The extent to which different manufacturing sources and long-range transport pathways contribute to perfluorooctanoate (PFOA) in the world's oceans, particularly in remote locations, is widely debated. Here, the relative contribution of historic (i.e., electrochemically fluorinated) and contemporary (i.e., telomer) manufacturing sources was assessed for PFOA, in various seawater samples by an established isomer profiling technique. The ratios of individual branched PFOA isomers were indistinguishable from those in authentic historic standards in 93% of the samples examined, indicating that marine processes had little influence on isomer profiles, and that isomer profiling is a valid source apportionment tool for seawater. Eastern Atlantic PFOA was largely (83-98%) of historic origin, but this decreased to only 33% close to the Eastern U.S. seaboard. Similarly, PFOA in the Norwegian Sea was near exclusively historic, but the relative contribution decreased to similar to 50% near the Baltic Sea. Such observations of contemporary PFOA in coastal source regions coincided with elevated concentrations, suggesting that the continued production and use of PFOA is currently adding to the marine burden of this contaminant. In the Arctic, a spatial trend was observed whereby PFOA in seawater originating from the Atlantic was predominantly historic (up to 99%), whereas water in the Archipelago (i.e., from the Pacific) was predominantly of contemporary origin (as little as 17% historic). These data help to explain reported temporal and spatial trends from Arctic wildlife biomonitoring, and suggest that the dominant PFOA source(s) to the Pacific and Canadian Arctic Archipelago are either (a) from direct emissions of contemporary PFOA via manufacturing or use in Asia, or (b) from atmospheric transport and oxidation of contemporary PFOA-precursors.,

We report here on the spatial distribution of C-4, C-6, and C-8 perfluoroalkyl sulfonates, C-6-C-14 perfluoroalkyl carboxylates, and perfluorooctanesulfonamide in the Atlantic and Arctic Oceans, including previously unstudied coastal waters of North and South America, and the Canadian Arctic Archipelago. Perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS) were typically the dominant perfluoroalkyl acids (PFAAs) in Atlantic water. In the midnorthwest Atlantic/Gulf Stream, sum PFAA concentrations (Sigma PFAAs) were low (77-190 pg/L) but increased rapidly upon crossing into U.S. coastal water (up to 5800 pg/L near Rhode Island). Sigma PFAAs in the northeast Atlantic were highest north of the Canary Islands (280-980 pg/L) and decreased with latitude. In the South Atlantic, concentrations increased near Rio de la Plata (Argentina/Uruguay; 350-540 pg/L Sigma PFAAs), possibly attributable to insecticides containing N-ethyl perfluorooctanesulfonamide, or proximity to Montevideo and Buenos Aires. In all other southern hemisphere locations, Sigma PFAAs were <210 pg/L. PFOA/PFOS ratios were typically >= 1 in the northern hemisphere, similar to 1 near the equator, and <= 1 in the southern hemisphere. In the Canadian Arctic, Sigma PFAAs ranged from 40 to 250 pg/L, with perfluoroheptanoate, PFOA, and PFOS among the PFAAs detected at the highest concentrations. PFOA/PFOS ratios (typically >>1) decreased from Baffin Bay to the Amundsen Gulf; possibly attributable to increased atmospheric inputs. These data help validate global emissions models and contribute to understanding of long-range transport pathways and sources of PFAAs to remote regions.

Among-lake variation in mercury (Hg) concentrations in landlocked Arctic char was examined in 27 char populations from remote lakes across the Canadian Arctic. A total of 520 landlocked Arctic char were collected from 27 lakes, as well as sediments and surface water from a subset of lakes in 1999, 2002, and 2005 to 2007. Size, length, age, and trophic position (delta(15)N) of individual char were determined and relationships with total Hg (THg) concentrations investigated, to identify a common covariate for adjustment using analysis of covariance (ANCOVA). A subset of 216 char from 24 populations was used for spatial comparison, after length-adjustment. The influence of trophic position and food web length and abiotic characteristics such as location, geomorphology, lake area, catchment area, catchment-to-lake area ratio of the lakes on adjusted THg concentrations in char muscle tissue were then evaluated. Arctic char from Amituk Lake (Cornwallis Island) had the highest Hg concentrations (1.31 mu g/g wet wt), while Tessisoak Lake (Labrador, 0.07 mu g/g wet wt) had the lowest. Concentrations of THg were positively correlated with size, delta(15)N, and age, respectively, in 88, 71, and 58% of 24 char populations. Length and delta(15)N were correlated in 67% of 24 char populations. Food chain length did not explain the differences in length-adjusted THg concentrations in char. No relationships between adjusted THg concentrations in char and latitude or longitude were found, however, THg concentrations in char showed a positive correlation with catchment-to-lake area ratio. Furthermore, we conclude that inputs from the surrounding environment may influence THg concentrations, and will ultimately affect THg concentrations in char as a result of predicted climate-driven changes that may occur in Arctic lake watersheds. Environ. Toxicol. Chem. 2010; 29: 633-643. (C) 2009 SETAC

Concentrations of mercury (Hg) have increased slowly in landlocked Arctic char over a 10- to 15-year period in the Arctic. Fluxes of Hg to sediments also show increases in most Arctic lakes. Correlation of Hg with trophic level (TL) was used to investigate and compare biomagnification of Hg in food webs from lakes in the Canadian Arctic sampled from 2002 to 2007. Concentrations of Hg (total Hg and methylmercury [MeHg]) in food webs were compared across longitudinal and latitudinal gradients in relation to delta(13)C and delta(15)N in periphyton, zooplankton, benthic invertebrates, and Arctic char of varying size-classes. Trophic magnification factors (TMFs) were calculated for the food web in each lake and related to available physical and chemical characteristics of the lakes. The relative content of MeHg increased with trophic level from 4.3 to 12.2% in periphyton, 41 to 79% in zooplankton, 59 to 72% in insects, and 74 to 100% in juvenile and adult char. The delta(13)C signatures of adult char indicated coupling with benthic invertebrates. Cannibalism among char lengthened the food chain. Biomagnification was confirmed in all 18 lakes, with TMFs ranging from 3.5 +/- 1.1 to 64.3 +/- 0.8. Results indicate that TMFs and food chain length (FCL) are key factors in explaining interlake variability in biomagnification of [Hg] among different lakes. Environ. Toxicol. Chem. 2010; 29: 621-632. (C) 2009 SETAC

Ice cores from the relatively low-lying ice caps in Svalbard have not been widely exploited in climatic and environmental studies due to uncertainties about the effect of melt water percolation. However, results from two recent Svalbard ice cores, at Lomonosovfonna (1250 m asl) and Austfonna (750 m asl), have shown that with careful site selection, high-resolution sampling and multiple chemical analyses, it is possible to recover ice cores with partly preserved annual signals. These cores are estimated to cover at least the past 600 years and have been dated using a combination of known reference horizons and glacial modeling. The delta(18)O data from both Lomonosovfonna and Austfonna ice cores suggest that the 20th century was the warmest during the past 600 years. A comparison of the ice core and sea ice records from this period suggests that sea ice extent and Austfonna delta(18)O are linked over the past 400 years. This may reflect the position of the storm tracks and their direct influence on the relatively low altitude Austfonna. Lomonosovfonna may be less sensitive to such changes and primarily record atmospheric changes due to its higher elevation. The anthropogenic influence on Svalbard environment is illustrated by increased levels of non-sea-salt sulphate, nitrate, acidity, fly-ash and organic contaminants particularly during the second half of 1900s. Decreased concentrations of some components in recent decades most likely reflect emission and use restrictions. However, some current-use organic pesticide compounds show growing concentrations in near surface layers. (C) 2003 Elsevier Ltd. All rights reserved.