Water column organic carbon composition as driver for water-sediment fluxes of hazardous pollutants in a coastal environment.

The environmental fate of hazardous hydrophobic pollutants in the marine environment is strongly influenced by organic carbon (OC) cycling. As an example, the seasonality in primary production impacts both water column OC quantity and quality, which may influence pollutant mass transport from the water column to the sediment. This study aims to better understand the role of water column OC variability for the fate of pollutants in a near-coastal area. We conducted an in situ sampling campaign in the coastal Baltic Proper during two seasons, summer and autumn. We used polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) as model compounds, as they represent a wide range in physicochemical properties and are ubiquitous in the environment. Freely dissolved, and OC-bound concentrations were studied in the water column and surface sediment. We found stronger sorption of pollutants to suspended particulate matter (SPM) during the summer compared to the autumn (average 0.6 and 0.9 log unit higher particle-water partition coefficients during summer for PAHs and PCBs). Our data suggest that stronger sorption mirrors a compositional change of the OC towards higher contribution of labile OC during the summer, characterized by two times higher fatty acid and 24% higher dicarboxylic acids in SPM during summer. High concentrations of OC in the water column during the autumn resulted in increased SPM-mediated sinking fluxes of pollutants. Our results suggest that future changes in primary production are prone to influence the bioavailability and mobility of pollutants in costal zones, potentially affecting the residence time of these hazardous substances in the circulating marine environment.

Stabilization of mineral-associated organic carbon in Pleistocene permafrost.

Ice-rich Pleistocene-age permafrost is particularly vulnerable to rapid thaw, which may quickly expose a large pool of sedimentary organic matter (OM) to microbial degradation and lead to emissions of climate-sensitive greenhouse gases. Protective physico-chemical mechanisms may, however, restrict microbial accessibility and reduce OM decomposition; mechanisms that may be influenced by changing environmental conditions during sediment deposition. Here we study different OM fractions in Siberian permafrost deposited during colder and warmer periods of the past 55,000 years. Among known stabilization mechanisms, the occlusion of OM in aggregates is of minor importance, while 33-74% of the organic carbon is associated with small, <6.3 µm mineral particles. Preservation of carbon in mineral-associated OM is enhanced by reactive iron minerals particularly during cold and dry climate, reflected by low microbial CO2 production in incubation experiments. Warmer and wetter conditions reduce OM stabilization, shown by more decomposed mineral-associated OM and up to 30% higher CO2 production. This shows that considering the stability and bioavailability of Pleistocene-age permafrost carbon is important for predicting future climate-carbon feedback.

Circum-Arctic release of terrestrial carbon varies between regions and sources.

Arctic change is expected to destabilize terrestrial carbon (terrOC) in soils and permafrost, leading to fluvial release, greenhouse gas emission and climate feedback. However, landscape heterogeneity and location-specific observations complicate large-scale assessments of terrOC mobilization. Here we reveal differences in terrOC release, deduced from the Circum-Arctic Sediment Carbon Database (CASCADE) using source-diagnostic (δ13C-Δ14C) and carbon accumulation data. The results show five-times larger terrOC release from the Eurasian than from the American Arctic. Most of the circum-Arctic terrOC originates from near-surface soils (61%); 30% stems from Pleistocene-age permafrost. TerrOC translocation, relative to land-based terrOC stocks, varies by a factor of five between circum-Arctic regions. Shelf seas with higher relative terrOC translocation follow the spatial pattern of recent Arctic warming, while such with lower translocation reflect long-distance lateral transport with efficient remineralization of terrOC. This study provides a receptor-based perspective for how terrOC release varies across the circum-Arctic.

Effects of Organic Carbon Origin on Hydrophobic Organic Contaminant Fate in the Baltic Sea.

The transport and fate of hydrophobic organic contaminants (HOCs) in the marine environment are closely linked to organic carbon (OC) cycling processes. We investigated the influence of marine versus terrestrial OC origin on HOC fluxes at two Baltic Sea coastal sites with different relative contributions of terrestrial and marine OC. Stronger sorption of the more than four-ring polycyclic aromatic hydrocarbons and penta-heptachlorinated polychlorinated biphenyls (PCBs) was observed at the marine OC-dominated site. The site-specific partition coefficients between sediment OC and water were 0.2-1.0 log units higher at the marine OC site, with the freely dissolved concentrations in the sediment pore-water 2-10 times lower, when compared with the terrestrial OC site. The stronger sorption at the site characterized with marine OC was most evident for the most hydrophobic PCBs, leading to reduced fluxes of these compounds from sediment to water. According to these results, future changes in OC cycling because of climate change, leading to increased input of terrestrial OC to the marine system, can have consequences for the availability and mobility of HOCs in aquatic systems and thereby also for the capacity of sediments to store HOCs.

Remobilization of dormant carbon from Siberian-Arctic permafrost during three past warming events.

Carbon cycle models suggest that past warming events in the Arctic may have caused large-scale permafrost thaw and carbon remobilization, thus affecting atmospheric CO2 levels. However, observational records are sparse, preventing spatially extensive and time-continuous reconstructions of permafrost carbon release during the late Pleistocene and early Holocene. Using carbon isotopes and biomarkers, we demonstrate that the three most recent warming events recorded in Greenland ice cores-(i) Dansgaard-Oeschger event 3 (~28 ka B.P.), (ii) Bølling-Allerød (14.7 to 12.9 ka B.P.), and (iii) early Holocene (~11.7 ka B.P.)-caused massive remobilization and carbon degradation from permafrost across northeast Siberia. This amplified permafrost carbon release by one order of magnitude, particularly during the last deglaciation when global sea-level rise caused rapid flooding of the land area thereafter constituting the vast East Siberian Arctic Shelf. Demonstration of past warming-induced release of permafrost carbon provides a benchmark for the sensitivity of these large carbon pools to changing climate.

Remobilization of Old Permafrost Carbon to Chukchi Sea Sediments During the End of the Last Deglaciation.

Climate warming is expected to destabilize permafrost carbon (PF-C) by thaw-erosion and deepening of the seasonally thawed active layer and thereby promote PF-C mineralization to CO2 and CH4. A similar PF-C remobilization might have contributed to the increase in atmospheric CO2 during deglacial warming after the last glacial maximum. Using carbon isotopes and terrestrial biomarkers (Δ14C, δ13C, and lignin phenols), this study quantifies deposition of terrestrial carbon originating from permafrost in sediments from the Chukchi Sea (core SWERUS-L2-4-PC1). The sediment core reconstructs remobilization of permafrost carbon during the late Allerød warm period starting at 13,000 cal years before present (BP), the Younger Dryas, and the early Holocene warming until 11,000 cal years BP and compares this period with the late Holocene, from 3,650 years BP until present. Dual-carbon-isotope-based source apportionment demonstrates that Ice Complex Deposit-ice- and carbon-rich permafrost from the late Pleistocene (also referred to as Yedoma)-was the dominant source of organic carbon (66 ± 8%; mean ± standard deviation) to sediments during the end of the deglaciation, with fluxes more than twice as high (8.0 ± 4.6 g·m-2·year-1) as in the late Holocene (3.1 ± 1.0 g·m-2·year-1). These results are consistent with late deglacial PF-C remobilization observed in a Laptev Sea record, yet in contrast with PF-C sources, which at that location were dominated by active layer material from the Lena River watershed. Release of dormant PF-C from erosion of coastal permafrost during the end of the last deglaciation indicates vulnerability of Ice Complex Deposit in response to future warming and sea level changes.