Effects of different cooking methods on fatty acid profiles in four freshwater fishes from the Laurentian Great Lakes region.

Fish is often promoted as a healthy part of the human diet due its high content of long chain n-3 polyunsaturated fatty acids (LC-PUFA). Previous studies have shown that cooked fish can have different fatty acid profiles than raw fillets, depending on the cooking method and fish species. In this study, the fatty acid content of broiled, baked or fried skinless, boneless fillets of four fish species from the tributaries of the Great Lakes, or connecting rivers, was compared to fatty acid profiles in raw sections from the same fillet. Cooking treatments had little effect on n-3 fatty acid content; however, fried treatments generally had higher n-6 and MUFA content, which is likely a result of the cooking oil used (canola). Broiling or baking is generally the most healthy option presented in this study, as these methods result in lower levels of less-favourable fatty acids; however, the choice of cooking oil may also influence the overall fatty acid content in cooked fish.

High levels of perfluoroalkyl acids in sport fish species downstream of a firefighting training facility at Hamilton International Airport, Ontario, Canada.

A recent study reported elevated concentrations of perfluorooctane sulfonic acid (PFOS) and other perfluoroalkyl acids (PFAAs) in surface water, snapping turtles, and amphipods in Lake Niapenco, downstream of Hamilton International Airport, Ontario, Canada. Here, our goals were to 1) determine the extent of PFAA contamination in sport fish species collected downstream of the airport, 2) explore if the airport could be a potential source, and 3) compare fish PFOS concentrations to consumption advisory benchmarks. The PFOS levels in several sport fish collected from the three locations closest to the airport (<40km) were among the highest previously published in the peer-reviewed literature and also tended to exceed consumption benchmarks. The only other fish that had comparable concentrations were collected in a region affected by inputs from a major fluorinated chemical production facility. In contrast, PFOS concentrations in the two most downstream locations (>70km) were comparable to or below the average concentrations in fish as observed in the literature and were generally below the benchmarks. With regards to perfluorocarboxylates (PFCAs), there was no significant decrease in concentrations in fish with distance from the airport and levels were comparable to or below the average concentrations observed in the literature, suggesting that the airport is not a significant source of PFCAs in these fish species. PFOS-based aqueous film-forming foam (AFFF) was used at a firefighting training facility at the airport in the 1980s to mid-1990s. Taken together, our results provide evidence that the historical use of AFFF at the airport has resulted in fish PFOS concentrations that exceed the 95th percentile concentration of values reported in the literature to date.

Cooking fish is not effective in reducing exposure to perfluoroalkyl and polyfluoroalkyl substances.

Consumption of fish is considered a part of a healthy diet; however, health risks from fish consumption exist due to potential exposure to various contaminants accumulated in fish. Cooking fish can reduce exposure to many organic chemicals in fish. Similar results have been presented for low levels of perfluoroalkyl and polyfluoroalkyl substances (PFASs), a class of contaminants of emerging concern, in grocery store fish. We examined the effectiveness of three cooking methods (i.e., baking, broiling, and frying) on reducing PFAS levels in four sport fish species. Samples of Chinook salmon, common carp, lake trout and walleye were collected from four rivers in Ontario, Canada and skin-off fillets were analyzed for regular groups of PFASs such as perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkane sulfonic acids (PFSAs), as well as perfluoroalkyl phosphonic acids (PFPAs), perfluoroalkyl phosphinic acids (PFPIAs) and polyfluoroalkyl phosphoric acid diesters (diPAPs), which are PFASs of emerging concern. Perfluorooctane sulfonate (PFOS) was the dominant PFAS detected and the concentrations were more than an order of magnitude higher than those reported for fish from grocery stores in Canada, Spain, and China. Although concentrations of PFOS in fish fillets generally increase after cooking, amounts of PFOS largely remain unchanged. Relatively minor differences in changes in the fish PFAS amounts after cooking depended on fish species and cooking method used. We conclude that cooking sport fish is generally not an effective approach to reduce dietary exposure to PFASs, especially PFOS.

Determination of polyfluoroalkyl phosphoric acid diesters, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, perfluoroalkyl carboxylic acids, and perfluoroalkane sulfonic acids in lake trout from the Great Lakes region.

A comprehensive method to extract perfluoroalkyl carboxylic acids, perfluoroalkane sulfonic acids, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids, and polyfluoroalkyl phosphoric acid diesters simultaneously from fish samples has been developed. The recoveries of target compounds ranged from 78 % to 121 %. The new method was used to analyze lake trout (Salvelinus namaycush) from the Great Lakes region. The results showed that the total perfluoroalkane sulfonate concentrations ranged from 0.1 to 145 ng/g (wet weight) with perfluorooctane sulfonate (PFOS) as the dominant contaminant. Concentrations in fish between lakes were in the order of Lakes Ontario ≈ Erie > Huron > Superior ≈ Nipigon. The total perfluoroalkyl carboxylic acid concentrations ranged from 0.2 to 18.2 ng/g wet weight. The aggregate mean perfluorooctanoic acid (PFOA) concentration in fish across all lakes was 0.045 ± 0.023 ng/g. Mean concentrations of PFOA were not significantly different (p > 0.1) among the five lakes. Perfluoroalkyl phosphinic acids were detected in lake trout from Lake Ontario, Lake Erie, and Lake Huron with concentration ranging from non-detect (ND) to 0.032 ng/g. Polyfluoroalkyl phosphoric acid diesters were detected only in lake trout from Lake Huron, at levels similar to perfluorooctanoic acid.

Challenges and trends in the determination of selected chemical contaminants and allergens in food.

This article covers challenges and trends in the determination of some major food chemical contaminants and allergens, which-among others-are being monitored by Health Canada's Food Directorate and for which background levels in food and human exposure are being analyzed and calculated. Eleven different contaminants/contaminant groups and allergens have been selected for detailed discussion in this paper. They occur in foods as a result of: use as a food additive or ingredient; processing-induced reactions; food packaging migration; deliberate adulteration; and/or presence as a chemical contaminant or natural toxin in the environment. Examples include acrylamide as a food-processing-induced contaminant, bisphenol A as a food packaging-derived chemical, melamine and related compounds as food adulterants and persistent organic pollutants, and perchlorate as an environmental contaminant. Ochratoxin A, fumonisins, and paralytic shellfish poisoning toxins are examples of naturally occurring toxins whereas sulfites, peanuts, and milk exemplify common allergenic food additives/ingredients. To deal with the increasing number of sample matrices and analytes of interest, two analytical approaches have become increasingly prevalent. The first has been the development of rapid screening methods for a variety of analytes based on immunochemical techniques, utilizing ELISA or surface plasmon resonance technology. The second is the development of highly sophisticated multi-analyte methods based on liquid chromatography coupled with multiple-stage mass spectrometry for identification and simultaneous quantification of a wide range of contaminants, often with much less requirement for tedious cleanup procedures. Whereas rapid screening methods enable testing of large numbers of samples, the multi analyte mass spectrometric methods enable full quantification with confirmation of the analytes of interest. Both approaches are useful when gathering surveillance data to determine occurrence and background levels of both recognized and newly identified contaminants in foods in order to estimate human daily intake for health risk assessment.

Long-term environmental fate of perfluorinated compounds after accidental release at Toronto airport.

Perfluorooctane sulfonate (PFOS; a perfluorinated compound or PFC), its salts, and perfluorooctane sulfonyl fluoride have recently been listed in Annex B of the Stockholm Convention due to their widespread presence, persistence, and toxicity. Because of the persistent nature of PFCs, it is generally presumed that the impact of direct discharges of these chemicals on a receiving environment would be long-lasting. However, long-term environmental fate studies based on field measurements are rare. We examined spatial and long-term (9 year) temporal trends of PFCs in water, sediment, fish, and fish liver collected in 2003, 2006, and 2009 from 10 locations spanning ∼20 km in Etobicoke and Spring Creeks, where an accidental release of fire fighting foam containing PFOS from nearby Toronto International Airport occurred in 2000. Even a decade after the spill, sediment PFOS concentrations are still elevated in Spring Creek Pond which received the foam discharge; however, the major impact is relatively localized likely due to the stormwater management nature of the pond and the diluting effect of Etobicoke Creek. Fish and fish liver PFOS concentrations at a Spring Creek location downstream of Spring Creek Pond declined by about 70 and 85%, respectively, between 2003 and 2009. PFOS in water at locations further downstream in Etobicoke Creek have declined by >99.99% since the spill; however, the 2009 water and fish levels were ∼2-10 times higher than upstream locations likely due to the long-term impact of the spill as well as urbanization. The decrease in the upstream PFOS concentrations likely reflects the reduction of PFOS sources due to phased out production by 3M and regulations on the use of PFOS in fire fighting foams. Field-based sediment/water distribution coefficients (K(D)) and bioaccumulation factors (BAF) were calculated from environmental measurements. Log K(D) values were 0.54-1.65 for perfluoroalkyl sulfonates (PFASs) and 1.00-1.85 for perfluorocarboxylates (PFCAs). Log BAF(fish) ranged from 1.85 to 3.24 for PFASs and 0.88-3.47 for PFCAs, whereas log BAF(fish liver) ranged from 2.1-4.3 for PFASs and 1.0-5.0 for PFCAs.

Effect of cooking on concentrations of ß-estradiol and metabolites in model matrices and beef.

Because beef food products are generally cooked prior to consumption, the behavior of chemicals in these cooked foods is important in estimating human exposure. The heat stability of the natural estrogen ß-estradiol (ß-E2) and its metabolites α-estradiol (α-E2), estrone (E1), and several catechol estrogens was examined in heated vegetable oil and aqueous solutions. The chemicals were also incorporated into regular and extra lean ground beef and subjected to cooking. E1 and E2 were stable in aqueous solutions at 100°C, whereas the catechol estrogens exhibited first-order decay curves with half-lives of 2-10 min. Their stability improved to the same level as the other test chemicals when an antioxidant was added to the solution, suggesting that their disappearance was due to oxidation rather than thermal degradation. E1 and E2 were also stable in heated vegetable oil (160-180°C), whereas catechol estrogen decreased 30-50% over the 2 h duration of the experiments. Chemical losses from cooked beef appear to be related to the fat content of the beef, with greater losses occurring in regular ground beef (25-30%), compared to extra lean ground beef (5-20%). This study shows that cooking reduces but does not eliminate the potential for dietary exposure to growth promoters in ground beef.

Analysis of polyfluorinated compounds in foods.

Polyfluorinated compounds (PFCs) are a relatively new and diverse set of compounds analyzed as contaminants in food. Their unique physical-chemical properties dictate the methods used for their analysis. Current analyses of the more volatile PFCs involve gas chromatography-mass spectrometry; liquid chromatography-tandem mass spectrometry is generally used for the less volatile PFCs. Considerations in the analysis of PFCs in foods include contamination from the widespread presence of materials that contain various PFCs, endogenous interfering compounds, and matrix effects. Future opportunities for research on PFCs in food exist, particularly in the areas of biological molecule-PFC interactions and the effects of food processing on these interactions. Future research will be facilitated by the synthesis of a wider variety of analytical standards.

Short and medium chain length chlorinated paraffins in UK human milk fat.

Chlorinated paraffins (also called polychlorinated n-alkanes -- PCAs) are a class of industrial chemicals comprising chlorinated straight chain hydrocarbons. They have a wide range of applications and are now found in a range of environmental compartments. We analysed a total of 25 human milk-fat samples, donated by 18 individuals from the urban London and more rural Lancaster areas in the UK, for short chain PCAs (C(10)-C(13) sPCAs) and medium chain PCAs (C(14)-C(17) mPCAs), using gas chromatography-ECNI high-resolution mass spectrometry. Our study confirms that trace quantities of PCAs can reach human milk-fat. sPCAs were detected in all but four samples, while mPCAs were detected in all samples. The median sPCA concentration was 180 ng/g fat (range of 49 to 820 ng/g fat -- detected values only) and the median mPCA concentration was 21 ng/g fat (range of 6.2 to 320 ng/g fat). No differences were noted in ranges of observed values for either sPCAs or mPCAs between samples from London and Lancaster. Most samples also exhibited similar patterns of sPCAs and mPCAs. One sample exhibited a different pattern for sPCAs and mPCAs, an observation that may be related to differences in exposure or biological factors for this individual.

Spatial and temporal variability in air concentrations of short-chain (C10-C13) and medium-chain (C14-C17) chlorinated n-alkanes measured in the U.K. atmosphere.

Two studies were carried out on short-chain (C10-C13) and medium-chain (C14-C17) polychlorinated n-alkanes (sPCAs and mPCAs) in U.K. air samples. The first study entailed taking 20 24-h air samples with a pair of Hi-Vol air samplers at the Hazelrigg field station, near Lancaster University. These samples were carefully selected to coincide with times when air masses were predicted to have a fairly constant back trajectory for 24 h and to give a broad spectrum of different origins. The second study was a spatial survey of PCAs in the air at 20 outdoor sites in northern England and four indoor locations in Lancaster, using polyurethane foam (PUF) disk passive air samplers. Levels of the sPCAs in the Hi-Vol samples ranged from <185 to 3430 pg m(-3) (average 1130 pg m(-3)) and were higher than those previously measured at this site in 1997. Levels of the mPCAs ranged from <811 to 14500 pg m(-3) (average 3040 pg m(-3)); that is, they were higher than sPCAs. Both sPCA and mPCA air concentrations are of the same order of magnitude as PAH at this site. Back trajectory analysis showed that the history of the air mass in the 48 h prior to sampling had an important effect on the concentrations observed, with overland samples having higher levels than oceanic, implying that the U.K. is probably responsible for most of the PCAs measured in the U.K. atmosphere. Amounts of both sPCAs and mPCAs in the passive air samples followed a rural-urban gradient. PCAs appear to be released from multiple sources around the country, as a result of the diffusive, open industrial and construction use of the technical mixtures.

Congener-specific concentrations and carbon stable isotope ratios (delta13C) of two technical toxaphene products (Toxaphene and Melipax).

In this study we compared the contribution of individual congeners and the ratios of stable carbon isotopes of two technical toxaphene products. The former US-American product Toxaphene was from 1978 and the East-German product Melipax from 1979. Both technical products showed the known complexity in GC/ECD measurements. Contributions of 24 peaks to each of the technical products were determined by gas chromatography in combination high resolution electron capture negative ion mass spectrometry (GC/ECNI-HRMS). The percentages of the compounds studied in the technical mixtures ranged from approximately 0.05% to approximately 2.5% but showed some individual differences. 2,2,5,5,8,9,9,10,10-nonachlorobornane (B9-1025 or P-62) was identified as a major congener in both mixtures. 2-Endo,3-exo,5-endo,6-exo,8,8,10,10-octachlorobornane (B8-1413 or P26) and 2-endo,3-exo,5-endo,6-exo,8,8,9,10,10-nonachlorobornane (B9-1679 or P-50) were found at similar concentration in both technical products. Identical amounts of Melipax or Toxaphene were combusted to CO2 in an element analyzer and their delta13C values were determined relative to the international standard Vienna PeeDee belemnite (VPDB). The mean delta13C values of both products varied by 2.8% (determined at two different locations) which is roughly one order of magnitude more than the precision obtained in repetitive analyses of the individual products. Thus, both investigated products could be unequivocally distinguished by stable isotope ratio mass spectrometry (IRMS). IRMS analyses may thus be a suitable tool for tracing back toxaphene residues in environmental and food samples to the one or both of the products.

Vapour pressures, aqueous solubilities, Henry's Law constants, and octanol/water partition coefficients of a series of mixed halogenated dimethyl bipyrroles.

Basic physical-chemical properties of five bromine and chlorine containing mixed halogenated dimethyl bipyrroles (HDBPs) were determined using established methods. Subcooled liquid vapour pressures (P(o)(L,25)), aqueous solubilities (S(w,25)), and octanol/water partition coefficients (K(ow)) were determined using the gas chromatography-retention time, generator column, and slow-stirring methods, respectively. Henry's Law constants (H25) were estimated using experimentally-derived P(o)(L) and S(w,25) data. Values of all four properties were generally similar to those reported for other polyhalogenated aromatic compounds [P(o)(L,25) = (7.55-191) x 10(-6) Pa; S(w,25) = (1.0-1.9) x 10(-5) g/l; log K(ow) = 6.4-6.7; H25 = 0.0020-0.14 Pa m3/mol]. The effect of replacing a chlorine with a bromine atom significantly decreased P(o)(L,25) (log P(o)(L,25) = -0.4197 (# bromine atoms) - 2.643, p<0.01) and H25 (log H25 = -0.508 (# bromine atoms) + 0.394, p<0.02). There were no significant effects of bromine/chlorine substitution on S(w,25) or K(ow). A simple Level I equilibrium partitioning model predicted the environmental behaviour of HDBPs to be similar to a tetrabrominated diphenyl ether. Only slight differences in behaviour amongst HDBP congeners were predicted since substitution of a bromine for a chlorine (Cl/Br substitution) atom had less effect than H/Cl or H/Br substitution on P(o)(L,25), S(w,25), H25, and K(ow).

Anaerobic transformation of compounds of technical toxaphene. 2. Fate of compounds lacking geminal chlorine atoms.

The major toxaphene metabolites in sediment and soils (2-exo,3-endo,6-exo,8,9,10-hexachlorobornane [B6-923] and 2-endo,3-exo,5-endo,6-exo,8,9,10-heptachlorobornane [B7-1001]) were incubated with the isolated gram-negative bacterium Dehalospirillum multivorans. Within 14 d, biotransformation of B7-1001 was nearly quantitative, resulting in two penta- and six hexachlorobornanes, as well as one unsaturated hexachloro compound of technical toxaphene. The major transformation product (approximately 50% of all metabolites) was identified as 2-exo,3-endo,5-exo,8,9,10-hexachlorobornane (B6-903). Abiotic dehydrochlorination of B7-1001 with methanolic KOH resulted in the formation and subsequent identification of the lone unsaturated compound as 2,5-endo,6-exo,8,9,10-hexachloroborn-2-ene. Thus, dehydrochlorination was found to be a minor process of the anaerobic transformation of toxaphene. Biotransformation of 70% of amended B6-923 within 14 d demonstrated that reductive dechlorination was not exclusively associated with geminal Cl atoms, as previously suggested. Three pentachlorobornanes were identified as transformation products, one of which was identical with a transformation product of B7-1001. This commonality unequivocally proves this metabolite to be 2-exo,3-endo,8,9,10-pentachlorobornane. Fifteen previously unknown metabolites of B6-923, B7-1001, and other toxaphene compounds identified in this study were detected in sediment from Lake Ontario (Canada), underscoring the importance of microbial toxaphene transformation in natural, aquatic environments.

Bioaccumulation, biotransformation, and biochemical effects of brominated diphenyl ethers in juvenile lake trout (Salvelinus namaycush).

Juvenile lake trout (Salvelinus namaycush) were exposed to three dietary concentrations (0, approximately 2.5, and approximately 25 ng/g per BDE congener) of 13 BDE congeners (3-10 Br atoms) in the laboratory for 56 days, followed by 112 days of clean food, to examine bioaccumulation parameters and potential biochemical effects. The bioaccumulation of BDEs by the trout was highly influenced by biotransformation, via debromination, which resulted in bioaccumulation parameters that were much different than would be expected based on studies of chlorinated organic compounds (e.g., PCBs). Half-lives (t1/2's) for some BDE congeners (e.g., BDE-85 and -190) were much lower than expected based on their Kow, which was likely due to biotransformation, whereas t1/2's of other BDE congeners (e.g., BDE-66, -77, -153, and -154) were much longer than anticipated based on Kow. This was likely because the metabolites of BDE formed via debromination had the same chemical structure of these BDE congeners, which supplemented measured concentrations. The detection of three BDE congeners (an unknown penta, BDE-140, and an unknown hexa) in the fish that were not present in the food or in the control fish provide further evidence forthe debromination of BDEs. Half-lives of BDEs ranged from 38 +/- 9 to 346 +/- 173 days and biomagnification factors ranged from 1.6 (BDE-190) to 45.9 (BDE-100), but these bioaccumulation parameters need to be viewed with caution because they were highly influenced by debromination and relative abundance of individual BDEs that the fish were exposed to. CYP1A enzyme activity, measured as EROD, and free tri-iodothyronine (T3) concentrations in the plasma of lake trout varied significantly throughout the experiment but were not related to BDE exposure. In contrast, plasma levels of thyroxine levels (T4) were lower in both groups of PBDE-exposed fish compared with control fish after 56 days of exposure, and after 168 days in the high dose, suggesting that PBDEs may influence thyroid homeostasis at levels that are higher than what is normally found in the environment.

Biotransformation of N-ethyl perfluorooctanesulfonamide by rainbow trout (Onchorhynchus mykiss) liver microsomes.

Rainbow trout (Onchorhynchus mykiss) liver microsomes were incubated with N-ethyl perfluorooctanesulfonamide [N-EtPFOSA, C8F17SO2NH(C2H5)], to examine the possibility of in vitro biotransformation to perfluorooctane sulfonate (PFOS, C8F17SO3-) and perfluorooctanoate (PFOA, C7F15COO-). Incubations were performed by exposing trout liver microsomes to N-EtPFOSA at 8 degrees C in the dark. Reaction mixtures were analyzed after incubation periods of 0, 2, 4, 8, 16, and 30 h for N-EtPFOSA, PFOS, PFOA, and perfluorooctanesulfonamide (PFOSA, C8F17SO2NH2), a suspected intermediate. Amounts of PFOS and PFOSA were found to increase with incubation time, but only background levels of PFOA were detected. Three possible reaction pathways are proposed for the conversion of N-EtPFOSA to PFOS: (i) direct conversion of N-EtPFOSA to PFOS by deethylamination accompanied by conversion of the sulfone group to sulfonate, (ii) deethylation of N-EtPFOSA to PFOSA, followed by deamination to form PFOS, and (iii) direct hydrolysis of N-EtPFOSA. These findings represent the first report indicating a possible biotransformation of a perfluorosulfonamide to PFOS in fish and may help to explain the detection of PFOS, which is relatively involatile, and thus not likely to undergo atmospheric transport, in biota from remote regions.

Direct measurement of octanol-water partition coefficients of some environmentally relevant brominated diphenyl ether congeners.

Octanol-water partition coefficients (K(OW)) of nine environmentally relevant brominated diphenyl ether (BDE) congeners present in two technical mixtures were directly measured using a slow-stir technique. LogK(OW) values of tri- to heptabrominated BDE congeners ranged from 5.74 to 8.27, and were related to bromine content by the equation logK(OW)=0.621(#Br)+4.12(R(2)=0.970). The directly determined K(OW) values were generally lower than those calculated using fragment constant methods, particularly at higher levels of bromine substitution. The quasi-experimental approach of using fragment constants to modify a "backbone" compound of known K(OW) was much more successful than using the fragment constants to "build" the entire molecule. The tri- and tetrabrominated congeners are in the range of optimum bioaccumulation potential.