Not to be quoted without prior reference to the authors © Crown Copyright 2009 FD 09 /01 Investigation into the Levels of Environmental Contaminants in Scottish Marine and Freshwater Fin Fish and Shellfish A. Fernandes, F. Smith, R Petch, N Brereton, E. Bradley, S Panton, M Carr and M.Rose Authorised Signatories: _________________ _________________ A Fernandes M Rose OPHA Organic Contaminants OPHA Organic Contaminants October 2009 Food and Environment Research Agency Sand Hutton YORK YO41 1LZ Opinions and interpretations are outside the scope of UKAS accreditation. Measurements for all reported analyses are UKAS accredited apart from PFOS, PCNs, deca-BDE/BB, Me-Hg and Phthalates which are outside the scope of accreditation. Page 1 of 193 Investigation into the Levels of Environmental Contaminants in Scottish Marine and Freshwater Fin Fish and Shellfish Report Number: FD 09 /01 Authors: *A Fernandes, F Smith, R Petch, E. Bradley, N. Brereton, S Panton, M Carr and M.Rose Date: October 2009 Sponsor: Food Standards Agency Scotland Environmental Contaminants 6th Floor St Magnus House 25, Guild Street Aberdeen AB11 6NJ Sponsor's Project Number: S14040 FERA Contract Number: S6OT FERA File Reference: FLN 8888 Principal Workers: M Carr, K Harmannij, M Miller, E Greene, F Smith, S Panton, R Petch, J Holland, D Clarke, D Speck N. Brereton & A. Fernandes Team Leader: M Rose Distribution: 1. Dr Jacqui McElhiney 2. Dr M Rose 3. Dr A Fernandes 4. FLN 8888 5. FERA Information Centre Page 2 of 193 SUMMARY 1. Marine and freshwater fish bio-accumulate environmental contaminants, and coastal and river waters are recognised sinks for these chemicals. This study characterises a range of existing and emerging contaminants in the flesh of fish and shellfish species with a view to determine current levels of occurrence and to allow estimation of consumer exposure. 2. A range of fish species from marine and freshwater habitats were obtained comprising 32 marine samples, 16 freshwater samples and 5 marine shellfish samples. These were analysed for the following contaminants: • Heavy Metals • Chlorinated Dioxins (PCDD/Fs) • Polybrominated biphenyls (PBBs) • Polychlorinated biphenyls (PCBs) • Brominated dioxins (PBDD/Fs) • Polychlorinated naphthalenes (PCNs) • Polybrominated diphenylethers (PBDEs) • Phthalates Additionally some of the samples were also analysed for perfluorinated compounds (PFOS) and polycyclic aromatic hydrocarbons (PAHs). 3. The methodologies used for the analyses are largely UKAS accredited to the ISO 17025 standard and where applicable (e.g. dioxins and PCBs) follow EU commission regulations for quality criteria. Equivalent criteria were followed for those analytes not directly covered by accreditation. For chlorinated dioxins and PCBs, the concentrations of each sample have also been reported as toxic equivalents (TEQs). A similar approach was used for the PBDD/Fs and relevant PBBs, but the limitations of this interim measure must be recognised, i.e. the analogous chlorinated TEF values used, provide only an indicative estimate of toxicity (TEQ) for these brominated contaminants. 4. For the organic contaminants it is clear that no fish or shellfish samples in this study breach the existing regulated limits - for dioxin and PCB WHO-TEQ for example, the highest level was detected in a sample of roach with a concentration of 3.5 ng/kg against a maximum permitted value of 8 ng/kg. For the heavy metals, some expected minor excursions beyond the maximum limits for mercury occur in ling and blue ling (ling is known to bio-accumulate the metal), with measured values of 0.7 mg/kg and 0.6 mg/kg against a limit of 0.5 mg/kg. Page 3 of 193 5. The results of this study confirm the occurrence of a wide range of environmental contaminants in these species and underline the ubiquity and persistence of these compounds. This is evident from the occurrence of both, legacy contaminants (PBBs, PCNs and PCBs), as well as more recently introduced chemicals (deca-BDE and PFCs). 6. Fresh-water fish generally show higher levels of the major contaminants investigated (apart from arsenic and mercury) than marine species or shellfish. This is remarkable given that many of the fresh-water samples received were made up of a number of small sized fish (average 15-20 cms in length) that would be unlikely to be consumed. Given the bio-accumulative nature of these contaminants, it is probable that larger (and older) fish within the same locations would tend to show higher levels of contamination. 7. This report represents the first study of such a comprehensive set of contaminants in fish and as such is unique. The data will allow estimation of dietary intake for consumers of these foods, but considerable uncertainty would remain within these estimates, given the observations made in this study, particularly for the freshwater fish. The data also provides information on the current background levels of these emerging and existing contaminants. A parallel study on freshwater fish from uncontrolled waterways in other parts of the UK is currently underway. The combined information from these two sets of complementary data may allow more refined estimates of human exposure. Page 4 of 193 LIST OF CONTENTS SUMMARY 3 GLOSSARY 6 INTRODUCTION 7 EXPERIMENTAL 15 RESULTS AND DISCUSSION 30 REFERENCES 43 Table 1. Sample information 50 Table 2. Concentrations of heavy metals, (& speciated As and Hg) 52 Table 3. Concentrations of PCDDs and PCDFs 56 Table 4. Concentrations of non-ortho PCBs 69 Table 5. Concentrations of ortho- PCBs 77 Table 6. Summary of dioxin and PCB WHO-TEQ 103 Table 7. Concentrations of PBDD/Fs and non-ortho PBBs 109 Table 8. Concentrations of PBDEs and ortho- PBBs 121 Table 9. Concentrations of PCNs 129 Table 10. Concentrations of Phthalates 135 Table 11. Concentrations of PFCs 141 Table 12. Concentrations of PAHs 142 Table 13. Results of Reference Material Analysis 144 Table 14. Summary of Contaminant Concentrations 149 Table 15. Ranking of samples 150 Annexe 1 Marine Scotland Report – Sample collection 151 Page 5 of 193 GLOSSARY Σ PBDD/F TEQ Sum of WHO -TEQ for individual PBDD/F congeners Σnon-ortho PBB TEQ Sum of WHO -TEQ for individual non -ortho PBB congeners BDE Brominated Diphenylether BCR Community Bureau of Reference BFR Brominated Flame Retardant CRM Certified Reference Material EFSA European Food Safety Authority GC -HRMS Gas chroma tography - high resolution mass spectrometry HPLC -MS/MS LC -MS in multiple reaction monitoring mode IUPAC International Union of Pure and Applied Chemistry LC -MS High Pressure Liquid Chromatography - mass spectrometry PAHs Polycyclic aromatic hydrocarbo ns PCB/PBB Polychlorinated biphenyl/ Polybrominated biphenyl PBDE Polybrominated Diphenylether PBDD/F Polybrominated dibenzo -p-dioxin/ furan PCDD/F Polychlorinated dibenzo -p-dioxin/ furan PFC Perfluorinated compound PTMI Provisional tolerable monthly intake PTV Programmed temperature vaporisation RM Reference Material SCF EU Scientific Committee on Food TDI Tolerable Daily Intake TDS Total diet survey TEF Toxic Equivalence Factor TEQ Toxic equivalence WHO World Health Organisation %U Percentage Uncertainty Page 6 of 193 INTRODUCTION Environmental contamination in fish and shellfish Marine and aquatic environments are recognised sinks for a range of environmental contaminants, and uptake and bioaccumulation by various fish and shellfish species has been widely documented. In particular, marine shellfish have a recognised potential for bio-accumulating contaminants and some species such as mussels, are commonly used as early indicators of local pollution. Consequently, marine fish and shellfish have been shown to make a significant contribution to human exposure of a range of environmental contaminants. Aquatic species also show a similar potential for contaminant bio-accumulation and there have been a number of reports of elevated contaminant levels in river and lake species such as trout, pike, carp, perch etc. In many parts of the world, including the European Union, fish caught from rivers and other fresh waters are often included in the diet. Within the UK however, it is unclear as to what extent these potential foods contribute to human exposure, due to lack of current knowledge on contaminant levels in the various species and the extent to which these species are consumed by certain sub-groups of the population such as anglers and others. Heavy Metals Some trace elements and in particular, heavy metals are established toxic contaminants. Some elements, such as copper, chromium, selenium and zinc are essential to health but may be toxic at high levels of exposure. Other elements have no known beneficial biological function and long-term, high-level exposures may be harmful to health. Environmental sources are the main contributors to contamination of food which is the major source of the overall exposure of consumers to metals and other elements, although other routes may also be significant (for example, oral exposure via the drinking water, inhalation exposure via the occupational setting). The presence of metals and other elements in food and the environment can also be the result of contamination by certain agricultural practices (e.g. cadmium from phosphate fertilisers), manufacturing and packaging processes (e.g. aluminium and tin in canned foods) and endogenous sources (e.g. as in ground waters in certain parts of the world). Furthermore, certain food groups naturally accumulate some elements and consequently contain high concentrations of these elements compared to other foods. For example, Page 7 of 193 fish and shellfish are known to accumulate arsenic and mercury and cereals can accumulate cadmium. Metals and other elements may enter marine and aquatic environments and bio-accumulate in species at any point during growth and harvesting. There have been many surveys of sea-fish for trace elements but fewer conducted on freshwater fish or on deep sea fish and very few that have been conducted with simultaneous analysis for organic contaminants. Heavy metals may be present in waterways as a result of the geology of the region, for example naturally occurring lead or zinc are found in some areas.