Sulfide and iron control on mercury speciation in anoxic estuarine sediment slurries

In order to understand the role of sulfate and Fe(III) reduction processes in the net production of monomethylmercury (MMHg), we amended anoxic sediment slurries collected from the Venice Lagoon, Italy, with inorganic Hg and either potential electron acceptors or metabolic byproducts of sulfate and Fe(III) reduction processes, gradually changing their concentrations. Addition of sulfide (final concentration: 0.2–6.3 mM) resulted in an exponential decrease in the sulfate reduction rate and MMHg concentration with increasing concentrations of sulfide. Based on this result, we argue that the concentration of dissolved sulfide is a critical factor controlling the sulfate reduction rate, and in turn, the net MMHg production at steady state. Addition of either Fe(II) (added concentration: 0–6.1 mM) or Fe(III) (added concentration: 0–3.5 mM) resulted in similar trends in the MMHg concentration, an increase with low levels of Fe additions and a subsequent decrease with high levels of Fe additions. The limited availability of dissolved Hg, associated with sulfide removal by precipitation of FeS, appears to inhibit the net MMHg production in high levels of Fe additions. There was a noticeable reduction in the net MMHg production in Fe(III)-amended slurries as compared to Fe(II)-amended ones, which could be caused by a decrease in the sulfate reduction rate. This agrees with the results of Hg methylation assays using the enrichment cultures of anaerobic bacteria: whereas the enrichment cultures of sulfate reducers showed significant production of MMHg (4.6% of amended Hg), those of Fe(III), Mn(IV), and nitrate reducers showed no production of MMHg. It appears that enhanced Fe(III)-reduction activities suppress the formation of MMHg in high sulfate estuarine sediments.     

Wintertime rates of net primary production and nitrate and ammonium uptake in the southern Benguela upwelling system

The elevated levels of primary productivity associated with eastern boundary currents are driven by nutrient- rich waters upwelled from depth, such that these regions are typically characterised by high rates of nitrate-fuelled phytoplankton growth. Production studies from the southern Benguela upwelling system (SBUS) tend to be biased towards the summer upwelling season, yet winter data are required to compute annual budgets and understand seasonal variability. Net primary production (NPP) and nitrate and ammonium uptake were measured concurrently at six stations in the SBUS in early winter. While euphotic zone NPP was highest at the stations nearest to the coast and declined with distance from the shore, a greater proportion was potentially exportable from open-ocean surface waters, as indicated by the higher specific nitrate uptake rates and f-ratios (ratio of nitrate uptake to total nitrogen consumption) at the stations located off the continental shelf. Near the coast, phytoplankton growth was predominantly supported by ammonium despite the high ambient nitrate concentrations. Along with ammonium concentrations as high as 3.6 µmol l^–1, this strongly suggests that nitrate uptake in the inshore SBUS, and by extension carbon drawdown, is inhibited by ammonium, at least in winter, although this has also been hypothesised for the summer.     

MgSO4 ION association in seawater

Examination of the consequences of the stoichiometric association constant $\text{K}{}^1{}_{\mathrm{<mtext>a</mtext>}}\text{= 41.7}$ for MgSO₄ in seawater as advocated by Johnson and Pytkowicz (1979) leads to a thermodynamic association constant K_a = 212.6, a value 32% greater than K_A = 160 derived from conductance data. Use of K_a = 160 leads to a $\text{K}{}^1{}_{\mathrm{<mtext>a</mtext>}}$ in essential agreement with the value of 10.2 reported by Kester and Pytkowicz (1969).     

Relocation effects of dredged marine sediments on mercury geochemistry: Venice lagoon,Italy

Understanding the biogeochemical process of Hg is critical in the overall evaluation of the ecological impacts resulting from the reuse of Hg-contaminated dredged sediment. Sediment banks (V1 and V2) were constructed with freshly dredged sediments from a navigational channel in Venice Lagoon, Italy, with the goal of clarifying potential differences in the biogeochemistry of Hg between the reused dredged sediments and those from surrounding sites (SS1 and S2). Toward this purpose, Hg and monomethylmercury (MMHg) concentrations, and Hg methylation rates (MMRs) in the surface 2.5 cm sediments were monitored, along with ammonium, iron, sulfate and sulfide concentrations in the pore waters of banks and surrounding sites from November 2005 to February 2007. Pore water analyses indicate that the bank sediments are characterized by lower levels of sulfate and iron, and by higher levels of ammonium and sulfide compared to the surrounding sediments. With respect to Hg speciation, the fractions of MMHg in total Hg (%MMHg/Hg) and the MMRs were significantly lower in the bank V1 compared to those in the reference site SS1, whereas the %MMHg/Hg and the MMRs were similar between V2 and S2. A negative correlation is found between the logarithm of the particle-water partition coefficient of Hg and the MMR, indicating that the reduced MMRs in V1 are caused by the limited concentrations of dissolved Hg. Organic matter appears to play a key role in the control of MMR via the control of Hg solubility.     

An inventory of factors that affect polysaccharide production by Phaeocystis globosa

Phaeocystis material contains polysaccharides that are built from at least eight different monosaccharides. Differences have been reported between the carbohydrate composition of different Phaeocystis species, and also between samples taken from Phaeocystis globosa blooms in different areas. In order to elucidate factors that could play a role in determining variation in carbohydrate composition and production, a number of Phaeocystis globosa strains were studied under laboratory conditions. Although there was a clear distinction of a northern and a southern cluster in the Phaeocystis globosa strains based on RAPD analysis, the differences in the composition of the mucopolysaccharides were relatively small. The contribution of glucose, however, ranged from 7–85% of total sugars. A strain that was cultured in seawaters of diverse origin produced polysaccharides of a different composition, suggesting the effect of environmental factors. The presence of bacteria affected neither the amount, nor the composition of the carbohydrates that were produced by Phaeocystis globosa. Glucose is part of both the intracellular polysaccharide pool and of the mucopolysaccharides in the colony matrix. Using specific digestion of the intracellular chrysolaminaran by laminarinase, the distribution of polysaccharides over different pools could be assessed. During growth of an axenic, mucus-producing strain, the portion of glucose present as chrysolaminaran appeared to increase. The polyglucose that was not digested by laminarinase remains unidentified. This study shows that environmental factors rather than strain differences determine differences in the sugar composition of Phaeocystis globosa, especially with respect to the glucose content of the material. A difference in the contribution of glucose could be correlated to the portion of cells in the culture that are not in the colonies. Our study emphasises that for studying polysaccharide dynamics in Phaeocystis globosa it is important to be able to discriminate between the different polysaccharide pools. Preliminary results of an enzymatic approach were promising     

Strontium and its isotopic composition in interstitial waters of marine carbonate sediments

The concentrations and isotopic compositions of strontium in interstitial waters from several DSDP sites, where sediments consist chiefly of carbonate oozes and chalks, are used as indicators of carbonate diagenesis by reference to a recently-produced curve showing detailed variations in the⁸⁷Sr/⁸⁶Sr ratio of seawater with time. Carbonate sediments of the Walvis Ridge show increases in interstitial Sr²⁺ concentrations in the upper carbonate-ooze sections with the highest concentrations near the ooze-chalk boundary where maximum rates of carbonate recrystallization occur. Below this, in situ production of Sr²⁺ diminishes and there is a diffusive flux of Sr to an underlying sink, presumably volcanogenic sediments or basalts, leading to Sr isotopic disequilibrium between carbonates and interstitial waters. In some other sites, however, there is no apparent Sr sink at depth and isotopic equilibrium is retained. Overall, diffusive smoothing of profiles exerts an important control on the⁸⁷Sr/⁸⁶Sr ratios, although lower ratios than contemporaneous seawater values in the carbonate oozes often correlate with zones of Mg²⁺ loss and reflect a combination of a flux of Sr²⁺ from the zone of maximum recrystallization rates together with a contribution from the in situ alteration of volcanic matter.     

Geochemistry of shallow sediments in Guaymas Basin, gulf of California: hydrothermal gas and oil migration and effects of mineralogy

Offset of prograde hydrothermal alterations by retrograde reactions is evident in sediments from a piston core (PC6, 8 m long) from the Guaymas Basin, Gulf of California. Geochemical and mineralogical analyses of sediments and pore fluids show superimposed geochemical signals that indicate currently active reactions are modifying previously formed secondary solids. Hydrothermal barite was formed in a previously active flow channel between 150 and 250 cm depth. Hydrothermal gypsum is presently dissolving at depths > 780 cm, below which hydrothermal fluid flow is channeled by a secondary dolomite layer. Thermal stress of organic matter generates hydrothermal gas and petroleum having wide ranges of compositions and maturities. A significant amount of hydrothermally generated oil has been transported laterally through a porous debris flow (approx. 240 cm subbottom), overwhelming the indigenous bituminous matter. Water soluble petroleum constituents have disseminated throughout the cored sediments. From 400 to 700 cm depth the immature organic matter continues to experience thermally-enhanced diagenesis, and an even higher thermal stress has occurred at the bottom of the core. Enhanced bacterial degradation of organic matter has led to depletion of pore water sulfate and enrichment of ammonium (NH₄⁺) in both pore fluid and sediment, resulting in formation of NH₄⁺ bearing secondary clay minerals at depths below 780 cm.     

A study of the chemistry of pore fluids and authigenic carbonates in methane seep environments: Kodiak Trench, Hydrate Ridge, Monterey Bay, and Eel River Basin

Analyses of the chemical and isotopic composition of carbonates rocks recovered from methane seepage areas of the Kodiak Trench, Hydrate Ridge, Monterey Bay Clam Flats, and the Eel River Basin, coupled with the studies of the chemistry of the pore fluids, have shown that these carbonates have grown within the sediment column. Geochemical profiles of pore fluids show that, in deep water seeps (Kodiak Trench—4450 m; Monterey Bay—1000 m; Hydrate Ridge—650 m), δ¹³C (DIC) values are low (isotopically light), whereas in the Eel River area ( 350–500 m), δ¹³C (DIC) values are much higher (isotopically heavier). In all cases, the δ¹³C values indicate that processes of methane oxidation, associated with sulfate reduction, are dominant in the shallow sediments. Data on the isotopic composition of authigenic carbonates found at sites in Kodiak Trench, Eel River Basin South, and Eel River Basin North indicate a variable composition and origin in different geochemical environments. Some of the authigenic carbonates from the study sites show a trend in their δ¹³C values similar to those of the pore fluids obtained in their vicinity, suggesting formation at relatively shallow depths, but others indicate formation at greater sediment depths. The latter usually consist of high magnesium calcite or dolomite, which, from their high values of δ¹³C (up to 23‰;) and δ¹⁸O (up to 7.5‰), suggest formation in the deeper horizons of the sediments, in the zone of methanogenesis. These observations are in agreement with observations by other workers at Hydrate Ridge, in Monterey Bay, and in the Eel River Basin.     

Particulate iron and manganese in the Santa Barbara Basin,California

Particulate Fe and Mn may be important trace metal scavengers in the water column as well as being probable indicators of biologically mediated redox processes. A study has been made of suspended particulate composition in the Santa Barbara Basin, a shallow near-shore basin off southern California with sub-oxic conditions below sill depth. Observations have revealed several interesting phenomena relating to the geochemistry of Fe and Mn. Most striking is a profound enrichment of particulate Fe in samples from the bottom two hundred meters. These particulates have a constant Fe/P mole ratio of about three and may originate at the sediment-water interface or may be transported to the basin from local marshes. For particulate Mn, enrichments are observed both in the sub-sill waters and near the base of the euphotic zone. A consideration of particle removal rates suggests that the sub-photic zone enrichment has a biogenic origin. In the sub-sill waters, enrichment in Mn is apparently due to the precipitation of dissolved Mn diffusing from the anoxic basin sediments. A simple mass balance suggests that most of the Mn lost from the sediments is transported from the Santa Barbara Basin in dissolved form.