Microbead beating extraction of avian eggs for polycyclic aromatic compounds.

Due to their relatively high trophic position and importance as a food source for many communities in the circumpolar north, seabird eggs are an important matrix for monitoring contaminant levels. In fact, many countries, including Canada, have established long-term seabird egg contaminant monitoring programs, with oil related compounds a contaminant of emerging concern for seabirds in several regions. Current approaches to measuring many contaminant burdens in seabird eggs are time-consuming and often require large volumes of solvent. Here we propose an alternative approach, based on the principle of microbead beating tissue extraction using custom designed stainless-steel extraction tubes and lids, to measure a suite of 75 polycyclic aromatic compounds (polycyclic aromatic hydrocarbons (PAHs), alkyl-PAHs, halogenated-PAHs and some heterocyclic compounds) comprising a wide-range of chemical properties. Our method was conducted in strict accordance with ISO/IEC 17025 guidelines for method validation. Accuracies for our analytes generally ranged from 70 - 120%, and intra and inter-day repeatability for most analytes were < 30%. Limits of detection/quantitation for the 75 target analytes were < 0.2/0.6 ng g-1. The level of contamination in our method blanks was significantly smaller in our stainless-steel tubes/lids relative to commercially available high-density plastic alternatives. Overall, our method meets our data quality objectives and results in a notable reduction in sample processing times relative to current approaches.

Isotopic evidence for bioaccumulation of aerosol lead in fish and wildlife of western Canada.

Lead (Pb) is a toxic element which is released as a result of anthropogenic activities, and Pb stable isotope ratios provide a means to distinguish sources and transport pathways in receiving environments. In this study, isotopes of bioaccumulated Pb (204Pb, 206Pb, 207Pb, 208Pb) were examined for diverse terrestrial and aquatic biota from three areas in western Canada: (a) otter, marten, gulls, terns, and wood frogs in the Alberta Oil Sands Region (AOSR), (b) fish, plankton, and gulls of Great Slave Lake (Yellowknife, Northwest Territories), and (c) wolverine from the Yukon. Aquatic and terrestrial biota from different habitats and a broad geographic area showed a remarkable similarity in their Pb isotope composition (grand mean ± 1 standard deviation: 206Pb/207Pb = 1.189 ± 0.007, 208Pb/207Pb = 2.435 ± 0.009, n = 116). Comparisons with Pb isotope ratios of local sources and environmental receptors showed that values in biota were most similar to those of atmospheric Pb, either measured in local aerosols influenced by industrial activities in the AOSR or in lichens (an aerosol proxy) near Yellowknife and in the Yukon. Biotic Pb isotope ratios were different from those of local geogenic Pb. Although the Pb isotope measurements could not unambiguously identify the specific anthropogenic sources of atmospheric Pb in biota, initial evidence points to the importance of fossil fuels currently used in transportation and power generation. Further research should characterize bioavailable chemical species of Pb in aerosols and important emission sources in western Canada.

Inter-annual variation of mercury in aquatic bird eggs and fish from a large subarctic lake under a warming climate.

Understanding changes in environmental mercury concentrations is important for assessing the risk to human and wildlife populations from this potent toxicant. Here, we use herring gull (Larus argentatus) eggs to evaluate temporal changes in total mercury (THg) availability from two locations on Great Slave Lake (GSL), Northwest Territories, Canada. Egg THg concentrations increased through time, but this change was due to shifts in gull diets. Stable nitrogen isotopes allowed adjustment of egg THg concentrations for dietary changes. Diet-adjusted egg THg concentrations showed no long-term trend. Consistent with that result, new statistical analysis of THg concentrations in three species of GSL fish showed minor or no temporal changes. Although a long-term trend was absent, inter-year differences in adjusted egg THg concentrations persisted. Contributions of environmental variables (i.e., river flow, lake level, air temperature, precipitation, and wildfire) to these differences were investigated. Egg THg concentrations were greater following years of lower lake levels and greater wildfire extent. Lake level could have affected mercury methylation. Increased wildfire could have enhanced terrestrial Hg releases to the atmosphere where it was transported long distances to GSL. Climate change may increase wildfire extent with impacts on Hg bioaccumulation in northern ecosystems. Egg Hg levels reported here are unlikely to pose health risks to gulls, but in light of ongoing environmental change, monitoring should continue. Our study emphasizes the importance of ancillary datasets in elucidating Hg trends; such information will be critical for evaluating the effectiveness of Hg mitigation strategies implemented as part of the Minamata Convention.

Methylmercury exposure in wildlife: A review of the ecological and physiological processes affecting contaminant concentrations and their interpretation.

Exposure to methylmercury (MeHg) can result in detrimental health effects in wildlife. With advances in ecological indicators and analytical techniques for measurement of MeHg in a variety of tissues, numerous processes have been identified that can influence MeHg concentrations in wildlife. This review presents a synthesis of theoretical principals and applied information for measuring MeHg exposure and interpreting MeHg concentrations in wildlife. Mercury concentrations in wildlife are the net result of ecological processes influencing dietary exposure combined with physiological processes that regulate assimilation, transformation, and elimination. Therefore, consideration of both physiological and ecological processes should be integrated when formulating biomonitoring strategies. Ecological indicators, particularly stable isotopes of carbon, nitrogen, and sulfur, compound-specific stable isotopes, and fatty acids, can be effective tools to evaluate dietary MeHg exposure. Animal species differ in their physiological capacity for MeHg elimination, and animal tissues can be inert or physiologically active, act as sites of storage, transformation, or excretion of MeHg, and vary in the timing of MeHg exposure they represent. Biological influences such as age, sex, maternal transfer, and growth or fasting are also relevant for interpretation of tissue MeHg concentrations. Wildlife tissues that represent current or near-term bioaccumulation and in which MeHg is the predominant mercury species (such as blood and eggs) are most effective for biomonitoring ecosystems and understanding landscape drivers of MeHg exposure. Further research is suggested to critically evaluate the use of keratinized external tissues to measure MeHg bioaccumulation, particularly for less-well studied wildlife such as reptiles and terrestrial mammals. Suggested methods are provided to effectively use wildlife for quantifying patterns and drivers of MeHg bioaccumulation over time and space, as well as for assessing the potential risk and toxicological effects of MeHg on wildlife.

Tetrabromobisphenol-A-Bis(dibromopropyl ether) Flame Retardant in Eggs, Regurgitates, and Feces of Herring Gulls from Multiple North American Great Lakes Locations.

The occurrence of tetrabromobisphenol-A-bis(2,3,-dibromopropyl ether) (TBBPA-BDBPE) flame retardant is generally unknown in wildlife. A highly sensitive, gas chromatography-mass spectrometry-based method was developed for TBBPA-BDBPE with optimized parameters for large volume injection. We report on TBBPA-BDBPE and temporal and spatial trends in herring gull egg pools and individuals from 14 colony sites across the Laurentian Great Lakes of North America. TBBPA-BDBPE identification was confirmed using liquid chromatography time-of-flight mass spectrometry and quantification with liquid chromatography tandem mass spectrometry analysis. TBBPA-BDBPE was quantifiable in 95% of egg pools from all colonies sampled in 2013-2017, and retrospective analysis of archived eggs (2001-2017) at 3 of the 14 colonies indicated that TBBPA-BDBPE concentrations were greater in pools from eggs collected in more recent years (

The river runs through it: The Athabasca River delivers mercury to aquatic birds breeding far downstream.

This study examined factors contributing to temporal variability (2009-2017) in total mercury (THg) concentrations in aquatic bird eggs collected in the Peace-Athabasca Delta and Lake Athabasca in northern Alberta. Factors examined included year of egg collection, site of collection, bird species, bird diets, annual surface-mineable oil sands production, forest fires, and flow of the Athabasca River. Surface mining activities associated with Alberta's Athabasca oil sands are situated north of Fort McMurray, Alberta, adjacent to the northward-flowing Athabasca River. Previous studies have found that oil sands industrial operations release mercury into the local (within ~50 km) environment. An information-theoretic approach revealed that the best model for explaining egg THg levels included Athabasca River flow, bird food source, and bird species. Variability in egg THg levels was partly a reflection of differences in food sources, e.g. proportions of aquatic versus terrestrial food in bird diets. Annual fluctuations in maximal flow of the Athabasca River were also important with eggs collected following years of high maximal flow exhibiting higher THg concentrations. Furthermore, eggs collected in years of high versus low flow differed in their stable Hg isotope composition with less mass-independent fraction of 199Hg and 201Hg in years of high flow. Riverine processes associated with suspended sediment were likely critical in regulating Hg availability to nesting birds. This study highlights the importance of the Athabasca River as a conduit for Hg transport to ecologically-sensitive downstream ecosystems such as the Peace-Athabasca Delta and Wood Buffalo National Park (a UNESCO World Heritage Site). Human activities that increase atmospheric Hg deposition to the Athabasca River watershed, or that enhance Hg releases to the river through erosion of Hg-bearing soils, will likely increase the availability of Hg to organisms inhabiting downstream areas.

Spatial trends in a biomagnifying contaminant: Application of amino acid compound-specific stable nitrogen isotope analysis to the interpretation of bird mercury levels.

Levels of biomagnifying contaminants are greatest in high-trophic level biota (e.g., predatory birds such as gulls). Gull eggs have been used to assess contaminant spatial patterns and sources, but such assessments must consider how organism trophic position may influence spatial inferences. Stable nitrogen isotopes (δ15 N) in bulk tissue are routinely used in this context. However, bulk δ15 N values are only useful if spatial differences in baseline δ15 N values are considered. Amino acid compound-specific stable nitrogen isotope analysis can generate estimates of baseline δ15 N values and trophic position from the same sample. In the present study, eggs (n = 428) of California (Larus californicus), herring (Larus argentatus smithsonianus), and ring-billed (Larus delawarensis) gulls were used to assess spatial patterns in mercury (Hg) availability in 12 western Canadian lakes located over 14 degrees of latitude, with amino acid compound-specific stable isotope analysis adjustment of egg Hg levels for trophic position. Mean trophic position-adjusted egg Hg levels (micrograms per gram, dry wt) were greatest at sites in receiving waters of the Athabasca River (X¯ = 0.70) compared to southern (X¯ = 0.39) and northern (X¯ = 0.50) regions. Research is required to investigate factors (e.g., local Hg released as a result of human activities, processes influencing Hg methylation) which may be responsible for greater Hg availability in the lower Athabasca River basin. However, it is clear that amino acid compound-specific stable isotope analysis is a valuable tool for assessing contaminant spatial patterns. Environ Toxicol Chem 2018;37:1466-1475. © 2018 SETAC.

Temporal trends in a biomagnifying contaminant: Application of amino acid compound-specific stable nitrogen isotope analysis to the interpretation of bird mercury levels.

Temporal trends in levels of biomagnifying contaminants, such as mercury (Hg), in top predators can provide insights into changes in contaminant bioavailability through time. However, interpreting contaminant temporal trends in predators can be confounded by temporal changes in their diets, which, in turn, could affect organism trophic position and exposure to biomagnifying contaminants. To address this issue, bulk stable nitrogen isotope analysis, that is, analysis of whole tissue, is widely incorporated into contaminant-monitoring programs for the estimation of organism trophic position. In the present study, we investigated lake-specific temporal trends in Hg levels in herring gull (Larus argentatus smithsonianus) eggs from Lakes Huron and Erie, 2 Laurentian Great Lakes. Levels of Hg in Lake Huron eggs declined, whereas Lake Erie eggs showed no change. Stable nitrogen isotope analysis of bulk material could not explain these interlake differences in Hg temporal trends. However, application of amino acid compound-specific stable nitrogen isotope analysis, in conjunction with other dietary tracers (i.e., fatty acids), provided insights into the factors regulating interlake differences in Hg temporal trends. Adjusting Hg levels in predators to account for temporal changes in their diets can have a significant impact on the interpretation of temporal trend contaminants data. In this case, it reconciled the apparently different Hg temporal trends observed in gull eggs from Lakes Huron and Erie. Environ Toxicol Chem 2018;37:1458-1465. © 2018 SETAC.

Stage of development affects dry weight mercury concentrations in bird eggs: Laboratory evidence and adjustment method.

Bird eggs are often used to monitor levels and trends of mercury (Hg) in the environment. Logistical issues in such studies sometimes require the use of eggs at different stages of development. Therefore, it is important to understand how embryonic age may affect egg Hg concentrations. Studies using dry weight Hg concentrations in eggs assume that dry mass (e.g., lipids) does not change through embryonic development and thus expressing concentrations on a dry weight basis adjusts for any changes that may occur in egg mass throughout development. That assumption is tested in the present study by injecting chicken eggs with Hg and measuring Hg concentrations in embryonic contents at different stages of artificial incubation. The results indicate that dry weight Hg concentrations in eggs at later stages of development are statistically greater than in undeveloped eggs. To address this issue, we developed a method of standardizing egg Hg concentrations for embryonic age based on egg contents density (egg contents mass/egg contents volume). A combined dataset (n = 225) from precocial and semi-precocial birds was used to demonstrate that egg contents density declines with increasing embryonic development. Based on this finding, we applied a formula to adjust egg dry weight Hg concentrations for stage of development: adjusted egg [Hg] = unadjusted [Hg] × (egg contents density). The application of this approach to adjust data from the chicken egg Hg injection study resulted in there being no statistically significant difference in dry weight Hg levels in eggs at different stages of embryonic development. The adjustment approach described in the present study is a straightforward method to account for stage of development when assessing Hg levels in avian eggs and should be widely applicable to studies of this nature. Environ Toxicol Chem 2018;37:1168-1174. © 2017 SETAC.

Mercury trends in colonial waterbird eggs downstream of the oil sands region of Alberta, Canada.

Mercury levels were measured in colonial waterbird eggs collected from two sites in northern Alberta and one site in southern Alberta, Canada. Northern sites in the Peace-Athabasca Delta and Lake Athabasca were located in receiving waters of the Athabasca River which drains the oil sands industrial region north of Fort McMurray, Alberta. Temporal trends in egg mercury (Hg) levels were assessed as were egg stable nitrogen isotope values as an indicator of dietary change. In northern Alberta, California and Ring-billed Gulls exhibited statistically significant increases in egg Hg concentrations in 2012 compared to data from the earliest year of sampling. Hg levels in Caspian and Common Tern eggs showed a nonstatistically significant increase. In southern Alberta, Hg concentrations in California Gull eggs declined significantly through time. Bird dietary change was not responsible for any of these trends. Neither were egg Hg trends related to recent forest fires. Differences in egg Hg temporal trends between northern and southern Alberta combined with greater Hg levels in eggs from northern Alberta identified the likely importance of local Hg sources in regulating regional Hg trends. Hg concentrations in gull and Common Tern eggs were generally below generic thresholds associated with toxic effects in birds. However, in 2012, Hg levels in the majority of Caspian Tern eggs exceeded the lower toxicity threshold. Increasing Hg levels in eggs of multiple species nesting downstream of the oil sands region of northern Alberta warrant continued monitoring and research to further evaluate Hg trends and to conclusively identify sources.

Mercury trends in herring gull (Larus argentatus) eggs from Atlantic Canada, 1972-2008: Temporal change or dietary shift?

Mercury (Hg) is a pervasive contaminant that can adversely affect predatory wildlife. Bird eggs provide insights into breeding females' Hg burdens, and are easily collected and archived. We present data on Hg trends in herring gull (Larus argentatus) eggs from five sites in Atlantic Canada from 1972 to 2008. We found a significant decrease in Hg at Manawagonish Island, New Brunswick and Île du Corossol, Quebec, but after correcting Hg for dietary shifts using stable isotopes (δ(15)N), these trends disappeared. Decreasing temporal trends of stable isotopes in gull eggs were observed at four sites, suggesting shifts in gull diets. At Gull Island, Newfoundland, diet-adjusted Hg increased from 1977 to 1992, dropped sharply between 1992 and 1996, and rose again from 1996 to 2008. After adjusting Hg trends for dietary shifts of herring gulls, it appears that environmental Hg in coastal ecosystems has remained relatively constant at most sites in Atlantic Canada over the last 36 years.

Flame retardants in eggs of four gull species (Laridae) from breeding sites spanning Atlantic to Pacific Canada.

To compare legacy and emerging flame retardant (FR) contamination in Canadian marine and freshwater ecosystems, eggs of four gull species (Laridae) were collected from 26 colonies spanning Pacific to Atlantic Canada, including in the Great Lakes basin. Fourteen polybrominated diphenyl ether (PBDE) congeners and 20 non-PBDE FRs were analyzed, but BDE-47, -99, -100, -153, -154 and -209, hexabromocyclododecane (HBCD) and Dechlorane Plus (DP) syn- and anti-isomers were common, and where concentrations of ∑PBDEs (37-610 ng/g wet weight, ww) â‰« HBCD (0.5-12 ng/g ww) > ∑DP (not quantifiable-5.5 ng/g ww). All other FRs were generally not detectable. Stable nitrogen and carbon isotopes used as dietary tracers provided insights into the diet choice influences on the exposure sources and contamination patterns (e.g., PBDE congener compositions) for individual gulls from the same colony. Eggs from gulls breeding near metropolitan regions of higher human densities showed greater PBDE burdens than from other ecosystems.

Twenty years of temporal change in perfluoroalkyl sulfonate and carboxylate contaminants in herring gull eggs from the Laurentian Great Lakes.

In this study, temporal trends and patterns of major C(4) to C(15) chain length PFCAs and PFSAs and some sulfonamide, fluorotelomer acid and alcohol precursors were determined in herring gull (Larus argentatus) egg pools. Samples were analyzed from fifteen collection years including 1990 and all years from 1997 to 2010, and from seven colonies located throughout the Great Lakes, ranging from remote to highly urbanized areas. Other than at the Toronto Harbour colony, the slopes of ∑PFSA concentrations (C(6), C(8), and C(10)) versus time were negative indicating general declines between 1990 and 2010. PFOS was the dominant PFSA regardless of colony or year, ranging from 80 to 99% of ∑PFSA. For ∑PFCA (C(8)-C(15)), slopes of concentrations versus time were generally positive with 4 of 7 colonies showing statistically significant (p < 0.05) increases in levels through time. Individual PFCAs showed similar increasing trends except for PFOA. Regardless of colony, the PFCA pattern was dominated by the C(10) to C(13) PFCAs. Consistent with the PFOS declines, concentrations of the PFOS precursor, PFOSA, declined at most colonies between 1990 and 2006 and post-2006 concentrations were below detection limits. Declining concentrations of the C(8) PFCs, PFOS, PFOA and PFOSA, were consistent with the phase out in 2002 by the 3M Company in North America of all of C(8) PFC-related chemistry products. Increasing production volumes of fluorotelomer based compounds, and degradation of these compounds to PFCAs may explain increasing trends of PFCAs in gull eggs. Dietary changes as measured by carbon and nitrogen stable isotopes, showed minimal relationships to PFC levels in gull eggs, which indicates the complexity of aquatic and terrestrial food of gulls and sources of PFCs.

Current concentrations and spatial and temporal trends in mercury in Great Lakes Herring Gull eggs, 1974-2009.

Current concentrations and spatial and temporal trends of total mercury (Hg) were assessed in eggs of the Herring Gull (Larus argentatus) over the period 1974-2009 at 15 sites in the Great Lakes: 2-3 sites per lake and one site in each of 3 connecting channels. Current (2009) concentrations ranged from 0.064 µg/g (wet weight) at Chantry Island (Lake Huron) to 0.246 µg/g at Middle Island (Lake Erie). There were significant inter-colony differences in mean Hg concentrations (2005-2009). Mercury concentrations at 14 of 15 sites declined from 23 to 86% between when it was first measured (usually 1974) and 2009. Declining temporal trends over the entire period (1974-2009) were significant at 10 of the 15 sites. On the other hand, there were no significant trends in mercury over the last 15 years. In the early years, declines of Hg in Herring Gull eggs tracked those in Rainbow Smelt (Osmerus mordax) in most Great Lakes. More recently, declines in gull eggs were more evident than in smelt and may be partially explained by temporal changes in the gull diet. When gull Hg data were adjusted for temporal changes in the gull diet, as inferred from stable nitrogen isotope values in eggs, significant declines in egg mercury levels were found only at 4 of 15 sites. Overall, Hg concentrations have declined in Great Lakes Herring Gull eggs over the period 1974-2009 but changes in the gull diet may be contributing, in part, to those declines. Examination of contaminant temporal trends in multiple indicator species will ensure accurate inferences regarding contaminant availability in the environment.

Perfluoroalkyl carboxylates and sulfonates and precursors in relation to dietary source tracers in the eggs of four species of gulls (Larids) from breeding sites spanning Atlantic to Pacific Canada.

In the present study, we identified and examined the spatial trends, sources and dietary relationships of bioaccumulative perfluorinated sulfonate (PFSA; C(6), C(8), and C(10) chain lengths) and carboxylate (PFCA; C(6) to C(15) chain lengths) contaminants, as well as precursor compounds including several perfluorinated sulfonamides, and fluorotelomer acids and alcohols, in individual eggs (collected in 2008) from four gull species [glaucous-winged (Larus glaucescens), California (Larus californicus), ring-billed (Larus delawarensis) and herring (Larus argentatus) gulls] from 15 marine and freshwater colony sites in provinces across Canada. The pattern of PFSAs was dominated by perfluorooctane sulfonate (PFOS; >89% of ΣPFSA concentration) regardless of egg collection location. The highest ΣPFSA concentrations were found in the eggs collected in the urbanized areas in the Great Lakes and the St. Lawrence River area [Big Chicken Island 308 ng/g ww, Toronto Harbour 486 ng/g ww, and Ile Deslauriers (HG) 299 ng/g ww]. Also, eggs from all freshwater colony sites had higher ΣPFSA concentrations, which were significant (p<0.05) in many cases, compared to the marine sites with the exception of the Sable Island colony in Atlantic Canada off the coast of Nova Scotia. C(6) to C(15) chain length PFCAs were detected in the eggs, although the pattern was variable among the 15 sites, where PFUnA and PFTrA dominated the pattern for most colonies. Like the ΣPFSA, the highest concentrations of ΣPFCA were found in the eggs from Big Chicken Island, Toronto Harbour, Ile Deslauriers (HG), and Sable Island, although not all freshwater sites had higher concentrations compared to marine sites. Dietary tracers [δ(15)N and δ(13)C stable isotopes (SIs)] revealed that PFSA and PFCA exposure is colony dependent. SI signatures suggested that gulls from most marine colony sites were exposed to PFCs via marine prey. The exception was the Mandarte Island colony in Pacific British Columbia, where PFSA and PFCA exposure appeared to be via terrestrial and/or freshwater prey consumption. The same was true for the freshwater sites where egg SIs suggested both aquatic and terrestrial prey consumption as the source for PFC exposure depending on the colony. Both aquatic (marine and freshwater) and terrestrial prey are likely sources of PFC exposure to gulls but exposure scenarios are colony-specific.

Metals and polycyclic aromatic hydrocarbons in colonial waterbird eggs from Lake Athabasca and the Peace-Athabasca Delta, Canada.

In 2009, aquatic bird eggs from a variety of species were collected from three sites in northern Alberta, Canada. Two sites were located in receiving waters of the Athabasca River, which drains the oil sands industrial region north of Fort McMurray, Alberta. The third site, located on the Peace River, was remote from the influence of the Athabasca River. Levels of mercury, arsenic, and polycyclic aromatic hydrocarbons (PAHs) were measured in the eggs along with nitrogen stable isotopes (δ¹5N) as an indicator of bird trophic position. Levels of As and PAHs in eggs were low, whereas Hg was measureable in all samples. Egg Hg levels increased with δ¹5N values (a proxy of food web trophic position); however, some eggs exhibited Hg levels greater than expected based on trophic position. These eggs were from sites in receiving waters of the Athabasca River, namely, Mamawi Lake and Egg Island. Levels of Hg in egg pools were correlated with naphthalene levels, perhaps indicating a common source of contamination. Temporal comparison of Hg levels in California gull (Larus californicus) eggs from the Lake Athabasca colony indicated that egg Hg burdens increased 40% from 1977 to 2009. More research is required to evaluate temporal trends in levels of environmental contaminants and to identify sources.

Evidence for sex differences in mercury dynamics in double-crested cormorants.

Aquatic fish-eating birds can demethylate methylmercury in their livers. In this study, we determined whether a previously documented male bias in mercury concentration in double-crested cormorants ( Phalacrocorax auritus ) was due entirely to the depuration of mercury into eggs or might also in part be related to sex differences in methylmercury demethylation or biliary excretion capability in the liver. We found egg depuration accounted for less than a fifth of the mercury concentration difference between males and females, hence not entirely explaining the sex difference. Females had a significantly steeper slope for the negative relationship between percent methylmercury (i.e., percentage of total mercury that is methylmercury) and total mercury concentration than did males. This suggests that females have a greater capacity to demethylate methylmercury, which might be reducing the amount of methylmercury available for depuration to eggs. We also found a significant negative relationship between methylmercury concentration and liver mass for females only; thus females might also have a greater capability to excrete methylmercury compared to males. Therefore, we conclude that the male bias in mercury concentration might also result from females having a greater capability to excrete mercury compared to males.

Reconcilable differences: the use of reference material to reduce methodological artifacts in the reporting of organochlorine pesticides and polychlorinated biphenyls.

Numerous long-term monitoring programs have assessed spatial and temporal trends of organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs). Changes in analytical approaches (e.g., gas chromatography coupled with electron capture detection [GC-ECD] versus mass spectrometric detection [GC-MSD]) can reveal artifacts in the reported concentrations. In-house reference material (RM) was used to determine the analytical artifacts in the measurement of OCs and PCBs in Great Lake herring gull eggs previously analyzed from 1994 to 1996 (GC-ECD) and 1997 to 1999 (GC-MSD). Approximately 19.0% of the variability of PCB congeners in gull eggs was associated with analytical artifacts, and differences among colonies were obscured. Although the discrepancy in sum PCBs (SigmaPCBs) was fairly small (2.1%), some congeners varied considerably between methods (> 60%). After statistically removing the artifacts, only 1.4% of the variability in PCBs of herring gull eggs was associated with artifacts, and differences among gull colonies became apparent. After excluding OCs near the detection limit in the RM, statistically removing the artifacts reduced some of the differences between methods for OCs. Analytical artifacts may potentially render inferences difficult, confounded, and erroneous. When combining contaminant data obtained using different methods, the methods should be assumed to give different results unless demonstrated otherwise. Assessments of the compatibility of analytical methodologies should be made using an appropriate RM.

Impact of changes in analytical techniques for the measurement of polychlorinated biphenyls and organochlorine pesticides on temporal trends in herring gull eggs.

Changes in analytical approaches during the tenure of monitoring programs for organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs) may affect estimates of temporal trends. We used an in-house reference material to create multiplication factors to adjust the estimates of OC pesticides and PCBs (Aroclor equivalents) in Great Lake herring gull eggs analyzed using electron capture detection (1987-1997) to be more equivalent to estimates using mass spectrometric detection (1998-2005) as well as accompanying differences in analytical procedures. We examined temporal trends in contaminant concentrations in herring gull eggs using change point regressions, to determine whether significant changes in long-term trends were associated with analytical methodology. The highest frequency of change point occurrences shifted from 1997 (when analytical methodology was altered) to 2003 after data adjustment. The explanatory power (r2) of the regressions was lower after adjustment, although only marginally so (mean r2 difference=0.04). The initial rates of decline before change points in contaminant concentrations were generally slower after the data adjustment, but after any change points the declines were not significantly different. The regression models did not change for 83.3% of the cases. The effects on the interpretation of long-term temporal trends in herring gull eggs, although not negligible, were minor relative to the magnitude of the temporal changes.

Trophic structure and mercury distribution in a Gulf of St. Lawrence (Canada) food web using stable isotope analysis.

Even at low concentrations in the environment, mercury has the potential to biomagnify in food chains and reaches levels of concern in apex predators. The aim of this study was to relate the transfer of total mercury (THg) and methylmercury (MeHg) in a Gulf of St. Lawrence food web to the trophic structure, from primary consumers to seabirds, using stable nitrogen (δ(15)N) and carbon (δ(13)C) isotope analysis and physical environmental parameters. The energy reaching upper trophic level species was principally derived from pelagic primary production, with particulate organic matter (POM) at the base of the food chain. We developed a biomagnification factor (BMF) taking into account the various prey items consumed by a given predator using stable isotope mixing models. This BMF provides a more realistic estimation than when using a single prey. Lipid content, body weight, trophic level and benthic connection explained 77.4 and 80.7% of the variation in THg and MeHg concentrations, respectively in this food web. When other values were held constant, relationships with lipid and benthic connection were negative whereas relationships with trophic level and body weight were positive. Total Hg and MeHg biomagnified in this food web with biomagnification power values (slope of the relationship with δ(15)N) of 0.170 and 0.235, respectively on wet weight and 0.134 and 0.201, respectively on dry weight. Values of biomagnification power were greater for pelagic and benthopelagic species compared to benthic species whereas the opposite trend was observed for levels at the base of the food chain. This suggests that Hg would be readily bioavailable to organisms at the base of the benthic food chain, but trophic transfer would be more efficient in each trophic level of pelagic and benthopelagic food chains.