Enhanced concentrations of dissolved gaseous mercury in the surface waters of the Arctic Ocean

During an almost three months long expedition in the Arctic Ocean, the Beringia 2005, dissolved gaseous mercury (DGM) was measured continuously in the surface water. The DGM concentration was measured using an equilibrium system, i.e. the DGM in the water phase equilibrated with a stream of gas and the gas was thereafter analysed with respect to its mercury content. The DGM concentrations were calculated using the following equation, DGM = Hg_eq / k_H' where Hg_eq is the equilibrated concentration of elemental mercury in the gas phase and k_H' is the dimensionless Henry's law constant at desired temperature and salinity. During the expedition several features were observed. For example, enhanced DGM concentration was measured underneath the ice which may indicate that the sea ice acted as a barrier for evasion of mercury from the Arctic Ocean to the atmosphere. Furthermore, elevated DGM concentrations were observed in water that might have originated from river discharge. The gas-exchange of mercury between the ocean and the atmosphere was calculated in the open water and both deposition and evasion were observed. The measurements showed significantly enhanced DGM concentrations, compared to more southern latitudes.     

Dissolved inorganic carbon (DIC) and its carbon isotopic composition in sediment pore waters from the Shenhu area,northern South China Sea

The Shenhu area is one of the most favorable places for the occurrence of gas hydrates in the northern continental slope of the South China Sea. Pore water samples were collected in two piston cores (SH-A and SH-B) from this area, and the concentrations of sulfate and dissolved inorganic carbon (DIC) and its carbon isotopic composition were measured. The data revealed large DIC variations and very negative δ ¹³C-DIC values. Two reaction zones, 0–3 mbsf and below 3 mbsf, are identified in the sediment system. At site SH-A, the upper zone (0–3 mbsf) shows relatively constant sulfate and DIC concentrations and δ ¹³C-DIC values, possibly due to bioturbation and fluid advection. The lower zone (below 3 mbsf) displays good linear gradients for sulfate and DIC concentrations, and δ ¹³C-DIC values. At site SH-B, both zones show linear gradients, but the decreasing gradients for δ ¹³C-DIC and SO₄ ²⁻ in the lower zone below 3 mbsf are greater than those from the upper zone, 0–3 mbsf. The calculated sulfate-methane interface (SMI) depths of the two cores are 10.0 m and 11.1 m, respectively. The depth profiles of both DIC and δ ¹³C-DIC showed similar characteristics as those in other gas hydrate locations in the world oceans, such as the Blake Ridge. Overall, our results indicate an anaerobic methane oxidation (AMO) process in the sediments with large methane flux from depth in the studied area, which might be linked to the formation of gas hydrates in this area.     

Organic matter in deepwater sediments of the Northern Gulf of Mexico and its relationship to the distribution of benthic organisms

Sediment samples were selected from 28 sites across the deep (212–3527 m) northern Gulf of Mexico (GOM) as part of the Deep Gulf of Mexico Benthos (DGoMB) program, and analyzed for geochemical parameters related to organic carbon (OC) distribution and characteristics. The results of this study indicate that the OC content of sediments in the deep northern GOM is controlled by several factors; including water depth, overlying water productivity, sediment carbonate content, sediment oxygen exposure time, OC sources, and regional influences. The best correlation between sediment OC content, on a CaCO₃-free basis, and other parameters examined was an inverse correlation of OC with water depth. The OC/SA ratio had a wide range of values and, along with variable sources of sedimentary OC, indicated that the organism-available concentration of metabolizable organic matter may not be simply related to sedimentary OC content. This was perhaps reflected in the observation that benthic macrofaunal and meiofaunal biomass abundances were well correlated with sedimentary OC, but the abundance of bacteria in sediments was not.     

Macrofaunal density and biomass in the Campeche Canyon, Southwestern Gulf of Mexico

The composition, density and community structure of the benthic macrofauna were investigated in sediments of the Campeche Canyon in the SW Gulf of Mexico. Total macrofaunal density ranged from 9466±2736 ind m⁻² at the continental shelf station to 1550±195 ind m⁻² in the canyon. Density values significantly diminished with distance from the coast and depth; only a few stations in the center of the canyon displayed larger density values (E-37 with 4666±1530 ind m⁻², E-36 with 5791±642 ind m⁻² and E-26 with 6925±2258 ind m⁻²). Densities were positively correlated to organic nitrogen in the sediment (r=0.82) and coarse silt (r=0.43), and negatively with depth (r=−0.74) and distance from the coast (r=−0.68). At all stations, the polychaete worms contributed most to the multi-species community structure. The nematodes and Foraminifera displayed their highest densities in the center of the canyon. The biomass values declined significantly with depth. We conclude that the macrofauna density and biomass changed in response to organic matter contents in the sediment, both with distance from the coast and with depth.     

Methylmercury production in sediments of Chesapeake Bay and the mid-Atlantic continental margin

Methylmercury (MeHg) concentration and production rates were studied in bottom sediments along the mainstem of Chesapeake Bay and on the adjoining continental shelf and slope. Our objectives were to 1) observe spatial and temporal changes in total mercury (HgT) and MeHg concentrations in the mid-Atlantic coastal region, 2) investigate biogeochemical factors that affect MeHg production, and 3) examine the potential of these sediments as sources of MeHg to coastal and open waters. Estuarine, shelf and slope sediments contained on average 0.5 to 1.5% Hg as MeHg (% MeHg), which increased significantly with salinity across our study site, with weak seasonal trends. Methylation rate constants (k_meth), estimated using enriched stable mercury isotope spikes to intact cores, showed a similar, but weaker, salinity trend, but strong seasonality, and was highly correlated with % MeHg. Together, these patterns suggest that some fraction of MeHg is preserved thru seasons, as found by others [Orihel, D.M., Paterson, M.J., Blanchfield, P.J., Bodaly, R.A., Gilmour, C.C., Hintelmann, H., 2008. Temporal changes in the distribution, methylation, and bioaccumulation of newly deposited mercury in an aquatic ecosystem. Environmental Pollution 154, 77] Similar to other ecosystems, methylation was most favored in sediment depth horizons where sulfate was available, but sulfide concentrations were low (between 0.1 and 10 μM). MeHg production was maximal at the sediment surface in the organic sediments of the upper and mid Bay where oxygen penetration was small, but was found at increasingly deeper depths, and across a wider vertical range, as salinity increased, where oxygen penetration was deeper. Vertical trends in MeHg production mirrored the deeper, vertically expanded redox boundary layers in these offshore sediments. The organic content of the sediments had a strong impact on the sediment:water partitioning of Hg, and therefore, on methylation rates. However, the HgT distribution coefficient (K_D) normalized to organic matter varied by more than an order of magnitude across the study area, suggesting an important role of organic matter quality in Hg sequestration. We hypothesize that the lower sulfur content organic matter of shelf and slope sediments has a lower binding capacity for Hg resulting in higher MeHg production, relative to sediments in the estuary. Substantially higher MeHg concentrations in pore water relative to the water column indicate all sites are sources of MeHg to the water column throughout the seasons studied. Calculated diffusional fluxes for MeHg averaged  1 pmol m^− 2 day^− 1. It is likely that the total MeHg flux in sediments of the lower Bay and continental margin are significantly higher than their estimated diffusive fluxes due to enhanced MeHg mobilization by biological and/or physical processes. Our flux estimates across the full salinity gradient of Chesapeake Bay and its adjacent slope and shelf strongly suggest that the flux from coastal sediments is of the same order as other sources and contributes substantially to the coastal MeHg budget.     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

Trace element and molecular markers of organic carbon dynamics along a shelf–basin continuum in sediments of the western Arctic Ocean

Molecular organic biomarkers together with trace element composition were investigated in sediments east of Barrow Canyon in the western Arctic Ocean to determine sources and recycling of organic carbon in a continuum from the shelf to the basin. Algal biomarkers (polyunsaturated and short-chain saturated fatty acids, 24-methylcholesta-5,24(28)-dien-3β-ol, dinosterol) highlight the substantial contribution of organic matter from water column and sea-ice primary productivity in shelf environments, while redox markers such as acid volatile sulfide (AVS), Mn, and Re indicate intense metabolism of this material leading to sediment anoxia. Shelf sediments also receive considerable inputs from terrestrial organic carbon, with biomarker composition suggesting the presence of multiple pools of terrestrial organic matter segregated by age/lability or hydrodynamic sorting. Sedimentary metabolism was not as intense in slope sediments as on the shelf; however, sufficient labile organic matter is present to create suboxic and anoxic conditions, at least intermittently, as organic matter is focused towards the slope. Basin sediments also showed evidence for episodic delivery of labile organic carbon inputs despite the strong physical controls of water depth and sea-ice cover. Principal components analysis of the lipid biomarker data was used to estimate fractions of preserved recalcitrant (of terrestrial origin) and labile (of marine origin) organic matter in the sediments, with ranges of 12–79%, 14–45%, and 37–66% found for the shelf, slope, and basin cores, respectively. On average, the relative preserved terrestrial organic matter in basin sediments was 56%, suggesting exchange of organic carbon between nearshore and basin environments in the western Arctic.     

Similarity of electrophoretic dissolved protein spectra from coastal to pelagic seawaters

Dissolved proteins in seawater samples collected from a coastal area of Tokyo Bay, Sagami Bay and a location off the Kuroshio Current were investigated by one-dimensional sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and high resolution two-dimensional electrophoresis (2-DE). Four to nine protein bands were detected in SDS-PAGE in the apparent molecular weight (MW) range from 12 kilo Dalton (kDa) to 49 kDa. The 2-DE technique distinguished 10 to 46 protein spots exhibiting isoelectric point (pI)/MW ranging 4.3–9.2/12–63 kDa. The elecrophoretic patterns were similar between the coastal and pelagic samples, as well as previously reported patterns from various pelagic areas. The close similarity of electrophoretic mobility on both SDS-PAGE and 2-DE gels indicates the compositional homogeneity of dissolved proteins in seawater throughout a broad range of marine environments. Proteinaceous dissolved organic matter (DOM) that was unresolved and smeared staining characteristics on both SDS-PAGE and 2-DE gels was first observed in Tokyo Bay waters in the present study and its possible sources are discussed. Although the two protein species, 48 kDa and 39 kDa proteins, have been identified as homologues of Porin P and low molecular weight-alkaline phosphatase of Pseudomonas aeruginosa PAO1, respectively, four strains of P. aeruginosa and two species of Pseudomonas spp. have been newly identified as the source organisms of these proteins using the N-terminal amino acid sequence data determined in previous studies.     

MedFlux: Investigations of particle flux in the Twilight Zone

The MedFlux project was devised to determine and model relationships between organic matter and mineral ballasts of sinking particulate matter in the ocean. Specifically we investigated the ballast ratio hypothesis, tested various commonly used sampling and modeling techniques, and developed new technologies that would allow better characterization of particle biogeochemistry. Here we describe the rationale for the project, the biogeochemical provenance of the DYFAMED site, the international support structure, and highlights from the papers published here. Additional MedFlux papers can be accessed at the MedFlux web site (http://msrc.sunysb.edu/MedFlux/).