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					Chemical Contaminants in Food
          Packaging
       First Food Safety Congress
             Istanbul, Turkey
            December 4, 2009



                           Forrest L. Bayer, Ph.D.
                           Director Packaging Scientific &
                           Regulatory Affairs
      Presentation Scope
    Packaging Contaminants
Regulatory considerations
Packaging materials
Packaging deliverables
Material composition
Risk perception
Packaging Contaminants
Urban Legends
The shape of things to come
Regulatory Considerations
    Basic Tenets of Worldwide
     Packaging Regulations
 Packaging shallnot endanger the
 consumer through product
 adulteration by migration from
 packaging

 The package will not detract from the
 organoleptic properties (taste/smell)
 of the food
 Global Regulatory Approaches

 General safety requirements – common to every
  country
 General safety only – Mexico, some Asian and South
  American countries, South Africa
 Mandatory positive lists – EU, MERCOSUR
 Voluntary positive lists – Japan, Germany
 No objection or opinion letters –Canada, (U.S. for
  recycled plastics)
 Combination approach – U.S.
 Pre-market registration – Argentina, Brazil, some
  Eastern European countries
    Legal requirements
It is the responsibility of the
 manufacturer of the food product
 to guarantee that the food placed
 on the market is safe
Packaging Deliverables
     Packaging Delivers Safe and
            Quality Food
 Extends the shelf life of food products
   – Preserves the compositional integrity of food
   – Prevents microbial contamination
   – Offers physical protection during food handling
     and storage
 Meets consumer’s convenience requirements
 Provides a tool to communicate with consumers
   – Nutrition information
   – Customer engagement tool
   – Promotion display
Package Failure
Interior Can Coatings:
Severe Coating Adhesion Loss
Interior Can Coatings:
     Severe Blistering
Interior Can Coatings:
     Interior Corrosion
Packaging Types and Materials
                Package Types
Rigid and Flexible Plastics      38%
Metal Containers                 19%
Glass                             8%
Paper/Paper Board                30%
Other                             5%
  – Film
  – Blister



Source: Pira International 2008
  Typical Polymeric Packaging
            Materials
 Polyolefins
   – PP
   – HDPE
   – LDPE
   – LLDPE
 PET
 Styrene
 PVC
 Nylon
 EVA
 ABS
 PU
       Additives to Polymeric
             Packaging
Antioxidants
Anti-statics
Antifogging agents
Anti blocks
Plasticizers
Slip agents
Thermal stabilizers
Light (UV) stabilizers
Colorants
Carriers
Package Material Composition
       High Density Polyethylene
                HDPE
   Ethylene                           Monomer
   Propylene                          Comonomer
   4-Methylpentene                    Comonomer         0.05 mg/kg
   1-Hexene                           Comonomer         3.0 mg/kg
   1-butene                           Comonomer
   1-Octene                           Comonomer         15.0 mg/kg
   Pentaerythol tetrakis[3-5-(di-     Antioxidant
    tertiarybutyl-4-hydrophenyl)propionate]
   Phosphorous acid, tris(2,4-di-tert  Antioxidant
    butylphenyl)ester
   Octadecyl-3-(3,5-di-tert-butyl-4-   Antioxidant      6.0 mg/kg
    hydroxyphenylproponate
   Erucamide,Oleamide,Stearamide       Slip Additives
   N,N-bis(hydroxyethyl)alkyl          Antistatic       1.2 mg/kg
    (C8-C18 amines)
   Glycerol Stearate                   Antiblocks
   Silica (Silicon dioxide)            Antiblocks
                         Polystyrene
   Styrene                            Monomer
   1.3-butadiene                      Comonomer         ND@ 0.02 mg/kg
   Acrylonitrile                      Comonomer         ND@ 0.02 mg/kg
    White mineral oil                 Extender
    Pentaerythol tetrakis[3-5-(di-    Antioxidant
    tertiarybutyl-4-hydrophenyl)propionate
   Phosphorous acid, tris(2,4-di-tert  Antioxidant
    butylphenyl)ester
   Octadecyl-3-(3,5-di-tert-butyl-4-   Antioxidant      6.0 mg/kg
    hydroxyphenylproponate
   Erucamide,Oleamide,Stearamide       Slip Additives
   N,N-bis(hydroxyethyl)alkyl          Antistatic       1.2 mg/kg
    (C8-C18 amines)
   Thiodipropanoic acid, didodecyl     Antioxidant      5.0 mg/kg
    ester (DLTDP)
   Thiodipropanoic acid, dioctadecyl Antioxidant        5.0 mg/kg
    ester (DLTDP)
   Alkyl (C8-C22) sulphonic Acids      Antistatic       6.0 mg/kg
     Polyethylene Terephthalate
             PETE/PEN
   Terephthalic acid                   Monomer  7.5 mg/kg
   Isophthalic acid                    Monomer  5.0 mg/kg
   Ethylene glycol                     Monomer 30.0 mg/kg
   Diethylene glycol                   Monomer 30.0 mg/kg
   1,4 Cyclohexanedimethyl             Monomer
   Antimony trioxide                   Catalyst 0.04 mg/kg
   Dimethyl terephthalate              Monomer
   Dimethyl Isophthalate               Monomer
   2,6-Naphthalene dicarboxylic acid   Monomer  5.0 mg/kg
   2,6-Naphthalene dicarboxylic        Monomer  0.05 mg/kg
    dimethyl ester
   2- Aminobenzamide                   Scavenger   0.05 mg/kg
              Plasticizers
Epoxidized Soybean Oil      ESBO
Epoxidized Linseed Oil      ELO
Di-2-ethylhexyl Phthalate   DEHP
Diisodecyl phthalate        DIDP
Diisononyl phthalate        DINP
 Di-2-ethylhexyl adipate    DEHA
Dibutyl phthalate           DBP
Dibutyl sebacate            DBS
Acetyl tributyl citrate     ATBC
                    Antioxidants
 Tinuvin P        2-(2’Hydroxy-5’methyl-phenyl) benzotriazole
 Tinuvin 326      2-(5-chloro-2H-benzenetriazole-2-yl)-6-(1,1-
                   dimethyl)-4-methylphenol
 Tinuvin 770 DF   Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate
 Tinuvin 234       2-[3-Hydroxy-3,5-bis(1-methyl-1-
                   phenyl)phenyl]benzotriazole
 Chimasorb 81     2-Hydroxy-4-n-octyloxybenzophenone
 Irganox 1076      Octadecyl-3-(3,5-di-tert.-butyl-4-
                    hydroxyphenyl)propionate
 Irganox 1330      (1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert.-butyl-4-
                    hydroxyphenyl)propionate

 Irganox 1010     Pentaaerythrityl-tetrakis-3-(3,5-di-tert.-butyl-4-
                   hydroxyphenyl)propionate
 Irgafos 168      Tris-(2,4-di-tert,-butylphenyl) phosphite
 Irgafos P-EPQ    Tetrakis(2,4-di-tert.-butylphenyl)-4,4’-
                   biphenylene diphosphonite
Risk Perception
 Risk Perception of Food Contact
            Materials
 Risk perception for food contact materials may differ
  from scientific reality
 Press releases and media headlines may help create
  a perceived risk
 Social and cultural factors can outweigh the
  scientific evidence
 As analytical techniques improve, ultra-trace levels
  of food contact substances are being detected and
  presented sometimes out of context
                 Recent Headlines
Chemical Fallout Watchdog Update: BPA Industry seeks to polish image
        The Milwaukee Journal Sentinel, 29 May 2009




              Is plastic killing us?
              The Globe and Mail ; 5 November 2005




                EU plans food packaging measures after Italy scare
                Reuters News ; 9 December 2005
Packaging Contaminants
       Packaging Contaminants
Monomers
Oligomers
Decomposition Products
  – Thermal
  – Oxidative
  – Photochemical
  – Ionizable
Solvents
Reaction Products
Impurities: non-intentionally added substances (NIAS)
Packaging Contaminant issues
      Recent Examples
 Bis-Phenol A
 Semicarbazide
 2- Isopropyl thioxanthone (ITX)
 Antimony
 Nonylphenol / Nonylphenol ethoxolates
 Benzophenone
 4-Methylbenzophenone
 Epoxidized Soy Bean Oil (ESBO)
 Di-2-ethylhexyl phthalate (DEHP)
 Perfluorooctnoic acid (PFOA)
 Perfluorooctnoic sulfonate (PFOS)
 Melamine
 BPA Health Effect Allegations

Prostate cancer
Breast cancer
Reduced sperm count
Increased prostate weight
Hyperactivity
Obesity
Altered immune system
Reproductive effects
Cardiovascular effects
Diabetes
    BPA: The Facts - Toxicology
 Not a carcinogen
   – No evidence of cancer in NTP bioassays in
     two species

 Not mutagenic
   – No in vitro or in vivo genetic or chromosomal
     effects in guideline studies

 Not a developmental toxicant
   – Did not cause birth defects or malformations

 Not a selective reproductive toxicant
   – Did not reduce fertility or impair ability to
     reproduce at doses not toxic to the mother
 Global Government and Regulatory
  Agencies that have reviewed BPA
 US FDA: Feb. 2009
 EU EFSA: July 2008; Jan. 2007
 FSNAZ Food Stds. Australia New Zealand:
  March 2009
 Canada Health Protection Branch: Oct. 2008
 German Federal Institute of Risk Assessment:
  Sept. 2008; Jan. 2006
 Japanese Ministry of Health: March 2006
 UK Food Standards Authority: April 2001
 California Prop 65 review committee July 2009
 Re Review by US FDA and WHO/FOA to initiate
2- Isopropyl thioxanthone (ITX)
Italian routine monitoring for PAHs in aseptic
 package milk found large unidentified peak
Compound determined to be a printing ink
 photo initiator (ITX)
Migration in milk found to be the result of
 contact transfer due to the packaging material
 roles having the printing ink side in contact
 with the food product side
        Semicarbazide (SEM)
Routine monitoring by an European major
 food/beverage producer found traces of
 semicarbazide
Originally believed to be due to a by product
 of an antibiotic (nitrofuran) unauthorized for
 food use; reported to the EU Commission
Investigation revealed SEM levels were due
 to “puffing” agent (azodicarbamide) used in
 “press on” / “twist off” closures
European Foods Safety Authority – not an
 issue
EU Commission banned its use
                     Antimony
      W. Schotyk et. al: J. Env. Monit. 2006, 8, 288–292
                  Called press conferences
Antimony in Canadian Spring Water ~3 ppt
Antimony in PET bottle Water initially 359 ppt
Antimony in bottle water after 3 ambient
 storage months = ~626ppt
   W. Schotyk/M. Karchler ENVIRON. SCI. & TECH.
Measured Sb in 132 bottle water samples from
 28 countries
After 6 months one sample increased from 725
 ppt to 1510 ppt
All were within regulated limits
     Antimony Regulated limits
World Health Organization (2003) raised limit
 from 10 micrograms/kg to 20 micrograms/kg
EFSA raised the migration limit (2004) from 20
 micrograms/kg to 40 micrograms/kg
Antimony occurs naturally in the environment
According to experts, the main exposure to
 antimony is from breathing air in an urban
 environment
Found naturally in foods such as:
   – carrots ~0.2 ppb
   – green peas ~ 0.7 ppb
   – baked potatoes ~1.8 ppb
   – Meat and shellfish products ~0.4 to 2.8 ppb
Urban Legends
            Urban Legends
Urban legend 1: Pet Water bottles left in the
 back of the car releases toxic chemicals into
 the water and this can cause breast cancer
 The heat reacts with the chemicals in the
 plastics and releases dioxin into the water.
Urban legend 2: Placing your water bottle in
 the freezer also releases dioxin from the
 plastic.. Additional versions of the legend
 have been attributed to Johns Hopkins and
 Walter Reed Memorial Hospital
              Urban Legends
 Urban Legend 3: Many are unaware of poisoning
 caused by re-using plastic bottles.
   – habit of using and re-using your disposable mineral
     water bottles or keeping them in your car
   – Not a good idea.
   – PET used in these bottles contains a potentially
     carcinogenic element (something called
     diethylhydroxyamine or DEHA).
   – The bottles are safe for one-time use only; if you
     must keep them longer, it should be for no more
     than a few days, a week max, and keep them away
     from heat as well.
            Urban Legends
 The originators of this statement did not
  bother to check their basic chemistry
  – The DEHA that is discussed is di-2-
       ethylhydroxy adipate a common
       plasticizer
  – DEHA is most probably from closure
 It is not di- 2- ethylhydroxyamine
The Shape of Things to come
    The Shape of Things to come


       Biomonitoring Initiatives
International Countries
Federal
State
         Ultra Trace Detection
Chasing ZEROS!! ppq-ppt????
 The Shape of Things to come
Engineered Nano materials
Ionization and food packaging materials
Active Packaging
                Summary
World of packaging is very complex
Regulations vary from country to country and
 are constantly changing as our knowledge
 increases
Contaminants may be real or perceived
Brand owners and suppliers must meet both
 the regulatory criteria and consumer demand
It is the responsibility of the companies
 placing their packages on the shelf to insure
 that they are fully compliant.
Thank You

				
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