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.     

Reactions which remove dissolved alumina from seawater

Dissolved alumina can coprecipitate with dissolved silica from seawater enriched with both compounds. This coprecipitation is almost complete within 1h and maintains the concentration of dissolved alumina near naturally occurring oceanic concentrations, well below the alumina concentration of 0.50 ppm A1 found to be stable in filtered Sargasso seawater at 2°C. Only 0.5 ppm Si is necessary to initiate this coprecipitation, which indicates that the concentrations of dissolved alumina that occur in seawater and in interstitial water are a function of the concentration of dissolved silica as well as of the alumina solubility.Dissolved alumina is also quickly removed by solid amorphous silica from solutions of seawater enriched in dissolved alumina and also by several marine sediments in contact with the solution. This process may be an important factor in authigenic mineral formation in marine sediments.     

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.     

Elemental geochemical records of seafloor hydrothermal activities in the sediments from the Okinawa Trough

The major and minor element contents in the sediment core H9 from the hydrothermal fields of the Okinawa Trough show a sharp change at the depth of 80 cm. The elements enriched in the upper 80 cm core are those enriched in the hydrothermal deposits and in the surface sediments recovered from the hydrothermal fields in the trough, which indicates the input of hydrothermal materials. Comparing with other hydrothermal sediments from Mid-ocean Ridges or the Lau Basin, the degree of the enrichment of elements iron, copper,cobalt, and nickel is relatively low. However, the enrichment of elements manganese, lead, arsenic, antimony and mercury is remarkable. The average contents of these elements in the upper 80 cm core sediments are three to six times those in the lower section, and 3~12 times those in the surface sediments which are not influenced by hydrothermal activities. Hydrothermal activities have contributed significant manganese, lead, arsenic, antimony and mercury to the sediments, and these elements are distinct indicators for the hydrothermal activity in the Okinawa Trough. The significant enrichment of these elements in Core H9 upward from the depth 80 cm indicates the start or the significant enhancing of the hydrothermal activity in this area at about 5 740 aB.P. The average accumulation rate of manganese during this period is about 40 461 μg/(cm2·ka), which is similar to the hydrothermal sediments in the Lau Basin or the East Pacific Rise.     

Vertical distributions of some chemical substances in surface sediments of a meromictic Lake Suigetsu

Vertical distributions of some chemical substances in the surface sediments of a typical meromictic lake, Lake Suigetsu, were measured. Metallic elements such as iron, manganese, nickel, zinc, copper and chromium showed no significant slopes in vertical direction. While, boron and total sulfur contents in the sediments decreased from the surface to the stratum 35–40 cm, and below which both substances showed no more appreciable changes. From an average sedimentation rate (about 1.1 mm/yr), estimated from the radiocarbon dating of the sediment, the sediments above the stratum 35–40 cm were thought to be deposited after the beginning of the salt water intrusion to the lake by the excavation of a canal in 1665, by which Lake Suigetsu was connected to a polyhaline lake (Lake Kugushi) directly connected to the sea. Vertical distributions of boron and total sulfur in the sediments and also of chlorinity of the interstitial waters seem to correspond to past change in the lake condition from freshwater one to a two-layered system of a deeper salt water covered by a upper freshwater.     

Geotechnical properties of a submarine slide area on the U.S. continental slope northeast of Wilmington canyon

Abstract

A relatively large submarine slide (slump block) and apparent unstable surficial sediments undergoing creep have been delineated in bathymetric and seismic reflection profiles along the U.S. Atlantic continental margin northeast of Wilmington Canyon. A downslope core transect was made over selected areas to assess the geotechnical properties of the sediments associated with the slide. Sediments are predominantly silty clays and clayey silts rich in illite, with lesser quantities of feldspar, kaolinite, chlorite, quartz, and smectite minerals. Surficial sediments (cored up to 12 m) upslope from the slump block reveal typical variations in the mass physical properties with core depth. Shear strength and wet unit weight show a steady increase with depth below the mudline commensurate with a decrease in water content. In contrast, surficial sediments downslope overlying the slump block generally have low shear strength and relatively high variability in other mass physical properties with core depth. Chemical evidence of slumping (as defined by the sulfate ion content) is not apparent in the pore waters collected from the upper 10 m of sediment. No important relationships are obvious among the physical and chemical properties, specifically the carbonates or complex solids of iron and manganese oxides or hydroxides. Sediment failure in the form of a major submarine slide appears to have been a significant deformational process during the geological past (late Pleistocene). Creep and associated deformational features recorded in the surficial sediments are presumably a result of recent geological processes.     

Early diagenesis in rapidly accumulating sediments on the Alboran slope, ODP site 976

The oxidation and reduction that occur during early diagenesis of sediments has been studied in the interstitial waters of a rapidly accumulating sedimentary sequence from the Mediterranean margin of Spain. A series of reactions that are mediated by progressively lower free energy derived from oxidation of organic matter is evident in the sedimentary sequence. Iron and manganese are rapidly reduced. Phosphate and alkalinity maxima at a subbottom depth of 15?m indicate maximal organic matter degradation. Methane first appears at ～20?m subbottom after sulfate is depleted, and its concentrations quickly climb.     

Interstitial water trace-metal chemistry of laminated sediments from the Gulf of California,Mexico

This report presents major and minor element profiles for interstitial waters recovered from the oxygen-minimum zone of the Gulf of California. The major elements and nutrients show concentration-depth profiles typical for anoxic, laminated sediments, with sulfate-reduction occurring close to the sediment-water interface, accompanied by increases in alkalinity and ammonia. Barium is solubilized near the sediment-water interface, but decreases below 10 cm depth, showing concentrations consistent with barite solubility. The dissolved concentrations of Mn, Fe, and Al are higher in the upper part of the sedimentary column; Mn and Fe due to reduction of oxides and Al probably because of dissolution of siliceous material. In contrast, dissolved Mo, V, and Cr show concentrations increasing with depth. The strong correlation of the concentrations of Mo, V and Cr with “yellow substance” absorbance reflect the importance of dissolved organic matter for the mobility of these elements during early diagenesis.     

Iron and manganese in the wake of the Kerguelen Islands (Southern Ocean)

As part of the ANTARES 3/F-JGOFS cruise, the distributions of dissolved iron and manganese were measured in October 1995 in the north–east wake of the Kerguelen archipelago (48°40′–49°40′S, 68°70′–70°50′E), an area that shows high phytoplankton biomass (CZCS and SeaWiFS data) in the middle of the High Nutrient Low Chlorophyll (HNLC) Southern Ocean. The study area (about 25,000 km²) comprised a branch of the Polar Front with Antarctic surface water (AASW) intruding northward, shouldering the shelf break of the Kerguelen Plateau. The coastal zone was clearly affected by material of lithogenic origin (riverine discharges, soil leaching by rain waters, aeolian inputs), as well as by inputs from the sediments (effluxes from the sediment–water interface, resuspension from the sediments), its near surface waters showing considerable enrichment in dissolved iron (5.3–12.6 nM) and in dissolved manganese (2.9–8.6 nM). The offshore waters, although less enriched in trace-metals, were also affected by trace-metal inputs from coastal and continental shelf origin. Dissolved iron and manganese concentrations in these waters were 0.46–0.71 and 0.68–1.3 nM, i.e. far over typical antarctic open ocean surface water concentrations of 0.16 nM for iron [Martin, J.H., Gordon, R.M., Fitzwater, S.E., 1990. Iron in Antarctic waters. Nature, 345: 156–158.] and around 0.1 nM for manganese [Martin, J.H., Gordon, R.M., Fitzwater, S.E., 1990. Iron in Antarctic waters. Nature, 345: 156–158; Sedwick, P.N., Edwards, P.R., Mackey, D.J., Griffiths, F.B., Parslow, J.S., 1997. Iron and manganese in surface waters of the Australian subantarctic region. Deep-Sea Res., 44: 1239–1253.]. The dissolved iron enrichment in coastal waters of the Kerguelen Islands is much more important (about 10 times for dissolved iron) than for the Galapagos Islands, another oasis in the HNLC Equatorial oceanic system, where the concentration increase in dissolved iron in the surface waters around the islands is mostly driven by upwelling of the Equatorial Under Current (EUC) as it reaches the Galapagos Platform.     

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.     

Life habit of vesicomyid clam,Calyptogena soyoae,and hydrogen sulfide concentration in interstitial waters in Sagami Bay,Japan

In and around the beds of vesicomyid clam (Calytogena soyoae) located off Hatsushima Island in Sagami Bay, central Japan, hydrogen sulfide concentration in bottom water and interstitial water was measured every 10 cm from just above seafloor to 40 cm deep usingin situ separative dialysis bags. While hydrogen sulfide over 0.01 mmol/kg was not measured from the seawater just above the dense clam beds, the concentration of hydrogen sulfide increased rapidly below 10 cm deep. The results indicate that the habit of the clam is correlated with high concentration of hydrogen sulfide contained in pore waters of sediments between depths of 10 and 20 cm from the bottom surface. Concentrations of hydrogen sulfide ranging from approximately 0.05 mmol/kg to 0.6 mmol/kg might be suitable requirement for the habitat ofC. soyoae.     

Interstitial water chemistry of the inner continental shelf sediments off the gironde estuary

The interstitial water composition ( , alkalinity, Ca²⁺, Mg²⁺, Sr²⁺, Na⁺, K⁺) and the cation exchange capacity (CEC) were determined for the muddy sediments of the continental shelf off the Gironde Estuary (France), in the area where the sediment represents the deposit of the muddy suspension of the river. In comparison with seawater concentrations, the pore waters below 10 cm depth, show depletions of and Ca²⁺ and below a 30 cm depth show depletions of Mg²⁺. Inversely, the upper 10 cm an enrichment of Ca²⁺ concentration, and an increase of K⁺ concentration to a 40 cm depth. High values of are observed at the top 4 cm. Alkalinity enrichment is observed along the length of the core. Applying the alkalinity models for the sediment below a 10 cm depth demonstrates generally that calculated alkalinities are higher than the measured ones. Ca²⁺ dissolution occurs at the first 10 cm and authigenic carbonate precipitation starts beneath that level. Mg²⁺ depletion is accompanied by bicarbonate loss. This proves that Mg²⁺ depletion is due to a Mg-silicate reaction. The result of the CEC does not confirm the Mg²⁺ uptake by clay minerals in exchangeable site, under reducing conditions. Diffusion and bioturbation play an important role in the pore water concentration at the top of the core.     

冲绳海槽中部现代海底热液活动在沉积物中的元素地球化学记录

对采自冲绳海槽中部现代海底热液活动区的H9岩心沉积物进行了常量、微量元素分析,结果表明大部分元素含量在岩心75~80 cm处有一个明显的突变,上段中明显富集多种微量元素,这些元素正好对应于海槽中非热液活动区沉积物中相对亏损的元素,是热液活动区沉积物中的富集特征元素.75~80 cm处岩心沉积物中元素含量突变标志着冲绳海槽中部现代海底热液活动的开始或显著加强.除锰外,在其他热液活动区(如洋中脊等)显著富集的铁、铜、钴、镍在该区富集程度不高,但铅、鉮、锑、汞在上段岩心沉积物中的平均含量较下段高3~6倍,较非热液活动区沉积物中含量高3~12倍.这些富集元素与冲绳海槽热液活动成因硫化物中富集元素非常一致,表明该区热液活动对沉积物中锰、铅、鉮、锑、汞具有重要贡献,锰、铅、鉮、锑、汞是海槽中部现代海底热液活动的特征性示踪元素组合.岩心沉积物中很好地记录了热液活动的发展演化,该区海底热液活动从距今5740a开始发生或显著增强,并且一直持续到现在,只是其间活动程度经历了强弱变化,岩心上段锰的平均堆积速率约为40.461μg/(cm2·ka),与其他热液活动区的相当.     

Interstitial water chemistry in deep-sea sediments from the Japan Sea

Vertical profiles of pH, Eh, and major and minor chemical constituents in interstitial waters have been studied in four piston cores from deep-sea basins of the Japan Sea. Sulfate concentration decreases remarkably with increasing depth in three cores, and hydrogen sulfide is observed in two cores although the overlying bottom water is highly aerated. Three types of interstitial waters are observed in the four cores: (1) alkalinity and manganese concentration increase gradually with increasing depth, and sulfate reduction is not appreciable, (2) alkalinity increases and sulfate concentration decreases remarkably, and hydrogen sulfide is not detected, and (3) alkalinity increases and sulfate concentration decreases remarkably, and hydrogen sulfide is observed. Factors controlling the chemical composition of interstitial waters are discussed.     

Behavior of manganese in aqua-benthic environment in the Hiro Bay

The horizontal and vertical distributions of manganese in sea water, interstitial water and sediments in the Hiro Bay, Seto Inland Sea, Japan, have been investigated. The outflow from a pulp mill is the primary source of manganese in this bay. The industrial waste water contained 0.19 mg l^–1 of manganese, mostly in a dissolved form. This manganese diffused out both horizontally and vertically into the surrounding sea water. The content of manganese in the liquid and solid phases in the sediments, however, are inverse with that in the sea water; namely the lowest concentration of manganese in the sediments was observed at the station near the outfall and manganese concentration increased with the distance from the outfall.     

基于PXRF的西南印度洋脊硫化物表层沉积物地球化学找矿研究

海底热液喷发形成的热液羽状流中富含成矿物质,并沉淀在距离热液喷口不等的范围内。对西南印度洋中脊热液喷口附近、距离喷口中等距离、远离喷口的六个表层沉积物样品开展了不同粒度沉积物的便携式XRF（PXRF）分析。结果表明,PXRF可以有效获得的洋中脊钙质沉积物中成矿元素的富集特征。>40目的沉积物样品具有较高的Cu、Zn、Fe、Mn等元素含量,40目以下沉积物中则相对稳定,可能与粗粒沉积物中玄武岩碎屑/玻璃含量较高有关,与镜下鉴定结果一致。以热液喷口为中心,表层沉积物中表现出Cu、Zn、As、Fe、Mn的元素分带,靠近喷口的沉积物中具有较高的成矿元素的含量,并具有较高的Cu/Fe、Zn/Fe比值或者Cu/Mn与Zn/Mn比值。上述结论表明,洋中脊沉积物中成矿元素的含量主要受与喷口的距离的影响,而与粒度的关系不大,洋中脊沉积物地球化学找矿应采用40目以下粒径沉积物作为分析样品。通过PXRF获得的Cu、Zn、As、Fe、Mn等元素含量及其比值特征可以作为海底多金属硫化物沉积物地球化学找矿的指标,该方法满足快速有效识别洋中脊沉积物中地球化学异常的要求。     

Early diagenesis in rapidly accumulating sediments on the Alboran slope, ODP site 976

 The oxidation and reduction that occur during early diagenesis of sediments has been studied in the interstitial waters of a rapidly accumulating sedimentary sequence from the Mediterranean margin of Spain. A series of reactions that are mediated by progressively lower free energy derived from oxidation of organic matter is evident in the sedimentary sequence. Iron and manganese are rapidly reduced. Phosphate and alkalinity maxima at a subbottom depth of 15 m indicate maximal organic matter degradation. Methane first appears at ∼20 m subbottom after sulfate is depleted, and its concentrations quickly climb. Received: 27 October 1997 / Revision received: 4 March 1998     

Marine barite in sediments from deep sea drilling project sites 424 and 424a (Galapagos hydrothermal mounds field)

The distribution of barite in sediments from D.S.D.P. sites 424 and 424A at the Galapagos hydrothermal mounds field is determined and the process of its formation is deduced. Barite in these deposits is associated with calcareous sediments and is completely absent from the hydrothermal material (manganese crusts and nontronite). Its concentrations tend to increase in the deeper sediments. Since manganese crusts contain significant amounts of Ba, a lack of barite in them is probably due to low concentrations of SO₄² in the sediment-seawater interface where they form. The formation of barite occurs within buried sediments, the interstitial waters of which are saturated with SO₄². The most probable source of SO₄²⁻ is the oxidation of H₂S which is released from the hydrothermal fluids percolating upwards through the sediments. Although nontronite is formed within buried sediments the environmental conditions occurring during its formation (reducing) prevent barite formation.The association of barite with calcareous sediments is due to the release of Ba by calcareous microorganisms and/or to high concentrations of Ca in the pore waters which maintain a high pH and hence SO₄²⁻ is stable.     

Rock magnetic property of gravity core CSH1 from the northern Okinawa Trough and the effect of early diagenesis

Detailed rock magnetic investigations were undertaken at 2~4 cm interval for the gravity core CSH1(with a length of 17.36 m) from the northern Okinawa Trough.Time-scale of the core was constructed by two characteristic tephras and foraminferal assemblages,indicating an age of 50 ka for the bottom of the core.Except for three tephras and abrupt decrease in surface,there are little changes in all kinds of rock magnetic parameters that can be correlated to the climate change for the last 50 ka.Different from the common sediments,most S-ratios(S equals the negative ratio of IRM-0.3T to SIRM,which is an indicator of low coercivity content)of the sediments are smaller than 0.9,which implies a substantial amount of magnetic minerals with high coercivity.The existence of iron sulphide(greigite or pyrrhotite) is revealed by representative susceptibility-temperature curves showing 200~350 ℃ Curie temperature in addition to 580 ℃ of magnetite,and also by awful smell during heating and dark heating products.Both the occurrence of authigenic iron sulphide and quick decrease of magnetic parameters near the surface clearly show that sediments from Core CSH1 have undergone early diagenesis.The featureless magnetic changes of the whole core except for three tephras mean that the post-depositonal alteration is so strong that most original signals have been destroyed.For the same reason,the organic matter in sediment and sulphate in pore water must have been consumed along with dissolution,precipitation of iron and manganese happening sequencially during the redox reaction series.Great caution must be taken when using these altered chemical parameters for the interpretation of climatic changes.     

Fine scale distribution of nitrous oxide in marine sediments

Vertical profiles of nitrous oxide and other inorganic nitrogen compounds in the sediments in Tokyo Bay and its vicinity were measured using the whole core squeezing method. Within the bay area, vertical profiles of nitrous oxide in the interstitial waters showed one or two distinctive peaks around the depth of 2–4 cm, which corresponded to the peaks of nitrite and nitrate. In situ formation of nitrous oxide through nitrification was suggested in those sediments, which was possibly activated by the presence of benthic animals. On the other hand, at the deep sediment off Tokyo Bay the profiles of nitrous oxide, nitrite and nitrate gave a monotonous single peak, indicating less bioturbated condition. Denitrification or dissimilatory nitrate reduction might be important for the formation of nitrous oxide peaks in the latter type of sediment.