Bacterial production of anomalously high dissolved sulfate concentrations in Peru slope sediments: steady-state sulfur oxidation,or transient response to end of El Niño?

Concentrations of dissolved sulfate and sulfur isotopic ratios of dissolved sulfide in surface sediments of the Peru shelf and upper slope indicate that the sediments can be divided into two depth intervals based on the dominant biogeochemical reactions. Although rates of bacterial sulfate reduction are high throughout Peru surface sediments, chemistry of the upper interval (<10–20 cm) is dominated by chemoautotrophic oxidation of dissolved sulfide and elemental sulfur, while the lower interval (>10–20 cm) is dominated by dissimilatory sulfate reduction. In three of the four cores examined here, pore water concentrations of sulfate in the top 10 cm of the sediment are significantly higher than those of the overlying seawater. Peak sulfate concentrations in pore water (37–53 mmol/l) are ∼1.3–1.9 times that of seawater sulfate and are located 1–6 cm below the sediment/water interface (SWI). The excess sulfate is most likely produced by oxidation of elemental sulfur coupled to reduction of nitrate, a reaction mediated by a facultative chemoautotrophic sulfide-oxidizing bacterium, Thioploca spp. Numerical simulations demonstrate that the anomalously high concentrations of dissolved sulfate can be produced by steady-state or non-steady-state processes involving high rates of bacterial oxidation of elemental sulfur. If bacterial sulfur oxidation is a transient phenomenon, then it is probably triggered by seasonal or El Niño-induced changes in water-column chemistry of the Peru undercurrent.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Mechanisms of sulfur incorporation and isotope fractionation during early diagenesis in sediments of the gulf of California

Sediment cores were taken from the Gulf of California, and pore waters recovered by mechanical squeezing. The chemistry and isotopic abundance of sulfur in these pore fluids were compared with coexisting solid phases to deduce the mechanisms involved in pyrite formation. The results suggest that burrowing activities of benthonic organisms supply sulfate sulfur to sediments to depths of approximately 0.5 m from the surface. This is inferred from essentially constant pore water concentration profiles of dissolved ions in horizons where sulfate reduction is demonstrated by the presence of iron sulfides.For a core from Pescadero Basin, it is estimated that beneath the mixed zone, diffusion adds 0.4% sulfur by dry weight of sediment, whereas burial of sulfate adds less than 0.1% sulfur. It is shown that diffusion can add isotopically light sulfur to sediments, due to more rapid relative addition of ³²SO₄^2? compared to ³⁴SO₄^2? down a concentration gradient maintained by bacterial processes. The overall net isotopic value of the sulfate so added is $\text{δ}{}^{34}\text{S = ?4.5‰}$. The depth distribution of S-isotope in sulfur is controlled by the balance between a bacterial kinetic isotope effect preferentially removing ³²S relative to ³⁴S, and the supply of sulfate by diffusion. The isotopic fractionation factor, α, calculated by a mathematical formulation which takes diffusion into account, is larger (1.060±0.010) than when sulfate reduction is assumed to occur in a closed system (1.035). The larger value is supported by the sulfur isotope distribution in metastable iron sulfide. Essentially, the same open-system α was calculated for a core from Carmen Basin.     

Multidisciplinary investigations exploring indicators of gas hydrate occurrence in the Krishna–Godavari Basin offshore, east coast of India

We report some main results of multidisciplinary investigations carried out within the framework of the Indian National Gas Hydrate Program in 2002–2003 in the Krishna–Godavari Basin offshore sector, east coast of India, to explore indicators of likely gas hydrate occurrence suggested by preliminary multi-channel seismic reflection data and estimates of gas hydrate stability zone thickness. Swath bathymetry data reveal new evidence of three distinct geomorphic units representing (1) a delta front incised by several narrow valleys and mass flows, (2) a deep fan in the east and (3) a WNW–ESE-trending sedimentary ridge in the south. Deep-tow digital side-scan sonar, multi-frequency chirp sonar, and sub-bottom profiler records indicate several surface and subsurface gas-escape features with a highly resolved stratification within the upper 50 m sedimentary strata. Multi-channel seismic reflection data show the presence of bottom simulating reflections of continuous to discrete character. Textural analyses of 76 gravity cores indicate that the sediments are mostly silty clay. Geochemical analyses reveal decreasing downcore pore water sulphate (SO₄ ²⁻) concentrations (28.7 to <4 mM), increasing downcore methane (CH₄) concentrations (0–20 nM) and relatively high total organic carbon contents (1–2.5%), and microbial analyses a high abundance of microbes in top core sediments and a low abundance of sulphate-reducing bacteria in bottom core sediments. Methane-derived authigenic carbonates were identified in some cores. Combined with evidence of gas-escape features in association with bottom simulating reflections, the findings strongly suggest that the physicochemical conditions prevailing in the study area are highly conducive to methane generation and gas hydrate occurrence. Deep drilling from aboard the JOIDES Resolution during 2006 has indeed confirmed the presence of gas hydrate in the Krishna–Godavari Basin offshore.     

Sulfate reduction and sulfur fixation in sediment of a historically meromictic lake,Lake Suigetsu,Japan

Vertical distributions of sulfate, hydrogen sulfide, and iron (II) concentrations in interstitial waters and of sulfur content in sediment have been studied in a sediment core (73 cm long) from a meromictic lake, Lake Suigetsu, which changed from fresh-water to brackish conditions in 1664 A.D. The diatom assemblage of the sediment has also been analyzed. A boundary between high (>1.5%) and low (<0.2%) sulfur contents is found at a depth of 52 cm in the core. In the high sulfur layer (above 52 cm), the maximum sulfur content is 6.8% at 35 to 37 cm. The diatom assemblage, however, indicates that the boundary between fresh-water and brackish sediments lies at 40 cm. The hydrogen sulfide and iron (II) profiles in the interstitial waters indicate a sink for these chemical species near a depth of 40 cm. The discrepancy between the chemically-defined boundary at 52 cm and the paleontologically-defined boundary at 40 cm seems to be due to the downward migration of hydrogen sulfide and deposition of iron sulfide after the lake became brackish.     

Sedimentary sulfides in the Nearshore Georgia Bight

Sedimentary sulfide, iron, and organic matter were measured in neritic sediments from the Georgia Bight. The two measured depth integrated sulfur pools, FeS + HS⁻ and FeS₂, tended to decrease with increasing distance from shore out to 33 km. Total iron and organic matter were strongly correlated and both tended to decrease with increasing distance from shore. Sediment depth profiles of organic matter/reduced sulfur suggest relatively constant rates of sulfate reduction over the top 40 cm of sediment. Differences in within-station variance indicated regions of lower and higher spatial/temporal heterogeneity, that may be related to tidally driven circulation patterns. No seasonal cycles were evident in sedimentary sulfides.     

Tephrostratigraphy and paleo-environmental implications of Late Quaternary sediments and interstitial water in the western Ulleung Basin, East/Japan Sea

Two piston cores, collected from the western Ulleung Basin of the East/Japan Sea, were used to investigate the Late Quaternary tephrostratigraphy, lithology, and mineralogy of the sediments, as well as the elemental composition of both sediments and interstitial water, and their paleo-environmental implications. The cores show two lapilli tephra layers and one rhyolitic ash layer at the boundaries between sedimentary lithofacies units I, II, and III. These layers can be correlated with the well-known Ulleung-Oki (ca. 9.3 ka; boundary of units I/II), Ulleung-Yamato (ca. 25–33 ka), and Aira-Tanzawa (ca. 25.1 ka; boundary of units II/III) layers, respectively. These data suggest that the cores cover the period from the middle stage of marine isotope stage (MIS) 3 to the Holocene. In each core, a so-called dark laminated mud (DLM) layer in unit II commonly has high contents of Si and Al, suggesting that the DLM layer generally contains significant amounts of fine-grained silicates and/or aluminosilicates. In addition, these DLM layers are enriched in Fe relative to Mn, iron being predominantly bound in framboidal pyrite. The size distribution of pyrite in the DLM layers suggests that these have formed under anoxic (euxinic) conditions at times of reduced water circulation in the basin during sea-level lowstand (euxinic environment). The C/N ratios [5–12] suggest that sedimentary organic matter in the cores is predominantly of marine origin. Total organic carbon (TOC) contents increased shortly before Termination I. This could have been caused by an increased flux of marine organic matter in association with sea-level rise. The C and S values of units II and III (Late Pleistocene sediments; C: <2.0%; S: 0.5–2.1%) suggest a more euxinic environment than that of unit I (Holocene sediments; C: 1.0–3.5%; S: <1.0%). Concentrations of SO₄^2– in the interstitial water decrease with increasing burial depth, whereas CH₄ concentrations show the reverse trend. Therefore, it seems that sulfate reduction, probably related to microbial activity, predominates in the upper core sections (<5 m), shifting to methanogenesis in the lower core sections.     

Functional structure of laminated microbial sediments from a supratidal sandy beach of the German Wadden Sea (St. Peter-Ording)

Hidden for the untrained eye through a thin layer of sand, laminated microbial sediments occur in supratidal beaches along the North Sea coast. The inhabiting microbial communities organize themselves in response to vertical gradients of light, oxygen or sulfur compounds. We performed a fine-scale investigation on the vertical zonation of the microbial communities using a lipid biomarker approach, and assessed the biogeochemical processes using a combination of microsensor measurements and a ¹³C-labeling experiment. Lipid biomarker fingerprinting showed the overarching importance of cyanobacteria and diatoms in these systems, and heterocyst glycolipids revealed the presence of diazotrophic cyanobacteria even in 9 to 20 mm depth. High abundance of ornithine lipids (OL) throughout the system may derive from sulfate reducing bacteria, while a characteristic OL profile between 5 and 8 mm may indicate presence of purple non-sulfur bacteria. The fate of ¹³C-labeled bicarbonate was followed by experimentally investigating the uptake into microbial lipids, revealing an overarching importance of cyanobacteria for carbon fixation. However, in deeper layers, uptake into purple sulfur bacteria was evident, and a close microbial coupling could be shown by uptake of label into lipids of sulfate reducing bacteria in the deepest layer. Microsensor measurements in sediment cores collected at a later time point revealed the same general pattern as the biomarker analysis and the labeling experiments. Oxygen and pH-microsensor profiles showed active photosynthesis in the top layer. The sulfide that diffuses from deeper down and decreases just below the layer of active oxygenic photosynthesis indicates the presence of sulfur bacteria, like anoxygenic phototrophs that use sulfide instead of water for photosynthesis.     

Variations of methane induced pyrite formation in the accretionary wedge sediments offshore southwestern Taiwan

The accretionary wedge of offshore southwestern Taiwan contains abundant deposits of gas hydrate beneath the sea floor. High concentrations of methane in pore waters are observed at several locations with little data concerning historical methane venting available. To understand temporal variation of methane venting in sediments over geologic time, a 23-m-long Calypso piston core (MD05-2911) was collected on the flank of the Yung-An Ridge. Pore water sulfate, dissolved sulfide, dissolved iron, methane, sedimentary pyrite, acid volatile sulfide, reactive iron, organic carbon and nitrogen as well as carbonate δ¹³C were analyzed.Three zones with markedly different pyrite concentration were found at the study site. Unit I sediments (>20 mbsf) were characterized with a high amount of pyrite (251–380 μmol/g) and a δ¹³C-depleted carbonate, Unit II sediments (15–20 mbsf) with a low pyrite (15–43 μmol/g) and a high content of iron oxide mineral and Unit III sediments (<10 mbsf) by a present-day sulfate–methane interface (SMI) at 5 m with a high amount of pyrite (84–221 μmol/g) and a high concentration of dissolved sulfide.The oscillation records of pyrite concentrations are controlled by temporal variations of methane flux. With an abundant supply of methane to Unit I and III, anaerobic methane oxidation and associated sulfate reduction favor diagenetic conditions conducive for significant pyrite formation. No AOM signal was found in Unit II, characterized by typical organically-limited normal marine sediments with little pyrite formation. The AOM induced pyrite formation near the SMI generates a marked pyrite signature, rendering such formation of pyrite as a useful proxy in identifying methane flux oscillation in a methane flux fluctuate environment.     

Evidence of slumping/sliding in Krishna–Godavari offshore basin due to gas/fluid movements

The Krishna–Godavari (KG) offshore basin is one of the promising petroliferous basins of the eastern continental margin of India. Drilling in this basin proved the presence of gas hydrate deposits in the shallow marine sediments beyond 750 m water depths, and provided lithologic and stratigraphic information. We obtained multibeam swath bathymetry covering an area of about 4500 km² in water depths of 280–1800 m and about 1260 line km of high resolution seismic (HRS) records. The general lithology of midslope deposits is comprised of nannofossil-rich clay, nannofossil-bearing clay and foraminifera-bearing clay. The HRS records and bathymetry reveal evidence of slumping and sliding of the upper and midslope sediments, which result in mass transport deposits (MTD) in the northwestern part of the study area. These deposits exhibit 3–9.5 km widths and extend 10–13 km offshore. The boundaries of the MTDs are often demarcated by sharp truncation of finely layered sediments (FLS) and the MTDs are characterized by acoustically transparent zones in the HRS data. Average thickness of recent MTDs varies with depth, i.e., in the upper slope, the thickness is about 45 m, while in the lower slope it is about 60 m, and in deeper offshore locations they attain a maximum thickness of about 90 m. A direct indication for slumping and mass transportation of deposits is provided by the age reversal in ¹⁴C AMS dates observed in a sediment core located in the midslope region. Seismic profiling signatures provide indications of fluid/gas movement. We propose that the presence of steep topographic gradients, high sedimentation rates, a regional fault system, diapirism, fluid/gas movement, and neotectonic activity may have facilitated the slumping/sliding of the upper slope sediments in the KG offshore basin.     

Evidence of slumping/sliding in Krishna–Godavari offshore basin due to gas/fluid movements

The Krishna–Godavari (KG) offshore basin is one of the promising petroliferous basins of the eastern continental margin of India. Drilling in this basin proved the presence of gas hydrate deposits in the shallow marine sediments beyond 750 m water depths, and provided lithologic and stratigraphic information. We obtained multibeam swath bathymetry covering an area of about 4500 km² in water depths of 280–1800 m and about 1260 line km of high resolution seismic (HRS) records. The general lithology of midslope deposits is comprised of nannofossil-rich clay, nannofossil-bearing clay and foraminifera-bearing clay. The HRS records and bathymetry reveal evidence of slumping and sliding of the upper and midslope sediments, which result in mass transport deposits (MTD) in the northwestern part of the study area. These deposits exhibit 3–9.5 km widths and extend 10–13 km offshore. The boundaries of the MTDs are often demarcated by sharp truncation of finely layered sediments (FLS) and the MTDs are characterized by acoustically transparent zones in the HRS data. Average thickness of recent MTDs varies with depth, i.e., in the upper slope, the thickness is about 45 m, while in the lower slope it is about 60 m, and in deeper offshore locations they attain a maximum thickness of about 90 m. A direct indication for slumping and mass transportation of deposits is provided by the age reversal in ¹⁴C AMS dates observed in a sediment core located in the midslope region. Seismic profiling signatures provide indications of fluid/gas movement. We propose that the presence of steep topographic gradients, high sedimentation rates, a regional fault system, diapirism, fluid/gas movement, and neotectonic activity may have facilitated the slumping/sliding of the upper slope sediments in the KG offshore basin.     

~(35)SO_4~(2-)示踪法测定九龙江河口沉积中硫酸盐还原速率

在2011年7月利用35SO2-4培养示踪法测定九龙江河口两个站位(A站位位于咸淡混合区,盐度3~5;B站位位于海相区,盐度20~25)沉积柱中硫酸盐还原速率的垂直分布。结果显示A站位沉积柱中硫酸盐还原速率变化范围为54~2 345nmol/(cm3·d),从表层到底部先增大后减小,最大值出现在20cm深度附近;B站位硫酸盐还原速率在24~987nmol/(cm3·d)之间,分别在10cm和78cm深度附近出现两个峰值,分别为876nmol/(cm3·d)和987nmol/(cm3·d)。综合分析两个站位孔隙水中SO2-4、甲烷浓度和沉积物中总有机碳、温度和氧化还原电位的垂直变化趋势与其硫酸盐还原速率的分布规律,表明A站位沉积物中硫酸盐还原以有机矿化为主;B站位受到有机质矿化和甲烷厌氧氧化的共同作用;两个站位硫酸盐还原速率及垂直分布趋势受孔隙水中SO2-4浓度、有机质活性和温度的共同影响;根据各个层位硫酸盐还原速率估算两个站位硫酸盐还原通量(以硫计)分别为527.9mmol/(m2·d)和357.1mmol/(m2·d),表明硫酸盐还原是九龙江河口有机质厌氧矿化的重要路径。     

Turbidites and their association with past earthquakes in the deep Çınarcık Basin of the Marmara Sea

Two gravity cores (CAG-3 and C-15) from the tectonically active, 1,276-m deep Çınarcık Basin of the Marmara Sea each include three sandy turbiditic mud units (1 mm–2 cm thick) with sharp basal contacts. The high benthic foraminifer content of these units suggests that the sediments were transported by turbidity currents from the upper slope region. These units represent the thin edges of turbidites thickening towards the subsiding north-eastern part of the basin, and contain quartz, detrital calcite, intact shells and shell fragments, smectite, pyrite framboids, muscovite, biotite, epidote and garnet. Their clay fractions are more enriched in smectite than those of adjacent layers. AMS 14C ages (957±43 a.d. and 578±31 a.d.) of two upper and middle turbiditic units in core C15 overlap with the historical İstanbul-Thrace (intensity=10) and İstanbul-Kocaeli (intensity=9) earthquakes of 26 October 986 and 15 August 553, respectively. This overlap, together with sedimentological characteristics, strongly suggests that the turbiditic units are related to the tectono-seismic activity of the North Anatolian Fault. The age of the lowest turbiditic unit in core C-3 was found to be 6,573±87 a b.p. (calendar) by AMS 14 C. In terms of chronostratigraphic relationships and lithological composition, the turbiditic units in core CAG-3 cannot be correlated with those in C15. This can be explained by gravity-controlled sedimentation causing wedging out of turbidites towards the edge of the basin.     

珠江口淇澳岛海岸带沉积物中硫酸盐还原和不同形态硫的分布

对珠江口淇澳岛海岸带3个站位(QA-11,QA-9和QA-14)的沉积物中不同形态的还原硫(酸可挥发性硫,黄铁矿和有机硫)、总有机碳(TOC)和孔隙水中SO42-,甲烷浓度进行了测定,并且利用稳态扩散模型计算其中2个站位(QA-9和QA-14)硫酸盐还原通量[1.74和1.14 mmol/(m2.d)]和甲烷厌氧氧化通量[0.34和0.29 mmol/(m2.d)]。研究结果表明由于潮间带沉积物受到SO42-供给的限制,因此位于潮间带的QA-11站位硫酸盐还原带较浅(约16 cm);在潮下带的QA-9和QA-14站位,随离海岸距离和水深的增加,硫酸盐还原通量呈现减小的趋势,并且硫酸还原逐渐受到可利用活性有机质的限制;甲烷厌氧氧化对硫酸盐还原的贡献表现出增加的趋势,由19.2%增加至25.5%。三个站位沉积物中按不同形态还原硫含量由大到小列出,它们是有机硫(OS)、黄铁矿(DS)、酸可挥发性硫(AVS)。沉积物中AVS的空间分布与硫酸盐还原通量有正相关性。QA-11和QA-14站位的黄铁矿与AVS硫的含量比值大于3,分别为7.9和3.6,表明两个站位的黄铁矿形成可能受硫酸盐还原作用的控制;QA-9站位黄铁矿与AVS硫的含量比值为2.2,暗示AVS向黄铁矿转化受到可利用活性铁的限制。     

Nondetrital and total metal distribution in core sediments from the U-Tapao Canal, Songkhla, Thailand

The U-Tapao Canal is the main source of freshwater draining into the outer part of Songkhla Lake, which is the most important estuarine lagoon in Thailand. Songkhla Lake is located in southern Thailand between latitudes 7°08' and 7°50' N and longitudes 100°07' and 100°37' E. Acetic acid (HOAc)-soluble Cu, Fe, Mn, Pb, and Zn and the total concentration of these metals along with Al concentration, organic carbon, carbonate, sand, silt, and clay contents were determined in 4 sediment cores obtained at selected intervals from the mouth of the canal to 12 km upstream. Readily oxidizable organic matter in the cores varies from 1.52% to 7.30% and is generally found to decrease seaward. Total concentrations of Al (61.7–99.0 g kg⁻¹; 2.29–3.67 mol kg⁻¹), Cu (12.4–28.2 mg kg⁻¹; 195–444 μmol kg⁻¹), Fe (25.2–42.0 g kg⁻¹; 451–752 mmol kg⁻¹), Mn (0.22–0.49 g kg⁻¹; 4.0–8.9 mmol kg⁻¹), Pb (16.7–43.1 mg kg⁻¹; 80.6–208 μmol kg⁻¹), and Zn (48.6–122.7 mg kg⁻¹; 0.74–1.88 mmol kg⁻¹) vary to a certain extent vertically and seaward in the U-Tapao Canal core sediments. These concentrations are at or near natural levels and show no indication of anthropogenic contamination.Overall, the data show that total metal concentrations in the surface and near surface core sediments are enriched in varying degrees relative to Al in the order of Zn>Mn>Pb>Fe>Cu. Chemical partitioning shows that the enrichment in the surface and near surface sediments is related to the relatively high proportion of the total metal concentrations (Mn>Zn>Fe>Cu>Pb) that occur in the acetic acid-soluble (nondetrital) fraction, and they generally decrease with depth. Nondetrital Cu, Pb, and Zn likely derive from those metals held in ion exchange positions, certain carbonates, and from easily soluble amorphous compounds of Mn and perhaps those of Fe. Diagenetic processes involving Mn and to a lesser extent, Fe compounds, as well as the vertical changes in the oxidizing/reducing boundaries, appear to be the most important factors controlling the behavior of the metals in these cores. Organic matter and the aluminosilicate minerals, however, appear to be less important carriers of the metals studied.     

Reactive iron and its buffering capacity towards dissolved sulfide in sediments of Jiaozhou Bay,China

Reactive iron (Fe) oxides in marine sediments play a critical role in removal of free sulfide. In this study, 0.5 and 6 N HCl-extractable Fe, acid volatile sulfide (AVS), and pyrite were examined in sediments at three sites of eutrophic Jiaozhou Bay to investigate the interactions of sulfur and Fe and possible influences of eutrophication on free sulfide removal. The results indicate that formation and accumulation of AVS and pyrite are limited by low availability of labile organic matter, despite eutrophication of the bay water. Quick buffering of free sulfide proceeded mainly via consumption of 0.5 N HCl-extractable Fe (labile Fe), however, the consumption did not result in a depletion of the Fe pool. High residual buffering capacity enables a quick removal of free sulfide in porewater, and thereby it is difficult for sulfide to accumulate and to cause detrimental effects on benthic organisms at the present steady state. Significant effects of eutrophication on Fe and sulfur geochemistry is restricted only to the estuarine sediments which were subject to direct wastewater discharges, whereas no such effects were observed in other sediments of the bay.     

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.     

Sulfate reduction and anaerobic methane oxidation in Black Sea sediments

Beyond the shelf break at ca. 150 m water depth, sulfate reduction is the only important process of organic matter oxidation in Black Sea sediments from the surface down to the sulfate–methane transition at 2–4 m depth. Sulfate reduction rates were measured experimentally with ³⁵SO₄²⁻, and the rates were compared with results of two diffusion-reaction models. The results showed that, even in these non-bioirrigated sediments without sulfide reoxidation, modeling strongly underestimated the high reduction rates near the sediment surface. A hybrid modeling approach, in which experimentally measured rates in the upper sediment layers force a model that includes also the deeper layers, probably provides the most realistic estimate of sulfate reduction rates. Areal rates of sulfate reduction were 0.65–1.43 mmol SO₄²⁻ m⁻² d⁻¹, highest in sediments just below the chemocline. Anaerobic methane oxidation accounted for 7–11% of the total sulfate reduction in slope and deep-sea sediments. Although this methane-driven sulfate reduction shaped the entire sulfate gradient, it was only equivalent to the sulfate reduction in the uppermost 1.5 cm of surface sediment. Methane oxidation was complete, yet the process was very sluggish with turnover times of methane within the sulfate–methane transition zone of 20 yr or more.     

Precipitation of authigenic uranium in suboxic continental margin sediments from the Okinawa Trough

Concentrations of U and Th isotopes in Okinawa Trough and East China Sea sediment cores were determined by isotope dilution inductively coupled plasma-mass spectrometry (ID-ICP-MS) to investigate the behavior of redox sensitive uranium in suboxic hemipelagic sediments and determine their significance in oceanic uranium balance. ²³⁸U concentrations and ²³⁸U/²³²Th activity ratios in the East China Sea sediments showed no remarkable variation with depth. However, ²³⁸U and ²³⁸U/²³²Th ratios in the Okinawa Trough sediments were low in the surface oxidizing layer but increased where the suboxic condition was encountered. The distribution profiles of ²³⁰Th and ²³²Th concentrations were relatively constant with depth in both the Okinawa Trough and East China Sea sediment cores. These results suggested that there has been post-depositional precipitation of authigenic uranium within the suboxic Okinawa Trough sediment column. The post-depositional precipitation rates of authigenic uranium were estimated to be 47 ± 5 to >62 ± 8 ng cm⁻² yr⁻¹; these rates were comparable to those previously reported for several anoxic sediments. A mechanism controlling precipitation of uranium may be the downward diffusion of uranium U(VI), reduction to U(IV) and finally precipitation onto the solid phase. The accumulation rate of uranium for the Okinawa Trough sediments was approximately eight times higher than the world average rate reported for suboxic sediments. This removal of uranium in the oceanic budget increases the importance of the suboxic sediment sink.     

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.