Anaerobic Carbon Mineralisation Through Sulphate Reduction in the Inner Shelf Sediments of Eastern Arabian Sea

Monsoon-induced coastal upwelling, land run-off, benthic and atmospheric inputs make the western Indian shelf waters biologically productive that is expected to lead to high rates of mineralisation of organic matter (OM) in the sediments. Dissimilatory sulphate reduction (SR) is a major pathway of OM mineralisation in near-shore marine sediments owing to depletion of other energetically more profitable electron acceptors (O₂, NO₃ ^?, Mn and Fe oxides) within few millimetres of the sediment-water interface. We carried out first ever study to quantify SR rates in the inner shelf sediments off Goa (central west coast of India) using the ³⁵S radiotracer technique. The highest rates were recorded in the upper 10 cm of the sediment cores and decreased gradually thereafter below detection. Despite significant SR activity in the upper ～12 to 21 cm at most of the sites, pore water sulphate concentrations generally did not show much variation with depth. The depth integrated SR rate (0.066–0.46 mol m^?2 year^?1) decreased with increasing water depth. Free sulphide was present in low concentrations (0–3 μM) in pore waters at shallow stations (depth <30 m). However, high build-up of sulphide (100–600 μM) in pore waters was observed at two deeper stations (depths 39 and 48 m), 7–11 cm below the sediment-water interface. The total iron content of the sediment decreased from ～7 to 5 % from the shallowest to the deepest station. The high pyrite content indicates that the shelf sediments act as a sink for sulphide accounting for the low free sulphide levels in pore water. In the moderately organic rich (2–3.5 %) sediments off Goa, the measured SR rates are much lower than those reported from other upwelling areas, especially off Namibia and Peru. The amount of organic carbon remineralised via sulphate reduction was ～0.52 mol m^?2 year^?1. With an estimated average organic carbon accumulation rate of ～5.6 (±0.5) mol m^?2 year^?1, it appears that the bulk of organic matter gets preserved in sediments in the study region.     

Laboratory studies of the diagenesis and mobility of 239,240pu and 137Cs in nearshore sediments

Controlled laboratory experiments have been used to study the diagenetic chemistry of ^239,240Pu ¹³⁷Cs, and ⁵⁵Fe. Experiments using Buzzards Bay sediments in small tanks show that sulfate reduction is accompanied by the production of large pore water concentration gradients of alkalinity, phosphate, ammonia and dissolved organic carbon and the formation of subsurface maxima in Fe and Mn. These pore water profiles demonstrate that bacterially-mediated processes of organic matter degradation and redox reactions can be simulated in the laboratory.A vertical profile of ⁵⁵Fe in pore waters is reported for the first time: it follows the profile of stable Fe and as such has a large (200 dpm/100 kg) subsurface maximum between 2–4 cm depth. Comparison of ⁵⁵Fe/Fe ratios in sediments and pore waters shows that there is preferential solubilization of ⁵⁵Fe over stable Fe.The pore water activities of ^239,240Pu show no gradients within the large uncertainties of the counting statistics, but are two to four times higher than Buzzards Bay seawater (0.05 dpm/100 kg).The activity of ¹³⁷Cs in the pore water profile is constant (40 dpm/100 kg) within the large counting uncertainties and is twice that of Buzzards Bay seawater. Cs-137 does not appear to be involved in diagenetic chemistry but may increase in pore waters as a result of ion exchange reactions.Flux estimates based on the pore water data show that remobilization and transport of ^239,240 Pu in coastal sediments are not significant processes while the transport of ^l37Cs may be.     

Seasonal Influence of the Needle Rush <Emphasis Type="Italic">Juncus roemarianus</Emphasis> on Saltmarsh Pore Water Geochemistry

Previous studies have shown that saltmarsh macrophytes have a significant influence on sediment biogeochemistry, both through radial release of oxygen from roots and also via primary production and release of labile organic exudates from roots. To assess the seasonal influence of the needle rush, Juncus roemarianus, on saltmarsh sediment geochemistry, pore waters and sediments were collected from the upper 50 cm of two adjacent sites, one unvegetated and the other vegetated by Juncus roemarianus, in a Georgia saltmarsh during winter and summer. Pore waters collected at 1- to 2-cm intervals were analyzed for pH, alkalinity, dissolved phosphate, ammonium, Fe(II), Fe(III), Mn(II), sulfide, sulfate, and organic carbon. Sediments were collected at 5-cm intervals and analyzed for iron distribution in the solid phase using a two-step sequential extraction. The upper 50 cm of the sediment pore waters are mostly sulfidic during both winter and summer. The pore water and sediment geochemistry suggest organic matter degradation is coupled mostly to Fe(III) and sulfate reduction. In summer, there is greater accumulation of alkalinity, sulfide, ammonium, and phosphate in the pore waters and lower levels of ascorbate extractable Fe, which is presumed to be comprised primarily of readily reducible Fe(III) oxides, in the sediments, consistent with higher organic matter degradation rates in summer compared to winter. Lower pH, alkalinity, ammonium, and sulfide concentrations in sediments with Juncus, compared to nearby unvegetated sediments, is consistent with release of oxygen into the Juncus rhizosphere, especially during summer.     

Organic matter mineralization in sediment of a coastal freshwater lake and response to salinization

Solid phase and pore water chemical data collected in a sediment of the Haringvliet Lake are interpreted using a multi-component reactive transport model. This freshwater lake, which was formed as the result of a river impoundment along the southwestern coast of the Netherlands, is currently targeted for restoration of estuarine conditions. The model is used to assess the present-day biogeochemical dynamics in the sediment, and to forecast possible changes in organic carbon mineralization pathways and associated redox reactions upon salinization of the bottom waters. Model results indicate that oxic degradation (55%), denitrification (21%), and sulfate reduction (17%) are currently the main organic carbon degradation pathways in the upper 30 cm of sediment. Unlike in many other freshwater sediments, methanogenesis is a relatively minor carbon mineralization pathway (5%), because of significant supply of soluble electron acceptors from the well-mixed bottom waters. Although ascorbate-reducible Fe(III) mineral phases are present throughout the upper 30 cm of sediment, the contribution of dissimilatory iron reduction to overall sediment metabolism is negligible. Sensitivity analyses show that bioirrigation and bioturbation are important processes controlling the distribution of organic carbon degradation over the different pathways. Model simulations indicate that sulfate reduction would rapidly suppress methanogenesis upon seawater intrusion in the Haringvliet, and could lead to significant changes in the sediment’s solid-state iron speciation. The changes in Fe speciation would take place on time-scales of 20-100 years.     

Mobility of trace elements between the river water,the sediments,and the pore water of Las Catonas Stream,Buenos Aires Province,Argentina

The composition of river water, sediments, and pore waters (down to 30 cm below the bed) of Las Catonas Stream was studied to analyze the distribution of trace elements in a peri-urban site. The Las Catonas Stream is one of the main tributaries of Reconquista River, a highly polluted water course in the Buenos Aires Province, Argentina. The semi-consolidated Quaternary sediments of the Luján Formation are the main source of sediments for Las Catonas Stream. The coarse-grained fraction in the sediments is mainly composed of tosca (calcretes), intraclasts, bone fragments, glass shards, quartz, and aggregates of fine-grained sediments together with considerably amounts of vegetal remains. The clay minerals are illite, illite–smectite, smectite, and kaolinite. For the clay-sized fraction, the external surface area values are mostly between 70 and 110 m²g^?1, although the fraction at 15 cm below the bottom of the river shows a lower surface area of 12 m²g^?1. The N₂ adsorption–desorption isotherms at 77 K for this sample display a behavior indicative of non-porous or macroporous material, whereas the samples above and below present a typical behavior of mesoporous materials with pores between parallel plates (slit-shaped). As, Cr, Cu, and Cd concentrations increase down to 15 cm depth in the sediments, where the highest trace element and total organic carbon (TOC) concentrations were found, and then decrease toward the bottom of the core. Except for As, the levels of the other heavy metals show higher concentration in surficial waters than in pore waters. Distribution coefficients between the sediments, pore water, and surficial water phases indicate that As is released from the sediments to the pore and surficial waters. Cu content strongly correlates with TOC (mainly from vegetal remains), suggesting that this element is mainly bound to the organic phase.     

Evolution of organic matter in lignite-containing sediments revealed by analytical pyrolysis (Py–GC–MS)

Newly vegetated sites provide opportunities to enlighten organic matter (OM) transformation mechanisms in soils and sediments at very early stages of development which, in turn, is relevant to better understand general ecosystem functioning. Mine acid soils and sediments in the Lusatian open cast lignite mining district (Germany) contains a high concentration of fossil carbon (lignite) in ad mixture with recent OM from the local vegetation, both contributing to the humified OM pool. In this study, analytical pyrolysis (Py–GC–MS) was used to monitor the different C sources (lignite or plant derived) in developing mine tailing soils and sediments and their degree of degradation in contrasting environments. Representative vegetation and the organic carbon (OC) rich soil/sediment fraction (humus fraction) were sampled at two depths (0–5 and 5–10 cm) in three plots along a transect covering an upland forest soil, a partially submerged sediment at the land–water interface and a constantly submerged sediment. The analysis of plant (lipds, isoprenoids, methoxyphenols and carbohydrates) and possible lignite (alkyl napththalenes, alkyl benzenes and PAHs) biomarkers released after pyrolysis supports previous findings in the area using other proxies. It was possible to discern OM sources in soil/sediment humus fractions, both from the substrate (lignite) as well as from the prevailing vegetation of the area. Environmental conditions in the submerged sediment seem to favour OM protection and the accumulation of decomposing plant material, whereas more intense OM degradation seems to prevail in the land–water interface areas characterized by fluctuating water level. In addition, a well resolved series of organic sulfur compounds (OSCS) found in the submerged sediments of rehabilitated acid lakes, indicates the possible occurrence of particular mechanisms of C preservation in this extreme anoxic S rich environment, i.e. via sulphur “quenching” with plant derived lipids during early diagenesis.     

Early diagenesis of fatty acids in lacustrine sediments—III. Changes in fatty acid composition in the sediments from a brackish water lake

A 3-m sediment core taken from Lake Suigetsu, in which a shift from fresh to brackish water occurred about three hundred years ago, has been examined for variation with depth of organic carbon and fatty acids. From the difference in total amounts of sulphur between sediments under fresh and brackish water environments, the surface sediments above approximately 35 cm depth were deduced to be accumulated under a brackish water environment. The total contents of organic carbon and fatty acids, and percentage composition of fatty acids gave discontinuous profiles above and below the 35–40 cm sediment layer. At a depth of 12.5 cm, the distribution in chain length of the fatty acids changed from a unimodal (the predominance of C₁₂-C₁₈ over C₂₀-C₃₄) to a bimodal pattern, which was mirrored by the composition diversity index (CDI).Although the fatty acids in the surface sediments (0–40 cm) from Lake Suigetsu seemed to suffer milder degradation through microbial activity than those in a core (0–150 cm) from Lake Suwa, a freshwater eutrophic lake, both lacustrine sediments showed similar trends in the alteration of fatty acid composition with depth.     

Diagenetic processes in Holocene carbonate sediments: Florida Bay mudbanks and islands

The sedimentology, mineralogy and pore fluid chemistry of seven cores from the Holocene sediments of Florida Bay were studied to determine the physical processes and diagenetic reactions affecting the sediments. The cores were taken in a transect from a shallow mudbank onto a small adjacent island, Jimmy Key. Steady state models of pore fluid chemistry are used to estimate the rates of various reactions. In the mudbank sediments, little carbonate mineral diagenesis is taking place. No change in sediment mineralogy is detectable and pore water profiles of Ca²⁺, Mg²⁺ and Sr²⁺ show only minor variation. Chloride concentrations indicate substantial biological mixing of seawater from the bay into the sediments in one of the cores. Pore water analyses of sulphate and alkalinity show only a low degree of sulphate depletion and a decreasing extent of sulphate reduction downcore. Models of sulphate reduction in the mudbank show that there is substantial chemical exchange between the sediment pore fluids and water from the bay probably as a result of bio-irrigation. The sulphate and alkalinity data also suggest that the underlying Pleistocene rocks contain water of near normal seawater composition. Stratigraphic analysis and δ¹³C analyses of the organic carbon in the sediments of the island cores show that the sediments were primarily deposited in a subtidal mudbank setting; only the upper 20–30 cm is supratidal in origin. Nevertheless, island formation had a significant effect on pore fluid chemistry and the types of diagenetic reactions throughout the sediment column. Chloride in the sediment pore fluids is more than twice the normal seawater concentrations over most of the depth of the cores. The constant, elevated chloride concentrations indicate that hypersaline fluids which formed in ponds on the island are advected downward through the sediments. Models of the chloride profiles yield an estimate of 2·5 cm yr^?1 as a minimum advective velocity. Changes in pore water chemistry with depth are interpreted as indicating the following sequence of reactions: (1) minor high-Mg calcite dissolution and low-Mg calcite precipitation, from 0 to 35 cm; (2) Ca- or Mg-sulphate dissolution and low-Mg calcite precipitation, from 5 to 35 cm; (3) dolomite or magnesite precipitation together with sulphate reduction, from 35 to 55 cm; and (4) little reaction below 55 cm. In addition, one or more as yet unidentified reactions must be taking place from 5 to 55 cm depth as an imbalance in possible sources and sinks of alkalinity is observed. The imbalance could be explained if chloride is not completely conservative. Despite the pore fluid chemical evidence for diagenetic reactions involving carbonate minerals, no changes in sediment mineralogy were detected in X-ray diffraction analyses, probably because of the comparatively young age of the island.     

Effects of Tubificid Worm Bioturbation on Freshwater Sediment Biogeochemistry

The effects of freshwater infaunal invertebrates on sediment geochemical properties were studied through an experimental approach using indoor microcosms during a 56-day experiment. The bioturbating organisms were tubificid worms, which consume sediment at depth and deposit undigested material at the sediment?Cwater interface. Bioturbation intensity was determined using fluorescent tracers, and the distribution of redox-sensitive compounds was studied from replicate experimental units handled 7, 14, 21, 28 and 56?days after tubificid colonization. Worm activity transferred reduced particles and pore water at the sediment surface at a rate of 0.14?cm?day^?1. Compared to control experimental units, this recycled material represented at the end a several centimetre-thick layer enriched in water content, dissolved nitrate and sulphate, and depleted in oxygen, ammonium and dissolved Mn(II). Tubificids consumed O₂ in bottom water, so that the sediment was anoxic, allowing a direct flux of dissolved reduced species into overlying water. Lower ammonium and Mn(II) concentrations and fluxes in anoxic sediment possibly resulted from a decrease in anaerobic microbial metabolism due to competition for labile organic carbon with tubificids. Higher sulphate concentration resulted from burial of surface waters with particle at the sediment surface, but not from bio-irrigation of burrows. Nitrate was produced in anoxic condition, as observed in almost every mixed modern sediments.     

Cycling of trace metals (Mn, Fe, Mo, U, V, Cr) in deep pore waters of intertidal flat sediments

Trace metals (Mn, Fe, Mo, U, Cr, V) were studied in pore waters of an intertidal flat located in the German Wadden Sea. The study system is an example of a permeable tidal flat system where pore water exchange is affected by tidal driven pressure gradients besides diffusion. Permanently installed in situ samplers were used to extract pore waters down to 5 m depth throughout one year. The samplers were either located close to the tidal flat margin or in central parts of the tidal flat. Despite dynamic sedimentological and hydrological conditions, the general trends with depth in deep tidal flat pore waters are remarkably similar to those observed in deep sea environments. Rates of trace metal cycling must be comparably large in order to maintain the observed pore water profiles. Trace metals further show similar general trends with depth close to the margin and in central parts of the tidal flat. Seasonal sampling revealed that V and Cr vary concurrent with seasonal changes in dissolved organic carbon (DOC) concentration. This effect is most notable close to the tidal flat margin where sulphate, DOC, and nutrients vary with season down to some metres depth. Seasonal variations of Mn, Fe, Mo, and U are by contrast limited to the upper decimetres of the sediment. Their seasonal patterns depend on organic matter supply, redox stratification, and particulate matter deposited on sediment surfaces. Pore water sampling within one tidal cycle provides evidence for pore water advection in margin sediments. During low tide pore water flow towards the creekbank is generated by a hydraulic gradient suggesting that deep pore waters may be seeping out of creekbank sediments. Owing to the enrichment of specific elements like Mn in pore water compared to sea water, seeping pore waters may have an impact on the chemistry of the open water column. Mass balance calculations reveal that the impact of deep pore waters on the Mn budget in the open water column is below 4%. Mn deep pore water discharge of the whole Wadden Sea is estimated to be about 9% of the total dissolved riverine Mn input into the Southern North Sea.     

Spatial and temporal variabilities of hypoxia in the Rappahannock River,Virginia

Hypoxia/anoxia in bottom waters of the Rappahannock River, a tributary estuary of Chesapeake Bay, was observed to persist throughout the summer in the deep basin near the river mouth; periodic reoxygenation of bottom water occurred on the shallower sill at the river mouth. The reoxygenation events were closely related to spring tide mixing. The dissolved oxygen (DO) in surface waters was always near or at the saturation level, while that of bottom waters exhibited a characteristic spatial pattern. The bottom DO decreased upriver from river mouth, reaching a minimum upriver of the deepest point of the river and increasing as the water becaume shallower further upriver. A model was formulated to describe the longitudinal distribution of DO in bottom waters. The model is based on Lagrangian concept—following a water parcel as it travels upriver along the estuarine bottom. The model successfully describes the characteristic distribution of DO and also explains the shifting of the minimum DO location in response to spring-neap cycling. A diagnostic study with the model provided insight into relationships between the bottom DO and the competing factors that contribute to the DO budget of bottom waters. The study reveals that both oxygen demand, either benthic or water column demand, and vertical mixing have a promounced effect on the severity of hypoxia in bottom waters of an estary. However, it is the vertical mixing which controls the longitudinal location of the minimum DO. The strength of gravitational circulation is also shown to affect the occurrence of hypoxia. An estuary with stronger circulation tends to have less chance for hypoxia to occur. The initial DO deficit of bottom water entering an estuary has a strong effect on DO concentration near the river mouth, but its effect diminishes in the upriver direction.     

Composition and origin of organic matter in surface sediments of Lake Sarbsko: A highly eutrophic and shallow coastal lake (northern Poland)

We present an organic geochemical study of surface sediments of Lake Sarbsko, a shallow coastal lake on the middle Polish Baltic coast. The aim was to provide evidence concerning the origin of the organic matter (OM) and its compositional diversity in surface deposits of this very productive, highly dynamic water body. The content and composition of the OM in the bottom sediments were investigated at 11 sampling stations throughout the lake basin. OM sources were assigned on the basis of bulk indicators [total organic carbon (TOC), total nitrogen (TN), δ¹³C_TOC and δ¹⁵N and extractable OM yield], biomarker composition of extractable OM and compound-specific C isotope signatures. The source characterization of autochthonous compounds was verified via phytoplankton analysis. The distribution of gaseous hydrocarbons in the sediments, as well as temporal changes in lake water pH, the concentration of DIC (dissolved inorganic carbon) and δ¹³C_DIC were used to trace OM decomposition.The sedimentary OM is composed mainly of well preserved phytoplankton compounds and shows minor spatial variability in composition. However, the presence of CH₄ and CO₂ in the bottom deposits provides evidence for microbial degradation of sedimentary OM. The transformation of organic compounds in surface, bottom and pore waters via oxidative processes influences carbonate equilibrium in the lake and seasonally favours precipitation or dissolution of CaCO₃.The data enhance our understanding of the relationships between the composition of sedimentary OM and environmental conditions within coastal ecosystems and shed light on the reliability of OM proxies for environmental reconstruction of coastal lakes.     

Diagenesis of oxyanions (V, U, Re, and Mo) in pore waters and sediments from a continental margin

This research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way. We describe pore water and sediment measurements of iron (Fe), manganese (Mn), vanadium (V), uranium (U), rhenium (Re), and molybdenum (Mo) along a transect off Washington State (USA). Sediments become less reducing away from the continent, and the stations have a range of oxygen penetration depths (depth to unmeasurable O₂ concentration) varying from a few millimeters to five centimeters. When oxygen penetrates ∼1 cm or less, Fe is reduced in the pore waters but reoxidized near the sediment-water interface, preventing a flux of Fe²⁺ to overlying waters, whereas Mn oxides are reduced and Mn²⁺ diffuses to overlying waters. Both Re and U authigenically accumulate in sediments. Only at the most reducing location, where the oxygen penetrates 0.3 cm below the sediment-water interface, does the surface 30 cm of sediments become reducing enough to authigenically accumulate Mo.Stations in close proximity to the Juan de Fuca Ridge crest are enriched in Mn and Fe from hydrothermal plume processes. Both V and Mo clearly associate with Mn cycling, whereas U may be associating with either Mn oxides and/or Fe oxyhydroxides. Rhenium is uncomplicated by adsorption to Mn oxides and/or Fe oxyhydroxides, and Re accumulation in sediments appears to be due solely to the extent of reducing conditions. Therefore, authigenic sediment Re enrichment appears to be the best indicator for intermediate reducing conditions, where oxygen penetrates less than ∼1 cm below the sediment-water interface, when coupled with negligible authigenic Mo enrichment.     

Rates of iodine remineralization in terrigenous near-shore sediments

Much of the sedimentary geochemistry of iodine has been surmised from analyses of solid phase distributions without direct documentation of reactions or reaction rates. It is shown here that the anoxic production rate of dissolved I in nearshore terrigenous sediments decreases rapidly below the sediment-water interface and is strongly temperature controlled. An apparent activation energy of ~19.3 Kcal/mole comparable to that found for other microbially mediated reactions, describes the temperature dependence of release. Production of dissolved iodide is zeroth order with respect to natural ranges of pore water concentrations and apparently first-order with respect to a reactive I component in the solid phase. First order reaction coefficients in sediments from Mud Bay, South Carolina and Long Island Sound, Connecticut, U.S.A., are strongly depth dependent, varying from ~6.9/yr in the top few centimeters to an average of ~0.011/yr over the upper 70 cm. About 90% of the dissolved I flux comes from the top 10 cm with estimated values of ~ 15 and 29 μmoles/m²/day at 22–23°C in Mud Bay and Long Island Sound, respectively. The I/C net release ratio of decomposing material changes rapidly below the sediment surface. When temperature corrections are made, I remineralization rates from nearshore sediments below the bioturbated zone appear to be similar to those observed in deep water sediments underlying oxygenated waters.     

Bottom sediments and pore waters near a hydrothermal vent in Lake Baikal (Frolikha Bay)

We discuss the redox environments and the compositions of bottom sediments and sedimentary pore waters in the region of a hydrothermal vent in Frolikha Bay, Lake Baikal. According to our results, the submarine vent and its companion nearby spring on land originate from a common source. The most convincing evidence for their relation comes from the proximity of stable oxygen and hydrogen isotope compositions in pore waters and in the spring water. The isotope composition indicates a meteoric origin of pore waters, but their major- and minor-element chemistry bears imprint of deep water which may seep through permeable faulted crust. Although pore waters near the submarine vent have a specific enrichment in major and minor constituents, hydrothermal discharge at the Baikal bottom causes a minor impact on the lake water chemistry, unlike the case of freshwater geothermal lakes in the East-African Rift and North America.     

Comparison of continuous records of near-bottom dissolved oxygen from the hypoxia zone along the Louisiana coast

Oxygen depletion is a seasonally dominant feature of the lower water column on the highly-stratified, riverine-influenced continental shelf of Louisiana. The areal extent of hypoxia (bottom waters ≤2 mg l^?1 dissolved oxygen) in mid-summer may encompass up to 9,500 km², from the Mississippi River delta to the upper Texas coast, with the spatial configuration of the zone varying interannually. We placed two continuously recording oxygen meters (Endeco 1184) within 1 m of the seabed in 20-m water depth at two locations 77 km apart where we previously documented midsummer bottom water hypoxia. The oxygen meters recorded considerably different oxygen conditions for a 4-mo deployment from mid-June through mid-October. At the station off Terrebonne Bay (C6A), bottom waters were severely depleted in dissolved oxygen and often anoxic for most of the record from mid-June through mid-August, and there were no strong diurnal or diel patterns. At the station 77 km to the east and closer to the Mississippi River delta (WD32E), hypoxia occurred for only 50% of the record, and there was a strong diurnal pattern in the oxygen time-series data. There was no statistically significant coherence between the oxygen time-series at the two stations. Coherence of the oxygen records with wind records was weak. The dominant coherence identified was between the diurnal peaks in the WD32E oxygen record and the bottom pressure record from a gauge located at the mouth of Terrebonne Bay, suggesting that the dissolved oxygen signal at WD32E was due principally to advection by tidal currents. Although the oxygen time-series were considerably different, they were consistent with the physical and biological processes that affect hypoxia on the Louisiana shelf. Differences in the time-series were most intimately tied to the topographic cross-shelf gradients in the two locations, that is, station C6A off Terrebonne Bay was in the middle of a broad, gradually sloping shelf and station WD32E in the Mississippi River Delta Bight was in an area with a steeper cross-shelf depth gradient and likely situated near the edge of a hypoxic water mass that was tidally advected across the study site.     

Biogeochemical redox cycling of arsenic in mine-impacted lake sediments and co-existing pore waters near Giant Mine,Yellowknife Bay,Canada

Lacustrine sediments, submerged tailings, and their pore waters have been collected at several sites in Yellowknife Bay, Great Slave Lake, Canada, in order to investigate the biogeochemical controls on the remobilization of As from mining-impacted materials under different depositional conditions. Radiometric dating confirms that a mid-core enrichment of Pb, Zn, Cu and Sb corresponds to the opening of a large Au mine 60 a ago. This was evident even in a relatively remote site. Arsenic was enriched at mid-core, coincident with mining activity, but clearly exhibited post-depositional mobility, migrating upwards towards the sediment water interface (SWI) as well as down-core. Deep-water (15 m) Yellowknife Bay sediments that contain buried mine waste are suboxic, relatively organic-rich and abundant in microbes with As in pore waters and sediments reaching 585 μg/L and 1310 mg/kg, respectively. Late summer pore waters show equal proportions of As(III) and As(V) (16–415 μg/L) whereas late winter pore waters are dominated by As(III) (284–947 μg/L). This can be explained by As(III) desorption mechanisms associated with the conversion of FeS to FeS₂ and the reduction of As(V) to As(III) through the oxidation of dissolved sulfide, both microbially-mediated processes. Processes affecting As cycling involve the attenuating efficiency of the oxic zone at the SWI, sediment redox heterogeneity and the reductive dissolution of Fe(hydr)oxides by labile organic matter, temporarily and spatially variable.     

Changes in Nutrient Biogeochemistry in Response to the Regression of Zostera noltii Meadows in the Arcachon Bay (France)

From 1989 to 2007, a severe decline in Zostera noltii meadows was reported in the Arcachon Bay, with an accelerated regression after 2005. We investigated the inter-annual variability of the biogeochemistry of the sediment in an area affected by seagrass decline. In late summer and in winter of the years 2006, 2010, and 2011, sediment cores were collected at low tide on vegetated and adjacent non-vegetated sediments located in the eastern part of the Arcachon Bay. The geochemical analyses of sediment solid-phase organic carbon, reactive P and Fe, and the pore water concentrations of Fe²⁺, DIP, and NH₄ ⁺ are presented. The changes in the chemistry of sediment and pore water between 2006 and 2010 are interpreted as a consequence of the decrease in the Z. noltii biomass between 2006 and 2010. The absence of significant seasonal variations in biomass throughout the growth period (March–September) in 2011 is most likely related to the regression of Z. noltii meadow that strongly affects the study area. In contrast to the healthy meadow in 2006, the declining meadow favored the dissolution of sedimentary particulate phosphorus in winter. In late summer, the low biomass of seagrass resulted in a net release of ammonium in the pore water of the upper 20 cm of sediment. This study clearly shows that seagrass decay may enhance nutrient release in sediments, resulting in a significant supply of phosphorus to the water column of a magnitude comparable to annual inputs to the lagoon from the rivers and the tidal pump.     

Mechanisms controlling summertime oxygen depletion in western Long Island Sound

Physical profile data (salinity, temperature, oxygen, and downwelling irradiance) and in situ incubations of light and dark bottles were used to characterize vertical structure and elucidate mechanisms controlling summertime hypoxia in western Long Island Sound. The period of oxygen depletion corresponded with the period of thermally-controlled stratification. Bulk density differences between surface and bottom waters were only 1.2 to 2.7 sigma-t units; but they were apparently sufficient to resist destratification by winds and tides. Thus oxygen depletion was a cumulative process through the summer. During the stratification period, net oxygen production (measured using light BOD bottles) was confined to a narrow surface zone of 1.8–4.5 m. Below this zone was an intermediate zone of high net oxygen uptake, beneath which was a subpycnoclinic zone where oxygen uptake was very low. Rates of total oxygen uptake (dark bottles) were greatest in the surface layer and diminished with depth. There was close coupling between physical conditions and metabolic structure. Vertical patterns of oxygen production and removal were strongest in calm weather. The location of the intermediate zone corresponded with that of the oxycline. The thickness of the zone and the steepness of the oxycline were determined by the depth and intensity of both physical stratification and biological production and respiration. The biological structure was weakened by physical mixing in the upper water column, and the intermediate zone disappeared with fall destratification. We hypothesize that biological uptake within the water column influences oxygen depletion through two mechanisms. (1) In bottom waters, uptake rates per unit volume are low, but bulk uptake is a significant factor in oxygen depletion because of the large volume of water involved. (2) The intermediate zone, where respiratory uptake is also significant, is strategically located between the surface zone of oxygen renewal and the bottom zone of depletion, where it constitutes an active filter which reinforces the pycnocline as a barrier to vertical oxygen dispersion. The magnitude of direct oxygen removal in the water column relative to removal by sediment oxygen demand and the potential effects of this biological filtering mechanism are important considerations for understanding eutrophication dynamics and managing Long Island Sound. Dynamic models which (1) underestimate the role of water column uptake and (2) incorporate only the two-zone characteristics of physical stratification will tend to (a) overestimate the contribution of sediments to summertime oxygen deficits and (b) overestimate rates of vertical dispersion and reventilation of bottom waters.