Dioxin and PCBs in four commercially important pelagic fish stocks in the North East Atlantic
April 2003
A project financed by Nordisk Atlantsamarbejde (NORA) together with the Icelandic Association of Fishmeal Manufacturers and p/f Havsbrún Faroe Islands.
Dioxin and PCBs in pelagic fish stocks
1 2 3
Executive summary ............................................................................2 Introduction ........................................................................................3 Background.........................................................................................4 3.1 3.2 Dioxin and PCBs .......................................................................4 Fishmeal and oil production in Iceland and the Faroes.............6 Sampling procedures .................................................................8 Sample handling ........................................................................9 Chemical analyses ...................................................................10 Capelin .....................................................................................22 Blue Whiting............................................................................24 Iceland Herring ........................................................................26 Atlanto-Scandian Herring........................................................28 Age division of Blue Whiting..................................................31 Ratio of WHO-PCB : dioxin ..................................................34
4
Methods and materials ......................................................................7 4.1 4.2 4.3
5
Results................................................................................................12 5.1 5.2 5.3 5.4 5.5 5.6
6 7 8 9
Discussion ..........................................................................................35 Acknowledgements...........................................................................37 References .........................................................................................38 Appendix 1 ........................................................................................39
10 Appendix 2........................................................................................51 11 Appendix 3........................................................................................53
1
Dioxin and PCBs in pelagic fish stocks
1 Executive summary
Fishmeal and fish oil of European origin have been especially criticised in a report of the EU Scientific Committee on Animal Nutrition (SCAN) published in November 2000. Quote “Fishmeal and fish oil are the most heavily contaminated feed materials” with respect to dioxins. The report indicated “the greatest concerns arise from the use of fishmeals and fish oils of European origin”. The EU Directive 2001/102/EC dated November 2001, on undesirable substances and products in animal nutrition, specifies maximum limits for dibenzo-p-dioxins and dibenzofurans. These compounds are commonly called dioxin. This Directive established a maximum permissible level for dioxin of 1,25 ng WHOTEQ per kilogram fishmeal , and 6.00 ng WHO-TEQ per kilogram fish oil. These limits entered into force on 1.July 2002. The fishmeal and fish oil producers of Iceland and the Faroe Islands applied for a grant from the Nordisk Atlantsamarbejde (NORA) in March 2000 for the finance of an assignment with the objective to systematically collect information on dioxin as well as polychlorinated biphenyls (PCB), in samples of landed pelagic catches and the fishmeal and fish oil produced from each catch. This report presents the results of the sampling that commenced in January 2001 and was completed in December 2002. In total, 96 samples were analysed for dioxin and PCB content, from four important fish stocks of the N.E Atlantic; capelin, blue whiting, Icelandic summer spawning herring and Atlanto-Scandian spring spawning herring. The results demonstrate that most of the raw material is suitable for production of fishmeal and fish oil showing dioxin levels well below the EU limits. All of the fishmeal produced from these 4 fish stocks is within the given maximum limit for dioxin of 1,25ng WHO-TEQ per kg fishmeal. Based on the production figures of the past 3 years in Iceland and the Faroes, it is estimated that more than 85% of the fish oil production in these countries would have been below the permissible maximum level for dioxin of 6 ng WHO-TEQ per kg fishoil.
2
Dioxin and PCBs in pelagic fish stocks
2
Introduction
In November 2001, the European Commission (EC) published the Directive 2001/102/EC (1) amending Directive 1999/29/EC (2) on undesirable substances and products in animal nutrition where maximum limits on dibenzo-p-dioxin and dibenzofuran were stipulated for feedingstuffs. These maximum limits entered into force on 1 July 2002. The aim is to provide protective measures at the feed level with a view to protecting public health from the possible accumulative effects of dibenzop-dioxin and dibenzofuran. Parallel measures were also taken to set maximum levels for dioxin in foodstuffs in Regulation 2375/2001 (3). The Directive was the culmination of a scientific and political debate that had taken place since the Belgium Incident in 1999. The opinion of the Scientific Committee on Animal Nutrition published in November 2000 concluded that “fishmeal and fish oil are the most heavily contaminated feed materials” with respect to dioxins. The report indicated, “the greatest concerns arise from the use of fishmeals and fish oils of European origin”. It also pointed out that “limited data were available on the contamination of feed materials by WHO-PCB’s”, and suggested “scientific cooperation should be promoted in order to collect and collate information available in the different Member States at the EU level”(4). As a result of this discussion, the fishmeal and fish oil producers of Iceland and the Faroe Islands applied for a grant from the Nordisk Atlantsamarbejde (NORA) in March 2000 for the finance of an assignment with the objective to systematically collect information on dioxin and PCB’s in samples of landed pelagic catches and the fishmeal and fish oil produced from each catch. This report presents the results of the sampling that commenced in January 2001 and was completed in December 2002. The steering committee comprised: Derek Mundell, SR-mjöl hf. Reykjavík, Iceland (project leader) Magnus Pauli Magnussen, Food and Environmental Agency, Tórshavn, Faroe Islands Jón Reynir Magnusson, Association of Icelandic Fishmeal Producers, Reykjavík, Gudny Vang, pf Havsbrún, Fuglafjörður, Faroe Islands
3
Dioxin and PCBs in pelagic fish stocks
3 Background
3.1 Dioxin and PCBs
The scope of this study covers the polychlorinated dibenzodioxin (PCDD) commonly known as dioxin, polychlorinated dibenzofuran (PCDF) commonly known as furan, and polychlorinated biphenyls (PCB). In order to simplify, this report will use the term “dioxin” to refer to both dibenzodioxin and dibenzofuran. There are 75 possible PCDD congeners and 135 possible PCDF congeners giving a total of 210 congeners. Of these, 17 have been shown to be toxic, 7 PCDDs and 10 PCDFs. There are 209 possible PCB congeners of which 12 have been shown to have dioxin-like toxicity. In order to simplify, this report will use the term “WHO-PCB” to refer to these 12 PCBs with dioxin-like toxicity. Therefore altogether 29 congeners have dioxin-like toxicity and they are the subjects of this study. In addition to these 29 toxic congeners, the 7 so-called Marker PCBs were measured in all the samples. These do not exhibit dioxin-like toxicity, but have been previously used as indicators of PCB pollution. All of these compounds are lipophilic and resist degradation. These characteristics predispose them to long environmental persistence and to long-range transport. They accumulate in lipid tissue and in carbon rich matrices such as soils and ocean sediment. Dioxin and WHO-PCBs have similar chemical and toxic characteristics but the sources of release are different. Dioxins are essentially unintentional by-products in a number of chemical processes as well as almost all combustion processes. On the other hand, PCBs are intentionally produced compounds that were manufactured for decades until their use was banned in 1985. It is estimated that a total of 1,5 million tonnes were produced worldwide before the ban was enforced (5). Although dioxin is considerably more toxic than WHO-PCBs, the concentration of WHO-PCBs in the environment is much higher than dioxin. For this reason, the total toxic effect of the WHO-PCBs is often equal to or greater than that of dioxin. The 29 toxic congeners each exhibit very different levels of toxicity on mammals. For regulatory purposes, so called toxicity equivalency factors (TEF) have been internationally agreed for risk assessment of complex mixtures of these 29 congeners. The TEFs are based on acute toxicity values from in-vivo and in-vitro studies. This approach is based on the fact that there is a common, receptor-mediated mechanism of action for these compounds. It does not, however, take account of any synergistic or antagonistic effects between the individual congeners with regard to toxicity. Although the scientific basis cannot be considered to be flawless, the TEF approach has been adopted as an administrative tool by many agencies and permits conversion of quantitative analytical data for individual congeners into a single value of toxic equivalent (TEQ). It must be realised that the TEFs are based on the present state of knowledge and are subject to revision as new data becomes available. In 1997, at a meeting of the World Health Organization, the WHO-TEF values were established based on the existing knowledge (6). These factors have been used by the EU in their legislation and the results in this report are based on these WHO-TEFs. The toxic equivalents are therefore reported as concentration of WHO-TEQ. Table 1 lists these values along with an outline of the nomenclature of the toxic congeners involved in this study. 4
Dioxin and PCBs in pelagic fish stocks
Table 1: WHO toxic equivalency factors (TEF´s) for humans/mammals of dioxin (PCDD and PCDF) and the WHO-PCBs. (6) Congener
DIOXIN (PCDD and PCDF) PCDD 2,3,7,8-TCDD 1,2,3,7,8-PentaCDD 1,2,3,4,7,8-HexaCDD 1,2,3,6,7,8-HexaCDD 1,2,3,7,8,9-HexaCDD 1,2,3,4,6,7,8-HeptaCDD OctaCDD PCDF 2,3,7,8-TetraCDF 1,2,3,7,8-PentaCDF 2,3,4,7,8-PentaCDF 1,2,3,4,7,8-HexaCDF 1,2,3,6,7,8-HexaCDF 1,2,3,7,8,9-HexaCDF 2,3,4,6,7,8-HexaCDF 1,2,3,4,6,7,8-HeptaCDF 1,2,3,4,7,8,9-HeptaCDF OctaCDF WHO-PCB Non-ortho PCBs (IUPAC) 3,4,4´,5-TetraCB (81) 3,3´,4,4´-TetraCB (77) 3,3´,4,4´,5-PentaCB (126) 3,3´,4,4´,5,5´-HexaCB (169) Mono-ortho PCBs 2,3,3´,4,4´-PentaCB (105) 2,3,4,4´,5-PentaCB (114) 2,3´,4,4´,5-PentaCB (118) 2´,3,4,4´,5-PentaCB (123) 2,3,3´,4,4´,5-HexaCB (156) 2,3,3´,4,4´,5´-HexaCB (157) 2,3´,4,4´,5,5´-HexaCB (167) 2,3,3´,4,4´,5,5´-HeptaCB (189) PCDD - Polychlorinated dibenzo-p-dioxin 1 1 0,1 0,1 0,1 0,01 0,0001 Dibenzo-p-dioxin PCDF – Polychlorinated dibenzofurans 0,1 0,05 0,5 0,1 0,1 0,1 0,1 0,01 0,01 0,0001
TEF
Structure
Dibenzofuran
WHO-PCB - Polychlorinated biphenyls 0,0001 0,0001 0,1 0,01 0,0001 0,0005 0,0001 0,0001 0,0005 0,0005 0,00001 0,0001
- Biphenyl
Marker PCB´s – Polychlorinated biphenyls Marker PCBs (IUPAC) 2,4,4´-TriCB (28) 2,2´5,5´-TetraCB (52) 2,2´,4,5,5´-PentaCB (101) 2,3´,4,4´,5-PentaCB (118) 2,2´,3,4,4´,5´-HexaCB (138) 2,2´,3,4,4´,5´-HexaCB (138) 2,2´,4,4´,5,5´-HexaCB (153) 2,2´,4,4´,5,5´-HexaCB (180) Abbreviations: CDD, chlorinated dibenzodioxin; CDF, chlorinated dibenzofuran; CB, chlorinated biphenyls, - no dioxin-like toxicity.
5
Dioxin and PCBs in pelagic fish stocks
3.2 Fishmeal and oil production in Iceland and the Faroes
During the years 2000 to 2002, an average of 1,7 million tonnes of fish was landed annually and processed into fishmeal and fish oil in Iceland and the Faroes. In order to provide information on the quantity of fishmeal and oil produced, average figures for yield were used for each month and for each fish species. The following two figures show the estimated monthly fishmeal production (figure 1) and fish oil production (figure 2) based on the recorded average monthly catch landings and the estimated fishmeal and oil yields. Figure 1: Estimated fishmeal production in Iceland and the Faroe Islands, based on average landed catches 2000 – 2002.
25
% of estimated annual fishmeal production
20
Total average fishmeal production was 317.000 tonnes per annum
15
10
5
0
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Capelin
Blue whiting
Iceland herring
Atlanto-Scandian herring
Figure 2: Estimated fish oil production in Iceland and the Faroe Islands, based on average landed catches 2000 – 2002.
25
% of estimated annual fish oil production
20
Total average fish oil production was 110.000 tonnes per annum.
15
10
5
0
Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec
Capelin
Blue whiting
Iceland herring
Atlanto-Scandian herring
6
Dioxin and PCBs in pelagic fish stocks
4 Methods and materials
The commercially important pelagic fish species of the northeast Atlantic area are: Capelin (Mallotus villosus) Two herring stocks (Clupea harengus) o Icelandic summer spawning herring o Atlanto-Scandian spring spawning herring Blue whiting (Micromesistius poutassou) The sampling was designed to assess the dioxin and PCB content of these 4 fish stocks during the principal fishing seasons as well as in the fishmeal and fish oil produced from them. It was, however, realised that it could be difficult to follow this plan due to lack of fishing at the time when sampling should take place. The sampling was done by government-approved inspectors both in Iceland and on the Faroe Islands. Samples were taken only when boats were landing one fish species, and the factory in question was processing only that same species. Mixtures of two or more species were avoided. The landed catch in each case was rarely less than 1000 tonnes except in the case of Icelandic herring catches where a minimum of 500 tonnes was necessary. These precautions were required in order to be certain that the meal and oil samples were definitely from the raw material that was being sampled. It should be pointed out that all of the fishmeal in this project was produced by indirect hot air drying or by steam drying. Samples were taken as shown in table 2. Table 2: Number and type of samples on a monthly basis.
Capelin fish fishmeal fish oil fish fishmeal fish oil fish fishmeal fish oil fish fishmeal fish oil Jan 2 2 2 Feb 2 2 2 Mar 2 2 2 Apr May Jun Jul 4 4 4 Aug Sep Oct Nov Dec 5 3 3 3 1 1
Iceland Herring
1 1 1 2 2 2 1 1 1 2 2 2 1 1 1 1
3 1 1
Atl.-Scan. Herring
Blue Whiting
2 2 2
1 1 1
1 1 1
2 2 2
2 2 1
In some cases, only raw material samples were taken. There were two reasons for this deviation from the initial plan. Firstly, the catches of capelin in the autumn months were rather small during both years of the project. Five samples of capelin were taken during December 2001 and December 2002; thereof 3 sets complete with fishmeal and fish oil samples. The remaining two catches were too small (<500 mt) to justify sampling of the fishmeal and fish oil. Secondly, the herring catches were generally sorted according to size at landing, and the larger fish processed for human consumption. The smaller fish and the offcuts were processed into fishmeal and oil. 7
Dioxin and PCBs in pelagic fish stocks
This meant that sampling of the fishmeal and fish oil would not have been representative of the total catch. Nevertheless, it was possible to take 7 sets of herring samples out of the 12 catches which were sampled. This made a total of 96 samples that were taken during 2001 and 2002 depending on the availability of the fish stocks. In 29 cases the samples were taken from the same material as it passed through the processing system so that the fishmeal and fish oil was directly comparable with the raw fish. In addition to these samples, on two separate occasions during the landing of blue whiting in the Faroe Islands, randomly taken raw fish samples were divided into three groups of 25 fish according to size and subsequently investigated in order to provide an insight into the effect of fish age on dioxin and WHO-PCB levels in blue whiting.
4.1 Sampling procedures
Raw material: Only whole and undamaged fish were included in the sample. The size of the sample was as follows. Number of individual fish 100-110 30 - 40 100-110
Capelin Herring Blue Whiting
Each catch was sampled throughout the landing in order to give a representative sample of the whole load. At all stages of sample collection it was essential to avoid contact of the sample with plastic, rubber, mineral oil and grease. All containers were thoroughly cleaned with appropriate solvents before use in order to prevent contamination of the samples. After sampling in Iceland, the fish were frozen as soon as possible to prevent deterioration. In the Faroe Islands, the measuring of biological parameters and collecting of otoliths for age determination was performed on the fresh fish. Fish meal: Sampling of the meal commenced when it was certain that meal from the catch which had been sampled, had started to emerge from the production line. A 50 –100g. meal sample was taken after the meal cooler at one hour intervals while it was certain that the meal was still from the catch under investigation. To prevent contamination of the sample, all contact with plastic, rubber, mineral oil and grease was avoided. At the end of the sampling period, the collective sample was mixed well prior to taking two subsamples which were placed in glass containers that had been thoroughly cleaned. Aluminium foil was placed between the container and the lid so that the sample did not touch the lid’s lining. Fish oil: Sampling of the fish oil from the final centrifuge commenced when it was certain that oil from the catch which was sampled, had started to emerge from the final centrifuge. A 100ml. fish oil sample was taken at the outlet from the centrifuge 8
Dioxin and PCBs in pelagic fish stocks
at one hour intervals while it was certain that the oil was still from the catch under investigation. To prevent contamination of the sample, all contact with plastic, rubber, mineral oil and grease was avoided. At the end of the sampling period, the collective sample was mixed well prior to taking three subsamples which placed in the glass containers that had been thoroughly cleaned. Aluminium foil was placed between the container and the lid so that the sample did not touch the lid’s lining.
4.2 Sample handling
In Iceland, when all 3 samples in a set (i.e. 1 fish sample, 1 fishmeal sample and 1 fish oil sample) had been collected, they were sent to the Icelandic Fisheries Laboratories (IFL) in Reykjavík. On the Faroe Islands, a technician from the Faroese Fisheries Laboratory (FFL) registered all the biological parameters and collected the otoliths from the fresh fish immediately after landing at the Havsbrún plant. The otoliths were subsequently labelled and sent to FFL in Tórshavn for age determination. The samples were accompanied by the following information on the catch. Fish species Name and number of vessel Date of catch Area of catch Port of landing Size of catch Processing plant Date of sampling At IFL, Reykjavík and at the Havsbrún laboratory in the Faroes, each sample was identified with a serial number as follows: Raw material – Iceland Fishmeal – Iceland Fishoil – Iceland Raw material – Faroes Fishmeal – Faroes Fishoil – Faroes RM/IS -1, RM/IS -2 etc FM/IS -1, FM/IS -2 etc FO/IS -1, FO/IS -2 etc RM/FO -1, RM/FO -2 etc FM/FO -1, FM/FO -2 etc FO/FO -1, FO/FO -2 etc
Raw material. In Iceland, after thawing out the raw material samples, the fish were individually weighed, measured for length and in the case of capelin and blue whiting, their sex was determined. In order to determine the sex of herring, it would have been necessary to open the abdomen. It was decided not to do this since it would possibly have had an effect on the composition of the fish that were subsequently homogenised and analysed. Samples were taken for age assessment (otholith sample for blue whiting and capelin. Scale sample for herring). All care was taken not to 9
Dioxin and PCBs in pelagic fish stocks
damage nor contaminate the fish in this process of measurement. Immediately after the tissue samples had been taken, the fish was coarsely minced and a portion was homogenized as finely as possible before it was placed in a glass container with aluminium foil inside the lid. The container was then labelled with the allocated sample code number e.g. RM/IS – 1. On the Faroe Islands, an official from the Faroese Fisheries Laboratory prepared the samples in a similar way as in Iceland immediately after the biological parameters had been measured and the otoliths removed as described previously. On two occasions on the Faroe Islands, an additional blue whiting sample was taken and divided into 3 groups of 25 fish. Each fish was then weighed, measured for length, the sex was determined and then the otholiths removed for age determination. Each group was then homogenised separately before it was placed in a glass container. These samples were labelled RM-A/FO -# (smallest fish), RM-B/FO-# (medium sized fish) and RM-C/FO-# (largest fish). Fish meal: Each meal sample, as received from the factory inspector, was labelled with the allocated serial number e.g. FM/IS -1. Fish oil: Each oil sample as received from the factory inspector, was labelled with the allocated serial number e.g. FO/IS –1. All samples were deep frozen before being sent for dioxin and PCB analysis.
4.3 Chemical analyses
Fat: IFL measured fat in all raw material samples and fishmeal samples using extraction with petroleum ether (7). Moisture: IFL measured moisture in all raw material samples and fishmeal samples using oven drying at 105°C (8). Dioxin and PCBs: The steering committee selected the laboratory ERGO Forschungsgesellschaft mbH in Hamburg to perform these analysis. This laboratory has taken part in international interlaboratory quality control studies, organized by WHO and EU. ERGO is regarded as one of the laboratories most experienced in this type of analysis and has worked with the European fishmeal and fish oil industry for several years. ERGO’s experience of the fish matrices involved in this project, has proved to be important to the credibility of the results. The measurements were made by high resolution gas chromatography together with high resolution mass spectrometry (HRGC/HRMS). Prior to extraction, 13C-ULlabelled internal standards were added to the sample as listed in tables 3 and 4. After spiking, the samples were extracted with nanograde solvents for ultratrace-analyses by using a solid / lipid extraction. The extract was cleaned up on a multicolumn system 10
Dioxin and PCBs in pelagic fish stocks
involving carbon-on-glassfibre. The measurement was then made by means of highresolution gas chromatography and high-resolution mass spectrometry (HRGC/HRMS) with VG-AutoSpec and/or Finnigan MAT 95 XL using DB-5 capillary columns. Two isotope masses were measured for each component. The quantification was carried out by the use of internal/external standard mixtures (isotope dilution method). Table 3: Internal standards (13C-UL), PCDDs/PCDFs
PCDDs 2,3,7,8 1,2,3,7,8 1,2,3,4,7,8 1,2,3,6,7,8 1,2,3,7,8,9 1,2,3,4,6,7,8 1,2,3,4,6,7,8,9 PCDFs -Tetra-CDD 2,3,7,8 -Penta-CDD 1,2,3,7,8 2,3,4,7,8 -Hexa-CDD 1,2,3,4,7,8 -Hexa-CDD 1,2,3,6,7,8 -Hexa-CDD 1,2,3,7,8,9 2,3,4,6,7,8 -Hepta-CDD 1,2,3,4,6,7,8 1,2,3,4,7,8,9 -Octa-CDD 1,2,3,4,6,7,8,9
-Tetra-CDF -Penta-CDF -Penta-CDF -Hexa-CDF -Hexa-CDF -Hexa-CDF -Hexa-CDF -Hepta-CDF -Hepta-CDF -Octa-CDF
Table 4: Internal standards (13C-UL), WHO-PCB
Compound 3,3´,4,4´ 3,4,4´,5 3,3´,4,4´,5 3,3´,4,4´,5,5´ 2,3,3´,4,4´ 2,3,4,4´,5 2,3´,4,4´,5 2´,3,4,4´,5 2,3,3´,4,4´,5 2,3,3´,4,4´,5´ 2,3´,4,4´,5,5´ 2,3,3´,4,4´,5,5´ Compound 2,4,4' 2,2',5,5' 2,2',4,5,5' 2,2',3,4,4',5' 2,2',4,4',5,5'´ 2,2',3,4,4',5,5' -Tri-PCB -Tetra-PCB -Penta-PCB -Hexa-PCB -Hexa-PCB -Hepta-PCB -Tetra-CB -Tetra-CB -Penta-CB -Hexa-CB -Penta-CB -Penta-CB -Penta-CB -Penta-CB -Hexa-CB -Hexa-CB -Hexa-CB -Hepta-CB Nonortho PCBs IUPAC Code PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 IUPAC Code PCB-28 PCB-52 PCB-101 PCB 138 PCB 153 PCB 180
Marker PCBs
Mono-ortho PCBs
11
Dioxin and PCBs in pelagic fish stocks
5 Results
The results of these analyses are summarised in table 5 (capelin), table 6 (blue whiting), table 7 (Iceland herring) and table 8 (Atlanto-Scandian herring). All results are presented as upperbound1 values on a lipid basis in order to make it easier to compare raw material with the fishmeal and oil produced. In these tables the notation N/A means “not available”. For fishmeal and fish oil, the results are also expressed on a sample basis related to a feedingstuff with 12% moisture. This is presented in table 9 (capelin), table 10 (blue whiting), table 11 (Iceland herring) and table 12 (Atlanto-Scandian herring). This method of presentation is based on the requirement as stated in the EU Directive 2001/102/EC (1). On this basis, the Directive specifies that the maximum permissible limits are as follows: Fishmeal Fish oil 1,25 ng WHO-TEQ per kg fishmeal 6,00 ng WHO-TEQ per kg fish oil
The results in these three tables are presented as upperbound, lowerbound2 and mediumbound3 values as required by the EU Directive 2002/70/EC (9) dated 26.July 2002. The congener results in full can be found in appendix 1 on pages 39 - 50. The TEQ figures are expressed as upperbound values and the results in brackets indicate the limit of detection when the congener could not be detected. These tables in appendix 1 also include the results for the 7 marker PCBs that are used as a possible predictive tool in multivariate analysis reported in appendix 3. The summary of the results of the age division in the two separate landings of blue whiting, are presented in table 13. The details of the congener analyses for these two samples are presented separately in appendix 2 on page 51 – 52.
Upperbound values are calculated by using the limit of quantification for the contribution of each non-quantified congener to the TEQ. 2 Lowerbound values are calculated by using zero for the contribution of each non quantified congener to the TEQ. 3 Mediumbound values are calculated by using half of the limit of quantification for the contribution of each non-quantified congener to the TEQ.
1
12
Dioxin and PCBs in pelagic fish stocks
Figure 3: catches.
A map of the NE Atlantic showing the approximate position of the
The numbers refer to the sample numbers as described in the sample handling, and as used in the following tables.
13
Dioxin and PCBs in pelagic fish stocks
Table 5: Capelin. Summary of dioxin and WHO-PCB expressed on a lipid basis. Upperbound values. Catch location Average age (yrs) Sample type Catch date Fish Fat %
Non ortho PCB mono ortho PCB WHO-PCB
Code
Dioxin
ng WHO-TEQ/kg lipid
1,5 1,9 1,5 1,8 1,8 1,8 2,0 1,9 2,0 2,9 3,0 2,9 3,0 2,8 3,1 4,3 3,9 5,0 2,2 2,5 2,5 1,1 1,5 1,3 1,0 1,5 0,9 1,1 1,3 1,1 1,5 2,5 2,0 2,3 3,0 2,2 2,7 2,3 2,5 3,0 4,5 3,6 3,9 4,9 4,2 4,6 6,0 4,6 6,7 2,7 2,8 3,2 1,4 1,6 1,8 1,5 1,3 1,3 1,3 1,3 1,5 1,9 0,6 0,5 0,6 0,7 0,6 0,7 0,6 0,6 0,8 1,0 0,9 0,9 1,1 0,9 1,3 1,5 1,2 1,6 0,5 0,7 0,8 0,4 0,4 0,4 0,4 0,3 0,3 0,3 0,3 0,4 0,8 3,1 2,5 2,9 3,6 2,8 3,5 2,8 3,1 3,8 5,5 4,5 4,8 6,1 5,1 5,9 7,5 5,8 8,3 3,2 3,4 4,0 1,8 2,0 2,2 2,0 1,6 1,6 1,6 1,6 1,9 2,7
RM/IS-1 FM/IS-1 FO/IS-1 RM/IS-2 FM/IS-2 FO/IS-2 RM/IS-3 FM/IS-3 FO/IS-3 RM/IS-4 FM/IS-4 FO/IS-4 RM/IS-5 FM/IS-5 FO/IS-5 RM/IS-6 FM/IS-6 FO/IS-6 RM/IS-9 FM/IS-9 FO/IS-9 RM/IS-10 FM/IS-10 FO/IS-10 RM/IS-21 FM/IS-21 FO/IS-21 RM/IS-11 FM/IS-11 FO/IS-11 RM/IS-25 N/A N/A RM/IS-26 N/A N/A RM/IS-17 FM/IS-17 FO/IS-17 RM/IS-27 FM/IS-27 FO/IS-27 RM/IS-18 FM/IS-18 FO/IS-18
Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish
3,2
16,0
10-Jan-01
64°50'N 11°26'W
3,1
13,9
26-Jan-01
64°30'N 11°30'W
3,1
12,7
05-Feb-01
65°30'N 25°30'W
3,1
8,8
27-Feb-01
64°21'N 22°52'W
3,2
9,0
05-Mar-01
63°47'N 22°40'W
3,2
6,8
22-Mar-01
63°15'N 20°30'W
2,0
10,2
04-Jul-01
66°20'N 24°15'W
2,0
12,5
11-Jul-01
66°45'N 22°30'W
2,0
16,7
23-Jul-02
68°20'N 19°30'W
2,0
14,2
24-Jul-01
68°20'N 18°40'W
2,1
13,3
03-Dec-02
67°15'N 16°40'W
Fish
2,1
13,7
09-Dec-02
67°20'N 16°21'W
1,4
1,9
0,6
2,5
Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil
2,6
14,3
10-Dec-01
67°20'N 17°30'W
2,1
15,0
10-Dec-02
67°15'N 16°30'W
2,6
12,7
17-Dec-01
67°20'N 13°30'W
1,7 1,8 1,7 1,3 1,5 1,5 1,8 1,9 1,9
2,0 1,9 2,2 1,7 2,1 2,1 2,1 2,0 2,0
0,6 0,5 0,7 0,6 0,6 0,6 0,7 0,6 0,7
2,6 2,4 2,9 2,3 2,8 2,7 2,8 2,6 2,7
14
Dioxin and PCBs in pelagic fish stocks
Table 6: Blue Whiting. Summary of dioxin and WHO-PCB expressed on a lipid basis. Upperbound values. Catch location Average age (yrs) Sample type Catch date Fish Fat %
Non ortho PCB mono ortho PCB WHO-PCB
Code
Dioxin
ng WHO-TEQ/kg lipid
6,1 4,1 4,5 14,0 10,8 10,5 15,5 13,3 13,8 25,8 27,5 33,7 57,3 58,2 66,8 27,8 47,7 30,1 5,7 5,2 9,0 3,6 2,7 2,0 2,2 2,0 1,9 5,4 6,0 4,7 5,7 5,2 4,6 3,1 4,0 5,1 4,2 3,9 6,8 5,5 7,6 12,7 13,1 14,3 11,1 11,8 9,5 2,2 2,9 3,0 1,4 1,1 0,9 0,8 0,9 0,9 1,9 2,0 2,0 2,1 1,9 18,6 13,9 14,5 20,6 17,5 17,7 32,6 32,9 41,3 70,0 71,3 81,1 38,9 59,5 39,6 7,9 8,1 12,0 5,0 3,8 2,9 3,0 2,9 2,7 7,2 8,0 6,7 7,8 7,1
RM/FO-1 FM/FO-1 FO/FO-1 RM/FO-2 FM/FO-2 FO/FO-2 RM/FO-3 FM/FO-3 FO/FO-3 RM/FO-4 FM/FO-4 FO/FO-4 RM/FO-5 FM/FO-5 FO/FO-5 RM/FO-6 FM/FO-6 FO/FO-6 RM/FO-7 FM/FO-7 FO/FO-7 RM/FO-8 FM/FO-8 FO/FO-8 RM/IS-13 FM/IS-13 FO/IS-13 RM/IS-14 FM/IS-14 N/A
Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal
3,8
4,7
10-Feb-01
53°48'N 14°25'W
N/A
3,9
24-Feb-01
53°00'N 15°15'W
6,7 5,0 5,1
3,5
2,9
18-Mar-01
55°20'N 12°40'W
9,9 6,3 9,3
3,6
1,5
18-Apr-01
60°40'N 7°10'W
20,4 16,2 15,8
3,6
1,4
05-May-01
60°05'N 6°05'W
13,2 16,5 10,0
3,4
6,0
20-Aug-01
63°17'N 11°54'W
4,0 3,1 3,0
2,2
7,1
06-Sep-01
62°25'N 9°00'W
2,2 2,1 1,1
1,7
7,6
15-Sep-01
60°10'N 8°10'W
1,7 1,6 1,0
3,8
8,2
14-Nov-01
63°10'N 10°00'W
2,1 2,7 2,2
4,1
9,7
15-Nov-01
63°10'N 10°00'W
2,2 2,0
15
Dioxin and PCBs in pelagic fish stocks
Table 7: Iceland Herring. Summary of dioxin and WHO-PCB expressed on a lipid basis. Upperbound values.
Catch location
Average age (yrs)
Sample type
Catch date
Fish Fat %
Dioxin
Non ortho PCB
mono ortho PCB WHO-PCB
RM/IS-22 FM/IS-22 FO/IS-22 RM/IS-23 FM/IS-23 FO/IS-23 RM/IS-15 N/A N/A RM/IS-16 N/A N/A RM/IS-24 FM/IS-24 FO/IS-24 RM/IS-28 N/A N/A RM/IS-29 N/A N/A
Code
ng WHO-TEQ/kg lipid
2,0 2,4 1,7 2,7 2,4 2,5 2,4 2,5 2,1 3,1 1,7 1,2 1,4 1,4 1,3 1,1 1,6 4,4 3,6 3,9 3,8 3,8 3,2 4,7
Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish
7,2
19,1
28-Oct-02
65°55'N 26°30'W
5,5
16,8
16-Nov-02
65°20'N 27°30'W
1,8 2,5 1,5
5,1
13,0
26-Nov-01
65°30'N 27°00'W
2,4
Fish
3,2
16,7
28-Nov-01
65°30'N 27°00'W
1,2
1,4
0,7
2,1
Fish Fishmeal Fish oil Fish
8,2
16,5
02-Dec-02
66°05'N 25°25'W
2,9 3,0 1,9
3,5 2,9 2,8 5,1
2,8 1,7 1,6 3,3
6,3 4,6 4,4 8,4
9,3
15,9
04-Dec-02
66°15'N 13°30'W
3,9
Fish
7,8
17,4
09-Dec-02
66°15'N 13°30'W
3,5
4,9
3,0
7,9
16
Dioxin and PCBs in pelagic fish stocks
Table 8: Atlanto-Scandian Herring. Summary of dioxin and WHO-PCB expressed on a lipid basis. Upperbound values.
Catch location
Average age (yrs)
Sample type
Catch date
Fish Fat %
Dioxin
Non ortho PCB
mono ortho PCB WHO-PCB
RM/IS-19 FM/IS-19 FO/IS-19 RM/IS-7 FM/IS-7 FO/IS-7 RM/IS-20 FM/IS-20 FO/IS-20 RM/IS-8 FM/IS-8 FO/IS-8 RM/IS-12 N/A N/A
Code
ng WHO-TEQ/kg lipid
5,7 5,4 5,0 6,0 5,6 5,8 11,4 11,4 12,8 5,9 6,1 5,9 7,2 7,2 6,8 3,6 2,2 2,4 2,5 4,9 4,6 4,8 2,1 2,4 2,4 2,6 2,7 2,4 1,1 8,3 8,0 8,3 16,4 16,0 17,6 8,0 8,5 8,2 9,8 9,9 9,2 4,6
Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish Fishmeal Fish oil Fish
10,2
15,6
26-May-02
70°20'N 4°30'W
9,3
8,1
28-May-01
71°50'N 00°50'E
11,9 11,7 11,7
9,9
14,9
07-Jun-02
72°56'N 6°42'W
5,3 5,8 5,0
8,6
12,7
15-Jun-01
73°11'N 6°51'W
7,1 6,9 5,4
5,4
20,0
10-Sep-01
69°00'N 11°30'W
2,9
17
Dioxin and PCBs in pelagic fish stocks
Table 9: Capelin. Summary of dioxin and WHO-PCB expressed on a sample basis assuming 12% moisture. Upperbound, medium bound and lowerbound values.
Average age (yrs)
Catch location
ng WHO-TEQ/kg sample (basis of 12% moisture)
Sample type
Catch date
Fish Fat %
Code
Dioxin
WHO--PCB
Dioxin
WHO-PCB
Dioxin
WHO-PCB
Upperbound
0,27 2,59 0,30 3,06 0,35 3,37 0,47 4,23 0,53 5,23 0,60 7,29 0,34 3,54 0,24 1,93 0,18 1,45 0,19 1,67 0,27 2,51 0,30 2,40 0,31 2,35
Lowerbound
0,16 1,26 0,14 1,57 0,21 1,77 0,30 2,48 0,27 2,74 0,40 4,42 0,24 2,20 0,12 1,11 0,16 0,76 0,09 0,95 0,16 1,46 0,14 1,28 0,22 1,65 0,27 2,59 0,30 3,06 0,35 3,37 0,47 4,23 0,53 5,23 0,60 7,29 0,34 3,54 0,24 1,93 0,03 1,45 0,19 1,67 0,27 2,51 0,30 2,40 0,31 2,35
Mediumbound
0,19 1,28 0,17 1,60 0,22 1,79 0,31 2,52 0,28 2,75 0,40 4,42 0,25 2,21 0,15 1,12 0,17 0,80 0,13 0,96 0,18 1,46 0,15 1,29 0,23 1,66 0,27 2,59 0,30 3,06 0,35 3,37 0,47 4,23 0,53 5,23 0,60 7,29 0,34 3,54 0,24 1,93 0,11 1,45 0,19 1,67 0,27 2,51 0,30 2,40 0,31 2,35
FM/IS-1 Fishmeal FO/IS-1 FO/IS-2 FO/IS-3 FO/IS-4 FO/IS-5 FO/IS-6 FO/IS-9 Fish oil FM/IS-2 Fishmeal Fish oil FM/IS-3 Fishmeal Fish oil FM/IS-4 Fishmeal Fish oil FM/IS-5 Fishmeal Fish oil FM/IS-6 Fishmeal Fish oil FM/IS-9 Fishmeal Fish oil FM/IS-10 Fishmeal FO/IS-10 Fish oil FM/IS-21 Fishmeal FO/IS-21 Fish oil FM/IS-11 Fishmeal FO/IS-11 Fish oil FM/IS-17 Fishmeal FO/IS-17 Fish oil FM/IS-27 Fishmeal FO/IS-27 Fish oil FM/IS-18 Fishmeal FO/IS-18 Fish oil
3,2 3,1 3,1 3,1 3,2 3,2 2,0 2,0 2,0 2,0 2,6 2,1 2,6
0,21 1,30 13,9 26-Jan-01 64°30'N 11°30'W 0,20 1,62 12,7 05-Feb-01 65°30'N 25°30'W 0,22 1,80
16,0 10-Jan-01 64°50'N 11°26'W 8,8 9,0 6,8 10,2 12,5 16,7 14,2
0,31 2,56 05-Mar-01 63°47'N 22°40'W 0,29 2,76
27-Feb-01 64°21'N 22°52'W 22-Mar-01 63°15'N 20°30'W
0,40 4,42 04-Jul-01 66°20'N 24°15'W 0,25 2,22 11-Jul-01 66°45'N 22°30'W 0,18 1,13 23-Jul-02 68°20'N 19°30'W 0,17 0,83
24-Jul-01 68°20'N 18°40'W
0,16 0,97 14,3 10-Dec-01 67°20'N 17°30'W 0,20 1,46 15,0 10-Dec-02 67°15'N 16°30'W 0,16 1,30 12,7 17-Dec-01 67°20'N 13°30'W 0,23 1,67
18
Dioxin and PCBs in pelagic fish stocks
Table 10: Blue Whiting. Summary of dioxin and WHO-PCB expressed on a sample basis assuming 12% moisture. Upperbound, medium bound and lowerbound values.
Average age (yrs)
Catch location
ng WHO-TEQ/kg sample (basis of 12% moisture)
Sample type
Catch date
Fish Fat %
Code
Dioxin
WHO-PCB
Dioxin
WHO-PCB
Dioxin
WHO-PCB
Upperbound
0,22 3,95 0,37 4,53 0,36 8,18 0,82 0,75 12,74 1,28 15,62 1,85 36,34 3,60 71,38 2,60 34,84 0,71 10,52 0,25 2,55 0,22 2,40 0,67 5,89 0,88
Lowerbound
0,22 3,93 0,36 4,50 0,35 8,16 0,81 13,89 0,71 8,77 0,23 2,60 0,05 0,92 0,06 0,85 0,18 1,93 0,24 0,75 12,74 1,28 15,62 1,85 36,34 3,60 71,38 2,60 34,84 0,71 10,52 0,25 2,55 0,22 2,40 0,67 5,89 0,88
Mediumbound
0,22 3,94 0,37 4,52 0,36 8,17 0,82 13,90 0,72 8,77 0,25 2,60 0,09 0,95 0,09 0,88 0,20 1,93 0,25 0,75 12,74 1,28 15,62 1,85 36,34 3,60 71,38 2,60 34,84 0,71 10,52 0,25 2,55 0,22 2,40 0,67 5,89 0,88
FM/FO-1 Fishmeal FO/FO-1 Fish oil FM/FO-2 Fishmeal FO/FO-2 Fish oil FM/FO-3 Fishmeal FO/FO-3 Fish oil FM/FO-4 Fishmeal FO/FO-4 Fish oil FM/FO-5 Fishmeal FO/FO-5 Fish oil FM/FO-6 Fishmeal FO/FO-6 Fish oil FM/FO-7 Fishmeal FO/FO-7 Fish oil FM/FO-8 Fishmeal FO/FO-8 Fish oil FM/IS-13 Fishmeal FO/IS-13 Fish oil FM/IS-14 Fishmeal N/A
3,8 N/A 3,5 3,6 3,6 3,4 2,2 1,7 3,8 4,1
4,7 3,9 2,9 1,5 1,4 6,0 7,1 7,6 8,2 9,7
10-Feb-01 53°48'N 14°25'W 24-Feb-01 53°00'N 15°15'W 18-Mar-01 55°20'N 12°40'W 18-Apr-01 60°40'N 7°10'W
13,91 0,72 05-May-01 60°05'N 6°05'W 8,77 20-Aug-01 63°17'N 11°54'W 0,27 2,60 0,13 06-Sep-01 62°25'N 9°00'W 0,97
15-Sep-01 60°10'N 8°10'W 14-Nov-01 63°10'N 10°00'W 15-Nov-01 63°10'N 10°00'W
0,12 0,90 0,22 1,93 0,25
19
Dioxin and PCBs in pelagic fish stocks
Table 11: Iceland Herring. Summary of dioxin and WHO-PCB expressed on a sample basis assuming 12% moisture. Upperbound, medium bound and lowerbound values.
Average age (yrs)
Catch location
ng WHO-TEQ/kg sample (basis of 12% moisture)
Sample type
Catch date
Fish Fat %
Code
Dioxin
WHO-PCB
Dioxin
WHO-PCB
Dioxin
WHO-PCB
Upperbound
0,22 1,52 0,21 1,29 0,30 1,65 0,33 3,42 0,31 2,78 0,47 3,89
Lowerbound
0,21 1,38 0,20 1,28 0,29 1,63 0,33 3,42 0,31 2,78 0,47 3,89
Mediumbound
0,22 1,45 0,21 1,28 0,30 1,64 0,33 3,42 0,31 2,78 0,47 3,89
FM/IS-22 Fishmeal FO/IS-22 Fish oil FM/IS-23 Fishmeal FO/IS-23 Fish oil FM/IS-24 Fishmeal FO/IS-24 Fish oil
7,2 5,5 8,2
19,1 16,8 16,5
28-Oct-02 65°55'N 26°30'W 16-Nov-02 65°20'N 27°30'W 02-Dec-02 66°05'N 25°25'W
Table 12: Atlanto-Scandian Herring. Summary of dioxin and WHO-PCB expressed on a sample basis assuming 12% moisture. Upperbound, medium bound and lowerbound values.
Average age (yrs)
Catch location
ng WHO-TEQ/kg sample (basis of 12% moisture)
Sample type
Catch date
Fish Fat %
Code
Dioxin
WHO-PCB
Dioxin
WHO-PCB
Dioxin
WHO-PCB
Upperbound
0,45 4,44 0,81 10,26 0,45 4,43 0,56 4,74 0,67 7,29 1,11 15,47 0,65 7,25 0,80 8,12
Lowerbound
0,44 4,40 0,81 10,26 0,44 4,42 0,55 4,73 0,67 7,29 1,11 15,47 0,65 7,25 0,80 8,12
Mediumbound
0,45 4,42 0,81 10,26 0,45 4,43 0,57 4,74 0,67 7,29 1,11 15,47 0,65 7,25 0,80 8,12
FM/IS-19 Fishmeal FO/IS-19 Fish oil FM/IS-7 Fishmeal FO/IS-7 Fish oil FM/IS-20 Fishmeal FO/IS-20 Fish oil FM/IS-8 Fishmeal FO/IS-8 Fish oil
10,2 9,3 9,9 8,6
15,6 26-May-02 70°20'N 4°30'W 8,1 14,9 12,7 28-May-01 71°50'N 00°50'E 07-Jun-02 72°56'N 6°42'W 15-Jun-01 73°11'N 6°51'W
20
Dioxin and PCBs in pelagic fish stocks
Table 13: Two sets of age division. Summary of dioxin and WHO-PCB expressed on a lipid basis. Upperbound values.
Average age (yrs)
Fish Length (cm)
Sex ratio (M:F)
Fish weight (g)
Catch location
Catch date
Fish Fat %
Code
Dioxin
Non ortho mono ortho PCB PCB WHO-PCB
ng WHO-TEQ/kg lipid
RM-A/FO-3 RM-B/FO-3 RM-C/FO-3 RM-A/FO-7 RM-B/FO-7 RM-C/FO-7
2,1 4,2 5,7 0,5 1,5 2,2
4,3 18-Mar-01 55°20'N 12°40'W 1 : 0.19 3,1 2,5 8,8 06-Sep-01 62°25'N 9°00'W 8,5 6,6 1 : 0.47 1 : 2.60 1 : 1.78 1 : 1.27 1 : 1.78
22,8 27,1 32,5 17,8 23,0 26,1
52,6 93,8 159,8 33,6 73,3 95,8
5,0 10,1 20,0 1,5 2,0 3,0
11,9 26,5 72,2 2,1 3,7 5,6
3,0 6,1 18,7 0,7 1,3 2,0
14,9 32,5 90,8 2,8 5,0 7,6
21
Dioxin and PCBs in pelagic fish stocks
It is not the intention of this report to analyse all of these results statistically. A multivariate analysis was made, however, to find the best regressions within the available data. This work was done by Gudny Vang (p/f Havsbrún, Faroe Islands) and is presented in Appendix 3 on pages 53 - 57 The main purpose of the project was to collect data systematically in order to provide a solid base for future discussion on the subject of dioxin and PCBs in the fishmeal and fish oil produced from the four fish stocks under examination. The Steering Group would, however, like to draw the reader’s attention to the following trends and supports its observations by the use of graphs and histograms.
5.1 Capelin
During the past 30 years, capelin has been the most important pelagic stock fished in the area of the NE Atlantic, and has been utilised for fishmeal and fish oil production. The stock lives in the waters off the north of Iceland as far as Jan Mayen and to the East Greenland coast. Capelin becomes sexually mature at about one year of age and usually spawns at the end of their third year. The fish die after the spawning has taken place in March or April (10). The average annual capelin landings in Iceland and the Faroes amounted to a total of 1.075.000 tonnes during the past 3 years (2000 – 2002). Capelin has comprised about 64% of the catch landed for meal and oil production in these two countries, and has provided approximately 60% of fishmeal and 67% of fish oil produced there. Figure 4: Concentration of dioxin in all capelin samples, expressed on a lipid basis, together with the variation in fat level in the raw fish samples.
6 5
A
18 16 14
B
Dioxin ng WHO-TEQ / kg lipid
4 3 2 1 0
12 10 8 6 4 2 0
Fish fat %
Fat content and roe content are closely related to the capelin’s lifecycle. The fat content starts to increase during the third year of the lifespan usually reaching a
10 .01 .01 26 .01 .01 05 .02 .01 27 .02 .01 05 .03 .01 22 .03 .01 04 .07 .01 11 .07 .01 23 .07 .02 24 .07 .01 03 .12 .02 09 .12 .02 10 .12 .01 10 .12 .02 17 .12 .01
Raw material
Fish meal
Fish oil
Fish fat %
22
Dioxin and PCBs in pelagic fish stocks
maximum of 15 – 16% fat in October / November (section marked “B” on figures 4 and 5). During the following 3 months, the reproductive organs increase rapidly in size and the fish cease feeding. Therefore the body fat content drops rapidly during the period from late December until spawning takes place in March or early April when the fat level has dropped to 3% (section marked “A” on figures 4 and 5). On average during the past 3 years, 80% of the capelin has been fished during the months January to March. At that time of year the 3-year-old spawning fish is separated from the younger fish and the catches are therefore almost entirely comprised of 3-year-old fish. Since dioxin and PCBs are lipophilic and persistant, then when the fat level of the fish decreases rapidly as it does in the capelin during the last months of its life, it can be expected that dioxin and PCBs would become more concentrated in the lipid phase. This is reflected in the capelin results for January, February and March when the concentration of these compounds shows a steady increase in the lipid phase (Figure 4 dioxin and figure 5 WHO-PCB). Figure 5: Concentration of WHO-PCBs in all capelin samples, expressed on a lipid basis, together with the variation in fat level in the raw fish samples.
9 8 7 6 5 4 3 2 1 0 18 16 14 12 10 8 6 4 2 0
WHO-PCB ng WHO-TEQ / kg lipid
A B
10 .01 . 26 01 .01 . 05 01 .02 . 27 01 .02 . 05 01 .03 . 22 01 .03 .01
Raw material
During the summer capelin season in July, the 2-year-old fish is feeding and gradually becoming fatter. The fat level in July is normally about 11% and increases to about 16% in November as mentioned earlier. This means that dioxin and WHO-PCB levels in July are even lower than those in the winter-capelin (figures 4 and 5). On average, the level of WHO-PCB in the lipid phase of capelin is 70% higher than the dioxin level. The results for the dioxin concentration in fishmeal and fish oil were also expressed on a sample basis assuming 12% moisture content. In figure 6 these results are
04 .07 . 11 01 .07 . 23 01 .07 . 24 02 .07 . 03 01 .12 . 09 02 .12 . 10 02 .12 . 10 01 .12 . 17 02 .12 .01
Fish meal
Fish oil
Fish fat %
23
Fish fat %
Dioxin and PCBs in pelagic fish stocks
compared to the maximum permissible levels for dioxin in fishmeal and fish oil as stated in the EU Directive. Figure 6: Concentration of dioxin in all capelin-meal and -oil samples, expressed on a sample basis assuming 12% moisture.
7 Dioxin ng WHO-TEQ / kg sample 6 5 4 3 2 1 0 10.01.01 26.01.01 05.02.01 27.02.01 05.03.01 22.03.01 04.07.01 11.07.01 23.07.02 24.07.01 03.12.02 09.12.02 10.12.01
Fish meal
Fish oil
Limit fish meal
Limit fish oil
5.2 Blue Whiting
Blue whiting is a migratory stock living in the Atlantic waters from Portugal and north to the Barents Sea. It consists of several stocks but is treated by ICES as one stock since it has not been possible to define clear divisions between populations. It has been fished by EU, Norway and Russia as well as Iceland and the Faroes (11). The average annual blue whiting landings in Iceland and the Faroes amounted to a total of 474.000 tonnes during the past 3 years (2000 – 2002). Blue whiting has comprised about 28% of the catch landed for meal and oil production in these two countries, and has provided approximately 30% of fishmeal and 16% of fish oil production. Blue whiting spawn mostly in an area to the west of Scotland and Ireland in March – April, although there are other spawning areas off Portugal, the Faroe Islands, SW Iceland and in the Norwegian fjords. The fish can reach sexual maturity between 2-7 years old and can live for up to 20 years (10). This fish stores most of its fat reserves in the liver. The fat level of whole fish can vary from 1% in April / May directly after spawning, up to 8% during the winter months. It would seem that dioxin and WHO-PCB levels in the lipid phase vary inversely with the fat level in the fish (figure 7 dioxin and figure 8 WHO-PCB).
24
Dioxin and PCBs in pelagic fish stocks
Figure 7: Concentration of dioxin in all blue whiting samples, expressed on a lipid basis, together with the variation in fat level in the raw fish samples.
25,0 20,0
ng WHO-TEQ / kg lipid
12 10 8 6
Fish fat %
15,0 10,0 5,0 0,0
10.02.01 24.02.01 18.03.01 18.04.01 05.05.01 20.08.01 06.09.01 15.09.01 14.11.01 15.11.01
Dioxin
4 2 0
Raw material
Fish meal
Fish oil
Fish fat %
Figure 8: Concentration of WHO-PCBs in all blue whiting samples, expressed on a lipid basis, together with the variation in fat level in the raw fish samples.
90 80 70
WHO-PCB ng WHO-TEQ / kg lipid
12 10 8 6 4 2 0
10.02.01 24.02.01 18.03.01 18.04.01 05.05.01 20.08.01 06.09.01 15.09.01 14.11.01 15.11.01
60 50 40 30 20 10 0
Raw material
Fish meal
Fish oil
Fish fat %
Levels of these compounds in the whole fish fat is highest in April / May and lowest from September to November.
25
Fish fat %
Dioxin and PCBs in pelagic fish stocks
On average, the level of WHO-PCB in the lipid phase of blue whiting is 265% higher than the dioxin level. The results for the dioxin concentration in fishmeal and fish oil were also expressed on a sample basis assuming 12% moisture content. In figure 9 these results are compared to the maximum permissible levels for dioxin in fishmeal and fish oil as stated in the EU Directive. Figure 9: Concentration of dioxin in all blue whiting-meal and -oil samples, expressed on a sample basis assuming 12% moisture.
16 Dioxin ng WHO-TEQ / kg sample 14 12 10 8 6 4 2 0
10.02.01
24.02.01
18.03.01
18.04.01
05.05.01
20.08.01
06.09.01
15.09.01
14.11.01
15.11.01
Fish meal
Fish oil
Limit fish meal
Limit fish oil
5.3 Iceland Herring
The Icelandic spring spawning herring lives in coastal waters around Iceland and has been utilised since the mid 1970’s. The stock spawns in July off the SW and SE of Iceland and then migrates in search of feeding grounds off the west and east coasts. This herring stock becomes sexually mature at about 4 years of age and can live for 20 – 25 years (10). The catch is seasonal, mostly taking place in October to January off the east, south and west coasts of Iceland. The average annual landings of Icelandic herring in Iceland, which were used for fishmeal and fish oil production, amounted to a total of 40.000 tonnes during the past 3 years (2000 – 2002). Icelandic herring has comprised about 3% of the catch landed for meal and oil production, and has provided approximately 3% of fishmeal and 6% of fish oil production. These figures can be variable depending on the proportion of the total catch that is processed for human consumption. The average age of the catches in this study ranged from 3 to 9 years, which can be considered quite normal for this stock. The fat content of whole fish during the fishing season (September – January) is fairly stable at about 16% and does therefore not
26
Dioxin and PCBs in pelagic fish stocks
have an influence on dioxin and WHO-PCB levels. (figure 10 dioxin and figure 11 WHO-PCB). Figure 10: Concentration of dioxin in all Iceland herring samples, expressed on a lipid basis, together with the variation in fat level in the raw fish samples.
6 5
Dioxin ng WHO-TEQ / kg lipid
20 18 16 14
Fish fat %
4 3 2 1 0 28.10.02 16.11.02 26.11.01 28.11.01 02.12.02 04.12.02 09.12.02
12 10 8 6 4 2 0
Raw material
Fish meal
Fish oil
Fish fat %
Figure 11: Concentration of WHO PCBs in all Iceland herring samples, expressed on a lipid basis, together with the variation in fat level in the raw fish samples.
9 8 WHO-PCB ng WHO-TEQ / kg lipid 7 6 5 4 3 2 1 0
20 18 16 14 10 8 6 4 2 0 Fish fat % 12
28.10.02
16.11.02
26.11.01
28.11.01
02.12.02
04.12.02
09.12.02
Raw material
Fish meal
Fish oil
Fish fat %
27
Dioxin and PCBs in pelagic fish stocks
On average, the level of WHO-PCB in the lipid phase of Icelandic herring is 100% higher than the dioxin level. The results for the dioxin concentration in fishmeal and fish oil were also expressed on a sample basis assuming 12% moisture content. In figure 12 these results are compared to the maximum permissible levels for dioxin in fishmeal and fish oil as stated in the EU Directive. Figure 12: Concentration of dioxin in all Iceland herring-meal and -oil samples, expressed on a sample basis assuming 12% moisture.
7 Dioxin ng WHO-TEQ / kg sample 6 5 4 3 2 1 0
28.10.02
16.11.02
02.12.02
Fish meal
Fish oil
Limit fish meal
Limit fish oil
5.4 Atlanto-Scandian Herring
The Atlanto-Scandian herring stock (spring spawning herring) is found in the open seas of the northeast Atlantic. This stock spawns in February to April off western Norway, and the immature fish stay in Norwegian waters while the adult fish migrate in search of feed further out into the northeast Atlantic. (10) The average annual landings of Atlanto-Scandian herring in Iceland that were used for fishmeal and fish oil production, amounted to a total of 100.000 tonnes during the past 3 years (2000 – 2002). Atlanto-Scandian herring has comprised about 6% of the catch landed for meal and oil production, and has provided approximately 7% of fishmeal and 12% of fish oil production. These figures can be variable depending on the proportion of the total catch that is processed for human consumption. Fat content of whole fish during the months of fishing (May – September) can be very variable depending on the proportions of immature fish (high in fat) and newly spawned fish (low in fat) in the catch. Dioxin and WHO-PCB levels in the lipid phase are therefore quite variable, both because of the effect of fat level and also the effect of age. (figure 13, dioxin and figure 14, WHO-PCB).
28
Dioxin and PCBs in pelagic fish stocks
Figure 13: Concentration of dioxin in all Atlanto-Scandian herring samples, expressed on a lipid basis, together with the variation in fat level in the raw fish samples.
14 12
Dioxin ng WHO-TEQ / kg lipid
25 20
10
Fish fat %
8 6 4 2 0
15 10
5 0
26.05.02
28.05.01 Raw material
07.06.02 Fish meal
15.06.01 Fish oil Fish fat %
10.09.01
Figure 14: Concentration of WHO PCBs in all Atlanto-Scandian herring samples, expressed on a lipid basis, together with the variation in fat level in the raw fish samples.
20 18 WHO-PCB ng WHO-TEQ/kg lipid 16 14 10 8 6 4 2 0 26.05.02 28.05.01 Raw material 07.06.02 Fish meal 15.06.01 Fish oil 10.09.01 Fish fat % 0 5 10 Fish fat % 12 15 20 25
On average, the level of WHO-PCB in the lipid phase of Atlanto-Scandian herring is 50% higher than the dioxin level. The results for the dioxin concentration in fishmeal and fish oil were also expressed on a sample basis assuming 12% moisture content. In figure 15 these results are 29
Dioxin and PCBs in pelagic fish stocks
compared to the maximum permissible levels for dioxin in fishmeal and fish oil as stated in the EU Directive. Figure 15: Concentration of dioxin in all Atlanto-Scandian herring-meal and -oil samples, expressed on a sample basis assuming 12% moisture.
12
Dioxin ng WHO-TEQ / kg sample
10 8 6 4 2 0
26.05.02
28.05.01
07.06.02
15.06.01
Fish meal
Fish oil
Limit fish meal
Limit fish oil
30
Dioxin and PCBs in pelagic fish stocks
5.5 Age division of Blue Whiting
Fish samples from two of the landings of blue whiting in the Faroe Islands, were separated according to size. Despite the fact that the fish fat levels and sex ratios were very different in these six samples, it is nevertheless apparent that the levels of dioxin and WHO-PCB increase with age (figure 16 dioxin and figure 17 WHO-PCB). Figure 16: Regression of dioxin concentration in the lipid against fish age.
25,0
20,0
Dioxin ng WHO-TEQ / kg lipid
15,0
R2 = 0,9162
10,0
5,0
0,0 0 1 2 3 4 5 6
Age (yrs)
Figure 17: Regression of WHO-PCB concentration in the lipid against fish age
100 90 80
WHO-PCB ng WHO-TEQ / kg lipid
70 60 50 40 30 20 10 0 0 1 2 3
R2 = 0,852
4
5
6
Age (yrs)
31
Dioxin and PCBs in pelagic fish stocks
Fish length (figure 18, dioxin and figure 19, WHO-PCB) and fish weight (figure 20, dioxin and figure 21, WHO-PCB) are not as well correlated with the levels of these compounds. Figure 18: Regression of dioxin concentration in the lipid, against fish length.
25,0
20,0
Dioxin ng WHO-TEQ / kg lipid
R2 = 0,7586
15,0
10,0
5,0
0,0 10 15 20 25 30 35
Fish Length (cm)
Figure 19: Regression of WHO-PCB concentration in the lipid, against fish length
100 90 80
WHO-PCB ng WHO-TEQ / kg lipid
70 60 50 40 30 20 10 0
R2 = 0,73
10
15
20
25
30
35
Fish Length (cm)
32
Dioxin and PCBs in pelagic fish stocks
Figure 20: Regression of dioxin concentration in the lipid, against fish weight
25,0
20,0
Dioxin ng WHO-TEQ / kg lipid
R = 0,7603
15,0
2
10,0
5,0
0,0 10 30 50 70 90 110 130 150 170
Fish Weight (g)
Figure 21: Regression of WHO-PCB concentration in the lipid, against fish weight.
100 90 80
WHO-PCB ng WHO-TEQ / kg lipid
70 60 50 40 30 20 10 0 10 30 50 70 90
R2 = 0,774
110
130
150
170
Fish Weight (g)
33
Dioxin and PCBs in pelagic fish stocks
5.6 Ratio of WHO-PCB : dioxin
The following table shows the average levels of dioxin and of WHO-PCB for the 4 fish stocks in this investigation. All types of samples were included. The upperbound results in the lipid phase were used for this comparison as reported in tables 5, 6, 7 and 8. Table 14: Comparison of average levels of dioxin and WHO-PCB
Dioxin WHO-PCB
Capelin Blue Whiting Iceland Herring Atlanto-Scandian Herring
Ratio PCB / Number of dioxins samples ng WHO-TEQ /kg lipid 2,0 3,4 1,7 41 6,2 22,6 3,6 29 2,3 4,6 2,0 13 6,9 10,2 1,5 13
The age division samples of blue whiting show that there is a good correlation between the ratio of WHO-PCB : dioxin when compared to age. This is shown in the following figure 22.
Figure 22: Blue whiting age division samples. Regression of the ratio WHOPCB : dioxin, against age.
5,00 4,00 Ratio WHO-PCB / Dioxin 3,00 2,00 1,00 0,00 0 1 2 3 Age (yrs) 4 5 6
R2 = 0,9138
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Dioxin and PCBs in pelagic fish stocks
6 Discussion
According to the EU Directive 2002/32 (12), after 1.August 2003 it will be prohibited within the EEA, to blend down feed materials that exceed the maximum limit for dioxin. This will mean that fish oil which exceeds the limit for dioxin of 6 ng WHOTEQ per kg oil will either have to be sold for industrial use, or must be sent for decontamination. Fishmeal exceeding the maximum limit for dioxin of 1,25 ng TEQ per kg meal must be destroyed in a controlled manner or else be decontaminated. The results from this project demonstrate that most of the raw material is suitable for production of fishmeal and fish oil showing dioxin levels well below the EU limits. All of the fishmeal produced from these 4 fish stocks is within the given maximum limit for dioxin of 1,25ng WHO-TEQ per kg meal. Based on the production figures of the past 3 years in Iceland and the Faroes, it is estimated that more than 85% of the fish oil production in these countries would have been below the permissible maximum level for dioxin of 6 ng WHO-TEQ per kg fishoil. All capelin products were well within the given dioxin limits. All blue whiting meal was well within the limit for fishmeal. Blue whiting oil produced when the fish fat level is below approximately 4%, should be kept separate from other production until it has been measured for dioxin. There is a strong likelihood that the level of dioxin in this production is above the EU limit. During the period 2000 – 2001, there was an average blue whiting oil production of approximately 3000 tonnes in Iceland and the Faroes during the critical months of March, April and May. This is less than 3% of the total fish oil production during these 3 years. All Icelandic herring products were well within the given dioxin limits. All Atlanto-Scandian herring meal was well within the limit for dioxin. Fish oil produced from Atlanto-Scandian herring was close to or above the EU maximum limit for dioxin. The results indicate that if fish fat level in this stock goes below 13% then the dioxin level could be close to or above the EU maximum limit. This production should be kept separate from other fish oil until it has been measured for dioxin. During the three years from 2000 – 2002, there was an average herring oil production from this stock of approximately 12.000 tonnes in Iceland and the Faroes during the months of May, June and July. This is less than 12% of the total fish oil production during these 3 years. It is evident that concentrations of dioxin and WHO-PCBs are inversely related to the level of fat in the fish, but increase with the age of the fish. The age division samples of blue whiting indicate that in this species there could be a greater tendency to accumulate WHO-PCBs as opposed to dioxin, since the ratio of WHO-PCB to dioxin increases with age. Although similar data are not available for
35
Dioxin and PCBs in pelagic fish stocks
the other fish species in this study, it would appear that this tendency is not apparent in herring nor capelin. In addition to fish fat level and age there are at least three other factors that could possibly influence the relative levels of these compounds in the fish. Migration area. The ratio of WHO-PCB compared to dioxin is variable between fish stocks. This reflects the fact that the sources for these two groups of compounds are very different. It can be concluded that migration area has probably a direct effect on the levels of dioxin and WHO-PCB. Blue whiting is a migratory fish and as such could have been living in an area of the NE Atlantic that is very distant from the area where it is caught. Sex ratio of the catch. Females are able to reduce their dioxin and PCB load, each time they spawn. Evidence of this effect could not be seen in the results of the blue whiting. Capelin spawns only once and therefore the effect cannot be seen in that species. Sex was not determined on the herring samples as explained previously. Physiology. Blue whiting is a species that stores most of of its body fat in the liver, as opposed to capelin and herring that store their fat in adipose tissue throughout the body. This means that the blue whiting has most of the dioxin and PCBs in the liver tissue, which is where biotransformation of such compounds normally takes place. Further studies of the congener data in appendix 1 could clarify whether this could be a significant contributing factor to explain the higher WHO-PCB : dioxin ratio which is observed in the blue whiting results. This, however, is not within the scope of the present report. All of these five factors could be affecting the levels of dioxin and PCBs simultaneously. The results of this investigation, however, give a much clearer idea of the variations involved with these 4 pelagic stocks in the NE Atlantic and are most useful in clarifying the limitations the EU directives impose on the products from these stocks.
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Dioxin and PCBs in pelagic fish stocks
7 Acknowledgements
The steering committee should like to thank the Award Committee of Nordisk Atlantsamarbejde (NORA) for supporting this project. Without their understanding these valuable results would not be available to the industry. In addition we should like to thank the staff of the Icelandic Fisheries Laboratories, The Icelandic Marine Research Institute and the Faroese Fisheries Laboratory for their professional assistance with age determination and sample preparation. We also greatly appreciate the coordination work done by Miss Claudia Collingro and Dr Thomas Herrmann of ERGO with regard to the analysis and transfer of results. We should like to thank Thorhallur Jonasson, Quality Manager of SR-mjöl hf for his help in coordinating the sampling in Iceland. And finally we are grateful to Gudjon Atli Audunsson of IFL for the many useful discussions regarding the results and their presentation.
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Dioxin and PCBs in pelagic fish stocks
8 References
1. 2. 3. 4. 5. 6. 7. 8. 9. Council Directive 2001/102/EC of 27.November 2001 on "the undesirable substances and products in animal nutrition”, Official Journal of the European Communities L6, 10/01/2002 pp. 45 – 49 Council Directive 1999/29/EC of 27.April 1999 on “the undesirable substances and products in animal nutrition”, Official Journal of the European Communities L115, 04/05/1999 pp. 32 – 46 Council Regulation 2375/2001 of 29.November 2001 on “setting maximum levels for certain contaminants in foodstuffs”, Official Journal of the European Communities L321, 06/12/2001 pp. 1 – 5 Opinion of the Scientific Committee on Animal Nutrition on Dioxin Contamination of Feedingstuffs and their Contribution to the Contamination of Food of Animal Origin, 6th November 2000 J. Rantanen, Industrial and Environmental Emergencies; Lessons Learned. Organohalogen Compd. 10 (1992) 291 – 294 Martin Van den Berg et al. Toxic Equivalency Factors (TEFs) for PCBs, PCDDs, PCDFs for Humans and Wildlife, Environmental Health Perspectives 106 (1997) 775 – 792 AOCS Official Method Ba 3-38, 1997 ISO 6496-1999 Council Directive 2000/70/EC of 26.July 2002 on “establishing requirements for the determination of levels of dioxins and dioxin-lke PCBs in feedingstuffs”, Official Journal of the European Communities L209, 06/08/2002 pp. 15 – 21 Sjávarnytjar við Ísland (1998), Gunnarsson, K., Jónsson, G., and Pálsson, Ó., Mál and Menning, Reykjavík International Council for the Exploration of the Sea: Report nr 255 of the ICES Advisory Committee on Fishery Management, December 2002 Council Directive 2002/32/EC of 7.May 2002 on “the undesirable substances in animal feed”, Official Journal of the European Communities L140, 30/05/2002 pp. 10 – 21
10. 11. 12.
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Dioxin and PCBs in pelagic fish stocks
9 Appendix 1
The congener results are presented on pages 40 – 50. The figures in brackets indicate the limit of determination when the congener could not be detected. These results can be provided electronically by contacting the members of the steering committee. Derek Mundell Magnus Pauli Magnussen Jón Reynir Magnusson Gudny Vang derek@srmjol.is magnuspm@hfs.fo jr@fif.is gur@havsbrun.fo
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Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's RM/IS-1 Capelin Fish 16,1 25,1 1,6 : 1 3,22 10.1.2001 64°50' N / 11°26' W 67,8 16,0 0,137 0,240 (0,007) 0,001 (0,007) 0,002 0,000 0,674 0,022 0,410 0,015 0,006 (0,007) (0,008) 0,002 (0,001) (0,000) 0,014 0,001 2,459 0,038 0,139 0,031 0,322 0,008 0,093 0,025 0,002 0,001 1,540 2,512 0,620 3,132 0,765 1,248 0,308 1,556 0,246 0,402 0,099 0,501 1,3 4,2 3,5 3,2 5,6 5,0 1,2 24 6,1 11,5 0,226 (0,300) (0,030) 0,029 (0,030) 0,023 0,000 0,787 0,020 0,340 0,040 (0,030) (0,030) (0,030) (0,004) (0,003) (0,000) 0,010 0,001 1,944 0,031 0,104 0,024 0,244 0,007 0,082 0,027 0,001 0,002 1,923 1,986 0,491 2,477 0,235 0,243 0,060 0,303 0,221 0,228 0,056 0,285 0,8 3,1 2,9 2,4 3,9 3,4 1,0 18 0 100,0 0,112 0,219 (0,007) (0,009) (0,007) (0,001) (0,000) 0,648 0,024 0,405 0,016 0,008 (0,008) (0,011) (0,001) (0,001) (0,000) 0,011 0,001 2,260 0,037 0,143 0,039 0,317 0,010 0,098 0,028 0,002 0,001 1,477 2,309 0,638 2,947 1,477 2,309 0,638 2,947 1,477 2,309 0,638 2,947 1,4 4,1 3,3 3,2 4,8 5,0 1,1 23 FM/IS-1 Capelin Fishmeal FO/IS-1 Capelin Fishoil RM/IS-2 Capelin Fish 15,5 20,1 1 : 1.29 3,09 26.1.2001 64°30' N / 11°30 W 68,6 13,9 0,154 0,288 (0,007) 0,017 (0,007) 0,003 0,000 0,796 0,028 0,470 0,012 0,008 (0,007) (0,009) 0,003 (0,001) 0,000 0,018 0,001 2,903 0,044 0,159 0,038 0,364 0,011 0,103 0,003 0,002 0,001 1,810 2,966 0,682 3,648 0,801 1,313 0,302 1,615 0,252 0,412 0,095 0,507 1,5 4,8 3,7 3,6 5,8 5,5 1,4 26 6,4 11,6 (0,200) (0,200) (0,020) (0,020) (0,020) (0,009) (0,000) 0,823 0,022 0,402 0,031 (0,020) (0,020) (0,020) (0,004) (0,003) (0,000) 0,012 0,001 2,198 0,032 0,113 0,035 0,275 0,009 0,092 0,025 0,001 0,001 1,814 2,243 0,551 2,793 0,225 0,278 0,068 0,346 0,210 0,260 0,064 0,324 0,8 3,6 3,2 2,7 4,5 4,4 1,1 20 0 100,0 0,149 0,255 (0,012) (0,012) (0,010) (0,001) (0,000) 0,828 0,029 0,500 0,017 0,007 (0,012) (0,011) (0,001) (0,001) (0,000) 0,014 0,001 2,675 0,044 0,156 0,047 0,386 0,011 0,103 0,034 0,002 0,002 1,846 2,734 0,741 3,474 1,846 2,734 0,741 3,474 1,846 2,734 0,741 3,474 1,7 4,6 3,2 3,9 4,8 4,8 1,3 24 FM/IS-2 Capelin Fishmeal FO/IS-2 Capelin Fishoil RM/IS-3 Capelin Fish 15,6 22,2 1 : 1.08 3,14 5.2.2001 65°30' N / 25°30' W 70,2 12,7 0,163 0,280 (0,024) (0,024) (0,024) (0,004) 0,000 0,826 0,030 0,493 (0,024) (0,024) (0,024) (0,024) (0,003) (0,003) (0,000) 0,009 0,001 2,210 0,043 0,111 0,035 0,295 0,000 0,104 0,033 0,002 0,002 1,968 2,262 0,582 2,844 0,839 0,964 0,248 1,212 0,250 0,287 0,074 0,361 1,7 4,8 3,5 2,9 5,5 5,3 1,3 25 8,6 11,8 0,200 0,200 (0,020) (0,020) (0,020) (0,009) (0,000) 0,928 0,026 0,434 0,020 (0,020) (0,020) (0,020) (0,004) (0,003) (0,000) 0,013 0,001 2,470 0,038 0,142 0,036 0,231 0,006 0,110 0,035 0,002 0,002 1,945 2,522 0,562 3,084 0,251 0,326 0,073 0,398 0,229 0,298 0,066 0,364 0,8 4,3 4,0 2,3 5,3 5,0 1,3 23 0 100,0 0,177 0,298 (0,008) 0,013 (0,006) (0,001) (0,000) 0,912 0,033 0,555 0,014 0,009 (0,009) (0,011) (0,001) (0,001) (0,000) 0,015 0,001 2,941 0,050 0,178 0,047 0,451 0,013 0,104 0,030 0,002 0,002 2,049 3,007 0,826 3,832 2,049 3,007 0,826 3,832 2,049 3,007 0,826 3,832 1,6 5,1 4,0 4,5 6,0 6,2 1,6 29 FM/IS-3 Capelin Fishmeal FO/IS-3 Capelin Fishoil
40
Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's RM/IS-4 Capelin Fish 15,8 22,6 1,22 : 1 3,14 27.2.2001 64°21' N / 22°52'W 74 8,8 0,241 0,453 (0,009) 0,022 (0,009) 0,003 (0,000) 1,265 0,043 0,750 0,018 0,011 (0,009) 0,015 0,003 (0,001) 0,000 0,024 0,001 4,382 0,071 0,233 0,052 0,519 0,015 0,164 0,050 0,004 0,002 2,852 4,479 1,038 5,517 0,965 1,516 0,351 1,867 0,251 0,394 0,091 0,485 1,8 6,6 5,7 5,2 8,9 8,1 2,1 38 9,4 10,8 0,268 0,414 (0,020) (0,020) (0,020) 0,032 0,004 1,362 0,040 0,652 0,041 (0,020) (0,020) 0,028 0,007 (0,003) 0,000 0,017 0,001 3,496 0,056 0,194 0,051 0,438 0,012 0,159 0,043 0,002 0,002 2,950 3,570 0,901 4,471 0,352 0,426 0,107 0,533 0,319 0,386 0,097 0,483 0,8 6,0 5,7 4,4 7,5 6,8 1,8 33 0 100,0 0,188 0,434 (0,010) (0,022) (0,019) (0,024) (0,002) 1,237 0,048 0,845 0,032 0,016 (0,008) 0,015 (0,003) (0,001) (0,000) 0,015 0,001 3,785 0,070 0,171 0,064 0,469 0,000 0,171 0,052 0,003 0,003 2,904 3,871 0,932 4,802 2,904 3,871 0,932 4,802 2,904 3,871 0,932 4,802 2,1 6,4 4,7 4,7 8,0 7,7 2,0 36 FM/IS-4 Capelin Fishmeal FO/IS-4 Capelin Fishoil RM/IS-5 Capelin Fish 16,2 24,4 1,08 : 1 3,18 5.3.2001 63°47' N / 22°40' W 74,1 9,0 0,233 0,488 0,009 0,022 (0,008) 0,004 0,000 1,304 0,049 0,845 0,021 0,012 (0,008) 0,016 0,004 (0,001) 0,000 0,027 0,002 4,810 0,078 0,250 0,049 0,599 0,014 0,179 0,051 0,003 0,003 3,024 4,916 1,146 6,062 1,051 1,708 0,398 2,107 0,272 0,442 0,103 0,546 2,3 7,0 6,3 6,0 9,2 9,5 2,3 43 5,6 11,2 0,374 0,292 (0,030) (0,030) (0,030) 0,011 (0,000) 1,217 0,036 0,632 0,031 (0,030) (0,030) (0,030) 0,008 (0,004) 0,000 0,019 0,001 4,117 0,056 0,203 0,053 0,454 0,010 0,153 0,044 0,003 0,003 2,785 4,193 0,922 5,115 0,330 0,497 0,109 0,607 0,312 0,470 0,103 0,573 1,2 6,2 6,0 4,5 7,7 7,9 1,9 36 0 100,0 0,284 0,443 (0,008) 0,026 (0,007) (0,001) (0,000) 1,400 0,051 0,845 0,032 0,016 (0,009) 0,016 (0,001) (0,001) (0,000) 0,022 0,001 4,515 0,080 0,285 0,087 0,695 0,024 0,176 0,050 0,003 0,003 3,141 4,619 1,322 5,941 3,141 4,619 1,322 5,941 3,141 4,619 1,322 5,941 2,6 7,2 6,0 6,9 9,3 10,3 2,9 45 FM/IS-5 Capelin Fishmeal FO/IS-5 Capelin Fishoil RM/IS-6 Capelin Fish 16,1 20,9 1 : 2.33 3,18 22.3.2001 63°15' N / 20°30' W 75,3 6,8 0,171 0,638 0,030 0,041 0,028 0,006 0,000 1,917 0,065 1,223 0,046 0,031 (0,028) 0,034 (0,005) (0,004) (0,000) 0,029 0,001 5,855 0,106 0,302 0,081 0,760 0,014 0,254 0,082 0,004 0,004 4,263 5,992 1,500 7,492 1,174 1,650 0,413 2,063 0,290 0,407 0,102 0,509 3,5 9,6 7,9 7,6 12,5 12,5 3,1 57 7,2 10,8 0,310 0,506 (0,034) (0,048) (0,034) (0,014) (0,000) 1,791 0,059 0,913 0,050 (0,029) (0,029) (0,034) (0,005) (0,004) (0,000) 0,022 0,001 4,537 0,074 0,242 0,077 0,583 0,007 0,198 0,057 0,003 0,003 3,859 4,634 1,170 5,804 0,449 0,539 0,136 0,675 0,417 0,500 0,126 0,627 3,2 8,1 6,3 5,8 9,5 9,1 2,2 44 0 100,0 0,375 0,795 0,016 0,037 0,014 0,005 (0,000) 2,150 0,080 1,408 0,056 0,032 0,011 0,039 0,003 0,002 0,000 0,023 0,001 6,588 0,120 0,292 0,093 0,780 0,000 0,291 0,093 0,005 0,004 5,021 6,732 1,557 8,289 5,021 6,732 1,557 8,289 5,021 6,732 1,557 8,289 3,5 10,5 7,9 7,8 13,3 13,1 3,4 59 FM/IS-6 Capelin Fishmeal FO/IS-6 Capelin Fishoil
41
Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's RM/IS-7 FM/IS-7 FO/IS-7 RM/IS-8 FM/IS-8 FO/IS-8 A-S Herring A-S Herring A-S Herring A-S Herring A-S Herring A-S Herring Fish Fishmeal Fishoil Fish Fishmeal Fishoil 34,6 34,0 306,1 300,7 n/a n/a 9,3 8,6 28.5.2001 15.6.2001 71°50' N / 00°50' E 73,2 8,1 0,624 2,535 0,037 0,233 0,050 0,005 (0,000) 2,634 0,175 5,250 0,092 0,115 (0,010) 0,132 (0,002) (0,001) (0,000) 0,014 0,000 10,978 0,443 0,875 0,291 2,422 0,000 1,042 0,287 0,011 0,017 11,895 11,436 4,943 16,379 3,595 3,456 1,494 4,950 0,964 0,926 0,400 1,327 6,0 19,0 31,0 24,0 44,0 40,0 9,0 173 7,1 7,3 0,675 2,671 0,050 0,222 0,044 (0,012) 0,001 2,468 0,161 4,975 0,105 0,123 (0,040) 0,144 0,006 (0,005) 0,001 0,017 0,000 11,047 0,362 0,895 0,240 2,264 0,000 0,887 0,269 0,010 0,015 11,702 11,426 4,579 16,005 0,920 0,898 0,360 1,258 0,854 0,834 0,334 1,168 6,0 18,0 29,0 23,0 38,0 35,0 7,0 156 0 100,0 0,624 2,672 0,055 0,211 0,051 0,010 (0,000) 2,679 0,164 4,800 0,109 0,119 (0,011) 0,144 0,005 0,002 (0,000) 0,016 0,000 12,389 0,398 0,888 0,246 2,361 0,000 0,962 0,289 0,011 0,016 11,655 12,804 4,772 17,576 11,655 12,804 4,772 17,576 11,655 12,804 4,772 17,576 5,0 18,9 30,5 23,8 41,6 38,3 8,4 166 73°11' N / 6°51' E 68,6 12,7 0,369 1,534 0,027 0,137 0,028 0,004 (0,000) 1,708 0,105 3,000 0,070 0,070 (0,010) 0,083 0,002 (0,001) (0,000) 0,012 0,000 6,934 0,229 0,478 0,156 1,298 0,000 0,545 0,150 0,006 0,008 7,148 7,175 2,640 9,815 2,891 2,902 1,068 3,970 0,908 0,911 0,335 1,246 4,0 11,0 17,0 13,0 23,0 21,0 4,0 93 7,2 8,5 0,415 1,570 0,038 0,140 (0,035) (0,010) 0,000 1,533 0,091 2,820 0,055 0,063 (0,035) 0,077 (0,005) (0,005) (0,000) 0,011 0,000 6,954 0,212 0,523 0,158 1,362 0,000 0,523 0,155 0,006 0,009 6,892 7,178 2,735 9,913 0,631 0,657 0,251 0,908 0,586 0,610 0,233 0,843 3,0 11,0 16,0 14,0 22,0 21,0 4,0 91 0 100,0 0,315 1,171 0,022 0,101 0,031 0,005 (0,000) 1,281 0,074 2,210 0,049 0,053 (0,008) 0,064 0,002 (0,001) (0,000) 0,011 0,000 6,619 0,177 0,446 0,129 1,213 0,000 0,489 0,133 0,005 0,008 5,386 6,807 2,422 9,229 5,386 6,807 2,422 9,229 5,386 6,807 2,422 9,229 3,0 12,0 15,0 12,0 21,0 19,0 4,0 86 RM/IS-9 Capelin Fish 15,4 17,4 3,35:1 2,0 4.7.2001 66°20' N / 24°15' W 73,2 10,2 0,182 0,335 (0,010) 0,014 0,008 0,003 0,000 0,921 0,038 0,650 0,023 0,012 (0,010) 0,016 0,003 0,002 0,000 0,010 0,001 2,627 0,052 0,086 0,032 0,244 0,000 0,085 0,026 0,001 0,001 2,227 2,689 0,475 3,164 0,848 1,024 0,181 1,204 0,227 0,274 0,048 0,323 1,8 2,7 1,9 2,4 3,9 3,8 0,8 17 8,1 10,4 0,195 0,482 0,063 0,039 0,032 0,011 (0,000) 0,941 0,038 0,610 (0,029) (0,029) (0,029) (0,029) (0,004) (0,004) (0,000) 0,010 0,001 2,628 0,131 0,119 0,036 0,349 0,000 0,123 0,039 0,001 0,002 2,535 2,769 0,668 3,438 0,287 0,313 0,076 0,389 0,264 0,288 0,070 0,358 2,2 4,0 2,5 3,5 5,6 5,3 1,2 24 0 100,0 0,218 0,422 0,013 0,020 0,043 (0,004) (0,000) 1,010 0,041 0,685 0,021 0,013 (0,010) 0,016 (0,002) (0,001) (0,000) 0,011 0,001 3,145 0,054 0,143 0,048 0,433 0,000 0,138 0,049 0,002 (0,002) 2,519 3,210 0,815 4,025 2,519 3,210 0,815 4,025 2,519 3,210 0,815 4,025 1,9 5,0 2,6 4,3 6,7 6,9 1,4 29 FM/IS-9 Capelin Fishmeal FO/IS-9 Capelin Fishoil
42
Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's RM/IS-10 Capelin Fish 13,6 14,5 2,23:1 2,0 11.7.2001 66°45' N / 22°30' W 71,3 12,5 0,092 0,166 (0,008) 0,008 (0,008) 0,003 0,000 0,467 0,015 0,310 0,013 (0,008) (0,008) 0,008 0,003 0,001 0,000 0,005 0,000 1,406 0,024 0,068 0,024 0,193 0,000 0,094 0,019 0,001 0,001 1,118 1,436 0,400 1,835 0,487 0,625 0,174 0,799 0,140 0,179 0,050 0,229 1,1 2,5 1,5 1,9 2,9 2,9 0,5 13 8,6 12,9 (0,155) (0,233) (0,023) (0,023) (0,023) (0,007) (0,000) 0,550 0,021 0,350 0,023 (0,023) (0,023) (0,023) (0,003) (0,003) (0,000) 0,006 0,000 1,553 0,024 0,071 0,023 0,203 0,000 0,063 0,022 0,001 0,001 1,483 1,583 0,382 1,965 0,209 0,223 0,054 0,277 0,191 0,204 0,049 0,254 (1,6) 2,5 1,5 2,0 3,1 3,0 0,6 14 0 100,0 0,128 0,175 0,006 0,011 0,009 (0,004) (0,000) 0,544 0,020 0,360 0,008 0,003 (0,007) (0,009) (0,002) (0,001) (0,000) 0,007 0,000 1,714 0,030 0,079 0,027 0,242 0,000 0,067 0,021 0,001 (0,001) 1,286 1,751 0,438 2,188 1,286 1,751 0,438 2,188 1,286 1,751 0,438 2,188 1,0 3,1 1,8 2,4 3,4 3,5 0,6 16 FM/IS-10 Capelin Fishmeal FO/IS-10 Capelin Fishoil RM/IS-11 Capelin Fish 13,5 13,4 1,86:1 2,2 24.7.2001 68°20' N / 18°40' W 69,9 14,2 0,109 0,172 (0,014) (0,014) (0,014) (0,002) (0,000) 0,458 0,014 0,289 (0,014) (0,014) (0,014) (0,014) (0,001) (0,002) (0,000) 0,005 0,000 1,284 0,022 0,063 0,025 0,175 0,000 0,054 0,018 0,001 0,001 1,145 1,311 0,336 1,647 0,540 0,618 0,158 0,777 0,163 0,186 0,048 0,234 1,1 2,4 1,7 1,7 2,8 2,8 0,6 13 7,3 12,7 (0,157) (0,236) (0,024) (0,024) (0,024) 0,007 (0,000) 0,443 0,015 0,268 (0,024) (0,024) (0,024) (0,024) (0,003) (0,003) (0,000) 0,005 0,000 1,238 0,017 0,057 0,022 0,155 0,000 0,048 0,019 0,001 0,001 1,300 1,260 0,303 1,563 0,178 0,173 0,042 0,214 0,165 0,160 0,038 0,199 1,3 2,0 1,4 1,6 2,5 2,4 0,5 12 0 100,0 0,128 0,161 (0,006) 0,010 0,009 (0,004) (0,000) 0,454 0,015 0,290 0,005 0,004 (0,008) (0,009) (0,002) (0,001) (0,000) 0,005 0,000 1,488 0,023 0,071 0,022 0,201 0,000 0,061 0,020 0,001 (0,002) 1,105 1,517 0,376 1,893 1,105 1,517 0,376 1,893 1,105 1,517 0,376 1,893 0,9 2,6 1,6 2,0 3,1 2,8 0,6 14 FM/IS-11 Capelin Fishmeal FO/IS-11 Capelin Fishoil RM/IS-12 RM/IS-13 FM/IS-13 A-S Herring Blue Whiting Blue Whiting Fish Fish Fishmeal 31,5 28,1 280 143,1 n/a n/a 5,4 3,8 10.9.2001 14.11.2001 69°00' N / 11°30' W 61,2 20,0 0,256 0,570 0,017 0,040 (0,015) 0,004 (0,000) 0,756 0,035 1,150 0,030 0,028 (0,016) 0,026 (0,002) (0,003) (0,000) 0,011 0,000 3,457 0,096 0,178 0,093 0,509 0,000 0,205 0,055 0,005 0,007 2,947 3,564 1,050 4,615 1,519 1,837 0,541 2,379 0,589 0,713 0,210 0,923 2,0 5,0 9,0 5,0 8,0 10,0 2,0 41 63°10' N / 10°00' W 72,1 8,2 0,327 (0,220) (0,024) 0,049 (0,024) 0,007 (0,000) 1,100 0,055 0,190 0,040 0,030 (0,032) 0,044 (0,003) (0,004) (0,000) 0,010 0,000 5,238 0,119 0,312 0,175 0,880 0,000 0,395 0,102 0,008 (0,005) 2,149 5,368 1,877 7,245 0,631 1,578 0,552 2,129 0,176 0,440 0,154 0,594 5,0 7,0 14,0 9,0 15,0 21,0 6,0 77 6,2 8,9 0,395 (0,340) (0,036) 0,068 (0,035) 0,011 0,000 1,214 0,081 0,260 0,074 0,041 (0,034) 0,063 (0,006) (0,004) (0,000) 0,007 0,000 5,850 0,127 0,352 0,121 0,978 0,000 0,417 0,135 0,006 0,008 2,662 5,984 2,015 7,999 0,253 0,568 0,191 0,759 0,237 0,533 0,179 0,712 3,0 8,0 14,0 10,0 19,0 21,0 6,0 81
43
Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's 0 100,0 0,276 0,230 0,008 0,061 0,011 0,007 0,000 1,128 0,064 0,285 0,032 0,033 (0,003) 0,051 0,003 0,001 0,000 0,007 0,000 4,529 0,117 0,341 0,187 0,951 0,000 0,437 0,110 0,009 0,007 2,194 4,653 2,042 6,695 2,194 4,653 2,042 6,695 2,194 4,653 2,042 6,695 1,4 16,5 13,7 9,5 14,4 18,4 5,7 80 FO/IS-13 RM/IS-14 FM/IS-14 RM/IS-15 RM/IS-16 RM/IS-17 Blue Whiting Blue Whiting Blue Whiting ICE Herring ICE Herring Capelin Fishoil Fish Fishmeal Fish Fish Fish 28,9 31,9 28,7 15,4 159,5 263,5 195,2 18,3 n/a n/a n/a 1.0 : 1 4,1 5,1 3,2 2,6 15.11.2001 26.11.2001 28.11.2001 10.12.2001 63°10' N / 10°00' W 71,3 9,7 0,300 (0,260) (0,020) 0,046 (0,024) 0,007 (0,000) 1,067 0,062 0,235 0,040 0,033 (0,023) 0,053 (0,003) (0,003) (0,000) 0,010 0,000 5,577 0,144 0,309 0,195 0,945 0,000 0,457 0,153 0,006 0,005 2,176 5,732 2,070 7,801 0,735 1,937 0,700 2,637 0,211 0,556 0,201 0,757 2,0 7,0 14,0 9,0 15,0 21,0 6,0 74 4,7 13,3 0,271 0,247 (0,020) 0,049 (0,024) 0,008 0,000 0,901 0,068 0,285 0,037 0,033 (0,023) 0,054 0,004 (0,003) 0,000 0,009 0,001 5,093 0,121 0,303 0,199 0,960 0,000 0,348 0,105 0,005 0,005 2,027 5,224 1,925 7,148 0,283 0,729 0,269 0,998 0,270 0,695 0,256 0,951 2,0 17,0 15,0 10,0 14,0 20,0 5,0 83 65°30' N / 27°00' W 68,0 13,0 0,190 (0,250) (0,020) (0,020) (0,021) 0,004 (0,000) 0,925 0,032 0,795 0,024 (0,025) (0,024) (0,021) (0,003) (0,003) (0,000) 0,009 0,000 2,998 0,105 0,261 0,180 0,778 0,000 0,253 0,119 0,007 (0,008) 2,357 3,113 1,604 4,716 0,958 1,264 0,652 1,916 0,306 0,405 0,209 0,613 2,0 7,0 14,0 8,0 11,0 18,0 4,0 64 65°30' N / 27°00' W 64,1 16,7 0,160 (0,200) (0,016) (0,017) (0,018) 0,003 (0,000) 0,400 0,013 0,285 (0,018) (0,017) (0,017) (0,016) (0,002) (0,002) (0,000) 0,005 0,000 1,343 0,041 0,125 0,085 0,300 0,000 0,127 0,037 0,003 (0,004) 1,185 1,389 0,679 2,068 0,551 0,646 0,316 0,962 0,198 0,232 0,113 0,345 (1,1) 2,5 4,4 3,1 3,7 5,4 1,2 21 67°20' N / 17°30' W 70,8 14,3 0,190 (0,200) (0,023) (0,024) (0,020) 0,003 0,000 0,623 0,025 0,505 (0,021) (0,019) (0,020) (0,018) (0,003) (0,003) 0,000 0,011 0,000 1,968 0,043 0,104 0,079 0,265 0,000 0,096 0,040 0,002 (0,003) 1,697 2,023 0,589 2,612 0,831 0,991 0,288 1,279 0,243 0,289 0,084 0,373 2,6 4,3 3,2 2,6 3,8 5,4 1,1 23 7,4 11,5 0,200 (0,250) (0,026) 0,035 (0,027) 0,017 0,001 0,643 0,021 0,465 0,035 (0,030) (0,024) (0,027) 0,007 (0,004) 0,000 0,009 0,001 1,882 0,034 0,094 0,036 0,264 0,000 0,088 0,029 0,001 (0,002) 1,811 1,925 0,512 2,438 0,225 0,239 0,064 0,303 0,208 0,221 0,059 0,280 2,1 3,6 2,4 2,6 4,4 4,7 1,0 21 0 100,0 0,109 0,321 0,006 0,015 (0,003) (0,001) (0,000) 0,662 0,027 0,480 0,017 0,007 (0,003) 0,010 (0,001) (0,001) (0,000) 0,008 0,000 2,145 0,042 0,121 0,048 0,341 0,000 0,107 0,036 0,002 0,002 1,663 2,195 0,657 2,852 1,663 2,195 0,657 2,852 1,663 2,195 0,657 2,852 1,5 4,4 2,7 3,3 5,0 5,2 1,1 23 FM/IS-17 Capelin Fishmeal FO/IS-17 Capelin Fishoil RM/IS-18 Capelin Fish 15,7 19,4 1.50 : 1 2,6 17.12.2001 67°20' N / 13°30' W 71,2 12,7 (0,150) (0,250) (0,024) (0,024) (0,020) (0,003) (0,000) 0,680 0,026 0,485 (0,023) (0,025) (0,026) (0,022) (0,003) (0,003) (0,000) 0,011 0,001 2,088 0,048 0,117 0,052 0,347 0,000 0,122 0,048 0,002 (0,003) 1,764 2,148 0,691 2,839 0,778 0,947 0,305 1,252 0,224 0,273 0,088 0,361 2,0 4,8 3,3 3,5 4,4 5,6 1,4 25
44
Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's 5,4 13,0 0,240 0,245 (0,025) (0,023) (0,022) 0,013 0,001 0,675 0,028 0,555 0,024 (0,022) (0,022) (0,024) (0,003) (0,003) (0,000) 0,009 0,000 1,936 0,043 0,102 0,074 0,264 0,000 0,115 0,036 0,002 0,003 1,925 1,989 0,594 2,583 0,265 0,273 0,082 0,355 0,250 0,259 0,077 0,336 1,4 2,7 3,1 2,6 3,7 5,1 1,2 20 0 100,0 0,158 0,333 0,008 0,014 0,007 (0,003) (0,000) 0,792 0,028 0,515 0,014 0,007 (0,003) (0,012) (0,002) (0,001) (0,000) 0,009 0,000 1,909 0,042 0,115 0,082 0,349 0,000 0,122 0,036 0,003 0,003 1,896 1,960 0,709 2,669 1,896 1,960 0,709 2,669 1,896 1,960 0,709 2,669 (1,2) 6,8 3,9 3,5 4,0 5,3 1,4 26 FM/IS-18 Capelin Fishmeal FO/IS-18 Capelin Fishoil RM/IS-19 FM/IS-19 FO/IS-19 RM/IS-20 FM/IS-20 FO/IS-20 RM/IS-21 A-S Herring A-S Herring A-S Herring A-S Herring A-S Herring A-S Herring Capelin Fish Fishmeal Fishoil Fish Fishmeal Fishoil Fish 34,1 33,8 29,8 341,4 305,8 19,3 n/a n/a n/a n/a n/a n/a 4,0:1 10,2 9,9 2 26.5.2002 7.6.2002 23.7.2002 70°20' N / 4°30' W 66,4 15,6 0,316 1,316 0,024 0,097 0,022 (0,007) (0,000) 1,491 0,077 2,225 0,042 0,054 (0,003) 0,061 (0,003) (0,001) (0,000) 0,009 0,000 5,805 0,199 0,434 0,140 1,027 0,000 0,474 0,153 0,008 0,009 5,739 6,013 2,244 8,257 2,665 2,792 1,042 3,834 0,895 0,938 0,350 1,288 2,0 10,0 20,0 10,0 21,0 23,0 6,0 92 7,3 8,8 0,360 1,237 (0,032) 0,096 (0,036) 0,006 0,000 1,115 0,065 2,260 0,059 0,047 (0,037) 0,053 (0,005) (0,004) (0,000) 0,008 0,000 5,396 0,184 0,457 0,163 1,205 0,000 0,443 0,145 0,005 0,008 5,412 5,589 2,424 8,013 0,514 0,531 0,230 0,761 0,476 0,492 0,213 0,705 5,0 24,0 22,0 12,0 21,0 24,0 4,0 112 0 100,0 0,267 1,175 (0,021) 0,104 (0,020) 0,002 0,000 1,135 0,072 2,080 0,045 0,050 (0,004) 0,064 (0,001) (0,001) (0,000) 0,008 0,000 5,624 0,200 0,455 0,155 1,176 0,000 0,493 0,159 0,006 0,009 5,041 5,833 2,452 8,284 5,041 5,833 2,452 8,284 5,041 5,833 2,452 8,284 3,0 22,0 24,0 12,0 21,0 22,0 6,0 110 72°56' N / 6°42' E 66,4 14,9 0,303 1,208 0,019 0,090 0,021 (0,007) (0,000) 1,398 0,073 2,035 0,037 0,048 (0,003) 0,057 (0,003) (0,001) (0,000) 0,008 0,000 5,700 0,190 0,372 0,126 0,973 0,000 0,465 0,166 0,007 0,008 5,304 5,899 2,116 8,015 2,352 2,616 0,938 3,554 0,790 0,879 0,315 1,194 1,5 9,1 17,4 9,7 19,6 21,6 5,1 84 8,2 8,0 0,400 1,306 0,043 0,113 0,038 0,019 0,000 1,219 0,071 2,340 0,083 0,062 (0,033) 0,083 0,011 (0,005) 0,000 0,010 0,000 5,886 0,198 0,466 0,166 1,170 0,000 0,473 0,147 0,005 0,008 5,827 6,094 2,435 8,529 0,508 0,531 0,212 0,743 0,466 0,488 0,195 0,682 4,0 11,0 18,0 12,0 21,0 22,0 4,0 92 0 100,0 0,354 1,153 0,019 0,092 0,025 0,002 (0,000) 1,143 0,066 2,025 0,041 0,048 (0,005) 0,059 (0,001) (0,001) (0,000) 0,008 0,000 5,672 0,197 0,427 0,144 1,137 0,000 0,490 0,151 0,006 0,009 5,034 5,878 2,363 8,241 5,034 5,878 2,363 8,241 5,034 5,878 2,363 8,241 2,0 10,0 20,0 11,0 20,0 20,0 6,0 89 68°20' N / 19°30' W 68,6 16,7 0,060 0,145 0,006 0,015 0,004 (0,006) (0,000) 0,464 0,018 0,265 0,009 0,006 (0,003) (0,008) 0,009 (0,001) 0,000 0,004 0,000 1,500 0,030 0,077 0,035 0,220 0,000 0,064 0,024 0,001 0,001 1,020 1,535 0,421 1,955 0,543 0,816 0,224 1,040 0,170 0,256 0,070 0,327 1,1 2,6 1,9 2,0 2,9 3,5 0,8 15
45
Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's 7,3 11,9 0,146 0,210 (0,006) 0,017 (0,005) (0,006) (0,000) 0,626 0,019 0,380 0,008 0,008 (0,005) (0,017) 0,006 0,002 (0,000) (0,006) (0,000) (1,252) (0,037) 0,083 0,015 0,180 0,000 (0,055) (0,007) 0,002 (0,002) 1,461 1,296 0,342 1,638 0,188 0,166 0,044 0,210 0,174 0,154 0,041 0,195 (1,6) 3,1 2,4 1,8 3,8 4,3 0,9 18 0 100,0 (0,030) 0,121 (0,003) 0,008 0,003 (0,004) (0,000) 0,466 0,010 0,260 (0,012) (0,004) (0,003) (0,013) (0,005) (0,002) (0,000) 0,004 0,000 1,295 0,024 0,058 0,020 0,170 0,000 0,050 0,019 0,001 0,002 0,943 1,324 0,319 1,642 0,943 1,324 0,319 1,642 0,943 1,324 0,319 1,642 (1,0) 2,5 2,1 1,8 2,8 3,3 0,9 14 FM/IS-21 Capelin Fishmeal FO/IS-21 Capelin Fishoil RM/IS-22 FM/IS-22 FO/IS-22 RM/IS-23 FM/IS-23 FO/IS-23 RM/IS-24 ICE Herring ICE Herring ICE Herring ICE Herring ICE Herring ICE Herring ICE Herring Fish Fishmeal Fishoil Fish Fishmeal Fishoil Fish 34,5 32,2 34,4 362,2 280,1 351,44 n/a n/a n/a 7,2 5,5 8,2 28.10.2002 16.11.2002 2.12.2002 65°55' N / 26°30' W 61,7 19,1 0,100 0,250 (0,005) 0,020 (0,004) 0,001 (0,000) 0,830 0,028 0,700 0,010 0,011 (0,004) 0,010 0,001 (0,000) (0,000) 0,004 0,000 2,600 0,093 0,302 0,097 0,886 0,000 0,337 0,109 0,005 0,005 1,974 2,697 1,740 4,437 0,984 1,345 0,868 2,213 0,377 0,515 0,332 0,847 1,8 5,8 13,0 8,7 16,0 17,0 4,0 66 6,7 9,7 (0,100) 0,280 0,010 0,019 (0,006) (0,005) (0,001) 1,100 0,037 0,750 0,048 0,039 (0,004) 0,035 0,007 0,001 (0,000) 0,004 0,000 2,300 0,083 0,217 0,081 0,623 0,000 0,210 0,079 0,004 (0,006) 2,441 2,387 1,219 3,606 0,254 0,248 0,127 0,375 0,237 0,232 0,118 0,350 2,6 6,2 8,7 6,2 13,0 16,0 3,8 57 0 100,0 (0,100) 0,240 (0,010) (0,010) (0,010) (0,002) (0,000) 0,680 0,026 0,600 (0,009) 0,012 (0,010) 0,012 (0,001) (0,001) (0,000) 0,004 0,000 2,400 0,081 0,260 0,073 0,700 0,000 0,267 0,090 0,004 0,004 1,722 2,485 1,397 3,883 1,722 2,485 1,397 3,883 1,722 2,485 1,397 3,883 1,7 4,0 9,2 7,0 12,0 13,0 3,0 50 65°20' N / 27°30' W 63,5 16,8 0,100 0,200 (0,005) 0,018 (0,003) 0,002 0,000 0,760 0,029 0,600 0,014 0,013 (0,004) 0,009 0,001 (0,001) (0,000) 0,004 0,000 2,300 0,081 0,255 0,080 0,731 0,000 0,281 0,092 0,004 0,004 1,758 2,385 1,446 3,831 0,809 1,098 0,666 1,763 0,295 0,401 0,243 0,644 1,6 4,7 11,0 7,2 13,0 14,0 3,3 55 7,7 8,6 (0,100) 0,310 (0,007) 0,016 (0,006) (0,003) (0,000) 1,200 0,036 0,750 0,054 0,029 (0,004) 0,018 0,005 (0,000) (0,000) 0,004 0,000 2,400 0,082 0,198 0,135 0,588 0,000 0,277 0,086 0,003 0,004 2,538 2,487 1,289 3,776 0,237 0,232 0,120 0,352 0,218 0,214 0,111 0,325 2,2 5,5 10,0 5,9 12,0 13,0 3,1 52 0 100,0 0,110 0,180 (0,006) 0,012 (0,004) 0,001 (0,000) 0,620 0,021 0,480 0,010 0,008 0,005 0,010 0,001 (0,001) (0,000) 0,004 0,000 2,000 0,067 0,198 0,058 0,546 0,000 0,216 0,061 0,003 0,003 1,468 2,071 1,084 3,155 1,468 2,071 1,084 3,155 1,468 2,071 1,084 3,155 1,5 3,3 8,1 5,5 9,9 11,0 2,5 42 66°05' N / 25°25' W 64,7 16,5 0,150 0,390 (0,009) 0,026 (0,007) 0,001 (0,000) 1,100 0,046 1,100 0,015 0,019 (0,008) 0,020 0,001 (0,001) (0,000) 0,004 0,000 3,300 0,150 0,475 0,182 1,440 0,000 0,537 0,188 0,007 0,008 2,893 3,455 2,836 6,291 1,352 1,615 1,326 2,940 0,477 0,570 0,468 1,038 2,0 6,9 18,0 15,0 26,0 29,0 7,0 104
46
Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's 8,2 10,6 (0,100) 0,340 0,010 0,019 0,007 (0,003) (0,000) 1,400 0,047 0,900 0,055 0,036 (0,004) 0,030 0,005 (0,001) (0,000) 0,005 0,000 2,800 0,100 0,268 0,099 0,907 0,000 0,354 0,096 0,004 0,005 2,957 2,905 1,733 4,638 0,341 0,335 0,200 0,536 0,313 0,308 0,184 0,492 2,0 8,4 12,0 9,1 15,0 15,0 3,8 65 0 100,0 0,087 0,260 (0,009) 0,014 (0,007) 0,002 (0,000) 0,770 0,030 0,650 0,012 0,013 (0,007) 0,011 0,001 (0,001) (0,000) 0,005 0,000 2,700 0,092 0,278 0,091 0,869 0,000 0,288 0,087 0,004 0,004 1,873 2,797 1,621 4,418 1,873 2,797 1,621 4,418 1,873 2,797 1,621 4,418 1,8 4,5 11,0 8,7 14,0 16,0 3,6 60 FM/IS-24 FO/IS-24 RM/IS-25 ICE Herring ICE Herring Capelin Fishmeal Fishoil Fish 29,1 17,53 2,05 3.12.2002 67°15' N / 16°40' W 70,3 13,3 0,190 0,180 (0,008) 0,008 (0,005) (0,001) (0,000) 0,620 0,023 0,390 0,009 0,007 (0,006) 0,007 0,001 (0,001) (0,000) 0,007 0,000 1,900 0,037 0,128 0,052 0,378 0,000 0,169 0,040 0,002 0,003 1,455 1,944 0,771 2,715 0,651 0,871 0,345 1,216 0,193 0,259 0,103 0,361 2,0 5,8 5,9 3,7 7,3 7,6 1,7 34 RM/IS-26 Capelin Fish 29,7 17,59 RM/IS-27 Capelin Fish 29,6 17,43 FM/IS-27 Capelin Fishmeal FO/IS-27 Capelin Fishoil RM/IS-28 RM/IS-29 ICE Herring ICE Herring Fish Fish 35,2 34,7 383,1 358,0 9,3 4.12.2002 66°15' N / 13°30' W 6,8 11,5 (0,140) 0,230 (0,005) 0,011 (0,004) 0,019 0,004 0,660 0,019 0,360 0,011 0,007 (0,003) (0,010) 0,002 (0,000) 0,000 0,006 0,000 2,100 0,042 0,111 0,044 0,317 0,000 0,105 0,035 0,002 (0,001) 1,485 2,149 0,614 2,763 0,183 0,265 0,076 0,341 0,171 0,247 0,071 0,318 1,2 4,3 3,3 3,2 5,0 5,5 1,5 24 0 100,0 0,150 0,220 (0,006) 0,008 (0,004) 0,002 (0,000) 0,630 0,022 0,410 0,009 0,006 (0,005) (0,009) 0,000 (0,001) (0,000) 0,007 0,000 2,100 0,042 0,107 0,035 0,308 0,000 0,098 0,031 0,002 0,002 1,482 2,149 0,581 2,731 1,482 2,149 0,581 2,731 1,482 2,149 0,581 2,731 1,4 2,9 2,4 3,1 4,7 5,1 1,1 21 65,3 15,9 0,250 0,650 0,012 0,029 0,007 0,002 0,000 1,400 0,060 1,400 0,028 0,025 (0,004) 0,025 0,002 (0,000) 0,000 0,006 0,000 4,900 0,170 0,570 0,182 1,600 0,000 0,695 0,215 0,009 0,011 3,894 5,076 3,281 8,358 1,784 2,326 1,504 3,830 0,619 0,807 0,522 1,329 2,6 11,0 21,0 16,0 28,0 30,0 8,2 117 7,8 9.12.2002 66°15' N / 13°30' W 63,6 17,4 0,160 0,570 0,010 0,033 (0,004) 0,002 0,000 1,300 0,050 1,250 0,024 0,024 (0,003) 0,022 0,002 (0,000) 0,000 0,007 0,000 4,700 0,150 0,489 0,232 1,466 0,000 0,627 0,169 0,008 0,010 3,454 4,857 3,000 7,857 1,651 2,322 1,434 3,756 0,601 0,845 0,522 1,367 3,1 14,0 20,0 15,0 25,0 26,0 7,1 110
2,06 2,08 9.12.2002 10.12.2002 67°20' N / 16°21' W 70,4 13,7 0,060 0,160 (0,006) 0,008 (0,004) (0,001) (0,000) 0,610 0,037 0,445 0,012 0,006 (0,004) 0,006 0,001 (0,001) (0,000) 0,007 0,000 1,900 0,038 0,103 0,031 0,295 0,000 0,099 0,031 0,002 0,001 1,360 1,945 0,561 2,506 0,629 0,900 0,260 1,160 0,186 0,266 0,077 0,343 1,3 2,5 2,2 2,9 4,4 4,4 1,0 19 67°15' N / 16°30' W 69,2 15,0 0,120 0,180 (0,007) 0,008 (0,005) 0,001 0,000 0,560 0,020 0,350 0,008 0,006 (0,006) 0,005 0,001 (0,001) (0,000) 0,006 0,000 1,700 0,037 0,098 0,035 0,292 0,000 0,099 0,034 0,002 0,001 1,277 1,743 0,561 2,304 0,622 0,849 0,273 1,122 0,192 0,262 0,084 0,346 1,5 3,1 2,5 3,0 4,4 4,7 1,1 20
47
Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's RM/FO-1 FM/FO-1 FO/FO-1 RM/FO-2 FM/FO-2 FO/FO-2 RM/FO-3 FM/FO-3 FO/FO-3 Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Fish Fishmeal Fishoil Fish Fishmeal Fishoil Fish Fishmeal Fishoil 27,5 N/A 26,2 131,5 N/A 86 1 : 1.13 N/A 1 : 0.85 3,8 N/A 3,5 10.2.2001 24.2.2001 18.3.2001 53°48' N / 14°25' W 78,2 4,7 0,820 0,651 0,014 0,183 0,070 0,028 0,000 3,113 0,276 0,500 0,156 0,120 (0,010) 0,187 0,015 0,004 0,000 0,018 0,001 13,640 0,306 0,761 0,196 2,339 0,151 0,893 0,261 0,016 0,017 6,146 13,964 4,634 18,598 1,325 3,011 0,999 4,010 0,289 0,656 0,218 0,874 2,4 11,2 33,2 23,3 38,9 41,9 14,4 165 6,3 5,7 0,535 0,456 (0,039) 0,170 0,061 0,034 0,001 1,826 0,167 0,386 0,198 0,081 (0,035) 0,123 (0,025) (0,007) (0,000) 0,001 0,012 10,579 0,225 0,542 0,161 1,456 0,051 0,676 0,201 0,011 0,014 4,144 10,816 3,112 13,928 0,252 0,658 0,189 0,847 0,236 0,617 0,177 0,794 2,9 8,7 19,7 14,4 28,0 28,8 9,6 112 100,0 0,670 0,470 (0,011) 0,143 0,043 0,015 (0,000) 2,130 0,172 0,460 0,110 0,098 (0,012) 0,140 0,008 0,002 (0,000) 0,001 0,013 10,200 0,240 0,630 0,172 1,908 0,140 0,946 0,206 0,011 0,010 4,484 10,454 4,022 14,476 4,484 10,454 4,022 14,476 4,484 10,454 4,022 14,476 2,0 7,3 16,3 19,1 27,1 29,9 9,1 111 53°00' N / 15°15' W 78,2 3,9 0,964 0,690 0,013 0,219 0,062 0,026 0,000 3,387 0,276 0,512 0,186 0,139 (0,011) 0,209 0,024 0,005 0,000 0,001 0,021 15,109 0,345 0,819 0,211 2,643 0,180 0,970 0,296 0,015 0,014 6,723 15,476 5,147 20,623 1,203 2,769 0,921 3,689 0,262 0,604 0,201 0,804 2,5 12,4 33,7 26,4 40,9 46,6 16,1 179 6,1 7,8 0,873 0,535 (0,043) 0,188 0,047 (0,028) (0,001) 2,085 0,183 0,546 0,158 0,130 (0,040) 0,151 (0,028) (0,008) (0,001) 0,002 0,022 12,983 0,284 0,712 0,189 2,054 0,112 0,870 0,262 0,014 0,018 5,043 13,290 4,232 17,522 0,419 1,104 0,352 1,456 0,393 1,037 0,330 1,367 3,1 n.a. 27,9 20,5 33,2 35,7 12,4 133 100,0 0,710 0,540 (0,018) 0,182 0,047 0,017 (0,000) 2,602 0,197 0,385 0,129 0,117 (0,014) 0,178 0,011 0,003 (0,000) 0,001 0,016 13,500 0,300 0,628 0,169 1,837 0,159 0,864 0,249 0,014 0,010 5,149 13,816 3,929 17,746 5,149 13,816 3,929 17,746 5,149 13,816 3,929 17,746 2,4 9,1 19,2 18,4 36,1 34,9 10,0 130 55°20' N / 12°40' W 80,0 2,9 1,701 (1,071) (0,107) 0,332 (0,107) 0,033 0,000 4,678 0,441 0,523 0,241 0,163 (0,107) 0,327 0,021 (0,014) 0,000 0,001 0,032 25,280 0,531 1,093 0,316 3,241 0,167 1,485 0,420 0,026 0,030 9,869 25,843 6,778 32,621 1,431 3,747 0,983 4,730 0,286 0,749 0,197 0,946 7,6 20,3 47,9 32,4 68,2 119,2 27,1 323 5,9 6,0 0,844 0,660 (0,043) 0,290 0,067 0,030 0,001 2,988 0,297 0,454 0,221 0,147 (0,043) 0,236 0,018 (0,006) (0,000) 0,001 0,027 26,977 0,447 0,896 0,264 2,661 0,125 1,204 0,282 0,022 0,027 6,345 27,452 5,481 32,932 0,405 1,750 0,349 2,100 0,381 1,647 0,329 1,976 5,2 22,1 38,0 26,6 59,3 99,4 25,4 276 100,0 1,710 0,820 (0,009) 0,341 0,083 0,024 (0,000) 4,605 0,401 0,625 0,171 0,167 0,011 0,309 (0,014) (0,005) (0,000) 0,001 0,031 33,100 0,550 1,355 0,455 3,577 0,260 1,502 0,413 0,026 0,031 9,296 33,683 7,617 41,300 9,296 33,683 7,617 41,300 9,296 33,683 7,617 41,300 8,0 23,0 49,0 36,0 72,0 107,0 29,0 324
48
Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's RM/FO-4 FM/FO-4 FO/FO-4 RM/FO-5 FM/FO-5 FO/FO-5 RM/FO-6 FM/FO-6 FO/FO-6 Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Blue whiting Fish Fishmeal Fishoil Fish Fishmeal Fishoil Fish Fishmeal Fishoil 26,9 26,9 28,4 93 95,3 141,4 1 : 2.1 1 : 1.08 1 : 3.17 3,6 3,6 3,4 18.4.2001 5.5.2001 20.8.2001 60°40' N / 7°10' W 80,5 1,5 3,168 (1,881) (0,188) 0,735 (0,188) 0,069 0,001 10,429 0,935 (0,940) 0,470 0,393 (0,188) 0,746 0,044 (0,025) 0,000 0,002 0,062 56,000 1,253 2,375 0,613 5,376 0,247 3,187 0,788 0,054 0,069 20,400 57,317 12,709 70,026 1,569 4,409 0,978 5,387 0,306 0,860 0,191 1,050 12,7 32,7 86,8 53,8 143,0 236,7 57,3 623 7,6 5,3 3,460 1,399 0,107 0,824 0,196 0,073 0,001 7,069 0,744 0,639 0,481 0,390 (0,059) 0,687 0,039 0,010 (0,000) 0,001 0,043 56,922 1,183 2,223 0,649 5,986 0,188 3,126 0,843 0,048 0,065 16,178 58,150 13,127 71,277 0,928 3,335 0,753 4,088 0,857 3,082 0,696 3,778 9,7 28,3 75,0 60,3 135,5 189,6 51,7 550 100,0 3,300 1,120 (0,011) 0,686 0,159 0,048 (0,000) 7,604 0,750 0,765 0,333 0,338 0,023 0,629 0,029 (0,014) (0,000) 0,002 0,045 65,600 1,120 2,469 0,891 6,734 0,425 2,945 0,769 0,047 0,062 15,810 66,767 14,341 81,108 15,810 66,767 14,341 81,108 15,810 66,767 14,341 81,108 11,0 31,0 83,0 67,0 132,0 192,0 55,0 571 60°05' N / 06°05' W 80,8 1,4 1,681 (2,140) (0,214) 0,352 (0,214) (0,032) (0,001) 5,671 0,520 (1,070) 0,367 0,229 (0,214) 0,443 (0,026) (0,029) (0,001) 0,000 0,034 27,056 0,688 1,857 0,674 5,853 0,191 1,911 0,548 0,029 0,028 13,204 27,778 11,090 38,868 0,963 2,025 0,809 2,834 0,185 0,389 0,155 0,544 12,2 85,6 97,8 58,1 94,8 96,3 30,6 475 7,3 4,6 3,198 1,199 (0,067) 0,626 0,147 0,056 (0,001) 8,595 0,633 0,800 0,267 0,280 (0,067) 0,493 (0,019) (0,008) (0,001) 0,001 0,037 46,774 0,853 1,615 0,678 5,622 0,232 3,029 0,569 0,034 0,030 16,455 47,665 11,808 59,473 0,817 2,365 0,586 2,951 0,757 2,193 0,543 2,736 (5,3) (29,3) 82,6 56,0 126,6 105,3 37,3 442 0,0 100,0 1,505 0,659 0,017 0,381 0,104 0,033 0,000 5,512 0,390 0,523 0,202 0,199 0,018 0,407 0,018 0,006 0,000 0,001 0,023 29,405 0,675 1,664 0,530 4,743 0,058 1,885 0,546 0,029 0,032 9,971 30,104 9,488 39,591 9,971 30,104 9,488 39,591 9,971 30,104 9,488 39,591 9,0 28,0 55,0 47,5 91,0 90,5 29,0 350 63°17' N / 11°54' W 76,7 6,0 0,483 (0,483) (0,048) 0,060 (0,048) 0,034 0,005 1,873 0,103 (0,242) 0,097 0,060 (0,048) 0,242 0,104 0,034 0,008 0,000 0,004 5,558 0,109 0,525 0,137 1,429 0,050 0,054 0,019 0,001 0,014 3,973 5,672 2,229 7,901 1,023 1,460 0,574 2,035 0,238 0,340 0,134 0,474 1,2 8,5 19,3 14,5 26,6 30,2 9,7 110 7,8 9,2 0,345 (0,345) (0,035) 0,078 (0,035) (0,011) (0,001) 1,640 0,095 0,302 0,069 0,043 (0,035) 0,060 (0,009) (0,004) (0,001) 0,000 0,004 5,092 0,095 0,558 0,139 1,419 0,038 0,568 0,155 0,009 0,010 3,106 5,191 2,896 8,088 0,310 0,518 0,289 0,807 0,286 0,478 0,266 0,744 1,7 7,8 18,1 14,7 31,9 31,1 8,6 114 100,0 0,390 0,250 (0,003) 0,078 0,021 0,010 0,000 1,609 0,094 0,320 0,051 0,044 (0,006) 0,076 0,005 0,002 (0,000) 0,001 0,009 8,800 0,170 0,533 0,182 1,434 0,025 0,613 0,175 0,009 0,011 2,958 8,980 2,980 11,960 2,958 8,980 2,980 11,960 2,958 8,980 2,980 11,960 2,0 8,0 19,0 14,0 31,0 29,0 9,0 112
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Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether) Dioxin (PCDD / F) ng WHO-TEQ / kg 2.3.7.8-Tetra-CDD 1.2.3.7.8-Penta-CDD 1.2.3.4.7.8-Hexa-CDD 1.2.3.6.7.8-Hexa-CDD 1.2.3.7.8.9-Hexa-CDD 1.2.3.4.6.7.8-Hepta-CDD OCDD 2.3.7.8-Tetra-CDF 1.2.3.7.8-Penta-CDF 2.3.4.7.8-Penta-CDF 1.2.3.4.7.8-Hexa-CDF 1.2.3.6.7.8-Hexa-CDF 1.2.3.7.8.9-Hexa-CDF 2.3.4.6.7.8-Hexa-CDF 1.2.3.4.6.7.8-Hepta-CDF 1.2.3.4.7.8.9-Hepta-CDF OCDF WHO-PCBs ng WHO-TEQ / kg PCB 77 PCB 81 PCB 126 PCB 169 PCB 105 PCB 114 PCB 118 PCB 123 PCB 156 PCB 157 PCB 167 PCB 189 ng WHO-TEQ / kg on lipid basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis Based on PCDD/F Based on non-ortho-PCB Based on mono-ortho-PCB Based on total-WHO PCBs Marker-PCBs µg / kg on lipid basis PCB 28 PCB 52 PCB 101 PCB 118 PCB 138 PCB 153 PCB 180 Total Marker-PCB's RM/FO-7 Blue whiting Fish 25,4 99,69 1 : 1.5 2,2 6.9.2001 61°00' N / 7°40'W & 62°25' N / 9°00' W 75,5 7,1 (0,236) (0,472) (0,047) (0,047) (0,047) 0,007 (0,000) 0,837 0,053 (0,236) (0,047) (0,047) (0,047) (0,047) (0,006) (0,006) 0,000 0,000 0,007 3,537 0,083 0,230 0,093 0,666 0,000 0,272 0,078 0,005 0,005 2,182 3,626 1,350 4,976 0,632 1,051 0,391 1,442 0,155 0,257 0,096 0,353 2,6 (4,2) 7,5 6,7 13,3 13,3 3,3 51 6,2 6,9 (0,337) (0,449) (0,045) (0,045) (0,045) (0,007) (0,000) 0,684 0,050 (0,224) (0,045) (0,045) (0,045) (0,045) (0,006) (0,006) (0,000) 0,000 0,006 2,580 0,067 0,195 0,061 0,560 (0,000) 0,247 0,072 0,004 0,005 2,077 2,653 1,144 3,797 0,153 0,195 0,084 0,279 0,143 0,183 0,079 0,262 3,0 4,3 7,0 5,6 11,6 12,2 2,9 47 100,0 0,120 0,140 (0,010) (0,019) (0,011) (0,005) (0,000) 0,588 0,035 0,110 0,016 0,010 (0,010) 0,025 (0,003) (0,002) (0,000) 0,000 0,005 1,940 0,050 0,154 0,052 0,447 (0,000) 0,182 0,060 0,003 0,003 1,104 1,995 0,899 2,895 1,104 1,995 0,899 2,895 1,104 1,995 0,899 2,895 1,3 4,1 5,4 4,5 8,1 8,6 2,0 34 FM/FO-7 FO/FO-7 Blue whiting Blue whiting Fishmeal Fishoil RM/FO-8 Blue whiting Fish 23,5 81,7 1 : 1.85 1,7 15.9.2001 61°00' N / 7°50' W & 60°10' N / 8°10' W 75,4 7,6 (0,213) (0,426) (0,043) (0,043) (0,043) 0,005 (0,000) 0,490 0,032 (0,213) (0,043) (0,043) (0,043) (0,043) (0,005) (0,005) (0,000) 0,000 0,005 2,129 0,053 0,142 0,050 0,392 (0,000) 0,164 0,045 0,002 0,003 1,687 2,187 0,798 2,985 0,521 0,676 0,246 0,922 0,128 0,166 0,061 0,227 2,2 (3,9) 4,8 3,9 8,1 8,3 1,9 33 7,4 8,2 (0,215) (0,323) (0,032) (0,032) (0,032) (0,005) (0,000) 0,603 0,038 (0,162) 0,054 (0,032) (0,032) (0,032) (0,004) (0,004) (0,000) 0,000 0,005 1,938 0,054 0,151 0,045 0,421 (0,000) 0,174 0,060 0,003 0,004 1,603 1,998 0,858 2,855 0,142 0,177 0,076 0,253 0,131 0,164 0,070 0,234 3,2 4,5 5,9 4,2 8,5 8,9 1,9 37 100,0 0,110 0,120 (0,010) (0,019) (0,013) (0,005) (0,000) 0,522 0,035 0,120 0,015 0,018 (0,010) 0,027 (0,003) (0,001) (0,000) 0,000 0,006 1,800 0,050 0,147 0,049 0,441 (0,000) 0,178 0,051 0,002 0,003 1,028 1,856 0,871 2,726 1,028 1,856 0,871 2,726 1,028 1,856 0,871 2,726 1,5 4,1 5,2 4,4 7,9 8,0 1,9 33 FM/FO-8 FO/FO-8 Blue whiting Blue whiting Fishmeal Fishoil
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Dioxin and PCBs in pelagic fish stocks
10 Appendix 2
The congener results for the age determination samples are presented on page 52. The figures in brackets indicate the limit of determination when the congener could not be detected
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Dioxin and PCBs in pelagic fish stocks
Sample code Fish species Sample type Average fish length (cm) Average fish weight (g) Sex ratio (m/f) Average fish age (yrs) Date of catch Area of catch Sample moisture content % Sample fat content % (pet. ether)
Dioxin (PCDD/F ng WHO-TEQ / kg)
RM-A/FO-3 RM-B/FO-3 RM-C/FO-3 Blue whiting Blue whiting Blue whiting Fish Fish Fish 22,8 27,1 32,5 52,6 93,8 159,8 1 : 0.19 1 : 0.47 1 : 2.60 2,1 4,2 5,7 18.3.2001 same same 55°20' N / same same 12°40' W 77,8 78,2 78,7 4,3 3,1 2,5 1,442 (0,926) (0,093) 0,362 (0,093) 0,042 0,000 5,073 0,448 0,635 0,291 0,205 (0,093) 0,356 0,027 (0,012) 0,000 0,032 0,001 25,883 0,546 0,995 0,260 2,739 0,104 1,511 0,415 0,024 0,034 10,097 26,462 6,083 32,545 1,436 3,763 0,865 4,628 0,313 0,820 0,189 1,009 7,7 19,7 49,5 27,3 71,5 121,7 27,6 325 3,528 1,510 (0,116) 0,793 0,192 0,074 0,001 9,609 1,097 0,995 0,366 0,527 (0,116) 1,019 0,046 (0,016) 0,000 0,055 0,002 70,407 1,726 2,970 0,837 8,406 0,373 4,614 1,273 0,079 0,100 20,005 72,191 18,653 90,844 2,348 8,473 2,189 10,662 0,500 1,805 0,466 2,271 10,7 30,2 92,6 84,1 193,6 311,0 86,2 808
RM-A/FO-7 FM-B/FO-7 FO-C/FO-7 Blue whiting Blue whiting Blue whiting Fish Fish Fish 17,8 23 26,1 33,6 73,3 95,8 1 : 1.78 1 : 1.27 1 : 1.78 0,5 1,48 2,16 6.9.2001 same same 61°00' N / 7°40'W & same same 62°25' N / 9°00' W 71,4 72,0 73,5 8,8 8,5 6,6 0,217 0,326 (0,033) (0,033) (0,033) (0,005) (0,000) 0,511 0,027 (0,163) (0,033) (0,033) (0,033) (0,033) (0,004) (0,004) (0,000) 0,007 0,000 2,064 0,043 0,113 0,040 0,342 (0,000) 0,128 0,041 0,002 0,002 1,486 2,114 0,668 2,782 0,457 0,651 0,205 0,856 0,131 0,186 0,059 0,245 2,2 3,8 4,5 3,4 6,3 6,4 1,4 28 0,206 0,309 (0,031) (0,041) (0,031) (0,009) (0,000) 0,957 0,051 (0,154) (0,051) (0,031) (0,031) (0,041) (0,005) (0,004) (0,000) 0,009 0,000 3,603 0,072 0,219 0,087 0,635 (0,000) 0,269 0,077 0,004 0,005 1,954 3,684 1,296 4,980 0,593 1,118 0,393 1,512 0,166 0,313 0,110 0,423 2,8 4,7 7,6 6,4 12,4 12,0 3,1 49 0,359 0,478 (0,048) (0,072) (0,048) (0,012) (0,000) 1,435 0,084 0,239 0,072 (0,048) (0,048) (0,060) (0,006) (0,006) (0,000) 0,012 0,000 5,499 0,108 0,323 0,114 0,992 (0,000) 0,430 0,117 0,006 0,008 3,013 5,619 1,990 7,609 0,750 1,399 0,496 1,895 0,199 0,371 0,131 0,502 4,1 4,9 12,4 9,9 20,0 20,8 5,1 77
0,594 2.3.7.8-Tetra-CDD (0,580) 1.2.3.7.8-Penta-CDD (0,058) 1.2.3.4.7.8-Hexa-CDD 0,119 1.2.3.6.7.8-Hexa-CDD (0,058) 1.2.3.7.8.9-Hexa-CDD 0,031 1.2.3.4.6.7.8-Hepta-CDD 0,000 OCDD 2,719 2.3.7.8-Tetra-CDF 0,152 1.2.3.7.8-Penta-CDF (0,290) 2.3.4.7.8-Penta-CDF 0,123 1.2.3.4.7.8-Hexa-CDF (0,058) 1.2.3.6.7.8-Hexa-CDF (0,058) 1.2.3.7.8.9-Hexa-CDF 0,117 2.3.4.6.7.8-Hexa-CDF 0,012 1.2.3.4.6.7.8-Hepta-CDF (0,007) 1.2.3.4.7.8.9-Hepta-CDF 0,000 OCDF WHO-PCBs ng WHO-TEQ / kg) 0,022 PCB 77 0,001 PCB 81 11,678 PCB 126 0,227 PCB 169 0,526 PCB 105 0,145 PCB 114 1,476 PCB 118 0,067 PCB 123 0,605 PCB 156 0,175 PCB 157 0,011 PCB 167 0,011 PCB 189 ng WHO-TEQ / kg on lipid basis. 4,977 Based on PCDD/F 11,928 Based on non-ortho-PCB 3,016 Based on mono-ortho-PCB 14,944 Based on total-WHO PCBs ng WHO-TEQ / kg on dry matter basis. 0,964 Based on PCDD/F 2,310 Based on non-ortho-PCB 0,584 Based on mono-ortho-PCB 2,894 Based on total-WHO PCBs ng WHO-TEQ / kg on sample basis. 0,214 Based on PCDD/F 0,513 Based on non-ortho-PCB 0,130 Based on mono-ortho-PCB 0,643 Based on total-WHO PCBs Marker-PCBs µg/kg on lipid basis. 6,1 PCB 28 16,2 PCB 52 27,2 PCB 101 14,8 PCB 118 31,6 PCB 138 51,3 PCB 153 10,9 PCB 180 158 Total Marker-PCB's
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Dioxin and PCBs in pelagic fish stocks
11 Appendix 3
Multivariate data analyses – a possible tool for the industry providing rapid and less costly prediction of the concentration of dioxin in fishmeal and fish oil.
The analysis for dioxin and PCBs is expensive and takes several weeks for a specialised laboratory to perform. It would therefore be of interest for the fishmeal industry to develop a cheaper and faster indirect method for prediction of the dioxin concentration in its products. It is evident from the results in this report that the concentrations of dioxin and WHOPCB in fishmeal and fish oil are inversely related to the level of fat in the fish and directly related to the age of the fish. Simple regression analyses (univariate analyses) of the fat content in the fish versus the dioxin concentration in the lipid fraction of the resulting fishmeal or fish oil did not result in good correlations for any of the four fish species that were investigated. In blue whiting, however, the fat content in the fish correlated reasonably well with the logarithm of the dioxin concentration in the lipid fraction of the resulting fishmeal and the fish oil. If the data from table 6 of the main report is used, the correlation quotient is – 0,9213. The use of multivariate data analyses could be expected to improve the prediction of the dioxin concentrations in fishmeal and fish oil. It is well known that nature itself is multivariate, which means that any one parameter often depends on several factors. In this case, dioxin concentration in the lipid fraction of fishmeal and fish oil may depend on several of the other parameters monitored in this study. The advantage of using multivariate analysis on these data is that relationships between several variables can be investigated at the same time. This could lead to the use of easily accessible parameters to predict a parameter that is less easily accessible and more expensive to quantify. For the multivariate data analyses, the software programme “Unscrambler 7.8” from CAMO was used. Throughout this appendix, the following terms are used: PCA – Principal component analysis. PCA is a technique that can break down the data into a structural part and a noise part. PCA gives the best possible view of the structure. It indicates in what respect one sample is different from another, as well as showing which variables contribute most to this difference and whether those variables contribute in the same way, i.e. are correlated or independent of each other. Multivariate calibration – In a PCA, the modelling of only one X-matrix is analysed. In contrast, multivariate calibration involves two matrices, X and Y. A matrix of one or several variables is represented by Y while a matrix of one or several samples is represented by X. All calibrations in this appendix are presented in validation plots, where the x-axis is the measured Y and the y-axis is the predicted Y.
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Dioxin and PCBs in pelagic fish stocks
Multivariate regression model – The term multivariate regression model is a regression model for prediction of future samples. The x-axis is the measured Y, i.e. measured dioxin level expressed as ng WHO-TEQ/kg lipid and the y-axis is predicted Y, i.e. predicted dioxin level expressed as ng WHO-TEQ/kg lipid (1). The aim of this study was to make multivariate regression models for predicting the level of dioxin in capelin, blue whiting, Icelandic herring and Atlanto-Scandian herring.
Principal component analyses
Before a multivariate regression model is designed, a PCA is made by plotting all data from the project. This is used to investigate relationships between sets of data. Figure 1: PCA-plot showing X-loadings for all variables
PCDD
PCDD
Fat content and moisture are good examples of two variables demonstrating the utilization of PCA. Fat content and moisture are positioned in the plot at exactly the same distance from zero and in opposite quadrants, which means that these two variables are negatively correlated. This complies well with the recognised trends in this type of sample. This PCA shows that most of the PCDD/PCDF (dioxins), WHOPCBs and Marker PCBs results appear to be well correlated because of the clustering, except for PCB 81, OCDD and two PCDD´s. These exceptions could be outliers compared to the other PCDD/PCDFs and PCBs, but after checking these data there
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Dioxin and PCBs in pelagic fish stocks
was no direct explanation for these possible outliers, and therefore no reason for excluding them from a possible regression model. Based on these findings, the data can now be used for designing a regression model.
Designing the regression model
Figure 1 in this appendix indicates that it should be possible to get a good regression between PCDD/PCDF (dioxin) and one of the other variables. The GC/MS analyses for the 7 Marker PCBs is both easier and cheaper than analyses for dioxin. This makes the use of Marker PCBs an attractive predictive tool for dioxin level. Because of the variation of the Markers PCBs within samples, it is necessary to include all 7 Marker PCBs in the regression model. There are therefore 7 different X variables. All the analytical data for PCDD/PCDF (dioxins) and Marker PCBs in fish, fishmeal and fish oil are upperbound values expressed on a lipid basis. Figure 2: Regression model for all samples of capelin, Iceland herring, AtlantoScandian herring and blue whiting.
When building up the regression model, a full cross validation is selected. Figure 2 in this appendix shows the predicted values against the measured values for dioxins. This gives a correlation of 0,9236 indicating a stable calibration. The RMSEP (Root Mean Square Error of Prediction) has a high value of 1,4724, which is 37% of the mean of PCDD/PCDF for all of the 96 samples (4,0053). This value is too high and therefore not acceptable (2). The target must be to decrease the RMSEP. The search for outliers was not successful, so it was decided to split the regression model according to fish species.
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Dioxin and PCBs in pelagic fish stocks
Figure 3: Regression model for all capelin samples
Figure 4: Regression model for all blue whiting samples
The capelin plot (figure 3 in this appendix) gave a correlation of 0,8986, and a RMSEP of 0,4025, which is 20 % of the mean value for the capelin samples (2,0460). This model is acceptable, although there are only 41 samples in the capelin model, leading to some uncertainty. The regression can be used for prediction of dioxin level in new capelin samples after measuring only the 7 Marker-PCBs. Additional samples would improve the reliability of this predication. The blue whiting plot (figure 4 of this appendix) gave a correlation of 0,9752, and a RMSEP of 1,1850, which is 19% of
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Dioxin and PCBs in pelagic fish stocks
the mean value for the blue whiting samples (1,1850). This model is also acceptable, and can be used for prediction of dioxin level in new blue whiting samples. The two herring stocks consist of only 13 samples from each stock, which is not enough to make stable models. The good correlation of the two other models for capelin and blue whiting indicate that this should also be possible for the herring stocks providing sufficient data were available.
Conclusion
These two models, one for capelin and another for blue whiting, can be used for prediction of the concentration of dioxin (PCDD/PCDF) by measuring only the 7 Markers-PCB. They are based on analytical data for PCDD/PCDF and Marker PCBs in raw material (lipid based), fishmeal (lipid based) and fish oil from this project. Models are not static tools of prediction. The regression can change over a period of time. It is appreciated that the relationships suggested here apply only for these particular fish stocks at the time of the sampling. It is therefore imperative to periodically perform full HRGC/HRMS analyses in order to update and improve the models. The use of the multivariate data analysis as a predictive tool could, however, be of interest in this case because of the relative ease with which the 7 Marker PCBs can be measured compared to the full HRGC/HRMS analysis for dioxins.
References
1. Esbensen, Kim H., Multivariate Data Analysis – in practice, 4th edition, CAMO ASA. (2000) 2. Bro, Rasmus, Håndbog i Multivariabel Kalibrering, 1. Udgave, 1. oplag, DSR tryk (1996)
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