Surface seawater and boundary layer atmospheric samples were collected on the FS Polarstern during cruise ARKXX in the North Atlantic and Arctic Ocean in 2004. Samples were analyzed for persistent organic pollutants (POPs), with a focus on organochlorine pesticides, including hexachlorocyclohexanes (HCHs), chlordanes, DDTs, hexachlorobenzene (HCB), and polycyclic aromatic hydrocarbons. In addition, the enantiomer fractions (EFs) of pesticides, notably alpha-HCH and cis-chlordane (CC), were determined. Concentrations of dissolved HCB increased from near Europe (approximately 1-2 pg/L) toward the high Arctic (4-10 pg/L). For dissolved HCB, strongest correlations were obtained with the average air or water temperature during sampling, not latitude. In the western Arctic Ocean, surface waters with elevated concentrations of HCB (5-10 pg/ L) were flowing out of the Arctic Ocean as part of the East Greenland current In contrast to dissolved compounds, atmospheric POPs did not display trends with temperature. Air-water exchange gradients suggested net deposition for all compounds, though HCB was closest to air-water equilibrium. EFs for alpha-HCH in seawater ranged from 0.43 to 0.50, except for two samples from 75 degrees N in the East Greenland Sea, with EFs of 0.31 and 0.37. Lowest EF (0.47) for CC were also at 75 degrees N, other samples had EFs from 0.49 to 0.52. It is suggested that samples from around 75 degrees N in the Greenland Gyre represented a combination of surface and older/deeper Arctic water.

[1] Air and seawater samples were collected on board the R/V Polarstern during a scientific expedition from Germany to . Dominant PCBs in seawater were 28/31 and 52 (0.1-0.44 pg L À1 ), with PCBs 101, 118, and 138 < 0.1 pg L À1 . In seawater, PCB 52 displayed the highest concentrations in the northernmost samples, while PCBs 101, 118, and 138 showed slightly decreasing trends with increasing latitude. Fractionation was observed for PCBs in seawater with the relative abundance of PCBs 28 and 52 increasing and that of the heavier congeners decreasing with latitude. However, in air only 15-20% of the variability of atmospheric PCBs can be explained by temperature. Owing to large uncertainties in the Henry's Law constant (HLC) values, fugacity quotients for PCBs were estimated using different HLCs reported in the literature. These indicate that on average, deposition dominates over volatilization for PCBs in the Arctic region with a strong increase in the middle of the transect near the marginal ice zone (78-79°N). The increase in fugacity ratio is mainly caused by an increase in air concentration in this region (possibly indirectly caused by ice melting being a source of PCBs to the atmosphere).

Reconstructions of environmental changes at sub-decadal to decadal resolution based on central Baltic Sea sediments rely on accurate and precise high-resolution sediment depth/age relationships. A model chronology for Baltic Sea sediments is presented here based on established historical records of anthropogenic radionuclides ( 137 Cs/ 241 Am/bomb 14 C), polychlorinated biphenyls (PCBs), lead (Pb) and stable lead isotope ( 206/207 Pb ratios), and radionuclide 210 Pb and 14 C decay dating methods. Marker horizons consisting of chemical precipitates formed by documented Major Baltic Inflow (MBIs) events and an extended diatom bloom period were also integrated into the model. The main time markers in Baltic Sea sediments that formed during the last 120 years were the following: (i) the deepest observation of 210 Pb unsupp. (marking the 210 Pb dating horizon) and departure of Hg from natural background levels at c. AD 1900; (ii) first detectable presence of PCBs at AD 1935; (iii) radionuclide production (i.e. 241 Am) due to nuclear weapons testing between AD 1954 and AD 1975, with a peak in AD 1963; (iv) maximum heavy metal and PCB concentrations in the AD 1960s/1970s; (v) the Chernobyl nuclear accident in AD 1986 as a sharp 137 Cs increase; (vi) exceptionally strong diatom blooms with a massive diatom layer found in the Eastern Gotland Basin in AD 1988-1990 and (vii) characteristic manganese-carbonate layers in the deeper central basins formed by MBIs in AD 1993 and AD 2003. A precise and accurate sediment depth/age relationship can only be achieved in restricted areas of the Baltic Sea where continuous sedimentation has prevailed and there has been limited postdepositional disturbance. We demonstrate that parallel Hg and 137 Cs measurements can be used to assess the quality of sediment sequences for high-resolution environmental reconstructions. We show examples of sediment profiles that conform to the historical record, and examples from Western Baltic Sea areas where it appears to be impossible to establish accurate geochronologies.