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.     

Coprecipitation of zinc with silica in seawater and in distilled water

Dissolved silica can coprecipitate with zinc from seawater or distilled water that has been enriched with both elements. More than 2 ppm Si are necessary for the reaction to begin. The coprecipitation shows pH dependence. The addition of pulverized illite or natural sediment as suspended particulate material does not enhance the reaction in seawater. The organic material present in the nearshore seawater samples decreases the rate and extent of reaction, as indicated by comparisons of results of experiments using natural seawater with results obtained using UV-irradiated seawater. In unbuffered distilled water the reaction must compete with hydrolysis of zinc; however, reaction does occur, which indicates that the seawater matrix is not essential for the reaction. The coprecipitation can limit the concentration of zinc in seawater to less than the solubility concentration assumed for ZnCO₃ or Zn(OH)₂. The results suggest that a zinc silicate can precipitate directly from seawater or interstitial water as an authigenic mineral.     

Bioavailability of different chemical forms of dissolved silica can affect marine diatom growth

In this study, we demonstrate that dissolved silica obtained from mineral (crystalline quartz), biogenic amorphous (diatomaceous earth) and artificial amorphous sources (Aerosil) influence the growth rate of two marine diatoms, Chaetoceros sp. and Skeletonema marinoi. Diatoms were reared in four different experimental conditions in artificial seawater containing either dissolved silica previously obtained through dissolution of the mineral crystalline quartz or two amorphous substrates, biogenic diatomaceous earth or artificial Aerosil silica. Sodium metasilicate was used as control. When the silica in the different media reached concentrations higher than 107 μm , particles were eliminated by filtration and the diatom cells were inoculated. Maximum cell density, growth and silica assimilation rates of both species in the presence of dissolved silica derived from crystalline quartz and metasilicate were higher than those obtained with the other silica sources. These results are discussed against the background of previous geochemical studies that have shown that silica–water interactions are strictly dependent on the silica polymorphs involved and on the ionic composition of the solution. Our results demonstrate that the soluble silicon compounds generated in seawater by crystalline sources are highly bioavailable compared with those generated by biogenic and amorphous materials. These findings are potentially of considerable ecological importance and may contribute to clarifying anomalous spatial and temporal distributions of siliceous organisms with respect to the presence of lithogenic or biogenic silica sources in marine environments.     

环境因子对牙鲆精子运动能力的影响

于1997年5-6月,在山东荣成市石岛养殖场采用挤压法收集牙鲆亲鱼的精子,利用显微镜观察精子的活力,研究外界环境因子的变化对牙鲆精子运动能力的影响。结果表明,将蔗糖、NaCl、KCl、MgCl2、CaCl2等溶解于去离子水中,制成不同浓度即具有不同渗透压的溶液,不同渗透压的溶液对精子运动的诱导结果不同。EDTANa2溶液不能诱导精子运动。在人工海水中加入一定量的EDTANa2后,可使原先运动的精子静止;在该溶液中加入新的Ca2 后,将不再诱导原来受到EDTANa2抑制的精子。如用MgSO4代替溶液中的CaCl2,可诱导精子运动;而当用MgCl2代替溶液中的CaCl2,以及用CaCl2或NaCl代替MgSO4时,溶液即失去诱导精子运动的能力。在pH＝4.0-9、5的海水中,牙解精子均可正常运动。     

Experimental determination of the silica solubility and of the H4SiO 4 0 activity ratio in standard and desalinated seawater

The solubility of amorphous silica was studied in mixtures of riverine and marine waters simulating the water composition at the river-sea geochemical barrier. The value of the thermodynamical equilibrium constant was determined for the reaction of silicon solubility as K _r ⁰ = (1.71 ± 0.01) × 10^?3 at 22°C. A near-linear dependence was found for the activity ratio of the H₄SiO ₄ ⁰ and the salinity with the increase of this ratio from 1.00 in the riverine to 1.15 in the standard seawater.     

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.     

Factors controlling dissolved silica in coral reef surface water of Urasoko Bay, Ishigaki Island, Japan

From August 2006 to August 2007, the concentrations of dissolved silica (Si(OH)₄) were monitored in the surface water of Urasoko Bay and the mouth of the stream that runs into the bay. Urasoko Bay is located on the northern coast of Ishigaki Island, Okinawa, Japan, which is in a subtropical area of the North Pacific Ocean and is surrounded by a relatively poorly developed fringing reef. Added to these samples were freshwater from the upstream area and brackish water that exudes at the beach site, which were collected from April to June 2007. Rainwater samples were also collected during the study period. The concentration of Si(OH)₄ generally decreased from upstream to the bay site, and, on clear days, Si(OH)₄ data from all study sites (the bay, beach, stream mouth, and upstream) plotted against salinity fell on a single straight line. When the influence of rainwater was, the results were scattered below the straight line, which suggests dilution by rainwater with a much lower Si(OH)₄ concentration. These findings show that offshore seawater, rainwater, and upstream freshwater regulate the concentration of Si(OH)₄ in the surface water of Urasoko Bay.     

Release and uptake of dissolved silica in seawater by marine sediments

Natural marine sediments can release dissolved silica to silica-poor seawater and can remove silica from seawater enriched with dissolved silica. These are fast reactions, with sufficient reaction occurring within the first 48 hours to indicate clearly the direction of the reaction. The relative importance of these two processes varies with the ratio of clays to biogenic silica in the sediment. Both the release and the uptake reactions approach the interstitial water concentration of dissolved silica as an end point, which suggests that these reactions may influence this concentration. No change in sediment reactivity with respect to silica uptake or release reactions was observed with increasing depth in core for the three sediment cores investigated; this indicates that uptake sites are not saturated, and silica is available for dissolution for a long time after deposition.     

Hydrogen ion exchange on amorphous silica in seawater

The amount of hydrogen ion exchange on the surface of amorphous silica in seawater was measured as a function of pH at 2 and 25°C. Hydrogen ion exchange with the cations present in seawater is pH dependent and at 25°C the fraction of the surface in the cation form increases from 9% at pH 7 to 22% at pH 8. The exchange is temperature dependent and at 2°C and pH 8, 14% of the exchange sites are occupied by cations, as opposed to 22% of the exchange sites at 25°C. These results were used to calculate the buffer capacity of a model sediment consisting of pore water and amorphous silica. For a sediment of 70% porosity, pH 7.7, and 25°C, the buffer capacity of sediment plus pore water is 67 times the buffer capacity of pure seawater.     

表层海水硅同位素的分布特征及其影响因素

本文分析了采集自太平洋、印度洋和大西洋的表层海水溶解硅酸盐的δ30Si值,结果表明,太平洋表层海水的δ30Si值为0.45‰～2.91‰,平均值为(1.52±0.59)‰;印度洋表层海水的δ30Si值为0.98‰～2.30‰,平均值为(1.52±0.36)‰;大西洋表层海水的δ30Si值为0.90‰～2.23‰,其平均...     

Carbon dioxide in water and seawater: the solubility of a non-ideal gas

New measurements of the solubility of carbon dioxide in water and seawater confirm the accuracy of the measurements of Murray and Riley, as opposed to those of Li and Tsui. Corrections for non-ideal behavior in the gas phase and for dissociation in distilled water are required to calculate solubility coefficients from these sets of data. Equations for the solubilities of real gases are presented and discussed. Solubility coefficients for carbon dioxide in water and seawater are calculated for the data of Murray and Riley, and are fitted to equations in temperature and salinity of the form used previously to fit the solubilities of other gases.     

The role of sea ice formation in cycling of aluminium in northern Marguerite Bay,Antarctica

The use of dissolved Al as a tracer for oceanic water masses and atmospheric dust deposition of biologically important elements, such as iron, requires the quantitative assessment of its sources and sinks in seawater. Here, we address the relative importance of oceanic versus atmospheric inputs of Al, and the relationship with nutrient cycling, in a region of high biological productivity in coastal Antarctica. We investigate the concentrations of dissolved Al in seawater, sea ice, meteoric water and sediments collected from northern Marguerite Bay, off the West Antarctic Peninsula, from 2005 to 2006. Dissolved Al concentrations at 15 m water depth varied between 2 and 27 nM, showing a peak between two phytoplankton blooms. We find that, in this coastal setting, upwelling and incorporation of waters from below the surface mixed layer are responsible for this peak in dissolved Al as well as renewal of nutrients. This means that changes in the intensity and frequency of upwelling events may result in changes in biological production and carbon uptake. The waters below the mixed layer are most likely enriched in Al as a result of sea ice formation, either causing the injection of Al-rich brines or the resuspension of sediments and entrainment of pore fluids by brine cascades. Glacial, snow and sea ice melt contribute secondarily to the supply of Al to surface waters. Total particulate Al ranges from 93 to 2057 mg/g, and increases with meteoric water input towards the end of the summer, indicating glacial runoff is an important source of particulate Al. The (Al/Si)_opal of sediment core top material is considerably higher than water column opal collected by sediment traps, indicative of a diagenetic overprint and incorporation of Al at the sediment–water interface. Opal that remains buried in the sediment could represent a significant sink of Al from seawater.     

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.     

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.     

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.     

Mass solubility and aqueous activity coefficients of stable organic chemicals in the marine environment: polychlorinated biphenyls

The solubilities and aqueous activity coefficients of polychlorinated biphenyls were measured in distilled and saline water (30? salinity). Solubilities in distilled water ranged from 3 · 10^?4 g/l for dichlorobiphenyls to 6 · 10^?6 g/l for heptachlorobiphenyls; values in artificial seawater were about five times lower than the corresponding values in distilled water. In both cases, the solubilities decreased regularly with increasing degree of chlorination. The corresponding activity coefficients are inversely proportional to the chlorine content and range from 4 · 10⁷ to 4 · 10⁹ in distilled water and from 3 · 10⁸ to 1.5 · 10¹⁰ in saline water. Both the solubilities and activity coefficients agree well with those predicted from additivity considerations. The physical chemical aspects discussed in this paper can be applied in determining the solubility behavior of other stable organic molecules in the marine environment.     

Nitrogen, Oxygen and Argon Dissolved in the Northern North Pacific in Early Summer

Major gases dissolved in seawater were accurately determined with a shipboard gas chromatographic method. The standard deviations were 0.28, 0.34 and 0.36% for N₂, O₂ and Ar, respectively. The method was applied to water from the northwestern North Pacific Ocean collected in May to June 2000. We got 127 duplicate seawater samples from the surface 200 m layer at 11 stations. The O₂ concentrations obtained by this method agreed with those given by the Winkler method. All the seawater samples from the surface 200 m, especially those from the upper 30 m, were supersaturated with respect to atmospheric N₂ and Ar concentrations. In the topmost 30 m layer, the degrees of supersaturation in the inventory were 2.7–4.3% for N₂ (ΔN₂) and 1.7–2.6% for Ar (ΔAr), and their ratios, ΔN₂/ΔAr, ranged from 1.53 to 1.81. This supersaturation seems to be chiefly due to air bubbles injected into the water and dissolved due to the water pressure, because the N₂/Ar ratio of the air is around 2. The amounts of air bubbles dissolved in the upper 30 m water were relatively large, with mean value of 0.41 ml/kg or 18.4 μmol/kg. The ΔN₂, ΔAr and ΔN₂/ΔAr values were all positively well correlated with the wind velocities averaged for the last 24 hours prior to sampling, allowing the conclusion to be drawn that the weaker the wind velocity, the dissolved gas composition approaches in equilibrium with the air; while the stronger the wind velocity, it approaches in the air composition. This revised version was published online in July 2006 with corrections to the Cover Date.     

A review of the effect of salts on the solubility of organic compounds in seawater

The presence of electrolytes (salts) in aqueous solution modifies the solubility and related properties of organic compounds in water. Reported data for salting-out constants (Setschenow constants) which relate solubility to the salt concentration of aromatic and alkane hydrocarbons, and their chlorinated derivatives, and some organic acids have been compiled for 25 aqueous salt solutions at 20–25 °C. The salting-out sequences for various electrolytes are discussed and it is shown that the salting-out effect is greater for organic solutes with large molar volumes. A compilation of salting-out constants for NaCl solutions and seawater (natural or synthetic) with a variety of solutes, shows that the Setschenow constants are similar for natural or artificial seawater (at salinity of 30–35%.) and NaCl solutions (at 3.0–3.5% or 0.5 M). A simple correlation is suggested for estimating the Setschenow constants for a variety of organic solutes in seawater which typically yields a reduction in solubility by a factor of 1.36. The hydrophobicity of organic solutes is therefore increased by this factor, as is the air-water partition coefficient, implying an increased partitioning from aqueous solution into air, organic carbon and lipid phases. The effect must be quantified when comparing the behavior of organic contaminants in freshwater and marine conditions.     

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.     

Measurement of Noble Gas Solubility in Seawater Using a Quadrupole Mass Spectrometer

A quadrupole-based mass spectrometric system for determining noble gas (He, Ne, Ar, Kr and Xe) abundances in a liquid sample has been developed and applied to seawater equilibrated with the atmosphere at several temperatures. After known amounts of isotopic spikes (²²Ne, ³⁶Ar, ⁸⁶Kr and ¹²⁴Xe) were introduced into the preparation vacuum line, dissolved gases were extracted from seawater and well mixed with the spikes by ultrasonic vibration. Noble gases were purified using three-stage hot Ti getters and separated by two activated charcoal traps held at low temperature (liquid nitrogen and dry ice—ethanol). Noble gas abundances were measured by a relatively inexpensive quadrupole mass spectrometer based on the isotope dilution technique. Precisions obtained by repeated measurements for He, Ne, Ar, Kr and Xe are 1.5%, 0.4%, 0.4%, 0.4% and 0.6%, respectively. Noble gas abundances in air-saturated seawater at eight temperature steps (1.0°C, 5.5°C, 10.0°C, 14.4°C, 17.0°C, 21.3°C, 24.6°C, and 29.6°C) were measured using the analytical system. The overall variation of the abundances with temperature agrees well with those of NaCl brines reported in the literature. We propose here new constants to fit observed data to empirical equation of noble gas solubility in seawater with its temperature variation.