Is Glacial Meltwater a Secondary Source of Legacy Contaminants to Arctic Coastal Food Webs?

Climate change-driven increases in air and sea temperatures are rapidly thawing the Arctic cryosphere with potential for remobilization and accumulation of legacy persistent organic pollutants (POPs) in adjacent coastal food webs. Here, we present concentrations of selected POPs in zooplankton (spatially and seasonally), as well as zoobenthos and sculpin (spatially) from Isfjorden, Svalbard. Herbivorous zooplankton contaminant concentrations were highest in May [e.g., ∑polychlorinated biphenyls (8PCB); 4.43, 95% CI: 2.72-6.3 ng/g lipid weight], coinciding with the final stages of the spring phytoplankton bloom, and lowest in August (∑8PCB; 1.6, 95% CI: 1.29-1.92 ng/g lipid weight) when zooplankton lipid content was highest, and the fjord was heavily impacted by sediment-laden terrestrial inputs. Slightly increasing concentrations of α-hexachlorocyclohexane (α-HCH) in zooplankton from June (1.18, 95% CI: 1.06-1.29 ng/g lipid weight) to August (1.57, 95% CI: 1.44-1.71 ng/g lipid weight), alongside a higher percentage of α-HCH enantiomeric fractions closer to racemic ranges, indicate that glacial meltwater is a secondary source of α-HCH to fjord zooplankton in late summer. Except for α-HCH, terrestrial inputs were generally associated with reduced POP concentrations in zooplankton, suggesting that increased glacial melt is not likely to significantly increase exposure of legacy POPs in coastal fauna.

Trophic and fitness correlates of mercury and organochlorine compound residues in egg-laying Antarctic petrels.

Understanding the drivers and effects of exposure to contaminants such as mercury (Hg) and organochlorine compounds (OCs) in Antarctic wildlife is still limited. Yet, Hg and OCs have known physiological and fitness effects in animals, with consequences on their populations. Here we measured total Hg (a proxy of methyl-Hg) in blood cells and feathers, and 12 OCs (seven polychlorinated biphenyls, PCBs, and five organochlorine pesticides, OCPs) in plasma of 30 breeding female Antarctic petrels Thalassoica antarctica from one of the largest colonies in Antarctica (Svarthamaren, Dronning Maud Land). This colony is declining and there is poor documentation on the potential role played by contaminants on individual physiology and fitness. Carbon (δ13C) and nitrogen (δ15N) stable isotope values measured in the females' blood cells and feathers served as proxies of their feeding ecology during the pre-laying (austral spring) and moulting (winter) periods, respectively. We document feather Hg concentrations (mean ± SD, 2.41 ± 0.83 µg g-1 dry weight, dw) for the first time in this species. Blood cell Hg concentrations (1.38 ± 0.43 µg g-1 dw) were almost twice as high as those reported in a recent study, and increased with pre-laying trophic position (blood cell δ15N). Moulting trophic ecology did not predict blood Hg concentrations. PCB concentrations were very low (Σ7PCBs, 0.35 ± 0.31 ng g-1 wet weight, ww). Among OCPs, HCB (1.02 ± 0.36 ng g-1 ww) and p, p'-DDE (1.02 ± 1.49 ng g-1 ww) residues were comparable to those of ecologically-similar polar seabirds, while Mirex residues (0.72 ± 0.35 ng g-1 ww) were higher. PCB and OCP concentrations showed no clear relationship with pre-laying or moulting feeding ecology, indicating that other factors overcome dietary drivers. OC residues were inversely related to body condition, suggesting stronger release of OCs into the circulation of egg-laying females upon depletion of their lipid reserves. Egg volume, hatching success, chick body condition and survival were not related to maternal Hg or OC concentrations. Legacy contaminant exposure does not seem to represent a threat for the breeding fraction of this population over the short term. Yet, exposure to contaminants, especially Mirex, and other concurring environmental stressors should be monitored over the long-term in this declining population.

Potential Effect of Migration Strategy on Pollutant Occurrence in Eggs of Arctic Breeding Barnacle Geese ( Branta leucopsis).

Arctic-breeding geese acquire resources for egg production from overwintering grounds, spring stopover sites and breeding grounds, where pollutant exposure may differ. We investigated the effect of migration strategy on pollutant occurrence of lipophilic polychlorinated biphenyls (PCBs) and protein-associated poly- and perfluoroalkyl substances (PFASs) and mercury (Hg) in eggs of herbivorous barnacle geese ( Branta leucopsis) from an island colony on Svalbard. Stable isotopes (δ13C and δ15N) in eggs and vegetation collected along the migration route were similar. Pollutant concentrations in eggs were low, reflecting their terrestrial diet (∑PCB = 1.23 ± 0.80 ng/g ww; ∑PFAS = 1.21 ± 2.97 ng/g ww; Hg = 20.17 ± 7.52 ng/g dw). PCB concentrations in eggs increased with later hatch date, independent of lipid content which also increased over time. Some females may remobilize and transfer more PCBs to their eggs, by delaying migration several weeks, relying on more polluted and stored resources, or being in poor body condition when arriving at the breeding grounds. PFAS and Hg occurrence in eggs did not change throughout the breeding season, suggesting migration has a greater effect on lipophilic pollutants. Pollutant exposure during offspring production in arctic-breeding migrants may result in different profiles, with effects becoming more apparent with increasing trophic levels.

Elucidating the Behavior of Cyclic Volatile Methylsiloxanes in a Subarctic Freshwater Food Web: A Modeled and Measured Approach.

Cyclic volatile methylsiloxanes (cVMS) are used in personal care products and emitted to aquatic environments through wastewater effluents, and their bioaccumulation potential is debated. Here, a new bentho-pelagic version of the ACC-HUMAN model was evaluated for polychlorinated biphenyls (PCBs) and applied to cVMS in combination with measurements to explore their bioaccumulation behavior in a subarctic lake. Predictions agreed better with measured PCB concentrations in Arctic char (Salvelinus alpinus) and brown trout (Salmo trutta) when the benthic link was included than in the pelagic-only model. Measured concentrations of decamethylcyclopentasiloxane (D5) were 60 ± 1.2 (Chironomidae larvae), 107 ± 4.5 (pea clams Pisidium sp.), 131 ± 105 (three-spined sticklebacks: Gasterosteus aculeatus), 41 ± 38 (char), and 9.9 ± 5.9 (trout) ng g-1 wet weight. Concentrations were lower for octamethylcyclotetrasiloxane (D4) and dodecamethylcyclohexasiloxane (D6), and none of the cVMS displayed trophic magnification. Predicted cVMS concentrations were lower than measured in benthos, but agreed well with measurements in fish. cVMS removal through ventilation was an important predicted loss mechanism for the benthic-feeding fish. Predictions were highly sensitive to the partition coefficient between organic carbon and water (KOC) and its temperature dependence, as this controlled bioavailability for benthos (the main source of cVMS for fish).

Dechloranes and chlorinated paraffins in sediments and biota of two subarctic lakes.

Our understanding of the environmental behavior, bioaccumulation and concentrations of chlorinated paraffins (CPs) and Dechloranes (Dec) in the Arctic environment is still limited, particularly in freshwater ecosystems. In this descriptive study, short chain (SCCPs) and medium chain (MCCPs) CPs, Dechlorane Plus (DP) and analogues, and polychlorinated biphenyls (PCBs) were measured in sediments, benthic organisms, three-spined stickleback (Gasterosteus aculeatus), Arctic char (Salvelinus alpinus) and brown trout (Salmo trutta) in two Sub-Arctic lakes in Northern Norway. Takvannet (TA) is a remote lake, with no known local sources for organic contaminants, while Storvannet (ST) is situated in a populated area. SCCPs and MCCPs were detected in all sediment samples from ST with concentration of 42.26-115.29 ng/g dw and 66.18-136.69 ng/g dw for SCCPs and MCCPs, respectively. Only SCCPs were detected in TA sediments (0.4-5.28 ng/g dw). In biota samples, sticklebacks and benthic organisms showed the highest concentrations of CPs, while concentrations were low or below detection limits in both char and trout. The congener group patterns observed in both lakes showed SCCP profiles dominated by higher chlorinated congener groups while the MCCPs showed consistency in their profiles, with C14 being the most prevalent carbon chain length. Anti- and syn-DP isomers were detected in all sediment, benthic and stickleback samples with higher concentrations in ST than in TA. However, they were only present in a few char and trout samples from ST. Dec 601 and 604 were below detection limits in all samples in both lakes. Dec 603 was detected only in ST sediments, sticklebacks and 2 trout samples, while Dec 602 was the only DP analogue found in all samples from both lakes. While there were clear differences in sediment concentrations of DP and Dec 602 between ST and TA, differences between lakes decreased with increasing δ15N. This pattern was similar to the PCB behavior, suggesting the lake characteristics in ST are playing an important role in the lack of biomagnification of pollutants in this lake. Our results suggest that ST receives pollutants from local sources in addition to atmospheric transport.

Seasonal and latitudinal variability in the atmospheric concentrations of cyclic volatile methyl siloxanes in the Northern Hemisphere.

Field data from two latitudinal transects in Europe and Canada were gathered to better characterize the atmospheric fate of three cyclic methylsiloxanes (cVMSs), i.e., octamethyl-cyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). During a year-long, seasonally resolved outdoor air sampling campaign, passive samplers with an ultra-clean sorbent were deployed at 15 sampling sites covering latitudes ranging from the source regions (43.7-50.7 °N) to the Arctic (79-82.5 °N). For each site, one of two passive samplers and one of two field blanks were separately extracted and analyzed for the cVMSs at two different laboratories using gas-chromatography-mass spectrometry. Whereas the use of a particular batch of sorbent and the applied cleaning procedure to a large extent controlled the levels of cVMS in field blanks, and therefore also the method detection and quantification limits, minor site-specific differences in field blank contamination were apparent. Excellent agreement between duplicates was obtained, with 95% of the concentrations reported by the two laboratories falling within a factor of 1.6 of each other. Nearly all data show a monotonic relationship between the concentration and distance from the major source regions. Concentrations in source regions were comparatively constant throughout the year, while the concentration gradient towards remote regions became steeper during summer when removal via OH radicals is at its maximum. Concentrations of the different cVMS oligomers were highly correlated within a given transect. Changes in relative abundance of cVMS oligomers along the transect were in agreement with relative atmospheric degradation rates via OH radicals.

Optimization of a low flow sampler for improved assessment of gas and particle bound exposure to chlorinated paraffins.

An optimized low volume sampler was developed to determine both gas- and particle bound concentrations of short and medium-chain chlorinated paraffins (S/MCCPs). Background contamination was limited by the sampler design, providing method quantification limits (MQLs) at least two orders of magnitude lower than other studies within the gas (MQL: 500 pg (ΣSCCPs), 1.86 ng (ΣMCCPs)) and particle (MQL: 500 pg (ΣSCCPs), 1.72 ng (ΣMCCPs) phases. Good repeatability was observed between parallel indoor measurements (RSD ≤ 9.3% (gas), RSD ≤ 14% (particle)) with no breakthrough/saturation observed after a week of continuous sampling. For indoor air sampling, SCCPs were dominant within the gas phase (17 ± 4.9 ng/m3) compared to MCCPs (2.7 ± 0.8 ng/m3) while the opposite was observed in the particle bound fraction (0.28 ± 0.11 ng/m3 (ΣSCCPs) vs. 2.7 ± 1.0 ng/m3 (ΣMCCPs)). Only SCCPs in the gas phase could be detected reliably during outdoor sampling and were considerably lower compared to indoor concentrations (0.27 ± 0.10 ng/m3). Separation of the gas and particle bound phase was found to be crucial in applying the appropriate response factors for quantification based on the deconvoluted S/MCCP sample profile, thus avoiding over- (gas phase) or underestimation (particle phase) of reported concentrations. Very short chain chlorinated paraffins (vSCCPs, C5-C9) were also detected at equal or higher abundance compared to SCCP congener groups (C10-C13) congener groups, indicating an additional human indoor inhalation risk.

Volatile siloxanes in the European arctic: assessment of sources and spatial distribution.

The purpose of this study was to investigate presence and potential accumulation of cyclic volatile methyl siloxanes (cVMS) in the Arctic environment. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were analyzed in sediment, zooplankton, Atlantic cod (Gadus morhua), shorthorn sculpin (Myxocephalus scorpius), and bearded seal (Erignathus barbatus) collected from the Svalbard archipelago within the European Arctic in July 2009. Highest levels were found for D5 in fish collected from Adventfjorden, with average concentrations of 176 and 531 ng/g lipid in Atlantic cod and shorthorn sculpin, respectively. Decreasing concentration of D5 in sediment collected away from waste water outlet in Adventfjorden indicates that the local settlement of Longyearbyen is a point source to the local aquatic environment. Median biota sediment accumulation factors (BSAFs) calculated for D5 in Adventfjorden were 2.1 and 1.5 for Atlantic cod and shorthorn sculpin, respectively. Biota concentrations of D5 were lower or below detection limits in remote and sparsely populated regions (Kongsfjorden and Liefdefjorden) compared to Adventfjorden. The levels of cVMS were found to be low or below detection limits in bearded seal blubber and indicate a low risk for cVMS accumulation within mammals. Accumulation of cVMS in fish appears to be influenced by local exposure from human settlements within the Arctic.

Reducing sampling artifacts in active air sampling methodology for remote monitoring and atmospheric fate assessment of cyclic volatile methylsiloxanes.

Active sampling methodology for atmospheric monitoring of cyclic volatile methylsiloxanes (cVMS) was improved to reduce sampling artifacts. A new sorbent, ABN Express (ABN), was evaluated for storage stability and measurement accuracy. Storage stability of cVMS on ABN showed less than 1% degradation of the individual 13C-labelled octamethylcyclotetrasiloxane (13C4-D4), decamethylcyclopentasiloxane (13C5-D5) and dodecamethylcyclohexasiloxane (13C6-D6) after 14 days storage at room temperature and at -20 °C whereas significant degradation was observed on ENV+ sorbent at room temperature (37-62 %) and -20 °C (9-16 %). 13C4-D4 formed on ENV+ spiked with 13C5-D5, and both 13C4-D4 and 13C5-D5 formed on ENV+ spiked with 13C6-D6. However, this was not observed on the ABN sorbent. Performance of ABN was compared to ENV+ through an 8-month Arctic sampling campaign at the Zeppelin Observatory (Ny Ålesund, Svalbard). Good agreement between ABN and ENV+ was observed for D4 in the spring/summer months. However, D5 and D6 was found to be consistently higher on the ABN sorbent during this time period with D6 showing the greatest deviation. During the winter months, larger deviations were observed between ABN and ENV+ sorbents with a factor of 4 times higher atmospheric concentrations of both D5 and D6 found on ABN; indicating sorbent related degradation on ENV+. Our findings show that the ABN sorbent provides greater stability and accuracy for atmospheric monitoring of cVMS. Implications of these improvements towards atmospheric fate processes will be discussed.

Snow buntings (Plectrophenax nivealis) as bio-indicators for exposure differences to legacy and emerging persistent organic pollutants from the Arctic terrestrial environment on Svalbard.

Eggs of snow buntings (Plectrophenax nivealis) were applied as a bio-indicator to examine differences in exposure to legacy persistent organic pollutants (POPs) and perflouroalkyl subtances (PFAS) from the terrestrial environment surrounding the settlements of Longyearbyen, Barentsburg and Pyramiden on Svalbard, Norway. Significantly higher concentrations of summed polychlorinated biphenyls (sumPCB7) in eggs collected from Barentsburg (2980 ng/g lipid weight (lw)) and Pyramiden (3860 ng/g lw) compared to Longyearbyen (96 ng/g lw) are attributed to local sources of PCBs within these settlements. Similar findings were observed for p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) where higher median concentrations observed in Pyramiden (173 ng/g lw) and Barentsburg (75 ng/g lw) compared to Longyearbyen (48 ng/g lw) may be influenced by guano inputs from breeding seabird populations, although other point sources cannot be ruled out. Concentrations of perfluorooctane sulphonate (PFOS) and several perfluorinated carboxylic acids (PFCAs) in snow bunting eggs were found to be statistically higher in the populated settlements of Longyearbyen and Barentsburg compared to the abandoned Pyramiden. Narrow foraging ranges of snow buntings during breeding season was useful in assessing point sources of exposure for PCBs and PFAS at particular sites with extreme differences observed between nest locations. SumPCB7 concentrations ranged from 2 µg/g ww to below detection limits between nest sites located less than a kilometer from each other in Pyramiden. Similar findings were observed in Longyearbyen, where several PFCAs ranged from 2 to 55 times higher between nest sites with similar spatial distances. These findings indicate that snow buntings can be a useful bio-indicator offering high spatial resolution for contaminant source apportionment in terrestrial environments on Svalbard.

Individual variability in contaminants and physiological status in a resident Arctic seabird species.

While migratory seabirds dominate ecotoxicological studies within the Arctic, there is limited knowledge about exposure and potential effects from circulating legacy and emerging contaminants in species who reside in the high-Arctic all year round. Here, we focus on the case of the Mandt's Black guillemot (Cepphus grylle mandtii) breeding at Kongsfjorden, Svalbard (79.00°N, 11.66°E) and investigate exposure to legacy and emerging contaminants in relation to individual physiological status, i.e. body condition, oxidative stress and relative telomere length. Despite its benthic-inshore foraging strategy, the Black guillemot displayed overall similar contaminant concentrations in blood during incubation (∑PCB11 (15.7 ng/g w.w.) > ∑PFAS5 (9.9 ng/g w.w.) > ∑Pesticides9 (6.7 ng/g w.w.) > ∑PBDE4 (2.7 ng/g w.w.), and Hg (0.3 µg/g d.w.) compared to an Arctic migratory seabird in which several contaminant-related stress responses have been observed. Black guillemots in poorer condition tended to display higher levels of contaminants, higher levels of reactive oxygen metabolites, lower plasmatic antioxidant capacity, and shorter telomere lengths; however the low sample size restrict any strong conclusions. Nevertheless, our data suggests that nonlinear relationships with a threshold may exist between accumulated contaminant concentrations and physiological status of the birds. These findings were used to build a hypothesis to be applied in future modelling for describing how chronic exposure to contaminants may be linked to telomere dynamics.

Enantiomer fractions of polychlorinated biphenyls in three selected Standard Reference Materials.

The enantiomer composition of six chiral polychlorinated biphenyls (PCBs) were measured in three different certified Standard Reference Materials (SRMs) from the US National Institute of Standards and Technology (NIST): SRM 1946 (Lake Superior fish tissue), SRM 1939a (PCB Congeners in Hudson River Sediment), and SRM 2978 (organic contaminants in mussel tissue--Raritan Bay, New Jersey) to aid in quality assurance/quality control methodologies in the study of chiral pollutants in sediments and biota. Enantiomer fractions (EFs) of PCBs 91, 95, 136, 149, 174, and 183 were measured using a suite of chiral columns by gas chromatography/mass spectrometry. Concentrations of target analytes were in agreement with certified values. Target analyte EFs in reference materials were measured precisely (<2% relative standard deviation), indicating the utility of SRM in quality assurance/control methodologies for analyses of chiral compounds in environmental samples. Measured EFs were also in agreement with previously published analyses of similar samples, indicating that similar enantioselective processes were taking place in these environmental matrices.

Enantiomeric fractions of chiral polychlorinated biphenyls provide insights on biotransformation capacity of arctic biota.

Chiral polychlorinated biphenyls (PCBs) were measured in an arctic marine food web from the Northwater Polynya (NOW) in the Canadian Arctic to examine potential biotransformation of chiral PCB atropisomers. Organisms under investigation included pelagic zooplankton, Arctic cod (Boreogadus saida), seabirds, and ringed seals (Phoca hispida). Previous studies using achiral methods (e.g., biomagnification factors) have shown that chiral PCB congeners biomagnified in the NOW food web, but provided little information about biotransformation of PCBs except in extreme cases (i.e., high biotransformation). In this study, highly nonracemic enantiomeric fractions (EFs) were observed in several seabird species and ringed seals, but racemic EFs were found in prey (zooplankton and fish). This suggests stereoselective and species-specific biotransformation of individual PCB stereoisomers by birds and mammals. These results are consistent with previously reported biotransformation activity of chiral organochlorine pesticides, alpha-hexachlorocyclohexane, and chlordane within these organisms. This study demonstrates the utility of using chiral analysis of PCBs to investigate biotransformation within biota of arctic food webs.

A broad cocktail of environmental pollutants found in eggs of three seabird species from remote colonies in Norway.

Eggs of 3 seabird species, common eider (Somateria mollisima), European shag (Phalacrocorax aristotelis aristotelis), and European herring gull (Larus argentatus), were surveyed for a broad range of legacy and emerging pollutants to assess chemical mixture exposure profiles of seabirds from the Norwegian marine environment. In total, 201 chemical substances were targeted for analysis ranging from metals, organotin compounds, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and associated metabolites, chlorinated paraffins, chlorinated and nonchlorinated organic pesticides, per- and polyfluoroalkyl substances (PFAS), dechlorane plus, octachlorostyrene, brominated flame retardants (BFRs), organophosphorous compounds, brominated and alkyl phenols, cyclic siloxanes, and phthalates. Of the chemicals targeted, 149 substances were found above the detection limits, with metals dominating the contaminant profile and comprising 60% of the total contaminant load. Polychlorinated biphenyls, pesticides, organophosphorous compounds, and PFAS were the dominant contaminant classes of organic pollutants found within the seabird species, with the highest loads occurring in herring gulls, followed by shag, and common eider. New generation pollutants (e.g., PFAS, organophosphorous compounds, and alkylphenols) were detected at similar or higher concentrations than the legacy persistent organic pollutants (POPs). Time trends of reported concentrations of legacy POPs appear to have decreased in recent decades from the Norwegian coastal environment. Concentrations of detected pollutants do not appear to have a negative effect on seabird population development within the sampling area. Additional stress caused by pollutants, however, may affect seabird health more at the individual level.

Allometric relationships to liver tissue concentrations of cyclic volatile methyl siloxanes in Atlantic cod.

Spatial distribution and relationship of allometric measurements (length, weight and age) to liver concentrations of cyclic volatile methyl siloxanes (cVMS) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclosiloxane (D6) in Atlantic cod (Gadus morhua) collected near the community of Tromsø in Northern Norway were assessed. These congeners were benchmarked against known persistent polychlorinated biphenyls (PCBs 153 and 180) to assess accumulation behavior of cVMS. D5 was the dominate cVMS detected in all fish livers with lipid normalized concentrations up to 10 times or greater than those observed for PCB 153 and 180. D4 and D6 concentration were negatively correlated with fish length and weight, indicating a greater elimination capacity compared to uptake processes with increasing fish size for these chemicals. These results indicate relationships between allometric measurements and cVMS concentrations may account for concentration variations observed within fish and should be assessed in future studies evaluating cVMS bioaccumulation potential.

Spatial and temporal distribution of chiral pesticides in Calanus spp. from three Arctic fjords.

Concentration and enantiomeric fractions (EFs) of chiral chlorinated pesticides (α-hexachlorocyclohexane (α-HCH), trans-, cis- and oxychlordane) were determined in Arctic zooplankton, mainly Calanus spp. collected in the period 2007-11 from Svalbard fjords and open pack-ice. The temporal and spatial enantiomer distribution varied considerably for all species and chiral pesticides investigated. An overall enantiomeric excess of (+)-oxychlordane (EF 0.53-0.86) were observed. Cis-chlordane was close to racemic (EF 0.46-0.55), while EF for trans-chlordane varied between 0.29 and 0.55, and between 0.38 and 0.59 for α-HCH. The biodegradation potential for trans-chlordane was higher compared to cis-chlordane. The comprehensive statistical evaluation of the data set revealed that the EF distribution of α-HCH was affected by ice cover to a higher extent compared to cis-chlordane. Potential impact from benthic processes on EFs in zooplankton is an interesting feature and should be further investigated. Enantiomeric selective analyses may be a suitable tool for investigations of climate change related influences on Arctic ecosystems.

Plasma concentrations of cyclic volatile methylsiloxanes (cVMS) in pregnant and postmenopausal Norwegian women and self-reported use of personal care products (PCPs).

Dermal application of personal care products (PCPs) is considered an important human exposure route for siloxanes. Their presence as minor or major constituents in many personal care products (PCPs) and cosmetics is of concern for human exposure. The aim of this study was to quantify cyclic volatile methylsiloxanes (cVMS) in blood plasma of pregnant and postmenopausal women, and to investigate possible links to self-reported use of PCPs for the latter group. Participants were recruited from two studies, namely the Norwegian Women and Cancer Study (NOWAC) and the North Norwegian Mother-and-child Study (MISA). For the NOWAC cohort, 94 plasma samples from postmenopausal women were analyzed (blood drawn in 2005) and information about PCP use and breast implants was derived from a self-administered questionnaire. In the MISA study, the collection of the plasma samples (blood drawn in 2009) constituted a re-sampling because the original serum vacutainers used were contaminated with cVMS. D4 (octamethylcyclotetrasiloxane) was the dominant compound in plasma for both cohorts. For the NOWAC samples, more than 85% of the women had D4 concentrations above the LOQ (2.74 ng/mL), while the detection frequency was only 18% for the MISA participants. The highest cVMS plasma concentrations were observed for D4: 12.7 ng/mL (NOWAC) and 2.69 ng/mL (MISA). For the other cVMS, decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) concentrations were below the detection limit in most samples. There was no significant correlation between the concentrations of D4 and the reported total body cream use. Sampling time (2005 versus 2009) and age of the donors could explain the differences between the two cohorts.

Positive vs. false detection: a comparison of analytical methods and performance for analysis of cyclic volatile methylsiloxanes (cVMS) in environmental samples from remote regions.

Contamination and analytical variation can significantly hinder trace analysis of cyclic methyl volatile siloxanes (cVMS); potentially resulting in the report of false positives at concentrations approaching detection limits. To assess detection and variation associated with trace cVMS analysis in environmental matrices, a co-operative laboratory comparison for the analysis of octametylcyclotetrasiloxane (D4), decamethylcylcopentasiloxane (D5), and dodecametylcyclohexasiloxane (D6) in sediment and biota from the Svalbard Archipelago was conducted. Two definitions of detection limits were evaluated in this study; method detection limits (MDL, matrix defined) and limits of detection (LOD, solvent defined). D5 was the only cVMS detected above both LOD (0.08-0.81ngg(-1)ww) and MDL (0.47-2.36ngg(-1)ww) within sediment by all laboratories where concentrations ranged from 0.55 to 3.91ngg(-1)ww. The percentage of positive detects for D5 decreased by 80% when MDL was defined as the detection limit. D5 was also detected at the highest frequency among all laboratories in fish liver with concentrations ranging from 0.72 to 345ngg(-1)ww. Similar to sediment, percentage of positive detects for D5 decreased by 60% across all laboratories for fish livers when using MDL (0.68-3.49ngg(-1)ww). Similar observations were seen with both D4 and D6, indicating that sample matrix significantly contributes to analytical response variation. Despite differences in analytical methods used between laboratories, good agreement was obtained when using MDL to define detection limits. This study shows the importance of incorporating variation introduced by sample matrices into detection limit calculations to insure data accuracy of cVMS at low concentrations.

Influence of season, location, and feeding strategy on bioaccumulation of halogenated organic contaminants in Arctic marine zooplankton.

The influence of season, location, feeding strategy, and trophic position on concentration, compositional pattern, and bioaccumulation factors (BAFs) of halogenated organic contaminants (HOCs; polychlorinated biphenyls, chlorinated pesticides, and brominated flame retardants) was investigated within an Arctic zooplankton food web. Water (dissolved fraction) and seven Arctic marine pelagic zooplankton species (including herbivores, omnivores, and predators) were sampled in May, July, and October 2007 at two stations in Kongsfjorden, Svalbard, Norway. The HOC concentrations in both water and zooplankton generally decreased from May to October. The HOC concentrations and patterns among zooplankton species were explained by their feeding strategies, roughly categorized as herbivores, omnivores, and predators, and not stable isotope-derived trophic position. Field-derived BAFs varied greatly, with higher BAFs in May compared with July and October. Furthermore, BAFs differed among the species according to their feeding strategies. The relationship between BAFs from the different seasons and K(OW) (octanol:water partitioning coefficient) showed comparable intercepts and different slopes between May and October, with all relationships diverging from the assumed 1:1 relationship between BAF and K(OW). Differences in HOC concentrations and BAFs from herbivores to predators showed that biomagnification occurred in zooplankton. The results suggest that concentrations and patterns of HOCs in zooplankton species are influenced not only by equilibrium partitioning with water but also by feeding strategy.