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.     

Spectrophotometric and iodometric methods for the detection of hydrogen sulfide in the Black Sea: Comparison of the results of analysis

We discuss the results of analysis of published data and field and laboratory investigations aimed at the solution of the problem of comparabilityof the results of detection of hydrogen sulfide in the Black Sea by spectrophotometric and iodometric methods. We show that the reproducibility of the results of spectrophotometric analysis is higher than hat of the iodometric method only in the case where the content of sulfide in a sample is less than 10–30 μMl⁻¹. When larger concentrations are involved, the traditional iodometric analysis proves to be the most precise and reliable method for the detection of hydrogen sulfide in the Black-Sea waters. Translated by Peter V. Malyshev and Dmitry V. Malyshev     

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.     

山东半岛南部近岸全新世泥质区表层沉积物

泥质区沉积记录是全新世海洋环境演变的重要信息载体。中国近海沿岸发育着若干小型泥质沉积体,比较明确的有南海西部近海的泥质区,但尚未进行研究。通过对山东半岛南部近岸海域采集的浅地层剖面资料精细解释后发现,在该区近岸海域存在一个小型泥质沉积区,主要分布在青岛崂山头以北至乳山口附近的近岸海域,整体上平行海岸线呈条带状分布,由近岸向海逐渐变薄,等厚深度分布平行于岸线,沉积中心位于鳌山湾海域,沉积中心最厚可达22.5 m。AMS¹⁴C测年结果表明,该泥质区形成于全新世。本文利用在泥质区采集的表层沉积物的粒度、黏土矿物、碎屑矿物、地球化学元素等分析测试结果,对比研究区周边主要入海中小河流物质成分和黄河物质成分,探讨了山东半岛南部近岸海域泥质沉积区的沉积特征和物源情况。结果表明,该泥质区的形成是黄河与周边入海河流共同作用的结果。     

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.     

Evaluation of the budget for silicic acid in Cascadia Basin deep water

Between 2 and 3 km depth, North Pacific deep waters contain a plume of water with high silicic acid concentrations. The plume extends outward from Cascadia Basin (the Washington Margin), where waters can contain in excess of 200 μM off the coast of Oregon and Washington. To identify the source of the high Si concentrations in Cascadia Basin, we measured silicic acid and germanium concentrations in deep waters, and their fluxes from sediments using incubated cores. The mean flux of silicic acid into bottom waters is 0.81±0.05 mmol/m²-day, and the Ge/Si ratio of this flux is 0.7±0.1 μmol/mol. A box model, incorporating these results with hydrographic data, indicates that (1) no more than 5% of the silicic acid added to Basin deep waters can have a hydrothermal source (either hot or warm seeps), and (2) the total input of silicic acid to Basin deep waters is 0.06±0.02 Tmol/y. This input is nearly all from remineralized biogenic debris and should contribute about 0.5% of the 14 Tmol/y that are estimated to be necessary to maintain the North Pacific plume.     

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.     

生物硅的生成与溶解速率的研究——以胶州湾为例

营养盐的含量与元素间的比值直接控制着生态系统的生产力和浮游植物的种类组成.近岸海区硅藻可占初级生产的75%,但其生长速率受Si(OH)4含量的限制.胶州湾浮游植物的物种组成以硅藻为主.用29Si同位素示踪培养方法,采用四极杆质谱同位素稀释技术同时测定了胶州湾硅的生成速率与溶解速率.胶州湾生物硅(BSi)的含量为0.90～1.14 μmol/L,岩成硅(LSi)的含量为46.3～52.3 μmol/L.岩成硅是生物硅的约50倍.胶州湾BSi的含量处于世界近岸海区的低值范围,LSi的含量与LSi/BSi的比值均处于高值区.BSi的绝对生成速率为4～6 nmol/L*d,比生成速率为6～17/d.BSi的绝对溶解速率为<9 nmol/d,比溶解速率为<23/d.进一步开展胶州湾不同季节水体中BSi的生成速率与溶解速率的研究,是深入认识海湾浮游植物生长限制及其资源可持续利用的基础.     

Hydrological and chemical characteristics of the submarine freshwater source near Cape Aiya

The paper examines the results of two hydrological/chemical investigations of a submarine freshwater source in the vicinity of Cape Aiya. The supposition has been confirmed that some typical chemical indices, specifically, silicic acid content, may be used to reveal such sources. The acquired data point out that the freshwater source is steady functioning, which implies that subterranean freshwater reserves in this area are substantial. Translated by Vladimir A. Puchkin.     

Observations of the submarine discharge of underground waters (South Coast of the Crimea)

We analyze the results of the field hydrological and hydrochemical observations of the submarine discharge of underground waters near the cape Aiya (South Coast of the Crimea) obtained with the help of the measuring equipment developed at the Marine Hydrophysical Institute of the Ukrainian National Academy of Sciences. We measure the current velocities, temperature, salinity, and the contents of silicic acid and phosphates inside a karst cavity and in the test region around the cavity. We present three estimates of the output of submarine discharge and compute the amounts of silicic acid and phosphates carried out into the sea by the submarine source.     

On the rates of sulfide formation and oxidation in the Black Sea during the cold season

The rate of the hydrogen sulfide oxidation in the redox zone of the Black Sea and the rate of the hydrogen sulfide formation due to bacterial sulfate reduction in the upper layer of the anaerobic waters were measured during the period of February–April 1991. The measurements were made using a sulfur radioisotope under conditions close to those in situ. It was established that the hydrogen sulfide is oxidized in the layer where oxygen and hydrogen sulfide coexist, which is under the upper boundary of the hydrogen sulfide layer. The maximum rate of the hydrogen sulfide oxidation was recorded within the limits of the density values δτ of 16.20–16.30, while varying in the layer from 2 to 4.5 μM/day. The average rate of the hydrogen sulfide oxidation was 1.5–3 times higher than that during the warm season. Sulfide formation was not observed at most of the stations in the examined lower portion of the pycnocline layer (140 to 400 m depths). Noticeable sulfate reduction was detected only at one station on the northwestern shelf. A probable reason for such noticeable changes in the sulfur dynamics in the water mass of the Black Sea may be the intensified hydrodynamics in the upper layers of the water mass during the cold season. The data suggesting that hydrogen sulfide oxidation proceeds under the hydrogen sulfide boundary indicate the absence of the so called “suboxic zone” in this basin.     

Short-term and interannual variability of redox-sensitive chemical parameters in hypoxic/anoxic bottom waters of the Chesapeake Bay

A combination of CTD casts, discrete bottle sampling and in situ voltammetric microelectrode profiling was used to examine changing redox conditions in the water column at a single station south of the Bay Bridge in the upper Chesapeake Bay in late July/early August, 2002–2005. Short-term (2–4 h) fluctuations in the oxic/suboxic/anoxic interface were documented using in situ voltammetric solid-state electrodes. Profiles of dissolved oxygen and sulfide revealed tidally-driven vertical fluctuations of several meters in the depth and thickness of the suboxic zone. Bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ also varied over the tidal cycle by approximately an order of magnitude. These data indicate that redox species concentrations at this site varied more due to physical processes than biogeochemical processes. Based on analysis of ADCP data, tidal currents at this station were strongly polarized, with the principal axis of tidal currents aligned with the mainstem channel. Together with the chemical data, the ADCP analysis suggests tidal flushing of anoxic bottom waters with suboxic water from north of the site. The present study is thus unique because while most previous studies have focused on processes across relatively stable redox interfaces, our data clearly demonstrate the influence of rapidly changing physical mixing processes on water column redox chemistry.Also noted during the study were interannual differences in maximum bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺. In 2003, for example, heavy spring rains resulted in severe hypoxia/anoxia in June and early July. While reported storm-induced mixing in late July/early August 2003 partially alleviated the low-oxygen conditions, bottom water concentrations of sulfide, Mn²⁺ and Fe²⁺ were still much higher than in the previous year. The latter implies that the response time of the microbial community inhabiting the suboxic/anoxic bottom waters to changing redox conditions is slow compared to the time scale of episodic mixing events. Bottom water concentrations of the redox-sensitive chemical species should thus be useful as a tracer to infer prior hypoxic/anoxic conditions not apparent from ambient oxygen levels at the time of sampling.     

The key features of the bottom sediment composition in the anoxic Lake Mogil’noe

In the summer 2006, integrated geological, geochemical, hydrological, and hydrochemical studies were performed on the relict anoxic Lake Mogil’noe (down to 16 m depths) located on Kil’din Island in the Barents Sea. The chemical and grain-size composition of the bottom sediments were compared for the lake (a permanently anoxic basin) and the Baltic Sea Deeps (periodically anoxic basins). The vertical location of the hydrogen sulfide layer boundary in the lake (9–11 m depths) was practically the same from 1974 up to now. The concentrations of suspended particulate matter in the lake in June and July 2006 appeared to be close to its summer concentrations in the seawaters of the open part of the Baltic Sea. The mud from Lake Mogil’noe compared to those of the Baltic Sea Deeps are characterized by fluid and flake consistency and by pronounced admixtures of sandy and silty fractions probably of eolic origin. The lacustrine mud contain much plant remains; iron sulfides and vivanite were also found in ooze. The concentrations of 22 elements determined in the lacustrine bottom sediments were of the same levels as those found here 33 years ago. The concentrations also appeared to be close to those in the corresponding grain-size types of the bottom sediments in the Baltic Sea. The low C_org/N value (5% on average) in the mud of Mogil’noe Lake compared to the values for the mud of the Baltic Sea Deeps (10% on average) points to the considerable planktogenic component in the organic matter composition of the lacustrine mud. No indications were reveled for anthropogenic contaminations of the lacustrine bottom sediments with toxic metals.     

Evidence of microphytobenthic roles on coastal shallow water of the Seto Inland Sea,Japan

This study describes the temporal variation of microphytobenthic biomass and its controlling factors, as well as the impact of microphytobenthic activities on coastal shallow sediment in the eastern Seto Inland Sea, Japan. The chlorophyll a (Chl a), phaeopigments and sedimentary biophilic element (C, N, P and Si) contents in surface sediments, as well as nutrient concentrations at the sediment-water interface (overlying water and pore water) were observed monthly during November 2003 to May 2005 at one site in Shido Bay (water depth ca. 7 m) and at one site in Harima-Nada (35 m). No correlation was observed between the sedimentary biophilic elements and other parameters. The maximum chlorophyll a content of 48.2 μg g^–1 was found in surface sediments under the photon flux reaching the seafloor of 537 μmol photon m^–2 s^–1 during the winter period when water transparency was the highest at station S (Shido Bay). Our results suggest that higher chlorophyll a content in surface sediment was due to the fresh microphytobenthic biomass (mainly benthic diatom). We also found a significant negative correlation between Chl a and inorganic nutrients in pore water during the low temperature period, especially silicic acid. This result suggests that the silicic acid was assimilated largely during the increase of microphytobenthic biomass in surface sediment. This study suggests that the microphytobenthic roles may have a great effect on nutrient budgets during the large supply of irradiance (winter periods) for their photosynthetic growth in shallow coastal waters.     

Phytoplankton pigment distribution in relation to silicic acid, iron and the physical structure across the Antarctic Polar Front, 170°W, during austral summer

In order to study the factors controlling the phytoplankton distribution across the Antarctic Polar Frontal Region (PFR), surface pigment samples were collected during austral summer (January/February 1998) near 170°W. Both the Polar Front (PF) and the Southern Antarctic Circumpolar Current Front (SACCF) were regions of enhanced accumulation of phytoplankton pigments. The mesoscale survey across the PF revealed two distinct phytoplankton assemblages on either side of the front. The phytoplankton community was dominated by diatoms south of the PF and by nanoflagellates (primarily by prymnesiophytes) to the north. Surprisingly, chlorophyll a concentrations did not correlate with mixed-layer depths. However, an increase of the dominance of diatoms over prymnesiophytes was observed with decreasing mixed-layer depths. Despite this relationship, we conclude that the average light availability in the mixed layer was not an important factor influencing the shift in phytoplankton composition across the PF. Although no correlation was found between the surface distribution of the major phytoplankton taxa and dissolved iron or silicic acid concentrations, the location of the strongest vertical gradient in silicic acid and iron concentration coincides with the maximum abundance of diatoms. We conclude that the difference in taxonomic composition is a result of increased silicic acid and iron flux to the upper mixed layer as a result of the increased vertical gradient of these key nutrients south of the front.     

The direct titration of water-soluble sulfide in estuarine muds of Montsweag Bay,Maine

The use of an antioxidant buffer allows potentiometric titrations of dissolved sulfide, providing cadmium or lead rather than silver is used as titrant. The method yields a measure of water-soluble as contrasted with acid-soluble sulfide.The vertical distribution of water-soluble sulfide has been determined in eight sediment cores from Montsweag Bay, Maine. Concentration profiles are characterized by one or two distinct maxima near the surface at depths ranging from 30 cm in areas of slow sedimentation, to 120 cm in areas of rapid sediment accumulation. Concentrations of sulfide at the maxima range from 1 to 8 moles sulfur per cubic meter of in situ mud, or from 0.6 to 4. millimoles sulfur per liter of pore water. The sulfide-rich upper portion of the mud is poorly consolidated and custardy in texture. As they are likely to be resuspended during proposed channel modifications, it is appropriate to inquire as to the oxidative demand of these sediments arising from their hydrogen sulfide content alone. Using a conservative estimated mean of 5 moles sulfide/m³-mud, it is shown that a mixing ratio of less than 30 volumes of oxygen saturated seawater per volume of mud will render the water anoxic.     

Dissolved aluminium in the Weddell-Scotia Confluence and effect of Al on the dissolution kinetics of biogenic silica

In the Scotia and Weddell Seas the concentration of dissolved Al was 1–1.5 nM in ice-free surface waters, up to 3 nM in ice-covered waters and about 2.6 nM in bottom waters. The solubility and the dissolution rate of diatomaceous silica, obtained from net samples and from incubations in the presence or absence of dissolved Al, were inversely related to solid-phase Al/Si ratios. At in situ temperatures, dissolution rates for Antarctic diatoms are higher than those for diatoms from temperate regions. Effects on distribution patterns of silicic acid in the Weddell Sea are discussed.     

Silver in the subarctic northeast Pacific Ocean: Explaining the basin scale distribution of silver

Five vertical profiles of silver (Ag) in the subarctic northeast Pacific are presented. Dissolved (< 0.2 μm) Ag concentrations within the surface mixed layer range from 6–25 pM, with the highest observed values at the most coastal site. Elevated Ag concentrations at this station are most likely attributable to the estuarine circulation in the Juan de Fuca Strait. One open-ocean station (P20) exhibited a strong surface Ag maximum. The station was located at the edge of a Haida eddy which raises the possibility that such eddies transport Ag seaward from the coastal zone. Ag concentrations in the deep waters ranged from 60–80 pM. These measurements are consistent with other recent Ag data collected in the Pacific. Ag profiles throughout the Pacific Ocean yield a strong positive correlation between Ag concentration and dissolved silicic acid concentration. However, Ag is depleted relative to silicic acid at intermediate depths where dissolved O₂ concentrations are low, implying a possible removal of Ag from oxygen-depleted waters by scavenging and/or precipitation.     

几种褐藻多糖硫酸酯的提取、成分分析及抗氧化活性研究

褐藻多糖硫酸酯是一种含有硫酸基的水溶性杂聚糖,其化学组成对抗氧化活性有较大的影响。本文对三种褐藻来源的褐藻多糖硫酸酯及其降解产物化学组成和抗氧化活性进行了研究,阐明了不同来源褐藻多糖硫酸酯体外抗氧化活性的构效关系。实验结果表明:1)分子量对抗氧化活性有较大影响,但是对不同褐藻来源的褐藻多糖硫酸酯的影响趋势并不一致。2)岩藻糖、硫酸基和糖醛酸含量对清除超氧阴离子自由基的影响与分子量有一定的关系。对于低分子量样品,岩藻糖和硫酸基含量与抗氧化活性成正相关。3)岩藻糖和硫酸根的比值对羟基自由基的清除能力有一定影响,比值越大,羟基自由基的清除能力越强。分子量、岩藻糖、硫酸基和糖醛酸的含量对褐藻多糖硫酸酯的抗氧化活性的影响依次减小。本研究为褐藻多糖硫酸酯在抗氧化剂保健品和功能食品中的应用提供了基础数据,也为裙带菜、羊栖菜和铜藻的高值化利用提供了理论依据。