Anna Sobek

A comparison of PCB bioaccumulation factors between an arctic and a temperate marine food web.

To test how environmental conditions in the Arctic and the resulting ecological adaptations affect accumulation of persistent organic pollutants (POPs) in the marine food web, bioaccumulation of four polychlorinated biphenyls (PCBs) in an arctic (Barents Sea 77 degrees N-82 degrees N) and a temperate marine (Baltic Sea 54 degrees N-62 degrees N) food web were compared. Three different trophic levels were studied (zooplankton, fish, and seal), representing the span from first-level consumer to top predator. Previously published high-quality data on PCB water concentrations in the two areas were used for calculation of bioaccumulation factors (BAF). BAF was calculated as the ratio of the PCB concentration in the organism ([PCB](org); pg/kg lipid) to the dissolved water concentration (C(w); pg/L). The BAF(Arctic):BAF(Temperate) ratios were above 1 for all four PCB congeners in zooplankton (6.4-13.8) and planktivorous fish (2.9-5.0)), whereas the ratios were below 1 in seal. The mean ratio between arctic and temperate BAFs for all trophic levels and congeners (BAF(Arcti):BAF(Temperate)) was 4.8. When the data were corrected for the seawater temperature difference between the two ecosystems, the ratio was 2.0. We conclude that bioaccumulation differences caused by ecological or physiological adaptations of organisms between the two ecosystems were well within a water concentration variability of 50%. Further, our data support the hypothesis that lower seawater temperature lead to a thermodynamically favoured passive partitioning to organic matrices and thus elevated ambient BAFs in the Arctic compared to the Baltic Sea. This would imply that bioaccumulation in the Arctic may be described in the same way as bioaccumulation in temperate regions, e.g. by the use of mechanistic models parameterised for the Arctic.

Fate of Pharmaceuticals and Their Transformation Products in Four Small European Rivers Receiving Treated Wastewater.

A considerable knowledge gap exists with respect to the fate and environmental relevance of transformation products (TPs) of polar organic micropollutants in surface water. To narrow this gap we investigated the fate of 20 parent compounds (PCs) and 11 characteristic TPs in four wastewater-impacted rivers. Samples were obtained from time-integrated active sampling as well as passive sampling using polar organic chemical integrative samplers (POCIS). Seventeen out of the 20 PCs were detected in at least one of the rivers. All the PCs except acesulfame, carbamazepine, and fluconazole were attenuated along the studied river stretches, with the largest decrease found in the smallest river which had an intense surface water-pore water exchange. Seven TPs were detected, all of which were already present directly downstream of the WWTP outfall, suggesting that the WWTPs were a major source of TPs to the recipients. For anionic compounds, attenuation was the highest in the two rivers with the lowest discharge, while the pattern was not as clear for neutral or cationic compounds. For most compounds the results obtained from active sampling were not significantly different from those using POCIS, demonstrating that the cost and labor efficient POCIS is suitable to determine the attenuation of organic micropollutants in rivers.

Deep water masses and sediments are main compartments for polychlorinated biphenyls in the Arctic Ocean.

There is a wealth of studies of polychlorinated biphenyls (PCB) in surface water and biota of the Arctic Ocean. Still, there are no observation-based assessments of PCB distribution and inventories in and between the major Arctic Ocean compartments. Here, the first water column distribution of PCBs in the central Arctic Ocean basins (Nansen, Amundsen, and Makarov) is presented, demonstrating nutrient-like vertical profiles with 5-10 times higher concentrations in the intermediate and deep water masses than in surface waters. The consistent vertical profiles in all three Arctic Ocean basins likely reflect buildup of PCBs transported from the shelf seas and from dissolution and/or mineralization of settling particles. Combined with measurement data on PCBs in other Arctic Ocean compartments collected over the past decade, the total Arctic Ocean inventory of ∑7PCB was estimated to 182 ± 40 t (±1 standard error of the mean), with sediments (144 ± 40 t), intermediate (5 ± 1 t) and deep water masses (30 ± 2 t) storing 98% of the PCBs in the Arctic Ocean. Further, we used hydrographic and carbon cycle parametrizations to assess the main pathways of PCBs into and out of the Arctic Ocean during the 20th century. River discharge appeared to be the major pathway for PCBs into the Arctic Ocean with 115 ± 11 t, followed by ocean currents (52 ± 17 t) and net atmospheric deposition (30 ± 28 t). Ocean currents provided the only important pathway out of the Arctic Ocean, with an estimated cumulative flux of 22 ± 10 t. The observation-based inventory of ∑7PCB of 182 ± 40 t is consistent with the contemporary inventory based on cumulative fluxes for ∑7PCB of 173 ± 36 t. Information on the concentration and distribution of PCBs in the deeper compartments of the Arctic Ocean improves our understanding of the large-scale fate of POPs in the Arctic and may also provide a means to test and improve models used to assess the fate of organic pollutants in the Arctic.

Sorption of Phenyl Urea Herbicides to Black Carbon

In this work, we developed a dialysis technique to determine black carbon (BC; diesel soot)-water distribution coefficients (K(BC)) of nine phenyl urea herbicides (PUHs). The K(BC) at 1 microg/L ranged over 2 orders of magnitude, with diuron displaying the highest log K(BC) of 4.5. The K(BC) were 20-170 times higher than corresponding estimated partitioning coefficients to organic carbon (K(OC)). This is consistent with earlier findings for more hydrophobic compounds. There was a linear increase in log K(BC) with decreasing thermodynamic difference between the geometrically optimized and planar molecule conformation (DeltaE(planar)). Hence, previous observations of enhanced BC adsorption of planar compounds (e.g., non-ortho-polychlorinated biphenyls) were confirmed also for the polar PUHs. Further, the data suggested indirectly that for molecules with several different functional groups (such as the PUHs), specific electron donor and acceptor interactions may be of more relevance for the adsorption to BC than the ability of the molecule to undergo dispersive van der Waals interactions. Sorption coefficients estimated from poly parameter linear solvation energy relationships (pp-LSER) based on data for activated carbon were 1-1.5 log units higher than the experimental data for diesel soot. This illustrates the complexity in applying models developed for one BC form to another, and calls for more data on soot-water distribution descriptors.

Partitioning of polychlorinated biphenyls between Arctic seawater and size‐fractionated zooplankton

Concentrations of hydrophobic organic contaminants in zooplankton have been hypothesized to be governed by either near-equilibrium partitioning with surrounding water, growth dilution, or biomagnification. Concentrations of 17 polychlorinated biphenyls (PCBs) were measured in size-fractionated zooplankton, in phytoplankton (> 0.7 microm), and in the dissolved water phase (< 0.7 microm) in the surface water of the northern Barents Sea marginal ice zone east and north of Spitsbergen (Norway) and in the central Arctic Ocean at 89 degrees N. The linear partition model was used to indirectly assess if PCBs were equilibrated between water and the extractable organic matter (EOM) of zooplankton. As an independent test, the relation between the EOM-normalized partition coefficient (log K(EOM)) and trophic level (TL) of the zooplankton (based on delta 15N) was investigated. All log K-log K(OW) regressions were significant (n=18, p < 0.05, r2 = 0.65-0.95), being consistent with near-equilibrium partitioning and indirectly suggesting the absence of biomagnification. No correlation was found between log K(EOM) and TL, further supporting the apparent absence of biomagnification in zooplankton. One implication of these results is a reduced uncertainty in modeling of food web uptake, in which kinetic parameterizations of biodilution or biomagnification in zooplankton may be replaced by a simpler parameterization based on equilibrium partitioning.

Baltic Sea sediment records: unlikely near-future declines in PCBs and HCB.

UNLABELLED We present a comprehensive study on PCBs and HCB in dated sediment cores from the Baltic Sea covering the 20th century, and compare their spatiotemporal trends with those of PCDD/Fs from the same areas. PCB concentrations in coastal impacted sediment followed the temporal trend of estimated global emissions of PCBs and thus responded quickly to changes in global industrial use, whereas concentrations in offshore sediment needed 10-20 years longer to respond. Differences in spatiotemporal trends of PCDD/Fs and PCBs were smaller than expected based on documented differences in key sources and source areas. Sediment concentrations of HCB varied little over time and space, but concentrations are increasing in recent years. The steep PCB concentration reduction over time observed for the late 20th century levelled off during the last 20 years, and levels of PCBs appear to be at or near a steady-state condition. CAPSULE PCB concentrations in Baltic Sea sediments appear to be at or near steady-state, and no significant concentration decreases are to be expected in the near future.

Temporal trends of PCDD/Fs in Baltic Sea sediment cores covering the 20th century.

The pollution trend of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the Baltic Sea region was studied based on depth profiles of PCDD/Fs in sediment cores collected from six offshore areas, eight coastal sites impacted by industrial/urban emissions, and one coastal reference site. A general trend was observed for the offshore and coastal reference sites with substantial increase in PCDD/F concentrations in the mid-late 1970s and peak levels during 1985-2002. The overall peak year for PCDD/Fs in Baltic Sea offshore areas was estimated (using spline-fit modeling) to 1994 ± 5 years, and a half-life in sediments was estimated at 29 ± 11 years. For the industrial/urban impacted coastal sites, the temporal trend was more variable with peak years occurring 1-2 decades earlier compared to offshore areas. The substantial reductions from peak levels (38 ± 11% and 81 ± 12% in offshore and coastal areas, respectively) reflect domestic and international actions taken for reduction of the release of PCDD/Fs to the environment. The modeled overall half-life and reductions of PCDD/Fs in offshore Baltic Sea sediment correspond well to both PCDD/F trends in European lakes without any known direct PCDD/F sources (half-lives 30 and 32 years), and previously modeled reduction in atmospheric deposition of PCDD/Fs to the Baltic Sea since 1990. These observations support previous findings of a common diffuse source, such as long-range air transport of atmospheric emissions, as the prime source of PCDD/Fs to the Baltic Sea region. The half-life of PCDD/Fs in Baltic Sea offshore sediments was estimated to be approximately 2 and 4-6 times longer than in semirural and urban European air, respectively. This study highlights the need for further international actions to reduce the levels of PCDD/Fs in Baltic Sea air specifically and in European air in general.

An evaluation of the importance of the sampling step to the total analytical variance : A four system field-based sampling intercomparison study for hydrophobic organic contaminants in the surface waters of the open Baltic Sea

An evaluation of the importance of the sampling step to the total analytical variance : A four system field-based sampling intercomparison study for hydrophobic organic contaminants in the surface waters of the open Baltic Sea

Assessment of PCDD/F Source Contributions in Baltic Sea Sediment Core Records

Spatial and temporal trends of sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the Baltic Sea were evaluated by positive matrix factorization (PMF) and principal component analysis (PCA). Sediment cores were sampled at eight coastal, one coastal reference, and six offshore sites covering the northern to the southern Baltic Sea. The cores, which covered the period 1919-2010, were sliced into 2-3 cm disks among which 8-11 disks per core (in total 141 disks) were analyzed for all tetra- through octa-CDD/Fs. Identification and apportionment of PCDD/F sources was carried out using PMF. Five stable model PCDD/F congener patterns were identified, which could be associated with six historically important source types: (i) atmospheric background deposition (ABD), (ii) use and production of penta-chlorophenol (PCP), (iii) use and production of tetra-chlorophenol (TeCP), (iv) high temperature processes (Thermal), (v) hexa-CDD-related sources (HxCDD), and (vi) chlorine-related sources (Chl), all of which were still represented in the surface layers. Overall, the last four decades of the period 1920-2010 have had a substantial influence on the Baltic Sea PCDD/F pollution, with 88 ± 7% of the total amount accumulated during this time. The 1990s was the peak decade for all source types except TeCP, which peaked in the 1980s in the northern Baltic Sea and has still not peaked in the southern part. The combined impact of atmospheric-related emissions (ABD and Thermal) was dominant in the open sea system throughout the study period (1919-2010) and showed a decreasing south to north trend (always >80% in the south and >50% in the north). Accordingly, to further reduce levels of PCDD/Fs in the open Baltic Sea ecosystem, future actions should focus on reducing atmospheric emissions.

Flume experiments to investigate the environmental fate of pharmaceuticals and their transformation products in streams.

The hyporheic zone—the transition region beneath and alongside the stream bed—is a central compartment for attenuation of organic micropollutants in rivers. It provides abundant sorption sites and excellent conditions for biotransformation. We used a bench-scale flume to study the fate of 19 parent pharmaceuticals (PPs) and the formation of 11 characteristic transformation products (TPs) under boundary conditions similar to those in hyporheic zones. The persistence of PPs ranged from readily degradable with a dissipation half-life (DT50) as short as 1.8 days (acetaminophen, ibuprofen) to not degradable (chlorthalidone, fluconazole). The temporal and spatial patterns of PP and TP concentrations in pore water were heterogeneous, reflecting the complex hydraulic and biogeochemical conditions in hyporheic zones. Four TPs (carbamazepine-10,11-epoxide, metoprolol acid, 1-naphthol, and saluamine) were exclusively formed in the sediment compartment and released to surface water, highlighting their potential to be used as indicators for characterizing hyporheic transformation of micropollutants in streams. The accumulation of certain TPs over the experimental period illustrates that we might face a peak of secondary contamination by TPs far from the point of release of the original contaminants into a stream. Such TPs should be considered as priority candidates for a higher-tier environmental risk assessment.