Transport and fate of Danube Delta terrestrial organic matter in the Northwest Black Sea mixing zone

Within the framework of the European project EROS 21, a biogeochemical study of particles transported from the Danube Delta to the Northwestern Black Sea whose carbon cycle is dominated by riverine inputs was carried out in spring off the Sulina branch of the Danube Delta. The distribution of particulate organic carbon (POC), chlorophyll a (Chl a), C/N, and δ¹³C evidenced an omnipresent contribution of terrestrial organic matter throughout the study area together with a dilution of these inputs by freshwater and marine organisms. Four lipid series, n-alkanoic acids, n-alkanes, n-alkanols, and sterols were analyzed by gas chromatography and gas chromatography/mass spectrometry. Several signature compounds were selected to delineate dispersion of terrestrial organic carbon: (1) long-chain n-alkanoic acids in the range C₂₄–C₃₄, long-chain n-alkanes in the range C₂₅–C₃₅, long-chain n-alkanols in the range C₂₂–C₃₀, 24-ethylcholesta-5,22-dien-3β-ol (29Δ^5,22) and 24-ethylcholesterol (29Δ⁵) for vascular plant-derived material and (2) coprostanol (27Δ^0,5β) for faecal contamination associated with sewage effluents. A marked decrease was observed between the concentrations of different vascular plant markers characterizing the two end members: riverine at salinity 0.3 and marine at salinity 15.5. The decrease observed for marine/riverine end members (expressed as a function of organic carbon) varied in a large range, from 4% for n-alkanes to 18.6%, 20.4% and 24% for n-fatty acids, n-alkanols and sterols, respectively. These values reflect a combination of various processes: size-selective particle sedimentation, resuspension of different particle pools of different sizes and ages, and/or selective biological utilization. The multi-marker approach also suggested the liberation in the mixing zone of terrestrial moieties, tightly trapped in macromolecular structures of the riverine material. The greatest decrease for marine/riverine end members was observed for coprostanol (0.9%), underlining the efficiency of the mixing zone as a sink for sewage-derived carbon.     

Spring–summer cycling of DOC, DON and inorganic N in a highly seasonal system encompassing the Northeast Water Polynya, 1993

Dissolved organic nitrogen (DON), dissolved organic carbon (DOC) and inorganic nutrient concentrations were determined in samples from an area encompassing the Northeast Water Polynya from June to August 1993. In June, still ice-covered polynya area surface waters (PySW) had significantly higher (p<0.05) DOC concentrations (110 μM, n=68) than surface water outside the polynya area (96 μM, n=6). Melting ice and ice algae are suggested as DOC sources. DOC concentrations found in this study are consistent with other studies showing higher DOC concentrations in the Arctic than in other ocean areas. As the productive season progressed, DOC concentrations in Polynya surface water (PySW) decreased (p<0.05) from 110 to 105 μM, while DON concentrations increased (p<0.05) from 5.6 to 6.1 μM, causing a significant decrease (p<0.05) in the C : N ratios of DOM from spring (C : N ratio 20) to summer (C : N ratio 17). We found a significant (p<0.05) decrease in the DOM C : N ratio in all water masses within the polynya area as the productive season progressed. DON was the largest fraction of total dissolved nitrogen (TDN) in PySW and surface waters outside the polynya area. TDN was calculated as the sum of DON, nitrate, nitrite and ammonium concentrations. DON increased (p<0.05) from 62% to 73% of TDN in PySW from spring to summer, a result of increasing DON concentrations and decreasing inorganic nitrogen concentrations over the productive season. The seasonal accumulation of DON and the corresponding decrease in nitrate concentrations in waters with primary production indicate that it is important to take the DON pool into account when estimating export production from nitrate concentration decreases in surface waters. PySW TDN concentrations decreased (p<0.05) from 9.1 (n=61) to 8.6 μM (n=60) from spring (May 25 through June 19) to summer (July 1 through July 27). The seasonal decrease in surface water TDN concentrations corresponded to increases in TDN concentrations in deeper water masses within the Polynya. Most of the TDN increase in deep water was in the form of DON. A possible explanation is that PON was dissolved (partially remineralized) in the water column at mid depths, causing increases in the DON concentration. Transfer of N from PySW (with a short residence time in the polynya area) to Polynya Intermediate Water and deep waters of the Norske and Westwind Trough with multi-year residence times keeps N from leaving the polynya area. In spring, nutrients from degradation of OM in PyIW could support primary production. The role of PyIW as an OM trap could be important in supporting primary production in the polynya area.     

Thermogenic organic matter dissolved in the abyssal ocean

Formation and decay of thermogenic organic matter are important processes in the geological carbon cycle, but little is known about the fate of combustion-derived and petrogenic compounds in the ocean. We explored the molecular structure of marine dissolved organic matter (DOM) for thermogenic signatures in different water masses of the Southern Ocean. Ultrahigh-resolution mass spectrometry via the Fourier transform-ion cyclotron resonance technique (FT-ICR-MS) revealed the presence of polyaromatic hydrocarbons (PAHs) dissolved in the abyssal ocean. More than 200 different PAHs were discerned, most of them consisting of seven condensed rings with varying numbers of carboxyl, hydroxyl, and aliphatic functional groups. These unambiguously thermogenic compounds were homogenously distributed in the deep sea, but depleted at the sea surface. Based on the structural information alone, petrogenic and pyrogenic compounds cannot be distinguished. Surface depletion of the PAHs and first estimates for their turnover rate (> 1.2 · 10¹² mol C per year) point toward a primarily petrogenic source, possibly deep-sea hydrothermal vents, which is thus far speculative because the fluxes of combustion-derived and petrogenic matter to the ocean are not well constrained. We estimate that > 2.4% of DOM are thermogenic compounds, and their global inventory in the oceans is > 1.4 · 10¹⁵ mol C, significantly impacting global biogeochemical cycles.     

Black carbon in marine particulate organic carbon: Inputs and cycling of highly recalcitrant organic carbon in the Gulf of Maine

To increase our understanding of the roles of black carbon (BC), a highly sorptive and recalcitrant material, we measured BC concentrations and fluxes in marine particulate organic carbon (POC) out of the water column in the Gulf of Maine (GoM), a representative coastal area downwind of important BC sources of the Northeastern United States. Concentrations ranged from < 0.1 to 16 μg/L in the spring and late summer, typically contributing between 1 and 20% of the POC. Water-column export fluxes were near 10 g_BC/m²∙yr. These observations suggest that (a) up to 50% of the “molecularly uncharacterized” POC in this region's seawater is combustion-derived BC, and (b) the “bioavailabilities” of hydrophobic pollutants like polycyclic aromatic hydrocarbons (PAHs) would be influenced substantially by sorption to BC. The observed BC spatial distributions imply that a large part of the BC was carried offshore by wind and that much of it is accumulated in the coastal sediments. On a global scale, these results suggest the GoM and other coastal areas with similar BC loadings accumulate significant amounts of highly recalcitrant organic carbon that remineralizes on geological time scales in the world's oceans.     

Spring distribution of dissolved organic matter in a system encompassing the Northeast Water Polynya: Implications for early-season sources and sinks

This study addresses sources and diagenetic state of early-season dissolved organic matter (DOM) in the Northeast Water Polynya (NEWP) area northeast of Greenland from distributions of humic substance fluorescence (HSfl), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) in the water column inside and outside the NEWP area. The water masses of the polynya area had acquired their spring/summer temperature–salinity characteristics at the time of sampling, and also had individual, different DOM signatures. DOC concentrations were variable within and among water masses in the polynya area, indicating patchy local sources and sinks of DOC. PySW and polynya intermediate water (PyIW) had higher average DON concentrations and average lower C:N ratios than polynya bottom water (PyBW), indicating a larger fraction of fresh DOM in PySW and PyIW than in PyBW. Ice-covered, polynya area surface waters (PySW) had higher DOC concentrations (113±14 μM, n=68) than surface water (SW) outside the polynya area (96±18 μM, n=6). The DOM C:N ratios in a low-salinity, ice-melt subgroup of PySW samples indicate labile material, and these low-salinity surface waters appeared to have a local DOC and DON source. In contrast, HSfl was significantly lower inside than outside the NEWP area. Despite the lower HSfl values within the NEWP area, the PySW values were high when compared to open-ocean water. There were no local terrestrial sources for HSfl to the NEWP area and the East Greenland Current is therefore proposed as a likely source of allochtonous HSfl. When HSfl was used as a conservative tracer, up to 70% of the water in PySW and PyIW was found to be derived from SW, which contains a high fraction of water from the East Greenland Current. Similarly, a mixing model based on HSfl indicated that 80% of early-season DOC and 90–100% of early-season DON in PySW and PyIW were derived from SW, indicating a potentially high fraction of terrestrially-derived, relatively refractory DOM in the early-season NEWP area.     

楚科奇海表层沉积物的生源组分及其对碳埋藏的指示意义

工业革命以来大气中CO₂浓度由280 ppm剧增至375 ppm,是导致全球气候变暖的主要原因[1]。海洋作为大气CO₂的“汇”之一,每年可吸收人类释放CO₂气体总量的30%,对全球碳循环的收支平衡有重要作用[2]。两极地区是CO₂的主要汇区,也是全球变化的重要反馈窗口。因此,了解碳在北冰洋的生物地球化学循环过程是十分必要的[3-4]。海洋中的生源沉积物主要来自于海洋上层浮游生物碎屑的沉降,主要由蛋白石(以生物硅代替,BSi)、碳酸钙(CaCO₃)和有机质(通常用有机碳替代,TOC)组成[5]。     

Seasonal variation in the Ra/Ra ratio of coastal water within the Sea of Japan: Implications for the origin and circulation patterns of the Tsushima Coastal Branch Current

In the current study, low-background γ-spectrometry was employed to determine the ²²⁸Ra/²²⁶Ra activity ratio and ¹³⁷Cs activity of 84 coastal water samples collected at six sites along the main island of Japan (Honshu Island) within the Sea of Japan, including the Tsushima Strait, and two other representative sites on Honshu Island (a Pacific shore and the Tsugaru Strait) at 1-month intervals in 2006.The ²²⁸Ra/²²⁶Ra ratio of coastal waters in the Sea of Japan exhibited similar patterns of seasonal variation, with minimum values during early summer (²²⁸Ra/²²⁶Ra = 0.6–0.8), maximum values during autumn (²²⁸Ra/²²⁶Ra = 1.5–3), and a time lag in their temporal changes ( 2.5 months and over  1300 km distance). However, the 2 other sites represented no clear periodic variation.In contrast to the positive correlation between ¹³⁷Cs activity (0.6–1.7 mBq/L) and salinity (15–35), the ²²⁸Ra/²²⁶Ra ratio of coastal water samples from the Sea of Japan was not observed to correlate with salinity, and the increase in the ²²⁸Ra/²²⁶Ra ratio was not as marked (0.5–1; May–June 2004 and 2005) during the migration along Honshu Island. The input of land-derived water and/or the diffusion of radium from coastal sediments is unlikely to have affected the wide seasonal variation in the ²²⁸Ra/²²⁶Ra ratio observed in these water samples.The seasonal variation in the ²²⁸Ra/²²⁶Ra ratio recorded for the coastal waters of the Sea of Japan is considered to be mainly controlled by the remarkable changes in the mixing ratio of the ²²⁸Ra-poor Kuroshio and the ²²⁸Ra-rich continental shelf waters within the East China Sea (ECS). After passing through the Tsushima Strait, this water mass moves northeast along the coastline of the Sea of Japan as the Tsushima Coastal Branch Current (TCBC).