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The Arctic is undergoing dramatic changes which cover the entire range of natural processes, from extreme increases in the temperatures of air, soil, and water, to changes in the cryosphere, the biodiversity of Arctic waters, and land vegetation. Small changes in the largest marine carbon pool, the dissolved inorganic carbon pool, can have a profound impact on the carbon dioxide (CO2) flux between the ocean and the atmosphere, and the feedback of this flux to climate. Knowledge of relevant processes in the Arctic seas improves the evaluation and projection of carbon cycle dynamics under current conditions of rapid climate change. Investigation of the CO2) system in the outer shelf and continental slope waters of the Eurasian Arctic seas (the Barents, Kara, Laptev, and East Siberian seas) during 2006, 2007, and 2009 revealed a general trend in the surface water partial pressure of CO2) (pCO2)/ distribution, which manifested as an increase in pCO2) values eastward. The existence of this trend was defined by different oceanographic and biogeochemical regimes in the western and eastern parts of the study area; the trend is likely increasing due to a combination of factors determined by contemporary change in the Arctic climate, each change in turn evoking a series of synergistic effects. A high-resolution in situ investigation of the carbonate system parameters of the four Arctic seas was carried out in the warm season of 2007; this year was characterized by the next-to-lowest historic sea-ice extent in the Arctic Ocean, on satellite record, to that date. The study showed the different responses of the seawater carbonate system to the environment changes in the western vs. the eastern Eurasian Arctic seas. The large, open, highly productive water area in the northern Barents Sea enhances atmospheric CO2) uptake. In contrast, the uptake of CO2) was strongly weakened in the outer shelf and slope waters of the East Siberian Arctic seas under the 2007 environmental conditions. The surface seawater appears in equilibrium or slightly supersaturated by CO2) relative to atmosphere because of the increasing influence of river runoff and its input of terrestrial organic matter that mineralizes, in combination with the high surface water temperature during sea-ice-free conditions. This investigation shows the importance of processes that vary on small scales, both in time and space, for estimating the air-sea exchange of CO2. It stresses the need for highresolution coverage of ocean observations as well as time series. Furthermore, time series must include multi-year studies in the dynamic regions of the Arctic Ocean during these times of environmental change. [ABSTRACT FROM AUTHOR]

The Arctic now is undergoing dramatic changes, which cover the entire range of natural processes; from extreme increases in the temperatures of air, soil, and water, to changes in the cryosphere, the biodiversity of Arctic waters, and land vegetation. Small changes in the largest marine carbon pool, the dissolved inorganic carbon pool, can have profound impact on the carbon dioxide (CO2) flux between the ocean and the atmosphere, and the feedback of this flux to climate. Knowledge of relevant processes in the Arctic seas improves the evaluation and projection of the carbon cycle dynamics under conditions of rapid climate change. Investigation of the CO2 system in the outer shelf and continental slope waters of the Eurasian Arctic seas (the Barents, Kara, Laptev, and East Siberian seas) during 2006, 2007, and 2009 revealed a general trend in the surface water pCO2 distribution, which manifested as an increase in pCO2 values eastward. Existence of this trend was determined by different oceanographic and biogeochemical regimes in the western and eastern parts of the study area; the trend is likely increasing due to a combination of factors determined by contemporary change in the Arctic climate, each change in turn evoked a series of synergistic effects. A high-resolution in situ investigation of the carbonate system parameters of the four Arctic seas was carried out in the warm season of 2007, which was characterized by the next-to-lowest historic sea ice extent in the Arctic Ocean to that date. The study showed the different responses of the seawater carbonate system to the environment changes in the western vs. the eastern Eurasian Arctic seas. The large open, highly-productive water area in the northern Barents Sea enhances atmospheric CO2 uptake. In contrast, a growing CO2 evasion occurs in the outer shelf and slope waters of the East Siberian Arctic seas as a result of the increasing influence of river runoff and degradation of terrestrial organic matter, in combination with the high surface-water temperature due to the warm air temperature and decreasing albedo during sea ice free conditions. This investigation shows the importance of processes that vary on small scales, both in time and space, for estimating the air-sea exchange of CO2. It stresses the need for high-resolution coverage of ocean observations as well as time series. Furthermore, time series must include multi-year studies in the dynamic regions of the Arctic Ocean during these times of environmental change. [ABSTRACT FROM AUTHOR]

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 Malcarov) 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 seeding particles Combined with measurement data on PCBs in other Arctic Ocean compartments collected over the past decade, the total Arctic Ocean inventory of Σ7PCB was estimated to 182 ± 40 t (±1 standard error of the mean), with sediments(144 ± 40 t), intermediate (5±1t) 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 Σ7PCB of 182 ± 40 t is consistent with the contemporary inventory based on cumulative fluxes for Σ7PCB of 173 ± 36 t. Information on die 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 fete of organic pollutants in the Arctic. [ABSTRACT FROM AUTHOR]

Abstract: Settling-based surface ocean export of particulate organic carbon (POC) in the western Eurasian sector of the Arctic Ocean was investigated from the marginal ice zone (MIZ) of the northern Barents Sea to the North Pole area. Upper ocean profiles of POC were combined with corresponding dissolved and particulate 234Th activities measured with a low-volume at-sea direct beta counting protocol to constrain the 234Th-derived POC export in July and August of 2001 to 6−32mmolm−2 d−1 for the Barents Sea MIZ dropping to 2–6mmolm−2 d−1 for multi-year-ice (MYI) covered central Arctic stations in Nansen, Amundsen and Makarov basins. Secular equilibrium between 234Th and 238U activities in intermediate to deep waters in the Amundsen Basin (n=10) demonstrated that the at-sea measurement protocol was functioning satisfactorily. There was no distinction in POC export efficiency between the MIZ and the MYI-covered interior basins with an average ratio between 234Th-derived POC export and primary production (so-called ThE ratio) of 44%. A projected increase in primary production with retreat in areal extent of sea ice is thus likely to yield increased POC sequestration in the Arctic Ocean interior. [Copyright &y& Elsevier]

Assessment of the Arctic as a global repository of polychlorinated biphenyis (PCBs) and of uptake processes in the base of its marine food chain hinges on reliable information of PCB distribution In surface seawater, yet there is a scarcity of quality-assured PCB measurements in this key compartment. Here, surface seawater PCB concentrations and congener fingerprints are evaluated for all seven pan-Arctic shelf seas and for the interior basins. Particulate and dissolved PCBs were collected via trace-clean protocols on three basin-wide expeditions (AO-01, Beringia-2005, and ISSS-08). Concentrations of the sum of 13 abundant congeners (Σ13PCB) were 0.13 -21 pg/L, with higher concentrations in the shelf seas and lower concentrations in the Central Arctic Basin. Trichlorinated PCBs constituted about half of the total loadings in the Eastern Arctic (Beaufort, Chukchi, East Siberian, and Laptev Seas) and in the Central Basin, indicating an atmospheric source. In contrast, bexachlorinated PCBs were more abundant than tri-PCBs in the western sector, suggesting a role also for waterborne transport from regions of heavy PCB consumption in North America and Europe. Finally, the inventory of Σ13PCB in the polar mixed layer of the entire Arctic Ocean was 0.39 ton, which implies that only 0.0008% of historical PCB emissions are now residing in Arctic surface waters. [ABSTRACT FROM AUTHOR]

Climate change is expected to have a strong effect on the Eastem Siberian Arctic Shelf (ESAS) region, which includes 40% of the Arctic shelves and comprises the Laptev and East Siberian seas. The largest organic carbon pool, the dissolved organic carbon (DOC), may change significantly due to changes in both riverine inputs and transformation rates; however, the present DOC inventories and transformation patterns are poorly understood. Using samples from the International Siberian Shelf Study 2008, this study examines for the first time DOC removal in Arctic shelf waters with residence times that range from months to years. Removals of up to l0%-20% were found in the Lena River estuary, consistent with earlier studies in this area, where surface waters were shown to have a residence time of approximately 2 months. In contrast, the DOC concentrations showed a strong nonconservative pattern in areas with freshwater residence times of several years. The average losses of DOC were estimated to be 30%-50% during mixing along the shelf, corresponding to a first-order removal rate constant of 0.3 yr-1. These data provide the first observational evidence for losses of DOC in the Arctic shelf seas, and the calculated DOC deficit reflects DOC losses that are higher than recent model estimates for the region. Overall, a large proportion of riverine DOC is removed from the surface waters across the Arctic shelves. Such significant losses must be included in models of the carbon cycle for the Arctic Ocean, especially since the breakdown of terrestrial DOC to CO2 in Arctic shelf seas may constitute a positive feedback mechanism for Arctic climate warming. These data also provide a baseline for considering the effects of future changes in carbon fluxes, as the vast northern carbon-rich permafrost areas draining into the Arctic are affected by global warming. [ABSTRACT FROM AUTHOR]

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 μm), and in the dissolved water phase (<0.7 μm) 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°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 KEOM) and trophic level (TL) of the zooplankton (based on δ15N) was investigated. All log K-log KOW 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 KEOM 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. [ABSTRACT FROM AUTHOR]

Abstract: Detailed organic geochemical analyses were performed on surface water particulate samples of the lower Kalix River and northern Bothnian Bay collected during the spring flood of 2005. Both bulk geochemical and molecular biomarker analyses indicated a predominance of terrestrially-derived particulate organic matter (POM), both of higher plant and Sphagnum origin in the low salinity zone (LSZ) of the Kalix River estuary, with an increasing contribution of marine-derived POM in the offshore Bothnian Bay basin. Two-dimensional box modeling of the mixed surface layer in the LSZ indicated that 65% of the particulate organic carbon (POC) and between 73 and 93% of the terrestrial biomarker classes analyzed (high molecular weight n-alkanes, n-alkanoic acids and n-alkanols as well as sitosterol) were degraded in the course of their weeklong transit through the inner LSZ during the spring flood. This corresponds to field-based degradation rate constants for the biomarkers of 0.5 and 2.5 day−1, which are similar to results reported from mesocosm experiments for related compounds. The degradation rate constant for terrestrial POC of 0.38 day−1 was about 20 times larger than for DOC and suggests that POC mineralization stands for 44% of the total mineralization, which is much larger than previously considered. This sub-arctic river-export regime has a geochemistry resembling that of neighboring western Russian Arctic Rivers, suggesting that a large part of the OM coastally exported from northernmost Eurasian soils may be degraded within the vicinity of the river mouths and putatively be released as carbon dioxide. The 65% degradation of terrestrial POC in the coastal surface water of this sub-arctic recipient is substantially larger than a global-average of 35% used in recent budget estimates of the fate of terrestrially-exported POC on the pan-arctic shelves. Considering ongoing and predicted changes in the Arctic Region due to global warming a more efficient degradation of river-exported terrestrial POC may have far-reaching consequences for the large-scale biogeochemical cycling of carbon in the pan-arctic region and beyond. [Copyright &y& Elsevier]

There is a scarcity of data on the amount and distribution of the organochlorine pesticide dichlorodiphenyltrichloroethane (DDT) and its metabolites in intermediate and deep ocean water masses. Here, the distribution and inventories of DDTs in water of the Arctic shelf seas and the interior basin are presented. The occurrence of ∑6DDT (0.10-66 pg L-1) in the surface water was dominated by 4,4′-DDE. In the Central Arctic Ocean increasing concentrations of DDE with depth were observed in the Makarov and Amundsen basins. The increasing concentrations down to 2500 m depth is in accordance with previous findings for PCBs and PBDEs. Similar concentrations of DDT and DDEs were found in the surface water, while the relative contribution of DDEs increased with depth, demonstrating a transformation over time and depth. Higher concentrations of DDTs were found in the European part of the Arctic Ocean; these distributions likely reflect a combination of different usage patterns, transport, and fate of these compounds. For instance, the elevated concentrations of DDTs in the Barents and Atlantic sectors of the Arctic Ocean indicate the northbound Atlantic current as a significant conveyor of DDTs. This study contributes to the very rare data on OCPs in the vast deep-water compartments and combined with surface water distribution across the Arctic Ocean helps to improve our understanding of the large-scale fate of DDTs in the Arctic. [ABSTRACT FROM AUTHOR]

Little is known about the distribution of polybrominated diphenyl ethers (PBDE) -also known as flame retardants- in major ocean compartments, with no reports yet for the large deep-water masses of the Arctic Ocean. Here, PBDE concentrations, congener patterns and 400 inventories are presented for the different water masses of the pan-Arctic shelf seas and the interior basin. Seawater samples were collected onboard three cross-basin oceanographic campaigns in 2001, 2005, and 2008 following strict trace-clean protocols. Σ14PBDE concentrations in the Polar Mixed Layer (PML; a surface water mass) range from 0.3 to 11.2 pg L-1, with higher concentrations in the pan-Arctic shelf seas and lower levels in the interior basin. BDE-209 is the dominant congener in most of the pan-Arctic areas except for the ones close to North America, where penta- BDE and tetra-BDE congeners predominate. In deep-water masses, Σ14PBDE concentrations are up to 1 order of magnitude higher than in the PML. Whereas BDE-209 decreases with depth, the less-brominated congeners, particularly BDE-47 and BDE-99, increase down through the water column. Likewise, concentrations of BDE-71-a congener not present in any PBDE commercial mixtureincrease with depth, which potentially is the result of debromination of BDE-209. The inventories in the three water masses of the Central Arctic Basin (PML, intermediate Atlantic Water Layer, and the Arctic Deep Water Layer) are 158 ± 77 kg, 6320 ± 235 kg and 30800 ± 3100 kg, respectively. The total load of PBDEs in the entire Arctic Ocean shows that only a minor fraction of PBDEs emissions are transported to the Arctic Ocean. These findings represent the first PBDE data in the deep-water compartments of an ocean. [ABSTRACT FROM AUTHOR]

Abstract: Bacteriohopanepolyols (BHPs) are a diverse group of membrane lipids produced by a wide variety of bacteria and can be used as molecular biomarkers for bacterial processes and populations in both modern and ancient environments. A group of BHPs, including adenosylhopane and structurally related compounds, have been identified as being specific to soils, enabling the transport of terrestrial organic matter (terrOM) to the marine realm to be monitored. Estuary surface sediment samples were obtained from the five Great Russian Arctic Rivers (GRARs; Ob, Yenisey, Lena, Indigirka and Kolyma) and river sediments were obtained from two North American Rivers (Yukon and Mackenzie). Analysis of the BHP signatures, using high performance liquid chromatography–tandem mass spectrometry (HPLC–MS n ), indicated the presence of 15 different BHPs originating from a variety of different bacteria, as well as a significant presence of terrestrially derived OM. Total BHP abundance and the contribution of the “soil-marker” BHPs to the total BHP pool increased eastwards among the GRAR sediments. This suggests increasing terrestrial OM or increased preservation of OM as a result of shorter periods of permafrost thawing. The North American rivers showed greatly differing BHP levels between the Yukon and Mackenzie rivers, with a greater BHP input and thus a relatively higher soil OM contribution from the Yukon. The Indigirka River basin in the eastern Siberian Arctic appeared to be the epicentre in the pan-Arctic BHP distribution trend, with the highest “soil-marker” BHPs but the lowest tetrafunctionalised BHPs. Aminobacteriohopanepentol, an indicator of aerobic methane oxidation, was observed in all the sediments, with the source being either the marine environment or methane producing terrestrial environments. [Copyright &y& Elsevier]