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.     

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.     

Microbial biogeochemistry and bioturbation in the sediments of Great Bay, New Hampshire

The influence of bioturbation on certain aspects of the biogeochemistry of sulfur and iron was examined in shallow-water sediments of Great Bay Estuary, New Hampshire. A bioturbated (JEL) and non-bioturbated (SQUAM) site were compared. Annual sulfate reduction measured with ³⁵S, was 4·5 times more rapid at JEL. A significant portion of this difference was attributed to rapid rates which occurred throughout the upper 12 cm of sediment at JEL due to infaunal reworking activities. Sulfate reduction decreased rapidly with depth at SQUAM. FeS in the upper 2 cm at JEL increased in concentration from 3 to 45 μmol ml⁻¹ from early May to late July while only increasing from 3 to 8 μmol ml⁻¹ at SQUAM. Infaunal irrigation and reworking activities caused rapid and continous subsurface cycling of iron and sulfur at JEL. This maintained dissolved iron concentrations at 160–170 μM throughout the summer despite rapid sulfide production. Therefore, dissolved sulfide never accumulated in JEL pore waters. Although dissolved organic carbon (DOC) was generated during sulfate reduction, bioturbation during summer caused a net removal of DOC from JEL pore waters. Sulfate reduction rates, decomposition stoichiometry and nutrient concentrations were used to calculate turnover times of nutrients in pore waters. Nutrient turnover varied temporally and increased three-to five-fold during bioturbation. A secondary maximum in the abundance of recoverable sulfate-reducing bacteria occurred at 10 cm in JEL sediments only during periods of active bioturbation, demonstrating the influence of macrofaunal activities on bacterial distributions.     

Analysis and distribution of iron sulfide minerals in recent anoxic marine sediments

Acid-volatile sulfide (AVS), pyrite-sulfur, iron and organic carbon distributions were examined in sediments from a variety of oxic and anoxic marine environments. Multiple determinations of AVS using different acid conditions showed that most extractants give similar AVS concentrations, with the exception of stannous chloride in hot HCl which digested between 10 and 81% of pyrite-sulfur.An extensive examination of iron sulfide minerals in sediments, using scanning electron microscopy combined with simultaneous elemental analysis, showed that identifiable iron sulfides were almost always pyrite. Occurrence of greigite observable by SEM was limited to one site and mackinawite was not found in any samples. Thus, if these minerals are precursors to pyrite formation, as has been frequently hypothesized, they must be primarily present as coatings on other mineral grains or submicron particles.     

Molybdenum in pore waters of anoxic marine sediments by electron paramagnetic resonance spectroscopy

Pore water samples of anoxic sediments from Great Bay, N.H. and Jeffrey's Basin, New England continental shelf, have been analyzed for dissolved molybdenum by the electron paramagnetic resonance (EPR) spectroscopy technique of Hanson et al. (1977). The method has been modified so that only 0.50 ml of pore water sample is utilized for the analysis. The concentrations of Mo in the Jeffrey's Basin pore fluids are as much as an order of magnitude higher than that of the overlying water, while the estuarine water concentrations are only twice that of the overlying water.The Mo in the pore water is negatively correlated to dissolved Fe²⁺ and positively correlated to the precent of organic carbon in the sediments. This suggests that Mo is remobilized by the anaerobic degradation of sedimentary organic matter and is not directly incorporated into iron pyrite during early diagenesis.     

Sulfide control of cadmium and copper concentrations in anaerobic estuarine sediments

Equilibrium concentrations of the toxic trace metals copper and cadmium were calculated for the physico-chemical conditions characterizing pore waters of anaerobic estuarine sediments using available thermodynamic data and assuming simple sulfide minerals control solubilities. Polysulfide complexes are responsible for the solubility of copper in the cuprous (Cu(I)) oxidation state. Predicated copper concentrations, assuming covellite (CuS) is the controlling solid phase, are in reasonable agreement with copper analyses in a wide range of sulfidic waters and sediment pore waters. In the absence of thermodynamic data, no account could be taken of possible polysulfide complexes of cadmium. However, bisulfide complexes appear to account satisfactorily for observed solubilities assuming the existence of greenockite (CdS) as the controlling solid phase. Anaerobic estuarine sediments may act as a sink for copper and cadmium in the common situation in which free sulfide concentrations are controlled by the coexistence of iron sulfide and iron oxide minerals. However, where free sulfides reach high concentrations of 10^?3 M or more, the concomitant increase in concentration of bisulfide and polysulfide complexes may result in the sediments acting as a source of copper and cadmium.     

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.     

Diagenetic deposition of manganese in sediment of a historically meromictic lake,Lake Suigetsu,Japan

Vertical profiles of manganese concentration in interstitial waters and of manganese and iron contents in five chemically-separated fractions of sediments have been studied in a sediment core (73 cm long) from a meromictic lake, Lake Suigetsu, which changed from freshwater to brackish conditions in 1664 A.D. The interstitial waters show a minimum manganese concentration of 0.13 ppm near a depth of 10 cm and a maximum of 26 ppm near 65 cm in the core. A predominant amount of manganese, up to 0.17%, is found in the hydrogen peroxide-soluble fraction of sediments in layers above a depth of 52 cm. It is suggested that the manganese is included in stable iron sulfides such as pyrite. Manganese, which diffuses upward from the lower layer, is thought to be deposited along with stable iron sulfide during diagenetic formation of the latter near a depth of 10 cm in the core.     

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.     

Pyrite formation under conditions approximating those in anoxic sediments: II. Influence of precursor iron minerals and organic matter

In the paper (Wang and Morse, 1996) that preceded this study, we presented results of experiments performed using a silica gel crystal growth technique to produce pyrite under conditions approximating those commonly occurring in anoxic marine sediments. The primary focus of that study was on the chemical pathways that pyrite formation follows and how differing conditions influenced reaction kinetics and morphology of pyrite crystals. In this paper, we present results of further long-term (up to 1 y) studies of pyrite formation, using the silica gel experimental technique, in which we investigated the role that different precursor iron (hydr)oxide minerals and marine organic matter play in pyrite formation. The minerals studied were akaganeite (β-FeOOH), ferrihydrite (Fe₅HO₈ · 4H₂O), goethite (α-FeOOH), hematite (α-Fe₂O₃), lepidocrocite (γ-FeOOH), and magnetite (Fe₃O₄). Marine organic matter used in this study was freeze-dried plankton collected from near-surface water in the Gulf of Mexico. The influence of precursor iron (hydr)oxide mineralogy, although important for initial iron sulfidization rates, was relatively minor compared to other variables, such as solution pH and sulfide concentration, in controlling the rate of pyrite formation. Consequently, major variations in the observed rate of pyritization of different iron (hydr)oxide minerals in sediments (e.g., Canfield and Berner, 1987) may reflect large differences in surface areas of the minerals rather than their intrinsic reactivity and is a confirmation of the estimates of Canfield et al. (1992) that most iron oxides have similar reactivity. The presence of marine organic matter (freeze-dried plankton) caused an increase in the sulfidization rate of goethite and a major (about 20 ×) decrease in the rate of pyrite formation. This can be interpreted as indicating that organic matter-iron interactions are important in both iron (hydr)oxide dissolution, and pyrite nucleation and growth. A possible explanation for this behavior is that dissolved organic matter produced during the long experiments (up to 1 year) increased the rate of goethite dissolution while inhibiting pyrite nucleation and growth by complexing iron. The lessons learned in the study of other mineral reaction kinetics (e.g., calcite and aragonite), that rates determined in pure inorganic systems, may not always be reliably applied to natural systems where organic matter can significantly influence mineral dissolution and growth rates, are, alas, repeated here for pyrite.     

Trace metal concentrations in the Ross Sea and their relationship with nutrients and phytoplankton growth

Dissolved and particulate trace metal concentrations (dissolved Fe, Zn, Cd, Co, Cu and Ni; particulate Fe, Mn and Al) were measured along two transects in the Ross Sea during austral summer of 1990. Total Fe concentrations in southern Ross Sea and inshore waters were elevated >3.5 times that of northern waters. Dissolved Zn, Cd and Co concentrations were lower by factors of 4.5, 3.5 and 1.6 in southern surface waters relative to northern waters. Dissolved Cu and Ni concentrations were similar in both areas. Elevated Fe concentrations coincided with areas of increased productivity, phytoplankton biomass and nutrient drawdown, indicating that Fe is an important factor controlling the location of phytoplankton blooms in the Ross Sea. Particulate concentrations of Fe, Mn and Al indicate two possible sources of iron to the Ross Sea, resuspension of continental shelf sediments and iron incorporated in annual sea ice and released with meltwaters.     

Oxygen and Sulfides in Bottom Sediments of the Coastal Sevastopol Region of Crimea

Spatial variations in the distribution and fluxes of dissolved oxygen and sulfide in bottom sediments of Omega and Sevastopol bays have been studied. The results of analysis reveal that the distribution of dissolved oxygen and sulfide in pore water depends mostly on seasonal variations in the oxygen concentration in bottom water, grain size, the organic carbon content in bottom sediments, and, additionally for Sevastopol Bay, the iron content. The oxygen flux at the bottom of Sevastopol Bay is 20 times larger in winter–spring compared to that of Omega Bay. Anaerobic conditions in Sevastopol Bay sediments are observed much closer to the surface, with their subsequent development in bottom water.     

Processes controlling solubility of biogenic silica and pore water build-up of silicic acid in marine sediments

Dissolution experiments in batch and flow-through reactors were combined with data on sediment composition and pore water silicic acid profiles to identify processes controlling the solubility of biogenic silica and the build-up of silicic acid in marine sediments. The variability of experimentally determined biogenic silica solubilities is due, in part, to variations in specific surface area and Al content of biosiliceous materials. Preferential dissolution of delicate skeletal structures and frustules with high surface areas leads to a progressive decrease of the specific surface area. This may cause a reduction of the solubility of deposited biosiliceous debris by 10–15%, relative to fresh planktonic assemblages. Dissolution of lithogenic (detrital) minerals in sediments releases dissolved aluminum to the pore waters. This aluminum becomes structurally incorporated into deposited biogenic silica, further decreasing its solubility. Compared to Al-free biogenic silica, the solubility of diatom frustules is lowered by as much as 25% when one out of every 70 Si atoms is substituted by an Al(III) ion.The build-up of silicic acid in pore waters of sediments with variable proportions of detrital matter and biogenic silica was simulated in batch experiments using kaolinite and basalt as model detrital constituents. The steady-state silicic acid concentrations measured in the experiments decreased with increasing detrital-to-opal ratios of the mixtures. This trend is similar to the observed inverse relationship between asymptotic pore water silicic acid concentrations and detrital-to-opal ratios in Southern Ocean sediments. Flow-through reactor experiments further showed that in detrital-rich sediments, precipitation of authigenic alumino-silicates may prevent the pore waters from reaching equilibrium with the dissolving biogenic silica. This agrees with data from Southern Ocean sediments where, at sites containing more than 30 wt.% detrital material, the pore waters remain undersaturated with respect to the experimentally determined in situ solubility of biogenic silica.The results of the study show that interactions between deposited biogenic silica and detrital material cause large variations in the asymptotic silicic acid concentration of marine sediments. The production of Al(III) by the dissolution of detrital minerals affects the build-up of silicic acid by reducing the apparent silica solubility and dissolution kinetics of biosiliceous materials, and by inducing precipitation of authigenic alumino-silicate minerals.     

Trace metal solubility in salt marsh sediments contaminated with sewage sludge

As part of a study to investigate the effect of nutrient and metal pollution on salt marshes, a sewage sludge fertilizer has been applied to experimental plots in Great Sippewissett Marsh, MA, since 1974. The concentration of nutrients, soluble sulfides, and metals were measured in porewater from these plots every 4–6 weeks from April to December in 1980. Metal and nutrient concentrations in these plots were consistently greater than in corresponding control plots. Nutrients stimulated growth of Spartina alterniflora, the dominant vegetation on these plots, and higher grass production increased sediment oxidation. Concentrations of soluble sulfide in fertilized plots were an order of magnitude lower than in surrounding areas. For much of the year sulfides could not be detected in porewater from surface sediments of fertilized plots.The solubility of metals in sediments in fertilized plots was greatly increased by the decrease in sulfide concentrations. For much of the year, the top 4 cm of the sediments in fertilized plots were undersaturated with respect to all metal sulfide minerals. This undersaturation may account for the large loss of metals observed on these plots. It appears that in the surface sediments of these plots the retention of metals may be governed in part by adsorption onto iron oxyhydroxides.Precipitation of metal sulfides may be important in limiting the penetration of metals deeper into the sediment. At 6 cm, Zn and Cd were always close to the solubility of their respective sulfide minerals. Below 4 cm, iron was undersaturated with respect to all iron monosulfide minerals but supersaturated with respect to pyrite. Copper was supersaturated with respect to CuS and Cu₂S in all samples where sulfide was above the detection limit. Gel filtration experiments indicated that significant amounts of iron and copper were organically complexed in the porewater and may have been partially responsible for the large supersaturations.     

Reactive iron in Black Sea Sediments: implications for iron cycling

The distribution of reactive iron in sediments of the northwestern shelf, the shelf edge and the abyssal part of the Black Sea has been studied. In the euxinic Black Sea, iron sulfides (pyrite and iron monosulfide) are formed in the upper part of the anoxic water column and sink to the deep-sea floor where they are buried in the sediment. This flux of iron sulfides from the water column is reflected in enhanced concentrations of highly reactive iron and a high degree of pyritization (0.57–0.80) for the deep-water sediments of the Black Sea. The iron enrichment of deep-water sediments is balanced by a loss of highly reactive iron from the oxic continental shelf. Calculations from a numerical diagenetic model and reported in situ flux measurements indicate that the dissolved iron flux out of the shelf sediments is more than sufficient to balance the enrichment in reactive iron in deep-sea sediments, and that the majority of the dissolved iron efflux is redeposited on the continental shelf. This iron mobilization mechanism likely operates in most shelf areas, but its net effect becomes only apparent when reactive iron is trapped in sulfidic water bodies as iron sulfides or when iron is incompletely oxidized in low oxygen zones of the ocean and transported over long distances.     

Rare earth element geochemistry in cold-seep pore waters of Hydrate Ridge, northeast Pacific Ocean

The concentrations of rare earth elements (REEs), sulphate, hydrogen sulphide, total alkalinity, calcium, magnesium and phosphate were measured in shallow (<12 cm below seafloor) pore waters from cold-seep sediments on the northern and southern summits of Hydrate Ridge, offshore Oregon. Downward-decreasing sulphate and coevally increasing sulphide concentrations reveal sulphate reduction as dominant early diagenetic process from ~2 cm depth downwards. A strong increase of total dissolved REE (∑REE) concentrations is evident immediately below the sediment–water interface, which can be related to early diagenetic release of REEs into pore water resulting from the re-mineralization of particulate organic matter. The highest pore water ∑REE concentrations were measured close to the sediment–water interface at ~2 cm depth. Distinct shale-normalized REE patterns point to particulate organic matter and iron oxides as main REE sources in the upper ~2-cm depth interval. In general, the pore waters have shale-normalized patterns reflecting heavy REE (HREE) enrichment, which suggests preferential complexation of HREEs with carbonate ions. Below ~2 cm depth, a downward decrease in ∑REE correlates with a decrease in pore water calcium concentrations. At this depth, the anaerobic oxidation of methane (AOM) coupled to sulphate reduction increases carbonate alkalinity through the production of bicarbonate, which results in the precipitation of carbonate minerals. It seems therefore likely that the REEs and calcium are consumed during vast AOM-induced precipitation of carbonate in shallow Hydrate Ridge sediments. The analysis of pore waters from Hydrate Ridge shed new light on early diagenetic processes at cold seeps, corroborating the great potential of REEs to identify geochemical processes and to constrain environmental conditions.     

Dissolved silica concentrations and reactions in pore waters from continental slope sediments offshore from Cape Hatteras, North Carolina, USA

The pore water concentrations of dissolved silica in sediment cores from the continental slope offshore from Cape Hatteras, North Carolina, varied from 150 to almost 700 μ,M with depth in the top 40 cm of sediment. Sediment cores from 630 to 2010 m depth had very similar profiles of dissolved silica in their pore waters, even though these cores came from regions greatly different in slope, topography, sedimentation rate, and abundance of benthic macrofauna. Cores from 474 to 525 m were more variable, both with respect to pore water dissolved silica profiles, and with respect to sediment texture. Experiments indicate that both the rate of dissolution of silica and the saturation concentration decrease as sediment depth below the sediment-seawater interface increases. These data are consistent with depletion of a reactive silica phase in surface sediment, which may be radiolarian tests, or the alteration of biogenic silica to a less reactive form over time. Experimental results suggest that the pore water dissolved silica concentration in sediments below the top few centimeters may be higher than the sediments could now achieve. The flux of dissolved silica out of these sediments is estimated to be 15 μmoles cm⁻² yr⁻¹.     

Spatial and seasonal variations of sulphate,dissolved organic carbon,and nutrients in deep pore waters of intertidal flat sediments

Spatial and seasonal variations of sulphate, dissolved organic carbon (DOC), nutrients and metabolic products were determined down to 5 m sediment depth in pore waters of intertidal flats located in NW Germany. The impact of sediment permeability, pore water flow, and organic matter supply on deep pore water biogeochemistry was evaluated. Low sediment permeability leads to an enrichment of remineralisation products in pore waters of clay-rich sediments. In permeable sandy sediments pore water biogeochemistry differs depending on whether tidal flat margins or central parts of the tidal flat are studied. Pore water flow in tidal flat margins increases organic matter input. Substrate availability and enhanced temperatures in summer stimulate sulphate reducers down to 3.5 m sediment depth. Sulphate, DOC, and nutrient concentrations exhibit seasonal variations in deep permeable sediments of the tidal flat margin. In contrast, seasonal variations are small in deep pore waters of central parts of the sand flat. This study shows for the first time that seasonal variations in pore water chemistry are not limited to surface sediments, but may be observed down to some metres depth in permeable tidal flat margin sediments. In such systems more organic matter seems to be remineralised than deduced from surface sediment studies.     

Tidal sands as biogeochemical reactors

Sandy sediments of continental shelves and most beaches are often thought of as geochemical deserts because they are usually poor in organic matter and other reactive substances. The present study focuses on analyses of dissolved biogenic compounds of surface seawater and pore waters of Aquitanian coastal beach sediments. To quantitatively assess the biogeochemical reactions, we collected pore waters at low tide on tidal cross-shore transects unaffected by freshwater inputs. We recorded temperature, salinity, oxygen saturation state, and nutrient concentrations. These parameters were compared to the values recorded in the seawater entering the interstitial environment during floods. Cross-shore topography and position of piezometric level at low tide were obtained from kinematics GPS records. Residence time of pore waters was estimated by a tracer approach, using dissolved silica concentration and kinetics estimate of quartz dissolution with seawater. Kinetics parameters were based on dissolved silica concentration monitoring during 20-day incubations of sediment with seawater. We found that seawater that entered the sediment during flood tides remained up to seven tidal cycles within the interstitial environment. Oxygen saturation of seawater was close to 100%, whereas it was as low as 80% in pore waters. Concentrations of dissolved nutrients were higher in pore waters than in seawater. These results suggest that aerobic respiration occurred in the sands. We propose that mineralised organic matter originated from planktonic material that infiltrated the sediment with water during flood tides. Therefore, the sandy tidal sediment of the Aquitanian coast is a biogeochemical reactor that promotes or accelerates remineralisation of coastal pelagic primary production. Mass balance calculations suggest that this single process supplies about 37 kmol of nitrate and 1.9 kmol of dissolved inorganic phosphorus (DIP) to the 250-km long Aquitanian coast during each semi-diurnal tidal cycle. It represents about 1.5% of nitrate and 5% of DIP supplied by the nearest estuary.     

Upward transport of iron at the west shelf edge–slope of the Okinawa Trough in the East China Sea

We studied the behavior of chemical substances in the upper 300 m of the water column across the continental shelf–slope interface in the East China Sea off the Okinawa Trough. The behaviors of iron, inorganic nutrients, and humic-like fluorescent dissolved organic matter were strongly influenced by the extensive water exchange between the East China Sea and the Kuroshio Current across the shelf break and slope via upwelling and frontal processes. We attributed the high humic-like fluorescent intensity at the subsurface of the shelf break and slope regions to the lateral supply of humic-like fluorescent dissolved organic matter from the shelf sediments to the outer shelf region due to the intrusion of shelf water into Kuroshio subsurface water. We found that the behavior of iron at the continental shelf–slope was remarkably different from the conservative mixing of inorganic nutrients and humic-like fluorescent dissolved organic matter. In deep and bottom waters at the shelf–slope, high total iron concentrations, which were closely related to water transmittance, possibly resulted from the swept transport of iron-rich resuspended sediments over the shelf floor from the slope by the invading Kuroshio Intermediate Water close to the bottom.