Eric Braekevelt

Surficial Sediment Contamination in Lakes Erie and Ontario: A Comparative Analysis

Abstract Sediment surveys were conducted in Lakes Erie and Ontario to characterize spatial trends in contamination, to assist in elucidation of possible sources of contamination, and for identification of areas where contamination exceeded Canadian sediment quality guidelines for protection of aquatic biota. Sediment levels of metals including nickel, lead, zinc, chromium, and copper were compared to pre-colonial concentrations, and sediment enrichment factors, defined as the ratio of surficial concentrations to background concentrations determined from benthos cores, were calculated. Sediments in Lake Ontario exhibited elevated contamination compared to Lake Erie. The average enrichment factor for Lake Ontario (2.6) was comparable to the western basin in Lake Erie but greater than those for the central (1.3) and eastern (1.0) basins. There was a gradient toward decreasing sediment contamination from the western basin to the eastern basin of Lake Erie, and from the southern to the northern area of the central basin. Sediment contamination in Lake Ontario was similarly distributed across the three major depositional basins. The spatial distribution of metals was similar to those of other contaminants including mercury, polychlorinated biphenyls (PCBs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs). Lake-wide averages of sediment mercury, PCBs and PCDDs/PCDFs in Lake Erie were 0.185 μg/g, 96.5 ng/g, and 18.8 pg/g TEQs, respectively. Lake-wide averages of sediment mercury, PCBs and PCDDs/PCDFs in Lake Ontario were 0.586 μg/g, 100 ng/g, and 101 pg/g TEQs, respectively.

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.

Spatial and Temporal Trends in Sediment Contamination in Lake Ontario

Abstract A Lake Ontario sediment survey was conducted in 1998 to characterize spatial and temporal trends in contamination, and for comparison with data from previous surveys in order to assess any changes in environmental quality since the advent of measures to reduce contaminant sources. This survey was also designed to assist in tracing possible sources and vectors of contamination, and to identify areas where contamination exceeded Canadian sediment quality guidelines for the protection of aquatic biota. In addition, levels of a suite of eight metals were compared to pre-colonial concentrations, and surficial sediment enrichment factors were calculated. The highest levels of contaminants were observed at stations within the three major depositional basins; the spatial distributions across the individual basins were similar. Lake-wide averages for polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs) were 100 ng/g and 111 pg/g TEQs, respectively. Concentrations of mercury and lead were observed to have decreased from 0.79 μg/g and 125 μg/g, respectively, in 1968 to 0.59 μg/g and 69 μg/g, respectively, in 1998. Exceedances of the Canadian Sediment Quality Probable Effect Level (PEL) guidelines were most numerous for arsenic (67%), PCDDs/PCDFs (58%), mercury (62%) and lead (38%). Concentrations of PCBs at all sampling stations were below the Canadian PEL of 277 ng/g.

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.

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.

Comparison of an individual congener standard and a technical mixture for the quantification of toxaphene in environmental matrices by HRGC/ECNI-HRMS.

Both a technical standard and a recently commercially available standard containing 25 congeners were used to quantify toxaphene in a variety of environmental matrices, using high-resolution gas chromatography/electron capture negative ion high-resolution mass spectrometry (HRGC/ ECNI-HRMS). The purpose was to examine the differences between the two standards and to assess how well the congener standard describes the total toxaphene profile. At a resolving power of approximately 11,000 no interferences from other organochlorines were observed. Biotic matrices were enriched in octa- and nonachlorobornanes relative to the technical mixture, whereas abiotic matrices were enriched in hexa- and heptachlorobornanes. The hexa- and heptachlorobornanes were generally overestimated by the weighted response of the technical mixture, whereas the nonachlorobornanes were consistently underestimated. The extent to which the technical mixture over- or underestimates total toxaphene concentrations depends on the distribution of congeners among homologue groups and the abundance of particular congeners. The current 25-congener mixture described only approximately 35-75% of the total toxaphene response: more congeners are needed to adequately describe some matrices. Correction factors were developed that will allow laboratories to report reliable concentrations of individual congeners in samples that were quantified using the technical mixture, but they should be applied with caution, as they may be highly instrument dependent.

Determination of melamine, ammeline, ammelide and cyanuric acid in infant formula purchased in Canada by liquid chromatography-tandem mass spectrometry.

A liquid chromatography-tandem mass spectrometry-based isotope dilution method was developed for the analysis of the triazine compounds melamine (MEL), ammeline (AMN), ammelide (AMD) and cyanuric acid (CYA) in infant formula samples purchased in Canada in 2008 for the purpose of a combined exposure and risk assessment. Infant formula samples were extracted with 1:1 acetonitrile–water, cleaned up on disposable ion-exchange solid-phase extraction cartridges, and analysed by ultra-high-performance liquid chromatography-tandem mass spectrometry. MEL and CYA were detected in almost all infant formula products: the highest concentrations observed were 0.32 mg kg−1 MEL and 0.45 mg kg−1 CYA. Samples that were relatively high in MEL in this survey tended to be low in CYA, and vice versa. Concentrations of AMN and AMD were very low in all samples. The total of MEL-related compounds (sum of all four analytes) in all samples was below the interim standard of 0.5 mg kg−1 for infant formula products established by Health Canada.

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.

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.

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.