The monosaccharide spectra of natural waters

Monosaccharides were determined in waters and sediment pore waters from a wide variety of environments and locations. Desalting was performed by electrodialysis and concentrated extracts were analyzed by two forms of liquid chromatography. At least 12 sugars were identified. Glucose and fructose were the dominant monosaccharides in nearly all samples examined. Analyses of over 150 seawater and sediment pore water samples showed that fructose is highly significantly correlated (>0.99) with glucose concentrations. Laboratory kinetic experiments on the epimerization reaction, glucose ? fructose, in sterilized natural seawater in the dark, yielded a forward rate constant, k₁, of 1.2 × 10^?5 h^?1 at 25°C and 1.6 × 10^?7 h^?1 at 2°C. The approximate time required to attain equilibrium at 25°C was 1.1 y and at 2°C, 15.4 y; the measured equilibrium constant was in the range 0.3–0.4. The actual ratio of fructose to glucose in natural water samples was usually in the range 1.0–1.4/l, independent of the total monosaccharide concentrations, which varied in the samples by a factor of ～100. Several possible explanations for the apparent discrepancy in the determined and found ratios are discussed: the presence of universal, as yet, undiscovered major biological sources for fructose in marine environments; preferential utilization of glucose; preferential incorporation of fructose into or onto inorganic colloids; and preferential formation of fructose-transition metal ion associations.     

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.     

The activity of NaCl in seawater of 10–40‰ salinity and 5–25°C at 1 atmosphere

The activity of NaCl in artificial seawater was measured potentiometrically with Na⁺- and Cl^? -sensitive electrodes. The salinity of the solutions, examined at 25°C, ranged from 10–40‰ salinity. The change in the activity from 5–25°C was measured at 35‰ salinity.The molal mean activity coefficient of NaCl in 35‰ seawater at 25°C is 0.667. The relative partial molal enthalpy of NaCl in 35‰ seawater is ?130 ±50 cal mol^?1. This value is in good agreement with the value measured in pure 0.72 M NaCl.The results were compared with activity coefficients predicted by a specific interaction model and by an ion association model. Good agreement was found in both cases.     

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.     

锯缘青蟹碱性磷酸酶分离纯化及部分理化性质研究

于１９９５年２月在厦门海域采集锯缘青蟹,取其内脏经正丁醇抽提,硫酸铵分级分离ＤＥＡＥ－５２离子交换柱层析及ＳｅｐｈａｄｅｘＧ－２００凝胶过滤柱层析纯化,获得碱性磷酸酶 制剂,以快速 蛋白液相色谱及聚丙烯酰胺凝胶电泳检验萁 纯度,获得单一蛋白纯的酶 制剂。     

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.     

The fluorine complexation degree in seawater

Ionometric measurements of the complexation degree of fluorides in seawater of 5–35‰ salinity at 25°C were carried out using two procedures for the standardization of the measuring electrochemical circuits. It was shown that, if we determine the degree of the fluorine complexation in seawater using the measured values of the total coefficients of the activity, the fraction of free ions is much dependent on the value used of the activity coefficient of the free ions calculated by means of one of the versions of either the second or third approximation of the Debye-Huckel electrostatic theory of strong electrolyte solutions. With the more correct measurement of the fluorine complexation degree in seawater on the basis of the comparison of the EMF values in pure KCl-KF solutions and in mixtures of these solutions and seawater at equal ionic power and fluoride concentrations, a close correlation was revealed for the free ion fraction in three series of experiments at fluorine contents of 0.2, 0.3, and 0.4 mM (the concentration of the fluorine in seawater of 35‰ salinity amounts to 0.421 ± 0.014 mM.)     

Two-stage influences of hydrothermal fluids on pumice near the Iheya North hydrothermal field,Okinawa Trough

Hydrothermal precipitates and hydrothermal alteration products could record important information about temporal variations of seafloor hydrothermal systems. Geochemistry, mineralogy, and microscopic features of three pumice samples (T3-1, T3-2, and T3-3) near the Iheya North hydrothermal field were analyzed in this article. The results show that T3-3 sample has undergone at least two-stage influences by hydrothermal fluids. In the first stage, pure amorphous silica from hydrothermal fluid precipitated in the vesicles of all three T3 samples as a result of conductive cooling and fluid–seawater mixing. The precipitation temperatures according to oxygen isotope thermometer are approximately 13–21°C. In the second stage, T3-3 pumice underwent low-temperature hydrothermal alteration, during which the amorphous silica precipitates were redissolved, together resulting in losses of FeO and SiO₂ and gains of MgO, Pb, Zn, and Cu. Furthermore, ferruginous filamentous silica, which might be related to activities of Fe-oxidizing bacteria, was formed in the altered pumice. The transformation from pure amorphous silica precipitation to redissolution of the silica in T3-3 pumice might indicate a rise of temperature and/or decrease in silica concentrations in hydrothermal fluids, implying a changing hydrothermal environment.     

Dissociation of hydrogen sulphide in seawater and comparison of pH scales

The protonization constant of HS^? (K₁₂) has been determined potentiometrically (glass electrode) at atmospheric pressure in synthetic seawater in the salinity range 2.5–40‰ at 5 and 25°C and in NaCl solutions in the formal ionic strength of 0.1–0.8 M at 5 and 25°C. The difference between synthetic seawater and an NaCl solution with the same formal ionic strength can be explained in terms of the complexation of H⁺ by sulphate in seawater. These results can be used to compare the pH scales suggested by Hansson (1973c) and Bates (1975). Furthermore, comparison between the present values of K₁₂ and those of Goldhaber and Kaplan (1975) makes it possible to compare the conventional pH scale with Hansson's titration pH scale. The conditional protonization constant of HS^? in seawater of different salinities can be used to modify the Gran plots (Hansson and Jagner, 1973) for alkalinity measurements in anoxic seawater. Ion-pair formation between HS^? and Mg²⁺ or Ca²⁺ seems to be very weak.     

Prediction of the heat capacities of seawater and other multicomponent solutions from the Tammann—Tait—Gibson model

Equations are given for estimating the heat capacity of binary and multicomponent electrolyte solutions on the basis of the TTG model. These equations are used to calculate the heat capacity of seawater solutions up to a concentration of 45‰ for the temperature range 0–30°C and up to a concentration of 160‰ at 20°C. The deviations from the experimental values are less than the uncertainties due to smoothing and experimental errors. The results suggest that the heat capacity of other multicomponent solutions, including non-standard seawater solutions, could be predicted to within 0.1% or better, up to an ionic strength of about 3 M.     

The action of heavy metals on the gametes of the marine mussel, Mytilus edulis (L.)-II. Uptake of copper and zinc and their effect on respiration in the sperm and unfertilized egg

The addition of stock copper and zinc nitrate solutions to filtered seawater (pH 7·91) resulted in a large pH shift which was more pronounced with copper. The pH shift was minimized by increasing the buffering capacity of seawater using 10 mm Tris-Tes pH 7·91. Subsequent experimentation was carried out in both unbuffered and buffered seawater.In unbuffered seawater, both copper and zinc had a pronounced inhibitory effect on Mytilus edulis sperm respiration with 50% inhibition occurring at 0.65 mm (41·3 ppm) copper and 1.0 mm (65·4 ppm) zinc. Egg respiration was also inhibited by copper with 50% inhibition occurring at 0.9 mm (57·2 ppm) whereas zinc inhibited egg respiration by only 30% at 1·5 mM (98·1 ppm).In buffered seawater, both copper and zinc produced an inhibitory effect on sperm respiration. However, with copper the inhibition was much reduced whereas zinc had tthe same inhibitory effect as in unbuffered seawater. In contrast to unbuffered seawater, egg respiration was stimulated by copper but zinc produced a comparable respiratory inhibition. The uptake of both copper and zinc in sperm and egg in buffered seawater increased with increasing metal concentration. Metal ion uptake, when expressed as ng ions μl cell volume^?1, was approximately 3-fold greater in the sperm than in the eggs and in both cases zinc uptake exceeded copper uptake.At a seawater pH of < 7·5, in the absence of copper or zinc, the respiration of both egg and sperm was inhibited. The maximum levels of inhibition at pH 5·4 were 15% and 30% for sperm and egg, respectively.The differing actions of copper on egg respiration in buffered and unbuffered seawater appear to be due to enhanced copper uptake in unbuffered seawater.     

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.     

The diffusion coefficient of dissolved silica revisited

The diffusion coefficient of dissolved silica was determined for two different salinities, 36 and 0, at temperatures ranging from 2 °C to 30 °C and at an average pH value of 8.1. Our results show limited influence of salinity and a variation by a factor of 2 to 3 of the silica diffusion coefficient within the temperature range considered in this study. The values obtained at 25 °C are in agreement with previous work carried out at room temperature for seawater and freshwater. The dependency on temperature and viscosity of the diffusion coefficient agrees well with the Einstein–Stokes equation. The composition of the solvent appears to be an important factor because it modifies the viscosity and allows for the complexation of the dissolved silica with less mobile ions, while its pH controls the dissolved silica speciation. In seawater, the higher viscosity and the presence of dissociated and polymeric species result in a decrease of the diffusion coefficient compared to freshwater systems.     

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.     

长江口邻近海域沉积物和间隙水中硅的研究

以2011年6月和8月在长江口邻近海域采集的沉积物和间隙水样品为研究对象,讨论了沉积物中生物硅（BSi）和间隙水中溶解硅（DSi）的分布情况和影响因素,并初步探讨了生物硅的循环和保存。结果表明,表层沉积物中BSi的含量较低,且均小于1%。柱状沉积物中BSi的含量范围为0.34%~0.52%。C3、D1站位柱状沉积物中BSi的记录主要是由早期成岩过程控制,33#站位的分布特征主要是由水动力等变化控制。沉积物间隙水中DSi的浓度范围为101.6~263.9 μmol/L,低于纯BSi的溶解度;间隙水的pH值越大,沉积物的含水率越低,还原性越强,间隙水中DSi的含量越高。3站位生物硅的埋藏效率均较高,表明长江口邻近海域是潜在的硅的汇。沉积通量的分布与沉积速率和埋藏效率的分布一致,均有近岸高于远海的趋势。     

(Na,K)-phillipsite: Its stability conditions and geochemical role in the deep sea

Phillipsite occurs in the deep sea in areas of very slow sedimentation and as the final alteration product of basalt, suggesting that it is thermodynamically stable. The thermodynamic data for gibbsite, kaolinite, K-feldspar, Na-feldspar, analcime and H₄ SiO₄ (aq), as well as the activities of seawater constituents are reasonably well known. These values and estimated entropies for Na- and K-phillipsites permit an estimate of the free energy of formation (at 25°C) for Na-phillipsite (5337.6 ± 6.7 kcal/mole) and for K-phillipsite (5382.4 ± 1.9 kcal/mole). The decomposition of phillipsite to analcime at 250°C yields the same result, suggesting that phillipsite is indeed a stable mineral.Phillipsite does not regulate the concentration of Na⁺ and K⁺ in seawater, but probably affects the pH of bottom waters and the composition of interstitial waters. No indications exist of “frozen in” equilibria from hydrothermal reactions at 100–200°C as could be expected by submarine volcanism.     

海南岛新村湾营养负荷对海菖蒲的影响研究

对海南岛新村湾海草床的优势种——海菖蒲(Enhalus acoroides)的茎枝特征、茎枝密度、生物量和不同组织营养素含量进行了研究,并探讨了海水和沉积物间隙水营养负荷对其的影响。结果表明,(1)海菖蒲的茎枝特征(叶长、宽和枝重)、茎枝密度和地上生物量存在显著的空间差异,这些因子与海水和沉积物间隙水DIN含量呈负相关;(2)海菖蒲TN、TP质量分数随着样区的变化而产生显著差异,海菖蒲TN质量分数与其所在样区海水和沉积物间隙水DIN浓度呈显著正相关;(3)随着水体N负荷的增加,海菖蒲叶单位面积附着藻类生物量显著增加。本次研究的结果表明,网箱养殖引起的营养负荷是导致海草衰亡的潜在原因之一,引起了新村湾网箱养殖区海草床的退化。     

海水为溶剂合成纳米粉煤灰沸石及其性能表征

以海水为溶剂,采用熔融法合成了纳米粉煤灰沸石。粉煤灰与NaOH的质量比为1:1.2,熔融温度550℃,熟料质量与海水固液的体积比为1:5(g/mL),晶化温度100℃,晶化时间6h。通过仪器分析和化学方法,对产物的结构、形貌、性能进行表征。同时,研究了产物的矿物组成、形貌、比表面积、阳离子交换量及化学组成。结果表明:产物为NaX型沸石和羟基方钠石的复合型沸石,海水晶化粉煤灰通过碱熔融法得到沸石质量优于传统水热法。合成沸石的性能和各项应用指标表明,所合成的沸石具有良好的实际应用价值。     

Environmental tolerances of the beach-hopper Orchestia gammarellus (Pallas) (Crustacea:Amphipoda)

Orchestia gammarellus (Pallas) will tolerate temperatures from 0°C to c. 30°C but dies in < 1 h at 35°C. Both small and large animals survive > 96 h in water (aerated) between 1 and 60%(.) salinity. In distilled water and 100%(.) brine death occurred after 8–24 h. In fully saline water, pH reduction to c. 3·3 is tolerated. Highly alkaline (pH 11–13) conditions in low salinity media are rapidly fatal. Ammonium concentrations (in fully saline water) some five orders of magnitude higher than normal for seawater are tolerated, reflecting the enhanced ammonium concentration encountered in rotting weed beds. Cl⁻ ion concentration equivalent to that in normal seawater will not support O. gammarellus in the absence of Na⁺ ions. High NO₃⁻ concentrations (> 100 mg NO₃⁻ litre⁻¹) are fatal in < 24 h. A large range of NaCl concentrations is tolerated (one to two orders of magnitude dilution) by immersed animals. Animals will live longer in air, however, when fed low Na⁺ food than when immersed in seawater diluted to an equivalent ion strength. Ca²⁺ and K⁺ ions cannot substitute for Na⁺. Orchestia gammarellus will, however, tolerate wide variations in the ratio of Na⁺:K⁺ ions (i.e to a shift from 30:1 to 0·3.1) in hypo-osmotic media. At 10°C it will survive c. 5 h of anoxia. It will penetrate into strongly reducing conditions (− 318 mV) even with access to better oxygenated conditions. In nature, behavioural avoidance probably ensures that O. gammarellus does not encounter many of these parameters at acutely limiting values. That this species is so tolerant, however, bears on the evolutionary adaptability of talitrid amphipods to non-marine conditions. Desiccation sensitivity and Na⁺ ion dependency are the species' most important barriers to life on land.     

环境因子对溶藻弧菌(Vibrio alginolyticus)粘附大黄鱼(Pseudosciaena crocea)表皮粘液影响的研究

采用3H-TdR同位素示踪方法研究了环境因子对溶藻弧菌对大黄鱼表皮粘液粘附作用的影响。试验结果表明,溶藻弧菌能很好地粘附于大黄鱼表皮粘液,其粘附量在菌浓度不超过6.52×108cfu/ml情况下随菌浓度的升高而升高;粘附量在25℃下孵育180min趋于饱和,在180min以内与孵育时间呈正相关关系;粘附作用在温度25—30℃、pH值偏酸、盐度35条件下较强;在无Na (盐度为0)时,无粘附作用;Ca2 能显著加强溶藻弧菌的粘附作用,而Mg2 作用不明显。这些结果表明,溶藻弧菌对大黄鱼表皮粘液有较强的粘附作用,其粘附作用受温度、盐度、pH值等环境因子的影响。