Polychlorinated biphenyls (PCBs) as sentinels for the elucidation of Arctic environmental change processes: a comprehensive review combined with ArcRisk project results.

Polychlorinated biphenyls (PCBs) can be used as chemical sentinels for the assessment of anthropogenic influences on Arctic environmental change. We present an overview of studies on PCBs in the Arctic and combine these with the findings from ArcRisk-a major European Union-funded project aimed at examining the effects of climate change on the transport of contaminants to and their behaviour of in the Arctic-to provide a case study on the behaviour and impact of PCBs over time in the Arctic. PCBs in the Arctic have shown declining trends in the environment over the last few decades. Atmospheric long-range transport from secondary and primary sources is the major input of PCBs to the Arctic region. Modelling of the atmospheric PCB composition and behaviour showed some increases in environmental concentrations in a warmer Arctic, but the general decline in PCB levels is still the most prominent feature. 'Within-Arctic' processing of PCBs will be affected by climate change-related processes such as changing wet deposition. These in turn will influence biological exposure and uptake of PCBs. The pan-Arctic rivers draining large Arctic/sub-Arctic catchments provide a significant source of PCBs to the Arctic Ocean, although changes in hydrology/sediment transport combined with a changing marine environment remain areas of uncertainty with regard to PCB fate. Indirect effects of climate change on human exposure, such as a changing diet will influence and possibly reduce PCB exposure for indigenous peoples. Body burdens of PCBs have declined since the 1980s and are predicted to decline further.

Organochlorine pesticides and polychlorinated biphenyls along an east-to-west gradient in subtropical North Atlantic surface water.

Despite the fact that most persistent toxic substances have hardly been primarily emitted for several decades, their concentrations are only slowly decreasing in the global oceans. Surface seawater samples were collected along a 38°-24° N/28°-67° W transect in the subtropical North Atlantic Ocean. While the concentration levels of hexachlorobenzene (2.1-6.1 pg L-1), dichlorodiphenyltrichloroethane (DDT, up to 2.1 pg L-1) and polychlorinated biphenyls (PCB, 10.8-24.9 pg L-1) were in the same range as observed earlier in the North Atlantic, hexachlorocyclohexane (HCH, 90-627 pg L-1) was found elevated, partly also relative to previous measurements in the same sea region. Hereby, the ratio α-HCH/γ-HCH was very low, 0.09-0.13. Chlordane and endosulfan were found in the range <3.0-11.1 and <5.8-8.8 pg L-1 respectively. DDT metabolites, endrin and related pesticides were found below quantification limits. Spatial pollution patterns in surface seawaters seem to be determined by atmospheric and oceanic transport patterns, rather than by mixing and air-sea equilibrium. The comparison with global multicompartment chemistry-transport model predictions of surface seawater levels indicate underestimated degradation of PCBs and overestimated emissions of endosulfan.

Atmospheric transport of persistent organic pollutants to and from the Arctic under present-day and future climate.

The long-term atmospheric cycling and fate of persistent organic pollutants under the influence of a changing climate is a concern. A GCM's realization of present-day (1970-1999) and future (2070-2099) climate, the latter under a medium scenario of greenhouse gas emissions, is used to study meridional transports and their correlations with the Arctic and North Atlantic Oscillations (AO and NAO). Regions of import and export maxima into the Arctic are identified along the Arctic Circle. It is found that, under future climate conditions, the net export of PCB153 out of the Arctic will increase. The meridional net flux pattern of this substance is expected to become independent of AO and NAO. For DDT, a trend of decreasing net Arctic import will reverse to an increasing trend 100 years after peak emission, which is partly due to more frequent AO and NAO positive phases. It is concluded that the long-term accumulation trends in the Arctic of other persistent pollutants, including so-called emerging pollutants, are subject to the substances' specific behavior and fate in the environment and need to be studied specifically.

Long-term trends of continental-scale PCB patterns studied using a global atmosphere-ocean general circulation model.

Continental-scale distribution and inter-continental transport of four polychlorinated biphenyl (PCB) congeners (28, 101, 153, 180) from 1950 to 2010 were studied using the global multicompartment chemistry transport model MPI-MCTM. Following identical primary emissions for all PCB congeners into air, most of the burden is stored in terrestrial (soil and vegetation) compartments. Thereby, PCB-28, PCB-101 and PCB-153 show a shift of the soil burden maxima from source to remote regions. This shift is downwind with regard to the westerlies for Eurasia and upwind for North America and more prominent for the lighter PCBs than for PCB-153 or PCB-180. In meridional direction, all congeners' distributions underwent a northward migration in Eurasia and North America since the 1950s. Inter-continental transport from Eurasian sources accounts largely for contamination of Alaska and British Columbia and determines the migration of the PCB distribution in soil in North America. Trans-Pacific transport occurs mainly in the gas phase in boreal winter (December-January-February) at 3-4 km altitude and is on a multi-year time scale strongly linked to the atmospheric pressure systems over the Pacific. Inter-continental transport of the lighter, more volatile PCBs is more efficient than for the heavier PCBs.

The impact of organochlorines cycling in the cryosphere on global distributions and fate--2. Land ice and temporary snow cover.

Global fate and transport of γ-HCH and DDT was studied using a global multicompartment chemistry-transport model, MPI-MCTM, with and without inclusion of land ice (in Antarctica and Greenland) or snow cover (dynamic). MPI-MCTM is based on coupled ocean and atmosphere general circulation models. After a decade of simulation 4.2% γ-HCH and 2.3% DDT are stored in land ice and snow. Neglection of land ice and snow in modelling would underestimate the total environmental residence time, τ(ov), of γ-HCH and overestimate τ(ov) for DDT, both on the order of 1% and depending on actual compartmental distribution. Volatilisation of DDT from boreal, seasonally snow covered land is enhanced throughout the year, while volatilisation of γ-HCH is only enhanced during the snow-free season. Including land ice and snow cover in modelling matters in particular for the Arctic, where higher burdens are predicted to be stored.

The impact of organochlorines cycling in the cryosphere on their global distribution and fate--1. Sea ice.

Global fate and transport of γ-HCH and DDT was studied using a global multicompartment chemistry-transport model, MPI-MCTM, with and without a dynamic sea ice compartment. The MPI-MCTM is based on coupled ocean and atmosphere general circulation models. Sea ice hosts 7-9% of the burden of the surface ocean. Without cycling in sea ice the geographic distributions are shifted from land to sea. This shift of burdens exceeds the sea ice burden by a factor of ≈8 for γ-HCH and by a factor of ≈15 for DDT. As regional scale seasonal sea ice melting may double surface ocean contamination, a neglect of cycling in sea ice (in an otherwise unchanged model climate) would underestimate ocean exposure in high latitudes. Furthermore, it would lead to overestimates of the residence times in ocean by 40% and 33% and of the total environmental residence times, τ(overall), of γ-HCH and DDT by 1.6% and 0.6%, respectively.