0.1-1 mg/cm2/day       1-5 mg/cm2/day
exposure
                                                    or                      or                     or
                                                    0-198 mg/day            198-1980 mg/day        1980-9900 mg/day

*Exposed surface area: 1980 cm² (TGD, 2003)


Applying to the results of scenarios B and C a modifying factor of 0.2 for the median copper
fraction in inhalable dust for copper compounds (Table 4-32), the results indicate that dermal
exposure to copper from copper compounds ranges from zero to 396 mg/day. However, the
possibility of predicted exposures outside this range cannot be excluded.



RAPPORTEUR [ITALY]                                               57                        VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Conclusion – dermal exposure
The level of dermal exposure was estimated by two approaches, (i) using the measured data
for zinc compounds and (ii) by modelling. As copper exposure data were absent, zinc dermal
exposure data were considered relevant as the production of zinc compounds is broadly
analogous to the production of copper compounds. Depending of the copper compound, the
measured dermal exposures were either lower, similar or higher than predicted values
generated by the EASE model. The measured data were obtained at conditions typical of
normal production, so the measured exposures can be considered representative of normal
production conditions (Hughson, 2005). Thus the measured data are taken forward to the risk
characterization. The estimated typical and reasonable worst-case exposure levels to copper
for hands and forearms are respectively
- for copper (I) oxide 230 mg/day and 845 mg/day
- for copper (II) oxide 207 mg/day and 760 mg/day
- for copper chloride trihydroxide 154 mg/day and 566 mg/day
- for copper sulphate pentahydrate 66 mg/ and 243 mg/day
It is noted that the measured data indicate that there is potential for inadvertent ingestion of
copper, either through hand to mouth contact or from deposition into or around the perioral
region.


4.1.1.2.8            Formulation of Copper compounds
The exposure scenario for the production of Cu containing anti-fauling paints and wood
preservative (formulations) is addressed in dossiers developed under directive 98/8/EC and is
not considered here.

4.1.1.2.9            Professional exposure to coins

A possible source of exposure of workers is the frequent professional contact with copper
containing coins. In absence of a method to estimate exposure and following the procedure in
the Ni RA, no detailed risk characterisation is possible for this scenario. However, using the
data for consumers below with a skin exposure of 0.14 to 0.28 mg/day multiplied by the
dermal exposure rate of 0.3% gives a daily absorption of 0.00084 mg. Therefore, this lack of
detailed risk assessment is assessed as insignificant.


4.1.1.2.10           Particle size distributions
The particle size distribution of airborne copper in occupational settings is a prerequisite for
the prediction of deposition in the respiratory tract. The available data for the copper
industries covered by this risk assessment are summarised and discussed here.
Respirable monitoring data in various industry sectors
A number of companies have conducted sampling for copper in both the inhalable fraction, as
presented in preceding sections, and in the respirable fraction. Comparison of these results
enables the determination of respirable copper as a function of (total) inhalable copper. These




RAPPORTEUR [ITALY]                               58                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
results are shown in Table 4-39. For melting and casting of billets (PC6) and further
processing (PC9), respirable copper as a function of total copper ranges from 6-25% with a
median value of 9%. For smelting a single value of 13% is given while for non-foundry
operations in the manufacture of copper powders the single value of 4%.

Table 4-39 Copper in inhalable and respirable dust

                                         Inhalable (mg/m³)           Respirable (mg/m³)            Percent
                                                                                                  respirable
   ECI                PC             median                n         median            n
    07                4                  0.23              60         0.03            18             13%
    10                6/9                0.12              57         0.03            13             25%
    14                6               0.046                11        0.005            11             11%
    79                6               0.036                7         0.002             5             6%
   106           10 (foundry)            2.11              5          0.13             5             6%
                 10 (powders)            3.25              24         0.12            24             4%

Respicon data for various industry sectors
Particle size distributions for smelting, copper powder furnace operation and bagging of
copper oxychloride and copper(I)oxide measured using the Respicon sampler are shown in
Table 4-40.

Table 4-40 Particle size distribution of airborne copper

                                                   Copper                 particle size distribution (%)
                                                concentration
                                                 in inhalable    respirable        tracheo-         extra-thoracic
                                                     dust                          bronchial

                                                   mg/m³
 smelter, converter                                 0.95             12                33                  55
 furnace opn, copper powder production              0.21             39                23                  38
 bagging copper oxychloride                         0.03             20                25                  55
 bagging copper(I)oxide                             0.06             12                47                  41



The respirable fraction for the smelter was 12%, almost in exact agreement with the data for
ECI-07 (13%). The smelter sample was taken at the converter operator position. Inhalable
dust concentration was 0.95 mg/m³. The corresponding personal exposure result was 0.73
mg/m³. The lower personal exposure was due to the fact that the operator spent much of his
time in the control room. The particle size distribution was heavily skewed towards the
coarser, extrathoracic fraction (55%) with a small pulmonary (respirable) fraction (12%).
For copper powder furnace operation the measured PSD has a relatively high respirable
fraction of 39% compared to values of 6-25% respirable shown in Table 4-40. This is
probably attributable to the higher dust levels observed during the pouring and atomisation
phases relative to the melting phase as shown in Figure 4-11. The copper concentration in
inhalable dust was 0.21 mg/m³ compared to the corresponding personal exposure of 1.98
mg/m³. (The personal sampling result is considerably higher than other data reported and this



RAPPORTEUR [ITALY]                                              59                          VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
difference indicates the importance of the proximity to the source for such exposures). The
sample was taken over two batches in order to ensure an adequate sample mass was collected
for analysis. Since the LEV hood was not used during the first part of the sampling (as noted
in section Production of Copper powders) this may introduce some uncertainty in the
representativeness of this result.
Two common features are observed for the psd data for the bagging of both copper
compounds. Firstly, the respirable fractions were low (12-18%) The relatively coarse psd of
the airborne copper is consistent with what might be expected for this type of operation.
However, PSD data supplied for the bulk materials indicate that the PSD should be
predominantly in the respirable range. It is speculated that while closely packed in silos and
ducting, small particles may form clusters as is sometimes seen in airborne samples examined
microscopically although this cannot be demonstrated empirically in this case.

Particle size monitoring by cascade impactor in copper alloy casting operations
During melting and casting of copper and copper alloys, a detailed investigation of particle
size distributions of workplace aerosols in a non-ferrous foundry is reported (Cohen &
Powers, 2000). The monitoring involved personal and area sampling with five-stage (10, 4, 2,
1 and 0.5 µm) cascade impactors (PIXE). The composition of the copper and copper alloys
that were handled is given in Table 4-41 below:

Table 4-41 Composition, melt, and pour temperatures of material handled

                         Melt temperature      Pour temperature                     Composition
   Material handled
                                [°C]                  [°C]                Cu [%]      Zn [%]       Ni [%]
        Copper                  539                 593-649               99.99          -           -
      Cu-Zn-alloy             491-513               538-593               68-71        29-32         -
    Cu-Zn-Ni-alloy              598                 663-718               70-75         1          23-26


The sampling data given as a percentage of mass analysed on each filter stage and the re-
calculated standard deviations are summarised in Table 4-42 below:




RAPPORTEUR [ITALY]                                       60                        VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                         CHAPTER 4. HUMAN HEALTH
Table 4-42 Summary of air sampling data as a percentage of mass analysed on each filter stage, Cohen & Powers (2000)

                                                   Filter stage                Range            Arithmetic mean                SD
  Material handled              Job title                           n
                                                       [µm]                      [%]                    [%]                    [%]
                                                         10         1              -                    94                      -
                                                          2         1              -                     5                      -
                                 Caster                   1         1              -                     1                      -
                                                         0.5        1              -                    <1                      -
                                                        final       1              -                    <1                      -
        Copper
                                                         10         1              -                    88                      -
                                                          2         1              -                     8                      -
                          Assistant top caster            1         1              -                     2                      -
                                                         0.5        1              -                     2                      -
                                                        final       1              -                    <1                      -
                                                         10         3           77-96                   86                     9.5
                                                          4         3            3-17                   10                     7.3
                              Area sample                 1         3             1-4                    2                     1.5
                                                         0.5        3             1-4                    2                     1.8
                                                        final       3             0-1                   <1                     0.3
                                                         10         6           71-86                   77                     8.5
                                                          4*        2           13-17                   15                     2.9
                                                          2         6            3-17                    7                     3.5
                                 Caster
                                                          1         6             2-5                    4                     0.4
                                                         0.5        6             0-3                    2                     1.3
                                                        final       6             0-2                   <1                     0.2
      Cu-Zn-alloy                                        10         6           55-89                   78                    14.7
                                                          4*        3            7-16                   11                     4.3
                                                          2         6            2-19                    7                     7.1
                           Assistant pit caster
                                                          1         6            0-22                    2                     2.7
                                                         0.5        6             0-3                    1                     0.9
                                                        final       6            0-13                   <1                     0.1
                                                         10         6           82-90                   84                     1.5
                                                          4*        2            9-10                   10                     0.3
                                                          2         6            2-13                    4                     2.5
                          Assistant top caster
                                                          1         6             1-7                    4                     2.6
                                                         0.5        6             0-1                    1                     0.4
                                                        final       6             0-1                    1                     0.4
                                                         10         1              -                    94                      -
                                                          2         1              -                     5                      -
                                 Caster                   1         1              -                     1                      -
                                                         0.5        1              -                    <1                      -
                                                        final       1              -                    <1                      -
    Cu-Zn-Ni-alloy
                                                         10         1              -                    95                      -
                                                          2         1              -                     3                      -
                          Assistant top caster            1         1              -                     1                      -
                                                         0.5        1              -                    <1                      -
                                                        final       1              -                    <1                      -
*Data for this impactor stage exists only for a subgroup of the samples, leading to the sum of the percentages of the collected mass not
necessarily matching 100, since the average of the 4µm stage accounts for all samples.




RAPPORTEUR [ITALY]                                                  61                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
The low level of variation between particle size distributions of aerosols generated during the
individual tasks is shown in the figure below, with arithmetic means given for each stage and
task (calculation based on the assumption that these data are normally distributed).
Figure 4-12 Particle size distributions during melting and casting operations, arithmetic means of all available values for
each stage/task

                                         100%




                                         90%
  percentage larger than cut off point




                                         80%


                                                                                              Copper, Caster (n=1)

                                                                                              Copper, Assistant top caster (n=1)
                                         70%
                                                                                              Cu-Zn-alloy, Area sample (n=3)

                                                                                              Cu-Zn-alloy, Caster (n=6)

                                                                                              Cu-Zn-alloy; Assistant pit caster (n=6)

                                         60%                                                  Cu-Zn-alloy; Assistant top caster (n=6)

                                                                                              Cu-Zn-Ni-alloy, Caster (n=1)

                                                                                              Cu-Zn-Ni-alloy, Assistant top caster (n=1)


                                         50%
                                            100                     10                             1                                       0.1
                                                                         cut off point [µm]




In conclusion, the tabulated data and the graph show that in almost all circumstances, either
80% or more of the workplace aerosols consist of particles larger than 10 µm. Thus, only a
minor percentage of these copper workplace aerosols can be expected to be respirable. These
results are consistent with data reported in Table 4-39 (75-94% non-respirable in melting and
casting) and are similar to the data for smelting described above (87-88%).

From the data presented in the figure above, a calculation of MMAD values for the specific
job/alloy combinations can only be made by extrapolation. Despite that this is of limited
reliability, both quasi-linear and non-linear regression resulted in estimated MMADs clearly
above 20 µm even for the particle size distribution data set reflecting the “finest” aerosol (Cu-
Zn-alloy Caster). Hence, this estimation can be taken as a worst case assumption for the
calculation of MMAD values from the entire data set published by Cohen & Powers.
Table 4-43 Results of regession analysis

                                                                            MMAD
                                                Regression method                                                                  GSD
                                                                             [µm]
                                                     Linear*                  44.1                                                  6.7
                                                    Non-linear                26.3                                                  3.5
*The MMAD and the GSD were calculated by carrying out a regression analyses for all of the six samples and taking the geometric mean
of both estimations afterwards.




RAPPORTEUR [ITALY]                                                            62                                VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Particle size data for copper compounds

Particle size and dustiness of copper and copper compounds
Physical particle size distributions have been measured for copper powder, copper (I) oxide,
copper (II) oxide, copper oxychloride and copper sulphate pentahydrate, as presented in
Figure 4-13 below:

Figure 4-13 Physical particle size of copper compounds (determined by dry dispersion and laser diffraction)
 percentage smaller than cut off




                                   100%


                                   90%


                                   80%


                                   70%


                                   60%


                                   50%


                                   40%


                                   30%


                                   20%


                                   10%


                                    0%
                                          0,1                           1,0                 10,0                     100,0                            1000,0
                                                                                                                                         cut off size [µm]
                                                copper powder                    copper (I) oxide                    copper (II) oxide
                                                dicopper chloride trihydroxide   copper (II) sulphate pentahydrate

The particle size distributions above demonstrate that the difference between the median
particle sizes (d50) of the individual compounds may amount to almost two orders of
magnitude.
However, for the deposition of inhaled material in the respiratory tract, the mass median
aerodynamic diameter (MMAD) of the fraction of material that may become airborne during
normal handling and use is of importance.
For copper powder, copper (I) oxide, copper (II) oxide, copper oxychloride and copper
sulphate pentahydrate, data on dustiness and particle size distribution were obtained by using
the rotating drum (Heubach) method, according to DIN Norm 55 992. Dustiness is defined as
the propensity of a material to become airborne. This method is described in the current ECB
guidance document on particle size distribution of chemical substances (ECB, 2002) as “the
only method that uses a standard method to disperse the dust and gives a separation by mass
based on the respirable, thoracic and inhalable fractions.
In brief, a sample is introduced into a rotating drum apparatus (simulating mechanical
agitation during normal handling and use) and a stream of air is passed through the apparatus,
enabling collection of any material that becomes airborne under these conditions. The particle
size distribution of the fraction of material that becomes airborne under these conditions is
analysed by a cascade impactor that separates particles based on their mass median
aerodynamic diameter (MMAD), and is thus considered to more accurately reflect the particle



RAPPORTEUR [ITALY]                                                                        63                          VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
size distribution under workplace conditions for extrapolation purposes than the “total”
particle size.
The data obtained for the five different copper compounds is presented in Figure 4-14 below.
It is evident from these data that copper oxychloride and copper(I)oxide will give rise to a
similarly fine particle distribution under conditions of mechanical agitation. In contrast,
copper powder, copper (II) oxide and copper sulphate pentahydrate may be expected to be
much less mobile (as judged by their low total dustiness value), and more than 90% of
airborne material will have a median aerodynamic diameter much larger than 10 µm.

Figure 4-14 Particle size (aerodynamic diameter) distribution of copper compounds (Heubach method)

                                          100%


                                          90%


                                          80%
   percentage larger than cut off point




                                          70%


                                          60%


                                          50%
                                                                             copper powder


                                          40%                                Copper (I) oxide


                                          30%                                Copper (II) oxide


                                          20%                                Copper (II) sulphate pentahydrate


                                          10%                                Dicopper chloride trihydroxide



                                           0%
                                             100   10                          1                                 0.1
                                                        cut off point [µm]


From the data on particle size distribution of airborne matter obtained in the dustiness testing,
the MMAD and GSD values were calculated by quasilinear regression by fitting lognormal
distributions for each of the substances to its corresponding cascade impactor data (in
accordance with the procedure set forth in the draft OECD guidance document on acute
inhalation toxicity testing (OECD, 2004).




RAPPORTEUR [ITALY]                                          64                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Figure 4-15 Particle size density function of copper compounds




                                      12%

                                      11%
                                                                                                                  copper powder
                                      10%
                                                                                                                  Copper (I) oxide
                                      9%                                                                          Copper (II) oxide
       Percentage of collected mass




                                      8%                                                                          Copper (II) sulphate pentahydrate

                                                                                                                  Dicopper chloride trihydroxide
                                      7%

                                      6%

                                      5%

                                      4%

                                      3%

                                      2%

                                      1%

                                      0%
                                            0.0                5.0               10.0               15.0                20.0                          25.0
                                                                                          AD [µm]


MMAD values are intrinsically higher than physical particle sizes because of the link with the
square root the particle density. However, for quite a few compounds in Table 4-44 below,
the experimentally determined MMAD in the airborne fraction is much higher than the
physical particle size, indicating in such cases a tendency of these compounds to form
aggregates. The table below displays the thus obtained MMAD and GSD for each copper
compound.

Table 4-44 Dustiness and particle size information of copper and copper compounds

                                                                     Dustiness      D50 [µm]         Airborne
                                                                                                                      Airborne
Substance                                           CAS                value           phys.         D50 [µm]                                  References
                                                                                                                       GSD(2)
                                                                      [mg/g]        diameter(1)      MMAD(2)
                                                                                                                                             Franke (2004),
Copper powder                                     7440-50-8               7             129.0              71.7            3.9
                                                                                                                                              Selck (2004)
                                                                                                                                             Franke (2004),
Copper (I) oxide                                  1317-39-1             364               3.3               9.9            3.3
                                                                                                                                              Selck (2004)
                                                                                                                                             Franke (2004),
Copper (II) oxide                                 1317-38-0              49              32.5              60.7            3.8
                                                                                                                                              Selck (2004)
Copper (II)
                                                                                                                                             Franke (2004),
sulphate                                          7758-99-8              33             220.4              90.3            5.2
                                                                                                                                              Selck (2004)
pentahydrate
Dicopper chloride                                 1332-40-7;                                                                                 Franke (2004),
                                                                         48               2.3              12.2            4.1
trihydroxide                                      1332-65-7                                                                                   Selck (2004)

(1) physical diameter determined by dry dispersion and laser diffraction
(2) mass median aerodynamic diameter (MMAD) and GSD determined by rotating drum method and size-selective impaction

As an overall conclusion, with the exception of copper (I) oxide, the other copper compounds
all exhibit a similarl tendency to become airborne. The mass median aerodynamic diameters



RAPPORTEUR [ITALY]                                                                        65                       VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
of the airborne fraction deviate strongly from the “total” physical particle size, but are
considered more reflective of occupational circumstances, where mechanical agitation of
these materials during operations such as bagging, weighing, mixing etc. will cause this
fraction of the material to become airborne.
Conclusion

The particle size distribution collected at the workplace with the Respicon (Table 4.33) and
the calculated MMAD and GSD values for each compound are used as input parameters for
the prediction of fractional deposition behaviour in the respiratory tract, based upon which an
assessment of inhalation absorption factors is derived.


4.1.1.2.11           Summary of occupational exposure and data gaps
The available data for inhalation and dermal exposure allow a preliminary typical and RWC
risk characterisation to be conducted for most process codes. Stratification of the data by
process and job eliminates much of the variability apparent in the initial data classified simply
by process or company. Where high exposures and high variability remain, these can mostly
be explained by operational variables.
While coverage of routine operations for most processes is considered reasonable, data for
some ancillary and maintenance operations are rather sparse. Further data collection should
therefore be encouraged.
Inhalation exposures carried forward for risk characterisation are shown in Table 4-45 to
Table 4-49. In order to accommodate the exceptions and uncertainties described above, the
range of usual typical and RWC exposure for each process code are shown together with
those exposures which fall outside the range.
There are few recent reports of occupational exposure to copper in the literature. The data of
Cohen and Powers (2000) for melting and casting of copper alloys are in good agreement with
data presented here. Other data sometimes cited (Gleason, 1968) refer to copper levels
estimated from dust measurements and, in any case, are now redundant. Limited data from
national databases from France (INRS), Finland (FIOH) and the UK (HSE) are available but
are generally lacking in supporting information and appear to include copper exposure from
outside the copper industry. These data are therefore not relevant to the processes considered
here. Hence the importance of the data collected from ECI companies in the RA.
Particle size distribution of airborne copper to predict the fractional deposition in the
respiratory tract are shown in Table 4-50.
Dermal exposures carried forward for risk characterisation are shown in Table 4-51.
Workers engaged in the manufacture of copper powders and copper compounds generally
have higher exposures than workers in other processes. Extremely high exposures may occur
in the manufacture of copper powders mainly due to poorly controlled material transfer. In
other cases, the primary source of exposure appears to be process malfunctions and
intervention, process variables, particularly the method of bag filling and sealing, and possibly
handling of bags. The dustiness of the substances may also be a determinant of exposure.
Currently, there are insufficient compound-specific data to evaluate this further.




RAPPORTEUR [ITALY]                               66                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
It is important to take into account the limitations and uncertainties involved in using the
EASE model as currently assessed by the HSE (A. Phillips (HSE), personal communication).
Firstly, application of the EASE model is inapplicable to processes (such as hot metal
processes) for which there is no related EASE scenario. Secondly, the original exposure
estimates used to calibrate the model date from the 1980’s (prior to the COSHH Regulations
in the UK) where few if any control measures were present. Therefore these are not applicable
to contemporary exposures for processes where efficient control measures are common.
EASE estimates are not used for risk characterisation.

Table 4-45 Inhalation data carried forward for risk characterisation for        Data from Table 4-8 Exposures incorporating
primary and secondary smelting.                                                 RPE in parentheses.

                                                                    Typical                RWC
Risk characterisation                                             Cu(mg/m³)             Cu(mg/m³)
FURNACE OPERATION
 All smelting, converter and anode furnace operation                0.03-0.23            0.17-0.84
(except where indicated below)
Pooled                                                                0.12                 0.54*


ECI-07
anode furnace opn (incl tapping)                                      0.85                 1.55
anode furnace opn (incl tapping) using RPE                           (0.085)              (0.155)
                                                                    0.04-0.32            0.19-0.60
SAMPLING PLANT
Pooled                                                                0.19                 0.55


RAW MATERIAL HANDLING                                               0.02-0.29            0.07-1.03
Pooled                                                                0.02                 0.29
*Excluding the high exposure values of ECI-67 as they are no longer relevant.

Table 4-46 Inhalation data carried forward for risk               Data from Table 4-13.
characterisation for melting and casting
Risk characterisation                                               Typical                RWC
                                                                  Cu(mg/m³)             Cu(mg/m³)
PRODUCTION OF BILLETS (PC6), SAND AND DIE CASTINGS (PC7), WIREROD (PC8) except as
Indicated below
All operations (site specific data)                                 0.03-0.24            0.23-1.24
Pooled data                                                           0.12                  0.6

Table 4-47 Inhalation data carried forward for risk characterisation for further processing

Risk characterisation                                               Typical                RWC
                                                                  Cu(mg/m³)             Cu(mg/m³)
All operations (using RPE) (Table 4-17 )                            0.03-0.1          0.2-2.45 (0.245)
Pooled data                                                           0.04                  0.3




RAPPORTEUR [ITALY]                                             67                            VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Table 4-48 Inhalation data carried forward for risk characterisation         Data from Table 4-20. Range of exposures for
for copper powders.                                                          bagging, process opn and furnace opn. Exposures
                                                                             incorporating RPE in parentheses
Risk characterisation                                      Typical                      RWC
                                                         Cu(mg/m³)                   Cu(mg/m³)
ECI-97– operation specific                                0.34-0.59                   0.82-0.97
         -pooled                                            0.42                         0.92
ECI-105– operation specific                                1.95-6.9                   10.2-98.2
         -pooled                                            5.59                         19.0
ECI-106– operation specific                        0.77-9.70 (0.06-0.83)         3.69-11.16 (0.22-1.6)
         -pooled                                          2.6 (0.22)                 11.26 (1.13)



Table 4-49 Inhalation data carried forward for risk characterisation         Data from Table 4-29. Range of exposures for
for copper compounds.                                                        bagging, process opn and furnace opn.
                                                           Typical                      RWC
                                                         Cu(mg/m³)                   Cu(mg/m³)
ECI-91                                                      0.68                         1.43
ECI-93                                                      0.30                         0.80
ECI-110                                                     0.10                         0.76
ECI-112                                                     0.12                         0.31
Pooled data                                                 0.23                         0.82



Table 4-50 Particle size distribution of airborne copper to predict the fractional deposition in the respiratory tract

                                                         particle size distribution (%)
                                              respirable             tracheo-         extra-thoracic
                                                                     bronchial

 smelter, converter                                12                   33                  55
 furnace opn, copper powder production             39                   23                  38
 bagging copper oxychloride                        20                   25                  55
 bagging copper(I)oxide                            12                   47                  41



Table 4-51 Dermal exposure data carried forward for risk characterisation for all main scenarios.

                                                           Typical                      RWC
                                                        Cu(mg/person)              Cu(mg/person)
Smelting&refining                                            60                           85
Melting&Casting                                              60                           85
Further processing                                           60                           85
Cu-powder production                                         259                         952




RAPPORTEUR [ITALY]                                                 68                               VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
copper (I) oxide production                   230                845
copper (II) oxide production                  207                760
copper chloride trihydroxide production       154                566
copper sulphate pentahydrate production       66                 243
Pooled                                       180.5               663




RAPPORTEUR [ITALY]                                  69                  VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH


4.1.1.3              Consumer exposure
The data on copper in consumer products is sparse relative to that for indirect exposure. Trade
Organisations, the SPIN database (2004) and the Medline database were consulted.
According to the SPIN database (2004) copper and the four copper compounds can be found
in several products including paints, printing inks, lacquers and varnishes, colouring agents,
additives, impregnating agents, non-agricultural pesticides and preservatives, surface
treatment, electroplating agents, fertilisers, food/feedstuff flavourings and nutrients. Other
uses include coins, jewellery, cutlery, IUDs, hair care products. Finally, a unintential exposure
source of copper is cigarettes.
For several uses no details on concentration and specific use pattern were given, which makes
it difficult to predict consumer exposure.
More specified information was found for copper compounds used in the product categories
cigarettes, paint, cosmetics and toiletries, supplements, coins, jewellery, IUDs. The
calculations are in accordance with the TGD (EC, 2003).The default-values applied are
according to the TGD (EC, 2003) where these are given. Where assumptions are introduced in
order to estimate exposure (e.g from handling coins) these are judged as conservative with
respect to risk. As for other modes of exposure, all exposure data refer to external exposure as
indicated in the TGD. Absorbed doses expressed as a function of body weight are given in the
Risk Characterisation chapter. Consumer products are generally not considered a significant
source of exposure. The available data are discussed below.


4.1.1.3.1            Sources of exposures

Inhalation exposure

Cigarette smoke
Cigarette smoke contains traces of several heavy metals including copper. The metal content
of a range of cigarettes marketed in the UK (n=10) have been reported (Jung et. al., 1998).
The mean and standard deviation for copper were 9.57±3.12 µg per cigarette. Available data
for copper indicate that as little as 0.2% of copper in cigarettes is available in cigarette smoke,
a lower proportion than that for other metals (Mussalo-Rauhamaa et. al., 1986). Estimated
exposure as a function of consumption is plotted in Figure 4-16. Since exposure is
proportional to consumption, a RWC of 0.0005 mg/day is estimated based on the mean value
for consumption of 20 cigarettes per day.




RAPPORTEUR [ITALY]                               70                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Figure 4-16 Copper exposure from cigarette smoking

                        0.0010

                                     mean
                                     mean+sd
    exposure (mg/day)




                        0.0005




                        0.0000
                                 0   10          20            30        40
                                          cigarettes per day



Smoking rates among adults in most EU countries range from 25-35% with a minimum of
14% in Portugal and a maximum of 38% in Greece (www.who.int/tobacco/en/). Detailed data
for age and sex specific smoking rates for the UK indicate that smoking rates are highest
among young men aged 20-34 years (www.heartstats.org). Differences in smoking rates as a
function of sex are modest with a maximum difference of approximately 6% in the 20-34 year
age group. Social class is the major determinant of smoking rates but, even among manual
workers, smokers are still a minority (33% for 2001, the last year for which data are
available). Typical exposure is therefore taken as zero.

Summary
A RWC of 0.0005 mg/day is estimated based on the mean value for consumption of 20
cigarettes per day. Typical exposure is taken as zero.

Dermal exposure

Cosmetics and toiletries
Copper compounds are minor ingredients of some preparations marketed as cosmetics and
toiletries. Substances used in these preparations are listed in the EU Cosmetics Ingredients
Inventory and the US CTFA dictionary. Copper sulphate and copper powder are the only
substances included in the RA which is indicated in this list (Cosmetic, Toiletries and Perfums
Association (CTPA), private communication). Copper sulphate is listed as an “additive”
while the function of copper powder is not specified. However, quantitative information is not
available within the public domain. It is understood however that copper compounds are not
used as active ingredients in cosmetics and toiletries (CTPA personal communication). No
data are available on the occurrence of trace levels of copper as an impurity in cosmetics or
toiletries.
Copper peptides are used as anti-aging agents in several face creams marketed from the
United States on the internet. One manufacturer has carried out analytical determinations of



RAPPORTEUR [ITALY]                                                  71        VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
the copper content in its products along with those of rival products
(www.skinbiology.com/comparingcopperpeptides). The copper content of face cream is given
as 0.18% (as Cu ion) and that of creams intended specifically for the eyes (and therefore
applied to a much smaller surface area) as 0.28%. The corresponding values for a range of
rival products are given as ≤0.03%. Although copper peptides fall outside the scope of the
RA, The values of 0.03% and 0.18% are therefore taken as typical and RWC exposures
respectively. These values are used as a surrogate in the exposure assessment from cosmetics
and toiletries in the absence of directly relevant quantitative data on copper sulphate.
Exposure is calculated using the TGD defaults for contact and frequency as:
Exposure = frequency x mass x concentration
where:
frequency = frequency of application (TGD default for face cream = 1 application per day)
mass = mass applied (TGD default for face cream = 0.8g per application)
concentration = fractional copper content of preparation = 0.0003 or 0.0018
Typical and RWC exposures are therefore calculated as 0.24 mg/day and 1.44 mg/day
respectively.

Hair care products
The copper concentration in a range of commercial shampoos and conditioners (n=15) has
been reported (LeBlanc et al., 1999). The mean value was 75 µg/litre and the 90th percentile
was 120 µg/litre. These values are taken as the basis for typical and reasonable worst case
calculations respectively. The density of these products was not reported. Unit density is
assumed for the purpose of calculations and mass/mass concentrations are taken as 0.075 µg/g
and 0.120 µg/g accordingly. This is calculated using the TGD defaults as:
Exposure = frequency x mass x concentration x “rinse factor”
where:
frequency = frequency of application (TGD default for shampoo = 2-7 applications per week,
0.3-1 application per day)
mass = mass applied (TGD default for shampoo = 12g per application)
concentration = copper concentration in preparation = 0.075-0.120 µg/g (upper value used)
rinse factor for hair products (amount remaining) = 0.01 (SCCNFP, 2003)
Taking 0.3 and 1 applications per day for the typical and RWC estimates respectively, the
corresponding exposures are 4.3x10-6 mg/day and 1.4x10-5 mg/day.

Handling of coins
Coins in circulation in the EU may contain significant amounts of copper. In a study to
investigate leaching of copper from coins, patch tests were conducted in which a range of
coins were taped to skin for periods of 24-72 hours and copper released was recovered both
from the skin and coin surface (Fournier et. al., 2003). The highest rates of release were
observed for 1€, 0.50€ and £1 coins. The ranges found corresponded to release rates of



RAPPORTEUR [ITALY]                               72                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
approximately 80-120 µg/cm2/week equivalent to 0.48-0.71 µg/cm2/hour. Release rates from
2€ coins were slightly lower at approximately 60 µg/cm2/week.
In a further series of experiments, manipulation tests were performed to determine the transfer
of metals to the fingers following successive manipulation of coins (Fournier and Govers,
2003). Two sets of 58 2€ or 2 French franc coins were individually manipulated by volunteers
counting them from one container to another. (French francs are no longer in circulation and
these are not considered further). Each manipulation took an average of 2.6 secs to perform.
Wipe samples were taken from the three fingers used before and after the experiments to
determine the transfer of metals and to correct for background skin levels. The tests were
performed with and without pre-washing in demineralised water and also with prior polishing
of the coins. The results were expressed as the amount of copper transferred to the fingers
after the manipulation of a single coin. The results for 2€ coins (µg per manipulation with
90% confidence limits in parentheses) were; 1.4±0.2 for unwashed coins, 1.3±0.2 for washed
coins and 0.10±0.01 for polished coins. Clearly, pre-washings made negligible impact on
contamination while polishing had a major impact by removing transferable metal from the
coins’ surface.
This experimental method is considered more meaningful than simple leaching experiments
as it simulates the frictional and other handling components involved. However, as noted
above, the 2€ coins produced approximately 30-90% less copper in leaching tests than some
other coins (1€, 0.50€ and £1) in circulation in the EU. In order to give a realistic worst case
estimate for the selection of coins handled, the values obtained from the manipulation tests
described above are multiplied by a factor of 1.6. This represents a typical value by which the
2€ coins underestimate the release of copper relative to other coins.
In the absence of frequency/contact parameters for coins in the TGD, it is assumed that a
single coin is manipulated continuously for periods of 5 or 10 minutes. Given an average
manipulation time of 2.6 secs, this represents a total of approximately 115 or 230
manipulations respectively. It is further assumed that the coins handled are a mixture of
polished and unwashed coins representing the different stages of the coins’ lifecycle.
Applying a multiplier of 1.6 to the transfer rate of 0.10 µg per manipulation for polished coins
and 1.4 µg per manipulation for unwashed coins, gives an estimated transfer of copper to the
fingers (115/2*0.1*1.6) + (115/2+1.4*1.6) = 138 µg/day = 0.14 mg/day and (230/2*0.1*1.6)
+ (230/2+1.4*1.6) = 138 µg/day = 0.28 mg/day respectively.

Jewellery
Dermal exposure to copper jewellery may also occur. This applies in particular to jewellery
with a high copper content such as bracelets marketed for their supposed anti-rheumatic
properties. No data on the frequency of such exposure or the contact parameters are available
and an accurate quantitative assessment is therefore not possible. . As a worst case
approximation, the data cited above for coins are used where coins were taped to skin and
leaching determined by patch tests (Fournier et. al., 2003). Since coins typically are
comprised of 60-90% copper, this analogy is considered reasonable. The internal dimensions
of a bracelet are taken as 1.2x20cm = 24cm2. It is assumed that this surface area is in
continuous daily contact with the skin although this probably overstates the actual level of
contact. Based on the rate of the leaching of copper from coins, given by Fournier as 60-120
µg/cm2/week, this amounts to a dermal exposure of 60/120 x 24 = 1.4-2.9 mg/week or 0.2-
0.41 mg/day. It is assumed that jewellery of this nature is worn by relatively few individuals.




RAPPORTEUR [ITALY]                               73                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
An exposure of 0.41 mg/day is therefore taken as a RWC estimate and typical exposure is
taken as zero.

Wood preservatives and pesticides
Additional exposure will occur from the use of Cu containing pesticides and wood
preservative. This is however the subject of a separate risk assessment and is not considered
here.
Paints

A small amount of copper is used in special paints to give a metallic look. Copper content in
such paints can be as high as 25% copper (personal communication). Assuming a frequency
of 0.5 events/year with a dermal exposure of 4 - 11.8 g paint/event (TGD default for
spraying), the exposure will be 1.37 – 4.03 mg Cu/day. With a dermal absorption of 0.3% the
uptake is estimated to be between 0.004 and 0.012 mg Cu/day. It is assumed that paints of this
nature are used by relatively few individuals. An exposure of 4.03 mg Cu/day is therefore
taken as a RWC estimate and typical exposure is taken as zero.

Summary
Typical and RWC exposures to cosmetics and toiletries are calculated as 0.24 mg/day and
1.44 mg/day respectively.
Typical and RWC estimates for exposure to haircare products are respectively 4.3x10 -5
mg/day and 1.4x10-4 mg/day.
The typical and RWC estimated exposure to the fingers of copper from the handling of coins
is estimated 0.14 and 0.28 mg/day respectively.
The typical and RWC estimated exposure from wearing jewellery with a high copper content
is estimated at zero and 0.41 mg/day respectively.

Oral exposure

Dietary supplements
Copper is present in various forms of over the counter multi-mineral supplements. The UK
Food Standards Agency Expert Group on Vitamins and Minerals concluded that copper
concentrations in these products are “up to” 2mg (EVM, 2002). The proportion of the
population using copper supplements is unknown. However, the use of zinc supplements in
the UK and the Netherlands is believed to be less than 10%. The Scientific Committee on
Food in their opinion on the Tolerable Upper Intake Level of copper noted that “a very small
proportion of consumers take dietary supplements containing copper, but for those few who
did, median intakes from supplements were 0.1-0.5 mg/day”. The values are based on a
personal communication. Companies selling the supplements recommend taking 1 tablet per
day (e.g.
http://www.walgreens.com/store/product.jsp?CATID=100146&navAction=jump&navCount=1&id=pr
od3498 and http://www.health.co.uk/showdetails.asp?id=445). For the purpose of this risk
assessment, as a RWC it is assumed that a person takes 1 daily supplement of 2 mg
copper/day. Since the data for zinc supplementation clearly indicate that only a minority of
the population use supplements typical exposure is taken as zero.




RAPPORTEUR [ITALY]                               74                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Cutlery
Bolster and handles, which may be out of brass or other copper alloys, are not supposed to be
in contact with food in normal use.
Cutlery may be fully produced from brass or nickel-silver, but in such luxury products the
copper alloy is plated with silver, gold or tin; there is no direct contact between copper and
the food.
Such platings was considered during the discussions about metals in contact with food at the
Council of Europe (2001) which concluded that there is no safety problem and that there is no
need for specific recommendations or restrictions for the use of copper coated materials.
Wood preservatives and pesticides
Exposure to copper from pesticides and wood preservative is the subject of a separate risk
assessment and is not considered here. Some copper containing pesticides are in use and
residues maybe found in food. The market basket data and food analysis presented in chapter
4.1.1.5.2 will include the contribution of any pesticide residues to daily intakes.
Summary
For a RWC a daily intake of copper from supplements of 2 mg/day is assumed. A typical
exposure is taken as zero.


4.1.1.3.2            Summary of consumer exposure
Exposure estimates for the source considered above are summarized in Table 4-52.
Population estimates are derived whereby typical exposure is taken as zero if exposure to a
given source occurs only in a minority of the population.
Observation of copper industry workers in many companies and across all sectors indicates
that the observed exposed population (i.e. those engaged in production processes) is
exclusively male. In addition, workers reflect socio-economic trends in terms of smoking
habits. For these reasons, the consumer exposure scenarios outlined above are not directly
relevant to these workers. It is also assumed that copper industry workers are unlikely to take
copper in dietary supplements. Therefore, for the purpose of combining occupational and
consumer exposures for this group, a separate consumer scenario is determined. As typical
consumer scenario for workers it will be assumed workers are exposed via the dermal route to
0.14 mg Cu/day to coins and to 4.3x10-6 mg Cu/day via haircare products. As RWC consumer
scenario for workers it will be assumed workers are exposed via the dermal route to 0.28 mg
Cu/day to coins, to 1.4x10-5 mg Cu/day via haircare products and via the inhalation route to
0.001 mg Cu/person/day by smoking cigarettes.
As already indicated, these values represent external exposure. These are taken forward for
calculation of the corresponding absorbed dose in risk characterisation.




RAPPORTEUR [ITALY]                               75                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Table 4-52 Summary of population exposure estimates       Values carried forward for risk
for consumer exposure.                                    characterisation. External exposure
                                                          (mg/person/day)
  mg/person/day         Route of exposure           External exposure        External exposure
                                                         Typical           Reasonable worst case
                                      Cosmetics and toiletries

    Face cream               dermal                        0.24                     1.44

 Haircare products           dermal                      4.3x10-6                  1.4x10-5

       Paint                 dermal                        none                     4.03

                                               Other

 Cigarette smoking          inhalation                     none                    0.0005

 Handling of coins           dermal                        0.14                     0.28

  Copper jewellery           dermal                        none                     0.41

 Food supplements              oral                        none                     2.00




RAPPORTEUR [ITALY]                                          76                         VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH


         4.1.1.4            Humans exposed via the environment - local environment


4.1.1.4.1            Background and scope
The scope of the local exposure assessment is defined in the Environmental Risk Assessment
chapter of the TGD and is described in detail in the corresponding chapter of the voluntary
risk assessment for copper. Essentially this is a prospective assessment based on current
emissions designed to inform regulatory decisions on plant operation etc. Current emissions
are likely to be considerably lower than historical emissions due to the widespread use of
efficient APCE systems. Since copper may accumulate heavily in soil, measured levels in soil
inevitably incorporate historical deposition and are inappropriate for the risk assessment.
(Historical deposition arising from uncontrolled emissions has occurred continuously for
periods of up to 500 years in some cases). Instead, soil levels, based on 10 years continuous
deposition, are modelled using the EUSES model. Copper added by deposition is then added
to the regional background.
In contrast, recent data on measured airborne concentrations and deposition rates are likely to
predominantly reflect current emissions providing confounding sources (e.g. road traffic) are
minimised. Therefore these data are considered where available.


4.1.1.4.2            Information gathering

Analysis of ECI questionnaires
Data were collected through questionnaires sent to the companies of the different sectors. The
collected data are presented in the environmental section of the RA report, local exposure
chapter. Data described here are taken from this chapter where detailed descriptions of the
methodology may be found along with appropriate references to the TGD. The measured and
calculated data of relevance to the human health local indirect exposure assessment are
summarised by sector in Table 4-53. This comprises measured and calculated levels of
airborne copper, copper deposition and copper levels in soil. All calculated values are based
on the EUSES model as described in the chapter on the Environment. These data are
discussed further in the next sections.

Literature data
Data from the literature are also available for copper levels in soil and for soil to plant transfer
for fruit and vegetables entering the human food chain via the environment. Estimates for
indirect exposure are restricted to the consumption of fruit and vegetables grown in the
vicinity of the industry sectors considered. Other foodstuffs are assumed to be sourced
regionally. This is consistent with the approach adopted in other risk assessments (e.g. zinc,
cadmium).


4.1.1.4.3            Inhalation exposure
Table 4-53 indicates that limited measured data of relevance are available for airborne levels
for refiners and smelters. Companies report a range of typical values from 127-325 ng/m3



RAPPORTEUR [ITALY]                               77                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
with one company reporting a 90th percentile of 827 ng/m3. No details are available on the
measurement location with respect to the plant or to wind direction or the prevailing weather
conditions all of which may heavily influence the results. Some further data are available for
locations more distant from the plants (≥1km) although these are not relevant for the RA. In
general, no details are available on methods of sampling and analysis is nor on quality control
procedures employed, if any. Some other data, not shown in Table 4-53, refer to
measurements within site boundaries which are not relevant for the RA as specified in the
TGD.
Calculated airborne levels were calculated with EUSES, and based on copper levels measured
in stack emissions.3 Values vary widely within and between sectors. The median values by
sector range widely from 5 ng/m3 for semis producers to 518 ng/m3 for refiners and smelters.
The highest values for both refiners and smelters and for the wire rod and cables sectors (4549
and 2761 ng/m3 respectively) are for single companies within each sector that do not report
details of air pollution control equipment (APCE), although the wire rod and cable
manufacturer does report a “scrubber” (type unspecified). With a single exception, all other
companies in these sectors report the use of fabric filters which may therefore be considered
the industry standard. Data from incinerators indicates a reduction in emissions of two to three
orders of magnitude with the use of fabric filters consistent with manufacturers’
specifications. Results at the higher end of these ranges are therefore relevant to the specific
plants but are unrepresentative of the sector as a whole. The ingots and shapes and semis
sectors also report fabric filters (with or without inertial separation) as standard.
Calculated values do not include fugitive emissions. With highly efficient air pollution control
equipment (APCE), fugitive emissions may form the major component of total emissions and
calculated values are probable underestimates. The limited comparison possible for measured
and calculated data does not reflect this hypothesis with median calculated value for smelters
(518 ng/m3) up to approximately four times the measured concentrations. However, this may
simply reflect the uncertainties in the measured data described above. A comparison of
deposition data, discussed further below, suggests that this is indeed likely.
Typical and RWC inhalation exposures by sector are shown in Table 4-54. These are
calculated using the added copper concentrations in Table 4-53 with the addition of the
regional background of 100 ng/m³ and the default inhalation volume of 20 m3/day.
Using for example the maximum concentration in air for smelters and refiners, the external
exposure by inhalation (mg/person/day) is:
(4549 ng/m³ + 100 ng/m³) * 20 m³/person/day= 0.093mg/person/day
However, these values do not incorporate the effect of fugitive emissions. In order to make
allowance for fugitive emissions, the two highest maximum values in Table 4-54, 0.093


3 The exposure concentration in air is performed on the basis of the available dataset i.e. the emission data
presently available from industry. Generic scenarios -based on calculated emissions from sector-specific
maximum emission factors and production data- were applied to the sites for which no emissions are available.

Concentrations in air were calculated as the ‘added’ yearly average air concentration at 100 m from point source.
Concentrations were assessed from reported data on total point emission to air, number of days that emission
takes place, total fugitive emission to air, daily point emission to air (Chapter 3).




RAPPORTEUR [ITALY]                                     78                       VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
mg/day and 0.057 mg/day are taken forward to risk characterisation as reasonably
conservative estimates of RWC and typical inhalation exposure respectively.
No measured data for particle size distribution are available. It can be assumed from the use
of fabric filters that only very fine particulate matter is emitted by stacks from these plants.
However, the particle size distribution in the vicinity of the plants may be heavily dependent
on the fugitive emissions component. For example, a high proportion of wind-blown dust in
fugitive emissions may shift the airborne particulate to a much more coarse distribution. This
is highly plausible given that dusty materials are often kept in bulk in outside storage areas.

Table 4-53 Measured and derived copper levels in environmental compartments relevant for
indirect local exposure assessment                                                                      Source: Chapter 3


                         air conc (ng/m3)              deposition                    soil conc (mg/kg dry weight)
                                                      (mg/m2/day)
                                                                                         EUSES           EUSES calculation
                                                                                       calculation      based on calculated
                                                                                        based on            deposition
                                                                                       measured
                                                                                       deposition
    sector           measured    added conc      measured Calculated measured        Added Total          Added         Total
                                 calculated at                                       copper copper        copper       copper
 (number of                          100m                    Using
 companies                                                   EUSES
     in                           (median in                 model
parentheses)                     parentheses)                                                           (median in
                                                                                                       parentheses)
 refiners and        127-325       17-4549       0.18-0.44   6.1x10-4-   <5-3207     2.20-     26.6-     0.04-2.0      24.4-
   smelters                                       (≤1km)       0.16      (≤1km)      5.38      29.8                    26.4
                     90thP 827      (518)                                                                  (0.43)
     (10)                                                                  >1000
                                                                          (<1km)
wire rod and            n/a         1-2761          n/a      3.8x10-5-      n/a       n/a       n/a    4.6x10-4-1.39   24.4-
   cables                                                      0.10                                                    25.8
                                    (24.9)                                                                 (0.03)
     (19)

  ingots and            n/a        <1-1523          n/a      8.1x10-6-     24.5       n/a       n/a     <0.01-0.75     24.4-
    shapes                                                     0.06      (depth 60                                     25.2
                                    (58.6)                                  cm                             (0.03)
     (11)


    Semis               n/a        1.3-1552         n/a      4.7x10-5-   4.5-220      n/a       n/a     <0.01-9.95     24.4-
                                                               0.05      (≤2km)                                        34.4
     (48)                            (5.3)                                                                 (0.01)


   copper               n/a         <1-338          n/a      3.8x10-7-      n/a       n/a       n/a     <0.01-2.12     24.4-
 compounds                                                     0.01                                                    26.6
and powders                          (35)                                                                 (<0.01)

     (15)

n/a: not available




RAPPORTEUR [ITALY]                                             79                            VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Table 4-54 External inhalation exposure (mg/day) by sector (Table 4-53)

                                  Sector                        median      max
                           Refiners and smelters                 0.012      0.093
                           Wire rod and cables                   0.002      0.057


                            Ingots and shapes                    0.003      0.032
                                  Semis                          0.002      0.033
                     Copper compounds and powders                0.003      0.009


4.1.1.4.4               Drinking water
Exposure from drinking water is assessed separately as leaching from the distribution system,
is the major factor effecting exposure, as opposed to contamination of groundwater.
Concentrations of copper in groundwater are generally low, and are considered to be an
insignificant source of exposure (Chapter 3). The detailed assessment and typical and RWC
estimates can be found in the regional indirect exposure assessment.


4.1.1.4.5               Ingestion of dust
Typical and RWC estimates are included in the regional exposure assessment. No data are
available for the local risk assessment. However, estimates in the regional assessment are
considered conservative with respect to risk, with the RWC value of 1000 mg/kg
corresponding to actual measured levels in polluted soils (see Table 4-53).


4.1.1.4.6               Copper levels in soil

Copper deposition
Copper in airborne emissions may impact on the local soil by deposition. Calculated
deposition rates using the EUSES model are shown in Table 4-53 together with limited
measured data available for refiners and smelters only. Within the refining and smelting
sector, comparison of the calculated deposition data (6.1x10-4-0.16 mg/m2/d) with the limited
available measured data (0.18-0.44 mg/m2/d) in Table 4-53 suggests that measured values
may exceed calculated values by up to three orders of magnitude, although by much less at
the higher end of calculated deposition rates. As for inhalation data, methods of sampling and
analysis together with supporting information for key variables (windspeed/direction,
precipitation, particle size distribution etc) are not available.

Copper in soil – ECI data
The few available measured data for copper in soil are lacking in spatial and depth resolution
as well as sampling and analytical detail. As shown in Table 4-53, these data span a very
wide range from 0.1-3207 (or >1000) mg/kg dw within a distance of 1km from the plant and
are not considered valid for inclusion in the RA and are not discussed further. In addition,
they clearly are heavily impacted by historical pollution and are therefore beyond the scope of
the RA as indicated in section 4.1.1.4.1.



RAPPORTEUR [ITALY]                                        80              VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Estimates of added copper in soil are shown in Table 4-53 calculated using the EUSES model
based on 10 years of deposition at current emission levels including the application of sewage
sludge where applicable (criteria for the application of sewage sludge are given in the TGD,
see chapter on the environment). These estimates are based on calculated deposition rates for
all sectors data and also measured deposition for refiners and smelters. The results are
extremely low relative to the limited measured data available (and data from the literature
discussed below) for reasons already given. For results based on calculated deposition rates,
estimates across the sectors are mostly in a narrow range (<0.01-2.0 mg/kg dw) with the
exception of semis producers where the upper end of the range is 11.2 mg/kg dw. This higher
value is due to the application of sewage sludge in this case. Estimated soil copper
concentrations using the measured deposition rates for refiners and smelters (2.20-5.38 mg/kg
dw) are higher than the corresponding estimates based on calculated deposition rates (0.04-2.0
mg/kg dw). These differences are assumed to be due mainly to the impact of fugitive
emissions although they may also be effected by confounding sources (other industry, road
traffic etc). Resuspension of soil particles, depending on climatic conditions and vegetation,
may also influence measured deposition rates although the impact of resuspension is
considered low based on measurements around a smelter in Chile during operation and
shutdown (Romo-Kröger et. al., 1994).
The base level of copper in soil specified by the TGD is the level in “natural” soils calculated
as 24.4 mg/kg dw (chapter on the environment). To this, the added copper levels described
above are added for the local exposure assessment. This gives a maximum value of 24.4+9.95
=34.0 mg/kg dw with the addition of sewage sludge (for a semis producer) and 24.4+5.2 =
29.6 mg/kg dw without sewage sludge based on the upper range of measured deposition for
refiners and smelters. Given that these values incorporate either application of sewage sludge
or the impact of measured deposition rates they are considered reasonably conservative.

Copper levels in soil - Literature data
Copper levels in soil in the vicinity of copper and copper alloy works have been described in
several studies (Hunter et. al., 1987; Ylaranta 1996; Mehra et. al., 1999). Copper levels range
from approximately 70-800 mg/kg dw. The authors indicate, not atypically for the copper
industry, that some plants have been in operation for over 100 years. During most of this time,
little or no APCE has been present and current soil levels are largely a function of historical
pollution.


4.1.1.4.7            Copper levels in food

Background
The TGD methodology for determining soil/plants/human uptake pathways is wholly
inapplicable to metals. We therefore determine these pathways from analysis of findings
reported in the literature. We follow the TGD terminology of “biotransfer factors” (BTFs) in
describing the transfer of copper from soil to plants and into the human food chain.
Special consideration is given to aerial deposition as a pathway for human exposure.

Derivation of exposure from the literature
Copper levels in soil and plants, including lettuce and wheat, were measured in the vicinity of
a copper smelter in Finland (Yläranta, 1996). The smelter was described as producing 1% of



RAPPORTEUR [ITALY]                               81                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
world copper supply during the 1980’s. Copper levels in moss, a sensitive bioindicator of
recent deposition, were described as the highest recorded in northern Europe. Soils were
sandy or sandy clay loam. Copper levels and other soil variables were measured at various
distances up to 8.5 km from the smelter. Those nearest the plant (800-1500m) are of most
relevance to the RA. Control samples were obtained from a rural area not impacted by
industrial pollution. Soil samples were collected at depths of 0-25cm and 25-50cm. The
former are described further with respect to concentrations in plants. Soil samples were dried
and extracted with aqua regia (as a measure of total metal) and also with CH3CO2NH4/EDTA.
The sample treatment for plants was not specified.
Lettuce and wheat were grown in plots, over 3 seasons, located at clearly defined distances
from the smelter (800m, 1300m, 1500m) where the soil copper concentration was also
determined as shown in Table 4-55. In addition, soil samples from these locations were
removed and relocated to a controlled environment where the same crops were grown. This
“plot to pot” design allows the determination of copper uptake from polluted soil in the
absence of further aerial deposition during the growing period. “Bulk deposition”, essentially
a surrogate for total (wet and dry) deposition (Met Office, 1995), was measured over the
growing period. These results have been converted to mg/m2/d based on the author’s data.
Only the above-ground part of the lettuce appears to have been harvested for analysis
(Ylaranta, 1994). Both copper deposition and copper levels in soil were sensitive to distance
from the smelter. This gradient was closely reflected in the copper content of wheat grain but
not lettuce for which differences between growing seasons appear to have been more
significant. For this reason, the role of homeostatic regulation may be rather obscured in these
data. Most copper levels in all plants were significantly elevated above copper in control
samples. Low soil pH appears to have contributed to the uptake.

Table 4-55 Copper in soil and copper uptake by plants in the vicinity of a copper smelter           Source: Yläranta, 1996


Sample       Date           Bulk            pH         OC (%)           Soil            Soil         Wheat       Lettuce
                                                                    concentration   concentration    grain
location-               Deposition (1)                                                                          mg/kg/dw
                                                                     (mg/kg/dw)      (mg/kg/dw)     mg/kg dw
  type                    mg/m2/d
                                                                     aqua regia     CH3CO2NH4/
                                                                     extractable       EDTA
                                                                                     extractable
controls    1985-8                        5.7-6.3      1.8-2.0          8-20           1.3-4.5       2.3-5.2      3.7-8.8


 800m        1985           1.24            6.0          2.6            260             190            10           67
  plot
             1986           1.50            6.0          2.6            260             190            9.6          47
             1988           1.01            5.7          2.5            252             142            9.3          20
800m pot     1985                           6.0          2.6            260             190            7.1          33
             1986                           6.0          2.6            260             190            6.5          31
             1988                           5.7          2.5            252             142            6.7          15
 1300m       1985           0.46            4.9          2.8            161                 82         8.2          69
  plot
             1986           0.68            4.9          2.8            161                 82         8.0          49
 1300m       1985                           4.9          2.8            161                 82         5.3          40
   pot
             1986                           4.9          2.8            161                 82         6.1          58




RAPPORTEUR [ITALY]                                             82                           VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Sample            Date            Bulk              pH    OC (%)          Soil              Soil          Wheat     Lettuce
                                                                      concentration     concentration     grain
location-                   Deposition (1)                                                                          mg/kg/dw
                                                                       (mg/kg/dw)        (mg/kg/dw)     mg/kg dw
    type                       mg/m2/d
                                                                       aqua regia       CH3CO2NH4/
                                                                       extractable         EDTA
                                                                                         extractable
    1500m         1988            0.34              5.8    1.5            127                72            8.0         19
     plot
    1500m         1988                              5.8    1.5            127                72            6.8         12
      pot



Mean BTFs for plot and “plot to pot” experiments for food crops are summarised in Table
4-56. Much higher BTFs were observed for controls relative to experimental samples. This
indicates homeostatically reduced uptake at higher soil copper concentrations. Although the
data are rather limited, there is a clear design-dependent trend in BTFs with higher BTFs for
the plot experiments. This suggests that continued aerial deposition during growth plays a
considerable role in final plant copper content. These findings are somewhat complicated with
respect to human exposure due to uncertainty in how the samples were treated with respect to
washing. In general, there is also a clear trend for lower BTFs with increasing soil copper
(although the results for lettuce at 161 mg/kg soil copper are somewhat anomalous). Other
data not considered here in detail, support this observation, for example copper uptake by
spinach and cress in roadside soils (Schafer et. al., 1998).

Table 4-56 Mean biotransfer factors (BTF)1 for food crops impacted by aerial               Source: Yläranta, 1996
           deposition from a copper smelter.
    Soil copper                   Lettuce                         Wheat grain

     mg/kg dw              plot          plot to pot       plot           plot to pot
      252-260             0.17               0.10          0.04                 0.03

        161               0.37               0.30          0.05                 0.04

        127               0.15               0.09          0.06                 0.05

        8-16              0.41               0.59          0.26                 0.39
       control
1   BTF = copper in plant / copper in soil

However, the role of aerial deposition during growth is supported by further work of Hunter
and co-workers (1987) in which turves with grass were relocated from close to a refinery to a
control location. Fresh growth was therefore produced from soil containing copper
concentrations equal to those at the sample origin but in the absence of airborne deposition
impacting the original location comparable to the “plot to pot” design of Ylaranta although no
edible plants were grown. These data suggest that airborne deposition contributed
approximately 60% of the vegetation copper content at the refinery and 40% at the
intermediate location. The samples were unwashed prior to analysis so it is not possible to
distinguish between true uptake and deposition onto the vegetation. However, the latter
observation is consistent with the BTFs for plot and “plot to pot” studies reported by Yläranta,



RAPPORTEUR [ITALY]                                               83                         VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
(1996). Unfortunately, neither airborne copper nor deposition rates were measured in this
study. It can be reasonably assumed that deposition rates were considerably greater than they
are currently.
A study was conducted into copper concentrations in agricultural soils in Chile (Ginnochio et.
al., 2002). The soils had been impacted by aerial deposition from mining activities, although
not from refining or smelting, for many years. Copper concentrations in the soils ranged from
181-985 and 26-1235 mg/kg dw. Soil types were not specified. Tomato, lettuce and onion
crops were sown in soil removed from the contaminated areas (n=12) to a greenhouse. This
design was therefore comparable to the “pot” experiments in the plot to pot design of Yläranta
1996). Soil samples (0-20 cm) were sieved and dried. Total copper, copper saturated extract
and ionic copper were measured along with pH and organic content. The exact proximity of
the sampling locations with respect to the industry sources was not reported. Copper in whole
plant tissues from all crops was very closely correlated with the key variables of total copper,
ionic copper and pH (r >0.99). It should therefore be possible to accurately predict plant
copper in other scenarios if these variables are known. However, the key variables, other than
total copper, are wholly unknown in this RA for the local sites.
When plant copper was expressed simply as a function of total copper, reasonable correlations
can be obtained (lettuce r=0.72; tomatoes r=0.79; onions r=0.68). However, the proportion of
copper in the edible parts of the crops reported by Ginocchio and co-workers was low relative
to whole plant uptake. The mean proportions (copper in edible parts/copper in whole plants)
varied between the two districts studied as follows: tomato 17-27%, lettuce 11-21% and onion
49-54%. Uptake and translocation of copper into the edible parts of lettuce, tomatoes and, to
a lesser extent, onions appear to have been largely unrelated to soil copper levels (R.
Ginnochio, personal communication). Results for lettuce, tomatoes and onions are shown in
Figure 4-17, Figure 4-18, and Figure 4-19 respectively. These results do not take into
account the effect of deposition during growth and may therefore be moderate underestimates.
A similar study was conducted in Chile investigating copper levels in tomatoes and onions
(Badilla-Ohlibaum et. al., 2001). The authors indicate that this area may have been impacted
by smelter emissions. The study covered crops from two clusters of copper soil concentrations
with mean values of 162 mg/kg dw and 751 mg/kg dw. A range of soil parameters were
measured including total and ionic copper, pH and organic carbon. In contrast to the
Ginocchio study, no combination of soil parameters could predict the variation in plant
copper. Copper in the edible parts (although not the remainder) of the vegetables was wholly
uncorrelated with total soil copper suggesting plant levels were practically independent of soil
copper over a very wide range. Mean copper values for the edible parts of onions were
7.1±1.2 and 8.2±3.0 mg/kg dw at soil copper of <400 and >400 mg/kg dw respectively. The
corresponding values for tomatoes were 14.7±4.1 and 15.8±3.4 mg/kg dw at soil copper of
<400 and >400 mg/kg dw. These findings are broadly in agreement with those of Ginocchio
and co-workers (2002).
Similar findings were reported in another study of soils of varied origin not specifically
related to the copper industry (Allen, et. al., 2001). Copper in plant tissues from all crops was
poorly correlated with total copper content of the soils. Models to predict plant copper tissues
were specific for each plant but included parameters as pH, total N, total C. The range of
parameters in each model is however extensive and, as indicated above, are unknown in this
RA.
Although EU data on copper levels in vegetables grown on land impacted by the copper
industry are rather sparse, data are also available on copper in vegetables grown in urban soils



RAPPORTEUR [ITALY]                               84                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
with somewhat elevated levels of copper (Moir, 1992). The highest data reported was for soil
levels in the major conurbations of London and Birmingham. Geometric means (with ranges
in parentheses) were 91 (24-261) mg/kg dw for Hammersmith and Fulham in London, and
103 (35-546) in Birmingham. Copper levels for the edible parts of a range of vegetables
grown in these soils, including lettuce, were reported.
Versluijs and Otte (2001) made a literature review of bioconcentration of metals in crops.
Bioconcentration factors were calculated and BCF models developed for a range of metals
including copper and a number of crops. No differentiation was however made between metal
accumulated in the plant from soil and from aerial deposition. Only data were retained from
field experiments using soil types and crops relevant for the Netherlands, using the consumed
parts of crops, and using anthropogenically contaminated soils. For copper 46 data were
retained from 2 studies. Copper levels in soils ranged between 21 and 46 mg/kg dw. Copper
levels for the edible parts of a range of vegetables grown in these soils were reported. The
reported data for lettuce ranged between 8 and 16 mg/kg dw are in good agreement with those
found by Ylaranta (1996), Moir (1992) and Ginnochio (2002).

Figure 4-17 Copper in edible part of lettuce from “greenhouse” experiments.
                                                                                                Soil subject to copper industry pollution without deposition during growth. (Ginocchio, personal communication)

                                                                                       70
 copper in edible part of plant mg/kg dw




                                                                                       60

                                                                                       50

                                                                                       40

                                                                                       30

                                                                                       20

                                                                                       10

                                                                                        0
                                                                                            0      200      400      600        800     1000   1200   1400
                                                                                                             copper in soil (mg/kg dw)



Figure 4-18 Copper in edible part of tomatoes from “greenhouse” experiments.
                                                                                                Soil subject to copper industry pollution without deposition during growth (Ginocchio, personal communication)

                                                                                       16

                                                                                       14
                                           copper in edible part of plant (mg/kg dw)




                                                                                       12

                                                                                       10

                                                                                        8

                                                                                        6

                                                                                        4

                                                                                        2

                                                                                        0
                                                                                            0                  500                    1000             1500
                                                                                                              soil copper (mg/kgdw)




RAPPORTEUR [ITALY]                                                                                                                              85                         VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Figure 4-19 Copper in edible part of onions from “greenhouse” experiments.
                                                        Soil subject to copper industry pollution without deposition during growth (Ginocchio, personal communication)



                                               70
    copper in edible part of plant (mg/kgdw)




                                               60

                                               50

                                               40

                                               30

                                               20

                                               10

                                                0
                                                    0       200      400      600     800      1000    1200     1400
                                                                       soil copper (mg/kgdw)



Taken together, the available data indicate that, where elevated levels of copper in soil occur,
food crops tend to accumulate copper sparingly due to efficient homeostatic regulation.
Furthermore, this copper is heavily concentrated in the non-edible parts of the plant and, in
particularly, the root which is frequently contaminated with soil particles. Total soil copper
may be a predictor of copper in whole plants but is generally poorly correlated with copper in
the edible parts. Total copper, ionic copper and pH have been shown to very accurately
predict copper in whole plants although there is some conflicting evidence in this respect.
Aerial deposition during growth has been shown to have a considerable effect on plant copper
although its significance at current, relatively low, levels of deposition is unknown.
Data for copper in the edible parts of lettuce are summarised in Table 4-57. Reference values
are two means and the range (from Sweden and Australia) cited by IPCS (1998) are also
shown. For the experimental data, copper expressed as dry matter is converted to the
approximate wet weight equivalent for comparison with the reference values. The “plot” data
of Ylaranta (1996) appear highly elevated at soil copper levels that are relatively modest
(≤260 mg/kg dw) relative to those reported by Ginnochio. This may reflect the sample
collection method of Yläranta, particularly if collection was not limited to the edible parts and
the sample was not washed. Alternatively, this finding may be partly attributable to deposition
during growth. Mean copper levels in the edible tissues of lettuces grown in urban soils (GM
soil copper =91-103 mg/kg dw) and those collected by Versluijs and Otte are within the range
of reference means. It is noted that the range of all reference data (0.20-1.40 mg/kg wet wt) is
wider than most of the experimental data (excluding that of Ylaranta).
Similar data for tomatoes are shown in Table 4-58. Mean results for the experimental data (all
from Chile) are reasonably consistent. As for lettuce, the range of the experimental data falls
mostly within that of the reference values.
The data for onions are shown in Table 4-59. The single reference value, from the US Dept of
Agriculture, of 5.8 mg/kg dw is for onions grown in “unpolluted soils”. As a reference value,
this is not strictly comparable with data for lettuce and tomatoes (Table 4-57 and Table 4-58)
given by IPCS for which the upper end of the values is in excess of some experimental values
for the same vegetables grown in polluted soils. This finding suggests the “reference”
tomatoes and lettuce may have been subject to high copper levels in soil either from the



RAPPORTEUR [ITALY]                                                                                     86                          VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
natural background or some form of supplementation. Therefore the apparent enrichment for
onions, relative to the other vegetables, shown in Table 4-59 may reflect the fact that the
reference onions appear to have been grown in relatively pristine conditions. This is
consistent with the data of Ginnochio (2002) which indicate that copper in the edible part of
onions in somewhat more sensitive to total soil copper than is the case for lettuce or tomatoes
(Ginnochio, personal communication) as shown in Figure 4-19.

Table 4-57 Copper in lettuce

                                         soil copper                      copper in edible part         copper in edible part
                                                                              (mg/kg dw)                  (mg/kg wet wt) (1)
                                         (mg/kg dw)
                              mean                   range                mean            range                   range
Ref values                        -                    -                    -               -             means 0.47-0.72
                                                                                                          range 0.20-1.40(2)
Ylaranta 1994                  204                  127-260                45             19-69                0.76-2.76
copper smelter
Finland
Ginnochio et al,               630                  181-985                21             14-39                0.56-1.56
2002
copper mining Chile
                               428                  26-1235                19             15-26                0.60-1.04
Moir (1992)                 103(GM)                  35-546                13             10-19                0.40-0.76
urban soils
UK                           91 (GM)                 24-261                18             14-29                0.56-1.16
Versluijs and Otte                32                 21-46                 10             8-16                 0.32-0.64
(2001)
(1)   Except for ref values these are estimated at 96% water content
(2)   Values from two studies cited in IPCS, 1998


Table 4-58 Copper in tomatoes

                                  soil copper              copper in edible part (mg/kg         copper in edible part
                                                                       dw)                       (mg/kg wet wt) (1)
                                  (mg/kg dw)
                            mean           range              mean              range                  range
Ref values                    -                 -               -                 -                 0.29-1.10(2)
Badilla-Ohlbaum              450           400-500            15.0          11-19 (sd)                0.77-1.33
et al, 2001

Ginnochio et al,             630           181-985            12.3              11-14                 0.77-0.98
2002
copper mining
                             428           26-1235            10.9              8-14                  0.56-0.98
Chile
(1)   Except for ref values these are estimated at 93% water content
(2)   cited in IPCS, 1998




RAPPORTEUR [ITALY]                                                   87                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Table 4-59 Copper in onions

                           soil copper (mg/kg dw)    copper in edible part (mg/kg dw)           copper in edible part
                                                                                                  (mg/kg wet wt) (1)
                            mean            range         mean                range                    range
Ref values                     -              -              -                5..8 (2)                  0.64
Badilla-Ohlbaum              450          400-500           7.7              7-9 (sd)                0.77-0.99
et al, 2001
Ginnochio et al,             630          181-985           27                 9-57                  0.99-6.33
2002
                                          26-1235
copper mining
                             428                            11                 8-15                  0.88-1.65
Chile
(1)   Estimated at 89% water content
(2)   US Dept of Agriculture ref values for onions grown in unpolluted soils, cited by Ginnochio et al, 2002

Key points to consider in order to derive values for risk characterisation are; (i) deposition
may contribute substantially to copper in the edible parts of plants, (ii) leafy vegetables may
be particularly enriched in copper via deposition, (iii) although copper in the edible parts of
plants is relatively insensitive to soil copper, copper levels in soil in the studies cited are
nevertheless high relative to the levels applicable to the RA. Lettuce is therefore taken as a
conservative surrogate for all fruit and vegetable consumption. Data for copper in lettuce at
the lower end of the soil copper range, with and without deposition, are shown in Table 4-60.

Table 4-60 Copper in lettuce at lower end of soil copper concentration

                                                                       Copper in lettuce (mg/kg dw)
           Study                   Soil copper        No deposition          Urban deposition             Copper smelter
                                                                                                            deposition
                                   (mg/kg dw)
                                                                                                            (deposition
                                                                                                           (mg/m2/d) in
                                                                                                           parentheses)
       Ylaranta, 1996                 127                   12                            -                    19 (0.34)
         Moir, 1992                  24-35                   -                        10-24                        -
      Ginnochio, 2002                26-78                 15-17                          -                        -
      Versluijs and Otte             21-46                   -                           8-16                      -
           (2001)

* In section 4.1.1.4.6 the copper concentrations in soils around plants were calculated as 29.4 – 34 mg/kg dw. The range selected from
the Ginnochio 2002 study is a subset of the samples selected to be representative of the copper concentrations in European soils.


Excluding the Ylaranta copper smelter data, the highest values is for lettuce grown in the UK
subject to urban levels of deposition (10-24 mg/kg dw). The data for lettuce reported by
Versluijs and Otte are in the lower end of this range. The data for lettuce grown in the absence
of deposition (12-17 mg/kg dw, mean = 15 mg/kg dw) are within the range of the UK data
regardless of soil copper level. These data are therefore considered to be in good agreement.
The parallel data of Ylaranta, with and without deposition, indicate a differential of 7 mg/kg
dw in copper in lettuce at a deposition rate of 0.34 mg/m2/d comparable with measured
deposition rates in the local environment of smelters (0.18-0.44 mg/m2/d). A RWC copper




RAPPORTEUR [ITALY]                                                  88                               VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
content in lettuce is therefore taken as 15+7=22 mg/kg dw (4) corresponding to approximately
0.88 mg/kg wt. Multiplying this value by the TGD default for fruit and vegetable
consumption (1.584 kg/day) gives a notional intake of 1.39 mg/person/day. Reference to
Table 4-57 indicates mean reference values for lettuce of 0.47-0.72 mg/kg wt. Expressing the
higher reference value as a daily intake gives a corresponding intake of 0.72x1.584=1.14
mg/person/day. The difference between these estimates, 1.39-1.14=0.25 mg/person/day, is
taken as the additional external exposure arising from the consumption of locally produced
lettuce and is taken as the RWC estimate.
In order to derive a typical value, reference is made to Chapter 3. The ratio of RWC/typical
copper in air concentrations by company for smelters is 1.77. Based on the assumption that
deposition is proportional to airborne copper, this ratio is applied to the RWC of 0.25
mg/person/day, i.e. 0.25/1.77, giving an approximate estimate for typical added local dietary
intake of 0.14 mg/person/day (external exposure).


4.1.1.4.8              Values taken forward for risk characterisation
There are many data gaps in the local indirect exposure assessment. The data on measured
airborne levels and deposition rates are sparse, contain little information on sampling and
analytical methods and are lacking in meaningful supporting information. These data gaps
cannot be resolved further without additional data collection.
Inhalation exposure
Relevant data from Chapter 3 are shown in Table 4-53. Estimates of inhalation exposure are
shown in Table 4-54. The RWC external inhalation exposure is taken as 0.093
mg/person/day. This value is the maximum calculated airborne level (for smelters). The next
highest value (for the wire rod and cable sector) is 0.057 mg/person/day and is taken as
typical exposure. Maximum, rather than median, values are used in this way to include an
allowance for fugitive emissions in the absence of reliable measured data.
Dietary exposure
Estimates of dietary exposure are based on air to soil and soil to plant transfer. This procedure
is conducted according to the EUSES methodology whereby 10 years continuous deposition
at current emission levels is added to the natural background level in soil. The data in Table
4-53 indicate copper in soil levels arising from both measured and calculated deposition.
Given the anticipated impact of fugitive emissions, measured deposition rates might be
expected to result in higher copper levels in soil. However, the maximum predicted added soil
concentration in Table 4-53 is 9.95 mg/kg dw resulting from modelled deposition from semis
manufacturers. (The maximum added soil copper from measured deposition is 5.4 mg/kg dw).
The modelled value of 9.95 mg/kg dw incorporates the application of sewage sludge which
therefore outweighs the difference between measured and modelled deposition. This value is
therefore added to the background for “natural” soil of 24.4 mg/kg dw to give a soil
concentration of 34.4 mg/kg dw. This forms the basis of the estimation of soil to plant
transfer.
The best available estimates for RWC and typical external exposures from added copper in
locally produced food are 0.25 and 0.14 mg/person/day respectively. These values are based

(4 )
  The method of derivation reflects the likelihood that only a proportion of total vegetables consumed will be
sourced locally as assumed in other metal risk assessments, e.g. cadmium.



RAPPORTEUR [ITALY]                                     89                       VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
on daily fruit and vegetable intake expressed as lettuce which probably represents a
conservative surrogate for actual intake. These values are taken forward to risk
characterisation to be added to “baseline” intakes derived in the regional exposure assessment.
The local exposure estimates are neither methodologically nor statistically robust. Rather they
are intended as reasonably conservative estimates of additional copper intake from locally
produced fruit and vegetables. Regardless of the considerable uncertainties involved, these
estimates nevertheless reflect the fact that efficient homeostatic regulation of copper uptake in
plants, together with the measured/modelled deposition data, suggest that the additional
(local) exposure is likely to be quite marginal. It is also noted that uncertainty in the
treatment of samples with respect to washing in the Ylaranta (1996) study could further
render these estimates conservative in relation to normal domestic practice.
The values taken forward to risk characterisation are summarised in Table 4-61. The values
dietary intake are added to “baseline” intakes derived in the regional exposure assessment for
the risk characterisation of people living in the local environment.

Table 4-61 Summary of values for the local environment taken forward for risk characterisation

                                                                          Typical                RWC
External exposure through inhalation (mg/person/day)                       0.057                 0.093
Basis: TGD default 24 hr inhalation volume     (20m3)
External exposure through dietary intake (mg/person/day)                    0.14                 0.25
Intake additional to regional dietary intake




RAPPORTEUR [ITALY]                                         90                          VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH


         4.1.1.5            Humans exposed via the environment - regional environment
The methodology for the regional exposure assessment uses a database compiled from the
published literature. There are three reasons for this approach. Firstly, the TGD describes
methods exclusively applicable to organic compounds. Secondly, these methods apply to
xenobiotic substances and are not applicable to essential trace elements without modification,
specifically in respect of essentiality. Thirdly, as an essential trace element there is clearly a
more substantial literature on exposure to copper than envisaged in the TGD. The typical case
for both deficiency and excess is defined as the median exposure and the reasonable worst
case as the 10th (10P-RWC) and 90th percentile (90P-RWC) respectively. This convention is
followed as far as possible.
Three databases were searched at the British Library in London: 1) the Library’s
Environmental Abstracts database, 2) Medline and 3) Aqualine, a database dealing
exclusively with water-related research. Other authoritative sources such as the ICA database
and key publications by the WHO (IPCS) were also consulted.


4.1.1.5.1            Exposure via air
Monitoring data for copper in air is rather sparse. Urban levels in the UK for 1990 ranged
from 21-64 ng/m3(UK Met Office, 1995). The corresponding concentrations in rural areas
impacted by nearby industry or road traffic ranged from 11-27 ng/m3 (mean data for 1982-
1991). In the United States, airborne concentrations of ~200 ng/m3 have been reported (IPCS,
1998).
Recent data on copper concentrations in indoor air at UK locations indicates a mean of 99
ng/m3 and geometric mean of 88 ng/m3 (Lai et. al., 2004). Personal samplers were used to
determine TWA exposures in and out of the home. The results were a mean of 128 ng/m 3 and
geometric mean of 124 ng/m3.
Inhalation exposure however constitutes a quantitatively insignificant route, and the overall
regional exposure assessment will be insensitive to error in inhalation exposure. Taking a
default inhalation volume of 20 m3/day and a conservative exposure level of 100 ng/m3 gives
an inhalation intake of 0.002 mg/day. This is a factor of some 600 times lower than intake
from dietary exposure.


4.1.1.5.2            Exposure via food and water

Dietary exposure for adults
Two types of studies are considered in the assessment of exposure to copper in food; a)
duplicate diet studies, b) market basket studies.
In duplicate diet studies, a small group of subjects are followed intensively for a number of
days or possibly a larger group are studied for a single day. A duplicate portion of the
prepared meal to be eaten by the subject is collected for analysis of trace elements, usually by
atomic absorption spectroscopy. In most duplicate diet studies, portions of all beverages
consumed are also collected. This method has the advantage of determining the content of real
diets. Age and sex-specific differences can be determined, as can individual variations, within



RAPPORTEUR [ITALY]                               91                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
the limits of the available sample size. This design is particularly suited to workers and
residents of institutions where food is prepared collectively.
In market basket studies, the consumption of different types of foodstuffs is determined from
national databases and expressed on a per capita basis. The food basket is then purchased by
the investigators and analysed for copper. Market basket studies therefore have the advantage
of representing population exposure on an annual basis as opposed to the short-term exposure
of a small group of subjects measured in duplicate diet studies. As a result, a highly averaged
value is derived and variations in individual exposures, resulting from preferences for certain
foodstuffs, are not addressed. This approach is highly compatible with the TGD which states
that “extreme consumers of certain types of food” are excluded on the basis that they may
represent an extreme worst case beyond the RWC. A variation on the market basket study
entails the completion of food diaries by a group of subjects. Consumption of foodstuffs in the
database is then weighted by individual patters of consumption.
Some authors suggest that the duplicate diet study design can influence the behaviour of
subjects resulting in a moderate underestimation of habitual dietary intake (Bro et. al., 1990,
discussed below). Other authors cite good agreement between duplicate diet and market
basket data for the same country as an indication of little bias as a function of study design
(Schuhmaker et. al., 1993: Jorhem et. al., 1998, also see below).
The TGD contains its own food basket for consumption of foodstuffs for individual member
states (TGD Appendix III). However, it is expedient to use the published data for this risk
assessment as the food basket in the published version of the TGD comprises only “raw
materials” (meat, fish, dairy produce and fruit and vegetables). Therefore, it does not include
grain products, prepared foods, snacks or confectionary which are increasingly important
components of diets in developed countries and which are significant sources of copper. The
contributions of different foodstuffs to total copper intake as a function of age and sex are
shown in Figure 4-20 (Pennington and Schoen, 1996). Data for infants of 2 years (not shown)
is similar to that for adolescents (Figure 4-20). Similarly, data for older adults (60-65 yrs) is
similar to that for young adults (Figure 4-20). These data refer specifically to the United
States but are expected to be similar for the EU. For example, several authors report higher
levels of copper in grain products than that found in other major food groups (with the
exception of liver) (Landner and Lindestrom, 1999; Lamand et. al., 1994; Ysart et. al., 1999).
The additional food groups described above comprise between 29-44% of dietary copper
intake. Dairy produce and eggs, each included separately in the TGD basket, together account
for less than 10% of intake for all groups. These data demonstrate the appropriateness of
using published data in preference to the TGD basket of foods for all groups irrespective of
age or sex.
It is noted that market basket studies/tables do not incorporate the possible effect of contact
with pollutants in tap water during the preparation and cooking of food. However, during the
validation of the UK Total Diet study (discussed further below), this effect was determined as
insignificant (Peattie et. al., 1983).
Dietary copper levels for EU member states are discussed below.




RAPPORTEUR [ITALY]                               92                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Figure 4-20 Copper uptake by food group
                     (a) 14-16 yrs

      percent
 40
                                     fruit & vegetables

 30                                  grains


 20                                  meat


 10                                  mixed dishes, incl
                                     soups & desserts

                                     others (dairy, eggs,
  0
                                     nuts, beverages)
            F              M



                     (b) 25-30 yrs

      percent
 40                                  fruit & vegetables


 30                                  grains


                                     meat
 20

                                     mixed dishes, incl
 10                                  soups & desserts
                                     others (dairy, eggs,
  0                                  nuts, beverages)
            F              M




Austria

The nutritional status of the Austrian food intake was studied by Koenig and Elmadfa (1998).
The study provides information on trends in yearly consumption (per person) of different food
categories (milk, fish, fruit…). The study further evaluates the nutrient intake (energy,
vitamins, minerals….) of adults, young people and children. No copper data are provided for
children, adolescents nor adults. Daily copper intake levels of elderly persons from different
age groups (65 to 74 years, 14 to 84 years and >85 years) fall within the minimal daily
requirement, set between 1.5 to 3 mg Cu/day. For elderly persons, serum copper levels
indicated a marginal copper deficiency in 15-20% of the population. The data are not
sufficiently detailed to allow for statistical calculation and were hence not taken forward to
the risk characterisation.

Belgium
Dietary exposure to copper for several groups has been reported in a duplicate diet study
(Swerts et. al., 1993). Copper intake for elderly residents of a residential home was measured
over seven consecutive 24-hour periods. Mean copper intake was 1.1 mg/day. Copper intake
of vegetarians (n=3) and macrobiotics (n=3) was also investigated over shorter periods of 3-4
days. Intake for vegetarians was rather low at 0.80.3 mg/day (although the UK Total Diet
study found that British vegetarians have intakes of copper similar to that of omnivores).
Subjects following a macrobiotics diet had a copper intake of 1.50.4 mg/day. Figure 4-20
suggests a probable high intake of grains and fruit and vegetables is likely to account for this
finding. This group could therefore be regarded as atypical in the context of the TGD.
The copper intake of populations in military establishments and civilian hospitals were
measured in a duplicate diet study (Van Cauwenberghe et. al., 1995). Duplicate meals,
including beverages, were collected over a 7-day period. The age and sex distribution of the
subjects was not given. However, it may be reasonably assumed that the military personnel



RAPPORTEUR [ITALY]                                          93          VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
were of working age and predominantly male while the hospital populations are assumed to
be mixed. Mean daily intakes for the former group were 1.73 mg/day (range 0.93-2.46) and
1.83 mg/day (range 1.10-3.48). These values are high relative to other data presented here.
This may reflect a higher calorific intake for these groups rather than the selection of copper-
rich foodstuffs although details were not presented by the authors. Mean intakes for the
hospital groups were 1.47 and 0.93 mg/day (range 0.75-1.84 mg/day). Intakes of hospitalised
populations may be unrepresentative of habitual consumption, although it is noted that these
values are consistent with other data presented here.

Denmark
Copper intake of Danish men (n=100) aged 30-34 yrs was determined in a duplicate diet
study (Bro et. al., 1990). The men, from three geographical areas of Denmark and varied
socio-economic groups submitted samples of all food and beverages consumed over a 48-hour
period. Mean intake was 1.2 mg/day, median intake was 1.1 mg/day (range 0.3-4.4). In
addition, diet records were kept by the subjects and urinary excretion of nitrogen, potassium
and sodium was measured during the study period. By comparing intake and excretion of
these elements during the study, the authors estimated that a dietary intake deficit of
approximately 25% occurred during the sample collection period.

France
Copper intake among French adults was determined by a market basket study (Lamand et. al.,
1994). Household food consumption was determined from a national database and food
consumption was apportioned among family members as a function of age and sex-specific
energy requirements. Food items were purchased and analysed to determine intakes. Mean
intake was given as 1.3 mg/day for men and 1.1 mg/day for women although no indication of
variability was given.
In a duplicate diet study of young French men, non-drinking, non-smoking male hospital
employees (n=14) consumed three standard hospital meals during the 5-day working week
(Pelus et. al., 1994). Portions of food and beverages were analysed for copper content.
Subjects were asked not to consume additional food for the duration of the study but were not
followed continuously. Typical copper consumption was estimated as 1.23 mg/day and the
RWC, was 1.5 mg/day. Some bias may have been introduced by the study design as the
possible consumption of beverages, and perhaps, food items outside the study guidelines
cannot be excluded. On the other hand, subjects were encouraged to consume double portions
at mealtimes if they chose. The direction of any resulting bias is not readily apparent.
A large scale study of copper intake based on food diaries was carried out by INRS (INRS,
2004). Diaries were completed over five consecutive days by participants (n=1474). Meals
were then recreated and portions analysed. Mean copper intake was 0.98 mg/day and the 95 th
percentile was 1.55 mg/day.

Germany
Copper intake among men and women (n=56) from four geographical areas of Germany was
determined in a duplicate diet study (Anke et. al., 1990). Subjects were followed for one
week at home and work and duplicate portions of all food and beverages consumed were
analysed. The combined copper content of food and beverages ranged from 1.9-2.6 mg/kg
(dry matter). Mean copper consumption was 0.66 mg/day for women and ranged from 0.74-
0.92 mg/day for men. Sex and regional differences were not significant (p>0.05). Intake levels



RAPPORTEUR [ITALY]                               94                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
reported in this study were lower than comparable data for other countries. The authors note
that the regions where the study was conducted have low environmental background levels of
copper.
As part of a large study on human food, nutrition & health risks in Germany carried out
between 1987 & 1988, Heseker et al (1992) investigated, the daily copper consumption of a
representative German subpopulation (n=1994). The study calculated the daily copper
consumption of healthy adult men (n=856) and women (n=1138) from the individual’s daily
food & beverage consumption measured during 7 days. The daily food/beverage consumption
of the volunteers was weighted and categorized and subsequently converted in energy and
nutrient intake levels using a German nutrient conversion key (Bundeslebensmittelschlüssel
(BLS, version 1). The authors stated that calculations derived from the BLS must be
interpreted with great care, and were in some cases even disregarded. As weaknesses in the
BLS were known to the authors, the BLS was modified for some nutrients. Importantly, the
authors state that the study should mainly serve as a database of food-intakes rather than
nutrient intakes. The calculated overall mean and median copper consumption levels in this
study (Heseker et .al, 2002) were respectivey 1.97 and 1.88 mg/day. Frequentie distribution
curves showed 2.5-97.5 er percentiles of 0.9 and 3.5 mg Cu/day. Women showed significant
(p<0.05) less copper intake than men with median values of 1.7 mg Cu/day for women and
2.1 mg Cu/day for men. Copper intake was age dependent (p< 0.05). Highest values were
recorded in the young men between 18 & 24 years old, elderly persons (> 65 years old) had
significantly lower. Seasonal differences in food consumption did not influence the daily
copper intake. Alcohol consumption had no influence on the copper intake while cigarette
consumption tended to lower daily copper intake levels.

Netherlands
Copper intake among male and female subjects in the Netherlands was determined in a
duplicate diet study (Ellen et. al., 1990). Total food and beverage duplicate samples were
collected over a 24-hour period. Mean and median intakes were 1.2 mg/day. Sex-specific data
were not presented. The study was conducted during 1984-85. The authors note that,
compared to a similar study conducted during 1978-79, a reduction in mean intakes was
apparent. Although median values were equal, mean values fell from 1.4 to 1.2 mg/day with a
reduction in the upper end of the range from 5.9 to 3.3 mg/day.

Slovenia
Dietary copper intakes for elderly persons over 65 in a residential home (n=51) were
measured using a duplicate diet study design. (Pokorn et. al., 1998). Samples were collected
over one week. Mean copper intake was 0.9 mg/day. The authors suggest this may be a
moderate overestimate of actual intakes as all food presented was not necessarily consumed.

Spain
Copper intakes among subjects in NE Spain aged 30-50 yrs were measured using a duplicate
diet and total diet study in parallel (Schuhmacher et. al., 1993), the only available study of its
kind. Duplicate diet samples were collected over a period of one week. The total diet study
was conducted by analysing locally purchased foodstuffs and total intakes were weighted by
consumption (although the method for the determination of consumption was not stated).
Beverages, including tap water and alcoholic beverages, were also included. Mean dietary




RAPPORTEUR [ITALY]                               95                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
intakes for the duplicate diet and total diet studies were 1.12 mg/day and 1.16 mg/day
respectively.
Dietary copper exposures among university students in Spain were measured using a mixed
study design (Barbera et. al., 1993). Duplicate samples of lunch and dinner served in the
student dining room were analysed while intakes at breakfast were calculated from analysis of
foodstuffs and records of foods consumed. Diets were analysed over one week. Mean copper
consumption was 1.25 mg/day.
Dietary copper intake of elderly subjects was measured in a duplicate diet study (Rodriguez-
Palmero et. al., 1998). The subjects were residents of a municipal residential home in
Barcelona. Duplicate samples of meals were collected over 21 days to encompass the cyclical
menu provided. The prepared dishes were described as typical of dishes widely consumed in
Spain. Mean copper intake was reported as 1.00 mg/day. No breakdown of the study
population by exact age or sex was given.

Sweden
A large duplicate diet study of copper intake among adults (age 20-55 yrs and >65 yrs) was
conducted in Sweden (Abdullah et. al., 1989). The total number of subjects was 900. (The
exact number in each category is unknown and an equal distributed by age is assumed).
Samples of all food and beverages were collected over a 24 hr period by the subjects. Mean
intake was 1.33 mg/day for 20-55 yr olds and 1.27 mg/day for >65 yr olds.
Copper intake was determined by a market basket study (Becker and Kumpulainen, 1991).
The mean population intake was estimated as 1.2 mg/day. The food basket did not include
alcoholic drinks.
A duplicate diet study was conducted to determine the copper intake of Swedish women.
(Jorhem, et. al., 1998). 24 hr duplicate samples of all food and beverages were collected by
women aged 27-46 (n=15) for one week. Mean and median copper intakes were 1.1 mg/day.
When corrected for sex bias, these values are in excellent agreement with the market basket
data of Becker and Kumpulainen, (1991) and in reasonable agreement with the results
reported by Abdullah et. al., (1989). Jorhem and co-workers also compared their data for a
number of trace metals with the equivalent data from market basket studies and found
generally good agreement.

UK
UK population intakes of copper have been estimated since 1966 by a number of market
basket surveys and summarized as the UK Total Diet Study. Results for 1994 indicate a
population mean of 1.2-1.4 mg/day depending on the survey source (Ysart et al., 1999). The
97.5th percentile is given as 3 mg/day. No other measures of variability are available.
Although the basis of the estimates was revised in 1975 and 1981 (Peattie et. al., 1983), the
authors indicate that the findings remain essentially comparable allowing the determination of
trends from these data.
The 2000 UK Total Diet Study (FSIS, 2004), based on the analysis of copper levels in food
and the amount of food consumed, indicated an adult population mean exposure of 1.3 mg
Cu/day with a 97.5th of 2.3 mg Cu/day. Evaluation of the data over the course of the Total
Diet Study program (1976 to 2000) shows a decline in the mean population exposure from
1.8 mg Cu/day in 1976 to 1.3 mg Cu/day in 2000. Different adult age groups show similar



RAPPORTEUR [ITALY]                               96                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
mean exposure levels. The exposure of vegetarians was similar to the one of the general
population. Toddlers had the highest mean body weight based exposure level : 46 µg Cu/kg
body weight /day for toddlers compared to 18 g Cu/kg body weight /day for adults.
The food standard agency further evaluated dietary exposures to copper of vegetarians during
a 7 days duplicate diet study, involving 400 participants. The mean exposure of the
vegetarian population was 1.3 mg Cu/day, being very similar to the exposure of the general
population (FSSG, 2000).
Between June and December 2004, the UK Food Standard Agency (FSA) performed a multi-
element survey of allotment produce (FSIS, 2006). In this study, 12 allotments (a piece of
land rented from the authorities to grow fruit, vegetables and flowers), located close to roads
and/or industrial sites were investigated. Soil samples as well as 21 fruit and vegetable
samples were taken from each of the 12 allotments. The study showed that the copper
concentration in fruit and vegetables (mean values of 0.57 & 0.65 mg Cu/kg5 for
respectively rural & urban plots), cultivated on these soils (41 mg Cu/kg soil for rural soils
and 86 mg Cu/kg soil 5 for urban soils), were similar to the concentrations found in
commercial products. The study further calculated a daily intake of 0.14 mg Cu/day from
fruit & vegetables, using a conservative approach, whereby it was assumed that all vegetables
& fruits daily consumed had the maximum value measured in the fruits and vegetables across
the allotments (2.27 mg/kg peas). As this report considers a special case of cultivation on
relativel polluted soil, this study was not considered further. The study does however provide
additional evidence that even under realistic worst case assumptions, the daily copper intake
from food will only fluctuate marginally.
An alternative estimate of copper intakes in the UK was reported by Buss and Rose, (1992).
Intake was estimated by pre-weighing food about to be eaten and determination of copper
from nutritional databases. The study population comprised 2200 adults aged 16-64. The
results were 1.49 mg/day for men and 1.13 for women. Given that the food itself was not
analysed in this study the results may be less reliable than some of the other data presented
here.
Copper intakes among elderly, non-institutionalised subjects in the UK has been reported
(Bates et. al., 1999). In a similar manner to the study of Buss and Rose, intakes were
calculated from food tables based on 4-day diet records completed by subjects. Subjects were
divided into two age groups, 65-79 and >80. Among the younger group, mean intakes were
1.13 and 0.90 mg/day respectively for men and women (p<0.0001). Results for the older
group were 0.86 and 0.72 mg/day respectively (p=0.004).

Consumption of alcoholic beverages
Copper exposure also occurs through consumption of alcoholic beverages. Copper levels have
been determined in bottle-fermented Italian sparkling wines (Mazzoleni and Colagrande,
1993). The authors indicate that these products have a market share of 10% in Italy. Mean
values were 0.11 mg/litre (n=212). Results ranged from 0.03-0.77 mg/litre.
Similar analysis of Greek wines has been reported (Lazos and Alexakis, 1989). Mean results
and standard deviations were as follows: table white 0.23±0.30 mg/litre, table red 0.23±0.21
mg/litre, rosé 0.17±0.11 mg/litre, dessert wine 0.36±0.28 mg/litre. The authors indicate that


5   The study does not indicated if the values are dry or wet weight values



RAPPORTEUR [ITALY]                                       97                   VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
these results are similar to other data for European wines. The mean values reported here for
Italian and Greek wines range from 0.11-0.36 mg/litre with a mean of 0.22 mg/litre.
Average annual alcohol consumption for the EU in 2001 is given in the WHO alcohol control
database       as      9.2       litres      of       pure      alcohol        per       person
(www.euro.who.int/alcoholdrugs/policy/20020611). Information on the distribution is not
available. Given an alcohol content of 12% for wine, this corresponds to an annual wine
consumption of approximately 77 litres or 0.21 litres/day. Typical daily copper intake from
alcoholic beverages (calculated as wine) is therefore estimated as 0.22 mg/litre x 0.21 litres =
0.046 mg/day.

Dietary exposure for infants, children and adolescents
Daily copper intake by infants from breast milk, formula milk, solid food, non-milk fluids and
total diet have been reported for the UK in a duplicate diet study (Richmond et. al., 1993).
Mothers of healthy infants (n=39) aged 17-61 weeks submitted samples (n=222) over a one-
week period. Geometric mean total copper intake was 0.60 mg/day (range 0.25-1.61 mg/day)
of which approximately one-third came from milk. Daily intake from formula milk exceeded
that for breast milk, 0.24 and 0.15 mg/day respectively.
Copper intake among pre-school children in the UK was measured in a duplicate diet study
(Smart et. al., 1987). Children (n=97) aged 2 yrs3 months participated. 24 hr duplicate
samples of all food and beverages were collected by their mothers over one week. The mean
copper intake was 0.45 mg/day (90% CI =0.40-0.50). The authors reported that this finding
was very similar to other data for the UK.
Copper intake by German children was determined in a duplicate diet and diet record study
(Laryea et. al., 1995). Subjects were children aged an average of 6.9 yrs (range 5-9) (n=47).
24 hr duplicate diets inclusive of beverages were collected over two days and parents filled in
diet records for four days. Measured median copper intake was 0.6 mg/day (range 0.2-4.1
mg/day). Median copper intake estimated from the diet records was 1.0 mg/day. The authors
deemed the duplicate diet method more accurate and concluded that the diet record method
overestimated actual intakes.
Copper intake of infants was measured in a duplicate diet study in Belgium (Bosccher et. al.,
2002). The study population consisted of otherwise healthy children aged 2-3 years (n=35)
attending hospitals for bone fractures. Mean copper intake was 0.70 mg/day (sd=0.20).
The copper intake of adolescent girls aged 14-19 in the UK was estimated using weighed food
records in conjunction with a range of nutritional databases and manufacturers’ data
(Donovan and Gibson, 1996). Subjects were divided into groups consuming lacto-ovo-
vegetarian, semi-vegetarian or omnivorous diets. The latter group had lower copper intakes
(mean=1.1mg/day, sd=0.3) than their vegetarian/semi-vegetarian counterparts (mean=1.4-1.5
mg/day, sd=0.5).
The Swedish duplicate diet study conducted by Abdullah and co-workers (1989), described
above, also included the determination of copper intakes for children aged 11-14 yrs. Mean
intake was 1.46 mg/day.
The French INRS study (2004), also described above, measured intakes of children aged from
3-14 yrs from food diaries. Mean intake was 0.81 mg/day and the 95th percentile was 1.36
mg/day.




RAPPORTEUR [ITALY]                               98                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
The UK Total Diet Study (FSIS 2004) estimated total consumer dietary exposure to copper in
different age groups. Toddlers (1.5 -4.5 years) have a mean daily intake of 46 µg Cu/kg body
weight, young people (4 to 18 years) have a mean exposure of 30 µg Cu/kg body weight/day,
while adult typically consume 18 µg Cu/kg body weight/day.
Dietary exposure of adults, adolescents and children is summarised in Table 4-62.

 Table 4-62 Summary of typical and RWC dietary exposure data (mg/day)

                                        Reference or number of                  Typical                    10P-RWC                    90P-RWC
                                               studies
                                                                            Adults
predominantly <60                                  N=14                            1.2                        0.4-1.0                    2.0
>60                                                N=7                            1.02                    ≤0.4 ? (0.6)2                 ≤2.0
                                                                   Children and adolescents
<15 months                                Richmond et al, 1993                    0.60
2 yrs                                       Smart et al., 1987                    0.45                         0.40                     0.50
2-3 yrs                                   Bosccher et al., 2002                   0.70                         0.45                     0.95
5-9 yrs                                     Laryea et al., 1995                   0.60
11-14 yrs                                  Abdullah et al., 1989                  1.46                         0.88                     2.04
14-19 yrs                              Donovan and Gibson, 1996                1.10-1.50                     0.72-0.87                1.49-2.12


(1)   Estimates calculated from authors’ data. See text for derivation of 10P-RWC for risk characterisation and discussion thereof.
(2)   10P- RWC of 0.4 is considered anomalous and a value of 0.6 is used. See text for further discussion.
Ingestion of dust by children
Young children also incur exposure through ingestion of dust by hand to mouth contact. This
exposure may consist of a mixture of house dust and garden dust. Ingestion rates for children
aged 0-7 yrs are somewhat age dependent. The US EPA report geometric mean ingestion rates
for infants of 1-4 years as 111 mg dust/day. Values given for older children are 50/60 mg
dust/day for outdoor/indoor dust for children aged 2-5 years, and 20/2 mg dust/day for
outdoor/indoor ingestion by 6 year olds (US EPA, 2003). The USEPA IEUBK (Integrated
Exposure and Uptake Biokinetic) Model was developed to predict children’s exposure to lead
but     is     also    applicable    to    other      pollutants    ingested      in     dust
(www.epa.gov/superfund/programs/lead/ieubk). This model, suggests slightly higher intakes
somewhat more conservative with respect to risk. The IEUBK values are therefore used in the
exposure assessment.
Since copper levels in house dust have been shown to be consistently higher than those in
garden dust (Thornton et. al., 2002), house dust levels are used for the exposure estimate.
Geometric mean levels of copper in recent house dust samples from Wolverhampton, UK
(n=49) were 224 mg/kg (Thornton, personal communication). Geometric means for similar
samples from six British cities for 1981 were comparable ranging from 160-299 mg/kg (Lay
et. al., 2002).
House dust samples from Germany were collected from vacuum cleaner dust bags (Seifert et.
al., 2000a). The median and 90th percentiles (n=3894) were 76 and 218 mg Cu/kg
respectively. Median values were approximately 2-4 times lower than the geometric means



RAPPORTEUR [ITALY]                                                     99                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
reported for the UK. The available data suggest that collection of samples directly from the
floor or from vacuum cleaner dust bags produce similar results (Thornton et. al., 2002).
However, the German study is a national cross-sectional study with participating households
drawn from a range of locations structured by population size. It therefore includes many
samples from locations outside major conurbations whereas the UK data is drawn exclusively
from urban households where metal concentrations in dust are likely to be higher. Allowing
for these somewhat different approaches, the available data for the UK and Germany are in
reasonable agreement.
Exposure estimates are calculated using the IEUBK dust ingestion data and the copper in
household dust data in UK cities (Thornton et. al., 2002) with a median value of 250 mg/kg
for the city of Birmingham and an assumed RWC of 1000 mg/kg (I. Thornton, personal
communication). These are shown in Table 4-63.

Table 4-63 Dust and copper ingestion by children            (Age dependent ingestion values from IEUBK model)


                                   Dust ingested (mg/day)                      Copper ingested (g/day)
                                                                      Typical 1                      RWC 2
             0-1 yrs                        85                           21                               85
             1-4 yrs                        135                          34                           135
             6-7 yrs                        85                           21                               85
            7-12 yrs                        34                           8.5                              34
            12 yr old                       13.5                         3.4                          13.5
1   Basis: copper in dust = 250 mg/kg
2   Basis: copper in dust = 1000 mg/kg

Summary
The data for adults described above in section 4.1.1.5.2, excluding that for vegetarians and
macrobiotics, are summarised in Table 4-64 in which mean values are shown for all studies.
These typically range from 1.02-1.20 mg/day. Limited data for medians indicate that medians
are equal to, or slightly lower than, the corresponding means.
Heseker et al. 1992, reports higher values for Germany. The Heseker study was not
considered further because of several weaknesses: (1) results are based on calculated daily
intakes from actual weighed food consumption and existing nutrient conversion keys; (2) the
authors indicated several weaknesses in the used conversion keys; (3) the study relies on older
data (20 years old).
Gibson (1994) compiled several studies and concluded that omnivore dietary intake of adults
is approximately 1-1.5 mg Cu/day, being consistent with the range proposed above (1-1.3 mg
Cu/day).
The CSF 2003 reports mean/median daily intake levels for Ireland, The Netherlands, Italy and
UK ranging between 1.1 and 1.6 mg Cu/day, again being consistent with the range proposed
above (1-1.3 mg Cu/day). Two studies reported somewhat higher values: Elmadfa et al (1998)
reported a daily intake of elderly people between 1.5 and 3 mg/day and Heseker et al (1994)
reported values of 1.8 & 2.2 mg Cu/day.




RAPPORTEUR [ITALY]                                             100                           VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
It is of interest to note that the typical means/median values used in this RA report are in good
agreement with similar studies conducted outside the EU. For example, dietary copper intakes
for young adults aged 25-30 in the United States were 1.12 and 0.94 mg/day for men and
women respectively (Pennington and Young, 1991). Similarly, copper intakes in Chile for
men and women aged 20-64 were 0.9 and 1.0 mg/day respectively (Olivares et. al., 2004).
Where standard deviations are presented by the authors, data are assumed to be normally
distributed and the 10th and 90th percentiles are calculated accordingly. These represent RWC
estimates for deficiency and excess respectively. Results for 90th percentiles range mostly
from 1.4-2.0 mg/day for all adults. The 10th percentiles for most adults <60 yrs are typically
0.6-0.8 mg/day. Some values for elderly adults are much lower ranging from 0.1-0.3 mg/day
(Pokorn et. al., 1998; Bates et. al., 1999). Some of these estimates lie outside the range of the
experimental data. It is not clear if these values represent possibly very low intakes or whether
they arise from anomalously high standard deviations or some data which are non-normally
distributed. Conservative values for 10P-RWC and 90P-RWC are therefore taken as 0.6 and
2.0 mg/day respectively.
The mean ratio of male/female intakes is calculated as 1.26 (range 1.18-1.36). This ratio is
used to derive an estimate of population exposure where data are presented for a single sex
only. Where data are presented for both sexes, these values are simply averaged to give an
estimate of population exposure. When intakes for men and women are standardised by body
mass using the TGD default values (70kg/60kg), studies where exposure of both sexes is
measured indicate that male intakes remain higher by an average of 11% (range 0-33%).
Age specific population estimates, combined by sex as described above, are shown in Table
4-64. (This analysis is limited to those studies where subjects are sufficiently stratified by
age). The mean intake of those predominantly below 60 yrs is 1.20 mg/day (range 0.75-1.78
mg/day). Some of these studies include some subjects up to 74 yrs and are therefore not
wholly specific to the age range indicated. The mean intake of adults >60 yrs is 1.02 mg/day
(range 0.79-1.27 mg/day).
Results from studies in which the inclusion of all beverages is specified or not specified are
shown in Table 4-65. For the predominantly <60 yrs group, there is a slightly higher copper
intake for the group in which beverages are not specified (1.20 and 1.16 mg/day) which is
clearly not consistent with a hypothesis that typical exposures are heavily influenced by high
levels of copper in drinking water. For the >60 yrs group, only a single study that specifies the
inclusion of drinking water is available. This study gave by far the highest result for exposure
among this age group (1.27 mg/day, range excluding this value, 0.79-1.10) and its
significance is therefore unclear.
Age-dependent results for adults and children are summarised in Table 4-62. As indicated
above RWC estimates for adults are uncertain. For adults, a 90P-RWC of 2.0 mg/day and a
10P-RWC of 0.6 mg/day are taken forward for risk characterisation. These estimates are not
presented as statistically robust but as best estimates from the available data.




RAPPORTEUR [ITALY]                              101                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH

Table 4-64 Summary of dietary exposure to copper for adults (mg/day)

       Reference             Year       Country             Study Type             All bever    n         Sex            Age             Mean (10-90th percentiles)
                                                                                     ages
                                                                                   Included                                                M                             F

                                                                                                                     20-55                          1.33 (0.8-1.9)
     Abdullah et al.         1989       Sweden            Dup diet (24hrs)           Yes       ~300       m+f
                                                                                                                         >65                        1.27 (0.7-1.8)
       Anke et al.           1990       Germany            Dup diet (1wk)            Yes        56        m+f        20-60     0.83 (0.4-1.3) (note 1)               0.66 (0.3-1.0)
        Bro et al.           1990       Denmark           Dup diet (48hrs)           Yes       100         m         30-34          1.2 (0.4-2.0)
       Ellen et al           1990     Netherlands         Dup diet (24hrs)           yes       110        m+f        18-74                               1.2
Becker and Kumpulainen       1991       Sweden             Mkt bskt + anal            No              Adult population                                   1.2
                                                                                                                     25-30              1.22                             0.94
 Pennington and Young        1991         USA              Mkt bskt +anal             No       Pop        m+f
                                                                                                                     60-65              1.18                             0.86
     Buss and Rose           1992         UK          Food weighed+database          Yes       2200       m+f        16-64              1.49                             1.13
      Swerts et al.          1993       Belgium                Dup diet               No       Note       m+f        Elderly                        1.1 (0.8-1.4)
                                                                                                2
                                                                                                                     25-60              1.3                               1.1
      Lamand et al.          1994        France            Mkt bskt + anal            No       Pop        m+f
                                                                                                                         >60            1.2                               1.0
       Pelus et al.          1994        France           Dup diet (5 days)          Yes        14         m         25-35         1.23 (1.0-1.5)
 Van Cauwenbergh et al.      1995       Belgium           Dup diet (7 days)          Yes       n/a        m+f            <60                          1.73-1.83
      Jorhem et al.          1998       Sweden             Dup diet (1 wk)           yes        15          f        27-46                                           1.0 (0.6-1.4)
      Pokorn et al.          1998       Slovenia          Dup diet (24hrs)            ?         51        m+f            >65                   0.9 (0.3-1.5) (note 3)
Rodriguez-Palmero et al.     1998        Spain           Dup diet (21 days)           No       n/a        m+f            >60                             1.0
       Ysart et al.          1999         UK               Mkt bskt + anal            No              Adult population                                 1.2-1.4
                                                                                                                     65-79         1.13(0.3-2.0)                     0.90 (0.1-1.7)
       Bates et al.          1999         UK          Diet rec + d’base (4 days)      No       ~600       m+f
                                                                                                                         >80       0.86 (0.3-1.4)                    0.72 (0.2-1.3)




RAPPORTEUR [ITALY]                                       102                         VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH

                                                                                                                   24                     16-64          1.3
            FSIS                   2004            UK                 Mkt bskt + anal                 No                      m+f
                                                                                                                 towns                     >64           1.35
  Heseker et al. (note 4)          2002         Germany          Food weighed+database               yes                      m+f          >18     2.1          1.7

note 1 : Combined results for men were not presented. Values are the central values for mean and RWC
note 2 : Sample size not given. N=20 used as a conservative default to calculate CI. (Note, Pokorn et. Al. report n=51 for similar institution).
note 3 : 51 samples of food presented, may be overestimate of actual consumption.
note 4 : This study has several weaknesses and is not further considered




RAPPORTEUR [ITALY]                                                  103                              VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Table 4-65 Estimated population averages for mean dietary intake of copper   (Estimated from data in Table 4-64, further
                                                                             details in text)

                                  Population <60 yrs (or predominantly <60yrs)
                                       Year                  Age Range                Mean Intake (mg/day)
        Abdullah et. Al.               1989                     20-55                         1.33
          Anke et. Al.                 1990                     20-60                         0.75
           Bro et. Al.                 1990                     30-34                         1.08
          Ellen et al.                 1990                     18-74                         1.20
     Pennington and Young              1991                     25-30                         1.08
        Buss and Rose                  1992                     16-64                         1.31
        Lamand et. Al.                 1994                     25-60                         1.20
          Pelus et. Al.                1994                     25-35                         1.10
    Van Cauwenbergh et. Al.            1995                      <60                          1.78
         Jorhem et. Al.                1998                     27-46                         1.13
             FSIS                      2000                     16-64                         1.30
             mean                                                                             1.20
                                                 Population >60 yrs
                                         Year                Age Range               Mean Intake (mg/day)
          Abdullah et. Al.               1989                    >65                          1.27
      Pennington and Young.              1991                    60-65                        1.02
           Swerts et. Al.                1993                   Elderly                       1.10
          Lamand et. Al.                 1994                    >60                          1.10
           Pokorn et. Al.                1998                    >65                          0.90
     Rodriguez-Palmero et. Al.           1998                    >60                          1.00
           Bates et. Al.                 1999                    65-79                        1.02
            Bates et Al.                 1999                    >80                          0.79
               FSIS                      2004                    >64                          1.35
               mean                                                                           1.06
                                              Total population estimates
                                         Year                Age Range               Mean Intake (mg/day)
     Becker and Kumpulainen              1991                    Pop                          1.20
            Ysart et. Al.                1999                    Pop                          1.30
               mean                                                                           1.25




RAPPORTEUR [ITALY]                                         104                      VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
4.1.1.5.3            Copper levels in drinking water

Sources and variability of copper in drinking water
Copper pipes are widely used in residential and commercial water distribution systems.
"Corrosive waters" is a term used frequently to refer to waters that yield high copper
concentrations as a result of liberation of copper by-products from copper pipes to drinking
water (Lagos 1999; 2001). Resultant exposures have been linked with cases of acute
gastrointestinal illness as described in the chapter on acute health effects. Since the
distribution system itself may be the major source of copper in drinking water (particularly
where elevated levels occur) it is not relevant to consider concentrations at the supply end of
the distribution system in isolation. Concentrations should be measured at the tap to include
both components of exposure, i.e. input and leaching.
The causes of leaching from copper pipes are complex. Although metallic copper is
insoluble, oxidation/reduction corrosion processes take place at the copper-water interface
inside copper tubes. These corrosion products are subject to dissolution and precipitation
processes and lead to the liberation of dissolved copper species in the water and to the
formation of a precipitation layer on the copper tube, the latter process is often called pipe-
aging.
Theoretical corrosion research and practical experience have demonstrated some key
parameters that influence the corrosion, dissolution and precipitation processes in copper
pipes used for drinking water circulation: water chemistry (pH, CO2, O2, carbonates and
bicarbonates, sulphates, nitrates and chlorides, total organic carbo (TOC)), pipe age, water
velocity and water stagnation time in the pipe. It has indeed been recognized that decreased
pH and increased TOC appear to be the major factors associated with increased copper
liberation in the water.
Studies related to the influence of stagnation time on copper levels at the tap have shown
that the observed profiles on copper concentrations as a functions of equilibration time often
correspond to diffusion controlled processes. The diffusion of the dissolution products from
the pipe wall to the centre appear to determine copper concentrations and typical stagnation
curves show an increase in copper concentrations until a saturation level is reached.
Consequently, standing time can dramatically effect the copper concentration of water at the
tap on a timescale of minutes or seconds. For example, an initial copper concentration of
approximately 5 mg/litre was reduced by an order of magnitude after flushing for 30 seconds
(Knobeloch et. al., 1998). In order to determine copper concentrations representative of daily
intake, it is therefore critically important that composite sampling is conducted to reflect the
habits of the exposed person/s and the pattern of consumption. The Consumption Habit
Exposure Model (CHEM) has been proposed for this purpose (Lagos et. al., 1999).
In new systems, dissolution and subsequent precipitation processes may be elevated with a
decrease in copper concentrations evident following prolonged use as shown in Figure 4-21.
Theoretical models that accurately predict the corrosion products and the copper
concentrations in the tap water have not yet been formulated.




RAPPORTEUR [ITALY]                              105                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH

Figure 4-21 Copper concentration versus stagnation time in a copper pipe   Modified from Meyer (1996) – extracted from
                                                                           Lagos, 2001.




It is therefore necessary to estimate exposure for acute and chronic effects using appropriate
methods. The highest copper concentrations are likely to be found in first-draw water
following overnight standing in the pipes. Consumption of first-draw water is therefore likely
to represent the most significant exposure in respect of acute effects. In contrast, composite
sampling representative of daily consumption is the most appropriate indicator in respect of
chronic effects.

Exposure estimate for acute effects
The exposure estimate for acute effects therefore focuses on data for first draw (unflushed)
water taken from the recent literature for the EU.
In the study of Pettersson and Rasmussen (1999), described further below, copper
concentration in first draw samples from households in Malmo and Upsalla with 1178
resident children gave a median value of 0.72 mg/litre and a 90th percentile of 2.11 mg/litre.
As already indicated, this study covered a location where the aged distribution system was
known to create water quality problems and can be considered at the upper end of the likely
exposure range.
Copper levels in drinking water were reported in the German Environmental Study (GerESII),
a large-scale population survey covering a total of 2524 households described as
representative of former East and West Germany (Seifert et. al., 2000a; 2000b). Data
collection occurred during, or prior to, 1992. First draw samples were collected following
overnight stagnation (n=4003). The median value was 0.09 mg/litre and the 90th percentile
was 0.81 mg/litre. Flushed samples, collected in “the usual way” (n=3989) produced a median
of 0.05 mg/litre and a 90th percentile of 0.49 mg/litre. Since these results are effectively
national averages, they are assumed to cover corrosive water areas as well as those that may
be regarded as more typical. It is notable in these results that stagnant and running samples
vary only by a factor of approximately two.
In a follow-up study (GerESIII), further data were collected during 1998. The median first-
draw copper concentration (n=4761) was 0.15 mg/litre and the 90th percentile was 0.89



RAPPORTEUR [ITALY]                                       106                        VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
mg/litre, a slight increase relative to the corresponding values for the earlier GerESII study. In
contrast to other metals, values for former West Germany were moderately higher than those
for East Germany. This may reflect differences in the materials used in the distribution
systems. It is understood that results for GerESIII are as yet unpublished.
An interesting observation of the GerESII and GerESIII studies concerns the maximum
recorded values for copper in standing water for these large data sets with a combined sample
size of 8750. These values were 5.6 mg/litre and 11.0 mg/litre respectively. These values are
lower than the maximum first draw/composite samples reported by Eife and co-workers
(1999) for a modest number of samples from residential dwellings in Germany (15 mg/litre).
The exceptional circumstances that prompted this latter investigation therefore appear highly
unrepresentative and not relevant in the context of a reasonable worst case (90th percentile)
estimate.
Copper concentrations in stagnant and running water samples from households with young
children were collected in Göttingen, Germany (Dassel de Vergara et. al., 1999). A total of
919 stagnant samples were collected following overnight standing in the pipes. Exact
stagnation times were not reported. Of these samples, 9% were ≥ 0.5 mg/litre, and 4% ≥ 0.8
mg/litre. Of random daytime samples, 95% were ≤0.5 mg/litre. Typical or median values were
not presented.
Data from an unpublished study conducted for the European Commission DG XXIV 2003
describing copper concentrations in samples from a number of cities in various member states
were further analysed (Sundberg, 2003). Mean values for samples collected without flushing
were: Germany 0.02-0.03 mg/litre; France 0.01-0.02 mg/litre; the Netherlands 0.02-0.19
mg/litre, Greece and Ireland both 0.03 mg/litre. Curiously, mean values for cities in Italy,
Spain and Belgium sampled after flushing were mostly higher than values for other countries
before flushing: Italy 0.06-0.07 mg/litre; Spain 0.04-0.11 mg/litre, Belgium 0.16-0.63
mg/litre. The relatively high values for Belgium could not be attributed to acidic water
(pH=7.4-7.8) but were instead attributed to higher levels of total organic carbon than waters in
other countries.
Only average, minimum and maximum values were given in this study. Consideration of
other data presented already for first draw water indicates that the 90th percentile typically
exceeds the median by a factor of 3-5. Applying a factor of 5 to the mean results from this
study therefore represents a likely moderate overestimate of reasonable worst-case exposure.
The above data, together with estimates of the resulting exposures, are summarized in Table
4-66. Acute exposure is estimated by taking a realistic sample volume of 200-400 mls
corresponding to 1-2 mugs to represent a typical early morning beverage intake. This
consumption is treated as a bolus dose for the purpose of the exposure estimate. Table 4-66
indicates that typical copper concentrations in standing water range from 0.01-0.19 mg/litre
across a range of cities with a wide geographical spread and also from diverse locations
within a single country (Germany). Similarly, estimates of RWC copper concentrations range
mostly from 0.06-0.93 mg/litre. The spread of these data are very similar for both typical and
RWC estimates.
As a conservative estimate the typical and RWC acute effects estimates given by Pettersson
and Rasmussen for Malmo and Upsalla of 0.72 mg/litre and of 2.11 mg/litre respectively are
carried forward for risk characterisation.




RAPPORTEUR [ITALY]                              107                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH

Table 4-66 Summary of copper concentrations in standing water and assessment of acute exposure

Ref                        City/country        n           Typical                               Reasonable worst case estimate
                                                           copper            intake              copper            intake
                                                           concentration                         concentration
                                                                             (mg)                                  (mg)
                                                           (mg/litre)                            (mg/litre)

Pettersson and             Malmo and Upsalla   ≤1178       0.72              0.14-0.29           2.11              0.42-0.84      Highly corrosive water from aged
Rasmussen 1999                                                                                                                    distribution system
Dassel de Vergara et al,   Göttingen           919         n/a               n/a                 0.65              0.13-0.26      Top 91-96% of samples 0.5-0.8 mg/litre.
1999                                                                                                                              Midpoint (0.65) taken for exposure estimate
Seifert et al, 2000        Germany             4003        0.09              0.02-0.04           0.81              0.16-0.32      Representative coverage of former East
                                                                                                                                  and West Germany
(GerESII)
GerESIII, unpublished      Germany             4761        0.15              0.03-0.06           0.89              0.18-0.36      Representative coverage of former East
                                                                                                                                  and West Germany

Sundberg (2003)            Stuttgart           100         0.02              ≤0.01               0.08              0.02-0.03      No exceedences of WHO guideline of 2
                                                                                                                                  mg/litre found in any case in this study
                           Karlsruhe           100         0.01              ≤0.01               0.07              0.01-0.03
                           Mannheim            100         0.03              ≤0.01               0.13              0.03-0.05
                           Nancy               100         0.02              ≤0.01               0.09              0.02-0.04
                           Strassbourg         100         0.01              ≤0.01               0.06              0.01-0.02
                           Mulhouse            100         0.02              ≤0.01               0.12              0.02-0.05
                           Maastricht          100         0.02              ≤0.01               0.09              0.02-0.04
                           Eindhoven           100         0.06              0.01-0.03           0.32              0.06-0.13
                           Breda               100         0.19              0.04-0.07           0.93              0.19-0.37
                           Athens              100         0.03              ≤0.01               0.15              0.03-0.06
                           Dublin              100         0.03              ≤0.01               0.12              0.02-0.05




RAPPORTEUR [ITALY]                                     108                          VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
The data reported by Petersson and Rasmussen for Malmo and Upsalla fall outside the range
of other data in Table 4-66. As mentioned above, it is noted that the mean copper
concentration for running water from Kalmthout was 0.63 mg/litre, close to the median value
for standing water reported for Malmo and Upsalla. Concentrations in standing water in
Kalmthout are therefore likely to be higher. These data suggest a rather narrow range of
copper concentrations in standing water representative of locations throughout the EU and
locations where local factors related to the distribution system, water quality or other factors
result in a higher range of concentrations.

Exposure estimate for chronic effects
Few suitable published studies in which representative composite sampling was undertaken
were found for the EU (although there appear to be more for the US and for developing
countries). Where composite sampling data are available, these generally come from
monitoring campaigns set up to identify areas with suspected high concentrations. The
available studies also measure exposure of infants and may therefore not exactly represent the
consumption patterns of older children or adults. Pettersson and Rasmussen (1999 and 2003)
reported the exposure of infants to copper in drinking water in Sweden. Mothers were
instructed to submit samples from water used to make up the infants’ feed. In effect,
therefore, this study followed a duplicate diet design with respect to drinking water. The mean
50th percentile from consumed drinking water was 0.61 mg/litre and the 90th percentile 1.57
mg/litre. These values correspond to adult intakes of 1.44 and 3.14 mg/day respectively based
on the default consumption of 2 litres/day. However, the study was conducted in two Swedish
cities (Malmo and Upsalla) with aged and corroded delivery systems that had resulted in
numerous complaints concerning water quality. Indeed, the authors indicate that the study was
initiated partly in response to such complaints. The representativeness of these findings in
respect of the population as a whole is therefore highly questionable. A more typical value for
copper in Swedish drinking water is given as 0.03 mg/litre (Landner and Lindestrom, 1999).
This value is consistent with most data in Table 4-66.
Another study in which composite samples for infants were collected was conducted in Berlin
(Zeitz et. al., 2003). In this study two types of composite samples were collected (n=2619).
Median concentrations ranged from 0.32-0.45 mg/litre and 90th percentile concentrations from
0.96-1.20 mg/litre.
Typical exposure from drinking water has been estimated by WHO as approximately 9% of
dietary exposure. This formula is regarded as more representative of the average EU citizen.
Data for copper in first-draw water shown in Table 4-66, together with other data for running
water, suggests that this formula is indeed broadly reflective of typical exposure in areas with
non-corrosive water. The similarity in the data in Table 4-67 for duplicate diet studies that do
or do not specify the inclusion of all beverages also supports this observation.
Copper concentrations in bottled mineral water were reported by Allen and co-workers
(1989). Duplicate samples of 35 bottled waters, including leading brand name products
available in the EU, were reported. The median and 90th percentile values for the means of the
duplicates were 1.5 and 16.7 μg/litre respectively corresponding to 0.003 and 0.033 mg/day
for a default consumption of 2 litres/day.




RAPPORTEUR [ITALY]                              109                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                        CHAPTER 4. HUMAN HEALTH
Table 4-67 Mean dietary intake of copper: influence of beverages. (Summarised from Table 4-64)

                                                                   copper intake (mg/day)
                                                                   Number of studies in parentheses
                                                                   predominantly         >60 yrs
                                                                   <60 yrs
                                    Studies including all beverages
median                                                             1.1                   1.3(1)
range                                                              0.8-1.8 (7)           (1)
                     Studies not including, or not specifying inclusion of beverages
median                                                             1.20                  1.01
range                                                              1.1-1.30 (5)          0.8-1.10 (6)
(1)   single value

No published data from regulatory agencies were available. In the UK, the agency responsible
for monitoring drinking water quality, the Drinking Water Inspectorate (DWI), publishes data
on contaminants in tap water on an annual basis for individual water companies. Until
December 2003, the DWI has a quality threshold of 3 mg/litre for copper in drinking water
and only samples that breach this level are reported. Samples <3 mg/litre are simply regarded
as negative and values are not given. The national data have been reviewed by Fewtrell and
co-workers (2002) and the numbers of samples >3 mg/litre is given as one in 17,000. The
monitoring protocol is described as follows: “samples are the first litre of water that issues
from the consumers’ taps during a daytime visit to randomly selected houses.” No other
quantitative data are available. While it is clear that breaches of the DWI’s limit are
exceedingly rare, this fact alone is of little use for the risk assessment. However, these
findings for the UK are consistent with other data for flushed water samples.
Therefore, using available relevant data, four categories of exposure from drinking water are
identified: consumption of bottled water which effectively contributes minimal added
exposure; consumption of “typical” tap water, applicable to most EU citizens, in which low
levels of copper are present, and consumption of “moderately corrosive” or “corrosive” water
applicable to certain geographical sub-populations as described by Zeitz et. al. (2003) and
Pettersson and Rasmussen (1999) respectively. These data are summarised in Table 4-68.
Elevated levels of copper may also be present in new dwellings. Since no composite data are
available for new dwellings, the data for corrosive waters are used as a surrogate in the
exposure assessment.
A major data gap concerns the proportion of the EU population that is exposed to corrosive
waters which contribute heavily to the higher exposure estimates. The available data suggests
these are relatively small geographical subsets of the EU population. The contribution of
copper in drinking water to oral exposure, and the validation of existing dietary exposure
studies, could best be addressed by duplicate diet studies, inclusive of all beverages, in areas
with and without perceived water quality problems. Additional information on copper levels
in drinking water will become available in 2006 under the implementation of the EU drinking
water directive.




RAPPORTEUR [ITALY]                                        110                          VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                             CHAPTER 4. HUMAN HEALTH
Table 4-68 Estimate of copper exposure in drinking water for adults applicable for chronic effects

                                                             Exposure estimate (mg/day)
                                                           (mean concentration (mg/litre) in
                                                                   parentheses)
                 Exposure group                             Typical                 RWC
                                          Low exposure
Consumption of bottled water                                 <0.01                   0.03
                                                           (<0.005)                (0.015)
                                        Typical exposure
Basis: non-corrosive water, exposure = 10% of                0.11                    0.13
dietary exposure
                                                            (0.055)                (0.065)
                     Exposure to moderately corrosive water (from Table 4-66)
Zeitz et al (2003)                                       0.75 (0.6-0.9)          2.2 (1.9-2.4)
Berlin                                                      (0.375)                 (1.10)
                         Exposure from corrosive water (from Table 4-66)
Pettersson and Rasmussen (1999, 2003)                         1.2                    3.1
Malmo & Upsalla                                             (0.61)                  (1.57)


4.1.1.5.4                Exposure carried forward for risk characterisation

Acute exposure
Typical data for copper concentration in standing water are shown in Table 4-66. Higher
exposures from corrosive waters are found in specific locations, e.g. for domestic dwellings at
some locations in Sweden (Pettersson and Rasmussen, 1999). The proportion of the
population exposed to such levels is unknown. As a conservative estimate the typical and
RWC estimates given by Pettersson and Rasmussen for Malmo and Upsalla of 0.72 mg/litre
and of 2.11 mg/litre respectively are carried forward for risk characterisation.

Chronic exposure
Based on the data reported above, exposure estimates for adults are shown in Table 4-62.
Base estimates are derived for typical and 90P-RWC estimates for food (including drinking
water in some cases), mean intake from alcoholic drinks (0.05 mg/day) and inhalation
exposure. Projections for total oral exposure are based on the addition of four possible levels
of intake from drinking water corresponding to the data summarised in Table 4-68. Since
several studies of the duplicate diet studies shown in Table 4-64 specify the inclusion of
beverages, this approach results in a probable marginal overestimate of true intake. The 10P-
RWC estimate is taken as 0.6 mg/day.
Total oral exposure estimates for children are shown in Table 4-70, Table 4-71 and Table
4-72 for typical, 10P-RWC and 90P-RWC respectively. Food data are taken from Table 4-65.
Where only a single, i.e. typical, estimate of copper in food is available this is used in all the
estimates. In these cases, the 10P-RWC estimates may be an overestimate and vice-versa.
Dust ingestion data, matched as closely as possible by age, is taken from Table 4-63. As the
TGD gives no default consumption values for children, these are adapted from other sources




RAPPORTEUR [ITALY]                                           111                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
(US EPA, 1993). The mean adult consumption given by the US EPA (1.5 l/day) is 25% less
than the TGD default. Age-specific values for children and adolescents are therefore adjusted
accordingly. The cited values (litres/day), with adjusted values in parentheses are: less than 3
yrs 0.61 (0.81); 3-5 yrs 0.86 (1.15), and 6-17 yrs 1.14 (1.52). Estimates for copper from
drinking water are derived from Table 4-68 adjusted by age-specific consumption values.
Table 4-69, Table 4-70, Table 4-71, Table 4-72 indicate that the major factor in projected
higher exposures for adults and children is copper present in corrosive drinking water.
Although mostly a minor source of exposure, the available data suggest that copper levels in
drinking water may span a range of up to two orders of magnitude.
Values for typical exposure and for a RWC case (moderately corrosive water) will be carried
forward to the risk characterisation. Several sources suggest that higher estimates of copper in
water are a likely overestimate of actual consumption. In contrast to drinking water, copper
intake from food generally varies by little more than ±20% mostly by less. Although there are
few data for inhalation exposure, this route is insignificant in the context of overall exposure.




RAPPORTEUR [ITALY]                              112                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH

Table 4-69 Estimates of total oral exposure to copper (mg/day)

                                                                                 predominantly < 60yr                                          predominantly > 60yr
 Dietary exposure ( Table 4-62)                                           typical                        RWC                           typical                      RWC
 alcoholic                                                                 1.2                            2                             1.01                          2


 Total exposure estimate additional exposure from
 drinking (1)                                                     lower             upper       lower          upper         lower               upper      lower         upper
 low                                                                1.2              1.2          2              2               1                1           2            2
 typical                                                            1.3              1.3          2             2.1              1.1              1.1        2.1           2.1
 moderately corrosive                                                 2              3.4         2.8            4.2              1.8              3.2        2.8           4.2
 corrosive                                                          2.4              4.3         3.2            5.1              2.2              4.1        3.2           5.1

(1): lower estimates = dietary exposure added to typical drinking water exposure for relevant category in Table 4-68
   upper estimates = dietary exposure added to RWC drinking water exposure for relevant category in Table 4-68
   Dietary exposures include exposure from alcoholic drinks (0.05 mg/day)

Table 4-70 Estimated typical oral copper intake for children and adolescents

       Age              Food                              Typical water                                Dust              Total
    years            mg Cu/day                l/day        mg Cu/l        mg Cu/day               mg Cu/day            mg Cu/day
       <1.3              0.6                0.81              0.055                 0.045              0.021             0.67
        2               0.45                0.81              0.055                 0.045              0.034             0.53
     2 to 3              0.7                0.81              0.055                 0.045              0.034             0.78
     5 to 9              0.6                1.52              0.055                 0.084              0.021             0.70
   11 to 14             1.46                1.52              0.055                 0.084              0.006             1.55
   14 to 19              1.1                1.52              0.055                 0.084              0.003             1.19
   14 to 19              1.5                1.52              0.055                 0.084              0.003             1.59

Food data from Table 4-62, Dust data from Table 4-63, Copper in water concentration 0.06 mg/l: mean value (in parentheses) from Table 4-68


RAPPORTEUR [ITALY]                                                113                             VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE, DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-
8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                                                                           CHAPTER 4. HUMAN HEALTH
Table 4-71 Estimated 10P-RWC oral copper intake for children and adolescents

     Age               Food                      10thP RWC (Bottled water)                       Dust               Total
    years           mg Cu/day            l/day        mg Cu/l            mg Cu/day            mg Cu/day         mg Cu/day
     <1.3               0.6               0.81              0.005             0.004              0.021              0.63
       2                0.4               0.81              0.005             0.004              0.034              0.44
    2 to 3             0.45               0.81              0.005             0.004              0.034              0.49
    5 to 9              0.6               1.52              0.005             0.008              0.021              0.63
   11 to 14            0.88               1.52              0.005             0.008              0.006              0.89
   14 to 19            0.72               1.52              0.005             0.008              0.003              0.73
   14 to 19            0.87               1.52              0.005             0.008              0.003              0.88
Food data from Table 4-62, Dust data from Table 4-63, Copper in water concentration 0.01 mg/l: mean value (in parentheses) from Table 4-68



Table 4-72 Estimated 90P-RWC oral copper intake for children and adolescents

     Age               Food                             Typical water                            Dust               Total
    years           mg Cu/day            l/day mg        Cu/l mg             Cu/day           mg Cu/day         mg Cu/day
     <1.3               0.6               0.81              0.055             0.045              0.021              0.67
       2               0.45               0.81              0.055             0.045              0.034              0.53
    2 to 3              0.7               0.81              0.055             0.045              0.034              0.78
    5 to 9              0.6               1.52              0.055             0.085              0.021              0.70
   11 to 14            1.46               1.52              0.055             0.085              0.006              1.55
   14 to 19             1.1               1.52              0.055             0.085              0.003              1.19
   14 to 19             1.5               1.52              0.055             0.085              0.003              1.59

Food data from Table 4-62, Dust data from Table 4-63, Copper in water concentration 0.738 mg/l: mean value for moderately corrosive water (in parentheses) from Table 4-68




RAPPORTEUR [ITALY]                                              114                           VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH


           4.1.1.6                    Combined exposure
The estimated combined exposure to copper taken forward for risk characterization for
workers and the general population are summarized in Table 4-73 to Table 4-76 below. Data
have been extracted from Table 4-45 to Table 4-49 for occupational exposure assessment,
from Table 4-52 for consumer exposure assessment and from Table 4-61 and Table 4-69 for
indirect exposure data are
For workers, the RWC estimate is derived by combining the RWC occupational exposure
with the typical indirect exposure (higher typical food + typical drinking water) and the
typical consumer exposure. The typical estimate is derived by combining the typical
occupational exposure with the RWC indirect exposure (higer RWC food + typical drinking
water) and the RWC consumer exposure. RWC consumer exposure sources for workers
include the use of haircare products, handling of coins and smoking.

Table 4-73 Combined exposure data carried forward for risk characterisation for workers - Typical scenarios

                                                    External         External         External
Risk characterisation                              Inhalation         Dermal            Oral
                                                 Cu(mg/ p/day)     Cu(mg/p/day)    Cu(mg/p/day)
WORKERS EXPOSURE*
SMELTING AND REFINING FURNACE OPERATION
All smelting, converter and anode furnace
operation (site specific data, except where
                                                     0.3-2.3            60
indicated below)
Pooled                                                 1.2              60



ECI-07
anode furnace opn (incl tapping)                       8.5              60

anode furnace opn using RPE (incl tapping)            0.85



SAMPLING PLANT(site specific data)                   0.4-3.2            60
                                                       1.9              60
Pooled


                                                     0.2-2.9            60
RAW MATERIAL HANDLING (site specific data)
Pooled                                                 0.2              60

PRODUCTION OF BILLETS (PC6), SAND AND DIE CASTINGS (PC7), WIREROD
All operations (site specific data)                  0.3-2.4            60
Pooled data (PC8)                                      1.2              60
FURTHER PROCESSING
All operations (site specific data)                   0.3-1             60
Pooled data                                            0.4              60
RPE COPPER POWDER PRODUCTION
ECI-97– operation specific                           3.4-5.9           259



RAPPORTEUR [ITALY]                                           115                      VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
         -pooled                                               4.2                 259
ECI-105– operation specific                                  19.5-69               259
         -pooled                                              55.9                 259
ECI-106– operation specific                                  7.7-97.0              259
          - operation specific using RPE                     0.6-8.3               259
          -pooled                                              26                  259
          -pooled using                                        2.2                 259
COPPER COMPOUNDS PRODUCTION
ECI-91                                                         6.8                 230
ECI-93                                                         3.0                 207
ECI-110                                                        1.0                 207
ECI-112                                                        1.2                  66
Pooled                                                         2.3                 181
CONSUMER EXPOSURE                                             0.001                0.28
MAN EXPOSED VIA THE ENVIRONMENT-                              0.093                           2.35**
LOCAL

*assuming a respiratory volume of 10 m3 for a worker/day.
**2.1 from regional sources (Table 4-69) + 0.25 from local sources (Table 4-61)



Table 4-74 Combined exposure data carried forward for risk characterisation for workers – RWC
scenarios

                                                            External          External       External
Risk characterisation                                       Inhalation            Dermal       Oral
                                                        Cu(mg/p/day)       Cu(mg/p/day)    Cu(mg/p/day)
WORKERS EXPOSURE*
SMELTING AND REFINING
FURNACE OPERATION
All smelting, converter and anode furnace                    1.7-8.4                85
operation (site specific data, except where
indicated below)
Pooled                                                         5.4                  85

ECI-07
anode furnace opn (incl tapping)
                                                              15.5                  85
anode furnace opn using RPE (incl tapping)
                                                              1.55

SAMPLING PLANT (site specific data)
                                                             1.9-6.0                85
Pooled                                                                              85
                                                               5.5

RAW MATERIAL HANDLING (site specific data)                                          85
                                                             0.7-10.3
Pooled                                                                              85
                                                               2.9



RAPPORTEUR [ITALY]                                                   116                     VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
         PRODUCTION OF BILLETS (PC6), SAND AND DIE CASTINGS (PC7), WIREROD (PC8)
All operations (site specific data)                          2.3-12.4             85
Pooled data                                                     6.0               85
                                             FURTHER PROCESSING
All operations site specific data (using RPE)              2.0-24.5 (1.3)         85
Pooled data                                                     3.0               85
                                          COPPER POWDER PRODUCTION
ECI-97– operation specific                                    8.2-9.7             952
         -pooled                                                9.2               952
ECI-105– operation specific                                  102-982              952
         -pooled                                                190               952
ECI-106– operation specific                                 36.9-111.6            952
          - operation specific using RPE                      2.2-16              952
          -pooled                                              112.6              952
          -pooled using RPE                                    11.3               952
                                  COPPER COMPOUNDS PRODUCTION
ECI-91                                                         14.3               845
ECI-93                                                          8.0               760
ECI-110                                                         7.6               760
ECI-112                                                         3.1               243
Pooled                                                          8.2               663
CONSUMER EXPOSURE                                                0                0.14

MAN EXPOSED VIA THE ENVIRONMENT-                               0.057                     1.44**
LOCAL

*assuming a respiratory volume of 10 m3 for a worker/day.
**1.3 from regional sources (Table 4-69) + 0.14 from local sources (Table 4-61)


For the general population, the typical estimate is derived by combining the typical indirect
exposure with the typical consumer exposure. The RWC estimate is derived by combining the
RWC indirect exposure with the RWC consumer exposure excluding the use of supplements.
The use of supplements has been excluded in order not to combine indirect exposure for areas
with high levels of copper in drinking water with the use of copper supplements thereby
avoiding unreasonably conservative exposure scenarios.

Table 4-75 Combined exposure data carried forward for risk characterisation for the general population – Typical scenarios
Risk                        External            External          External
characterisation
                            Inhalation          Dermal            Oral
                            Cu(mg/p/day)        Cu(mg/p/day)      Cu(mg/p/day)
Consumer exposure                     0             0.38                  0
Man exposed via the
environment –regional            0.002               0                  1.2-4.3



RAPPORTEUR [ITALY]                                                    117                VRAR_CU_0706_HH_EXPOSURE
EU RISK ASSESSMENT - [COPPER, COPPER II SULPHATE PENTAHYDRATE, COPPER(I)OXIDE, COPPER(II)OXIDE,
DICOPPER CHLORIDE TRIHYDROXIDE] CAS [7440-50-8, 7758-99-8, 1317-39-1, 1317–38–0, 1332-65-6]
                                                                              CHAPTER 4. HUMAN HEALTH
Man exposed via the
environment –local          0.057            0            1.34-4.44




Table 4-76 Combined exposure data carried forward for risk characterisation for the general population – RWC scenarios
Risk                    External       External        External
characterisation
                        Inhalation     Dermal          Oral
                        Cu(mg/p/day)   Cu(mg/p/day)    Cu(mg/p/day)
Consumer exposure          0.0005           6.16              2
Man exposed via the         0.002            0             2.0-5.1
environment –regional
Man exposed via the         0.093            0            2.25-5.35
environment –local




RAPPORTEUR [ITALY]                                       118                         VRAR_CU_0706_HH_EXPOSURE

								
To top