The rate of oxidation of ferrous iron in seawater and the partition of elements between iron oxides and seawater

At the Minamichita Beach Land (Mihama-cho, Aichi, Japan), seawater is pumped up from underground and is supplied to aquaria. The underground seawater containsca. 2 ppm of Fe (II), 0.1 ppm of Mn (II) and a little dissolved oxygen. Iron oxide is formed in the seawater when aerated. The oxidation rate of Fe (II) was measured to be 1.4×10¹⁴ mol^–3 l ³ min^–1, which is comparable to the lowest values in the literature. The slow rate of Fe (II) oxidation obtained here can be attributed to the presence of organically bound iron in the seawater. The distribution coefficient of cations between seawater and iron oxide phase was in the order of Cu>Ni>Co>Cd>Mn, which is consistent with that predicted from their hydrolysis constants. The adsorption affinity sequence of oxyanions was phosphate >vanadate> molybdate. The difference in phosphate from the prediction of the adsorption theory was attributed to the formation of ferriphosphate on the oxide surface. On the basis of these data, the limitation and usefulness in the application of the distribution coefficients to marine environments were discussed.     

The partition of minor transition metals between manganese oxides and seawater

The behavior of transition metals (Co, Ni, Cu and Zn) on precipitation of manganese oxides from seawater pumped up from a well at the site of the Marine Science Museum, Tokai University, and collected from several tanks along the water supply system to an aquarium was investigated. The distribution coefficients of cobalt and nickel between manganese oxides and seawater were different at different sampling points along the water supply system. At sampling points with high rates of manganese oxide precipitation, the distribution coefficients were about one order of magnitude smaller than those at the points with low precipitation rates, while there were no remarkable differences in the distribution coefficients of copper and zinc among the sampling points. The distribution coefficients of minor transition metals, with the exception of copper, observed at the points with low precipitation rates were comparable to those measured experimentally using manganese dioxides.     

The role of water mass dynamics in controlling bacterial abundance and production in the middle Adriatic Sea

Month-to-month fluctuations in the abundance of bacteria and heterotrophic nanoflagellates (HNF) and bacterial production, as well as various chemical (nutrients, oxygen) and physical (salinity, temperature) parameters were analysed at a station located in the open middle Adriatic Sea during one decade (1997-2006). Being influenced by both coastal waters and open Adriatic circulation in the surface layer, and by the deep Adriatic water masses in the deep layers (100 m), this station is quite suitable for detecting the environmental changes occurring in the open Adriatic Sea with respect to the circulation of its water masses and their long-term changes and anomalies. Multivariate methods were used to identify seasonal and inter-annual changes of the investigated parameters, associating observed changes to the changes in Adriatic water masses and circulation regimes. The analyses showed that bacterial abundance and production were controlled by different water mass dynamics during 1997-2001 compared to 2002-2006 period, particularly noticeable in different seasonal patterns of biological parameters. The interplay between North Adriatic Dense Water (NAdDW) and Levantine Intermediate Water (LIW) resulted in a change in the available nutrients (NAdDW is poor in orthophosphates), and as a consequence different bacterial abundance and production. A few periods were examined in detail, such as 2004, when LIW inflow was particularly strong and was accompanied by an increase of bacterial and HNF abundances, as well as of bacterial production.     

Environmental influences on the long-term fluctuations in the abundance of gadoid species during estuarine residence

Samples taken regularly from the intake screens of West Thurrock power station between January 1977 and November 1992 were used to examine physico-chemical factors influencing the abundance of Gadidae species (poor cod, Trisopterus minutus; pouting, Trisopterus luscus; and whiting, Merlanguis merlangus) in the Thames estuary. Most sampled fish were age-0 and followed a dominant pattern of seasonal occurrence. Multiple regression was used to model variations in sample abundance in relation to fluctuations in estuarine environmental variables, interactions between environmental variables and seasonal factors. Model results were used to examine hypotheses concerning the relative importance of temperature, salinity, prey availability and seasonal factors as determinants of estuarine gadoid abundance. Temperature was the most important determinant of species sample abundance and negatively related to sample abundance in all cases. Salinity was a major determinant of pouting abundance and a minor determinant of whiting abundance, with seasonal factors significantly influencing the occurrence of all species. Crangon abundance was a minor determinant of whiting and poor cod abundance. Interactions between environmental variables played a minor role in determining the sample abundance of a single species, pouting. Determinants of Gadidae species abundances in the Thames appear to be a complex mix of seasonal and environmental influences, with seasonal influences determining the dominant cyclical pattern and influences of temperature having the greatest effects on short-term variations in the pattern.     

Use of an optical oxygen sensor to measure dissolved oxygen in seawater

The use of an optical oxygen sensor to measure dissolved oxygen in seawater was investigated. The sensor is based on the dynamic quenching of an oxygen-sensitive fluorochrome embedded in the tip. Dissolved oxygen in seawater samples collected from eight stations at depths ranging from 3000 to 6000 m was analyzed both with the optical sensor and by the Winkler titration method. The two sets of data did not differ significantly. The stability and simplicity of the method and the good agreement of the results with those of the titration method indicate that the sensor would be useful for fieldwork.     

Bacterial communities fluctuate in abundance and diversity under simulated oil-contaminated seawater conditions

Marine bacteria have recently been identified as a potent solution for petroleum hydrocarbon degradation in response to hazardous oceanic oil spills. In this study, a mesocosm experiment simulating a petroleum spill event was performed to investigate changes in the abundance, structure, and productivity of bacterial communities in response to oil pollution. Cultured heterotrophic bacteria and total bacteria showed a consistent trend involving an immediate decrease in abundance, followed by a slight increase, and a steady low-level thereafter. However, the changing trend of bacterial productivity based on bacterial biomass and bacterial volume showed the opposite trend. In addition, the density of oil-degrading bacteria increased initially, then subsequently declined. The change in the bacterial community structure at day 0 and day 28 were also analyzed by amplified ribosomal DNA restriction analysis (ARDRA), which indicated that the species diversity of the bacterial community changed greatly after oil pollution. Alphaproteobacteria (40.98%) replaced Epsilonproteobacteria (51.10%) as the most abundant class, and Gammaproteobacteria (38.80%) became the second most dominant class in the whole bacterial community. The bacterial communities in oil-contaminated seawater (32 genera) became much more complex than those found in the natural seawater sample (16 genera). The proportion of petroleum-degrading bacteria in the oil-contaminated seawater also increased. In this study, culture-dependent and culture-independent approaches were combined to elucidate changes in both bacterial productivity and community structure. These findings will contribute to a better understanding of the role that bacteria play in material cycling and degradation in response to oil pollution.     

Factors controlling the temporal and spatial variations in Synechococcus abundance in a monsoonal estuary

Temporal and spatial variations in Synechococcus abundance were investigated over an annual cycle (February'10–January'11) along a salinity gradient (0–35) in the tropical Zuari estuary, influenced by south-west monsoons. Synechococcus exhibited salinity preferences with phycoerythrin-rich cells at salinities >2 (Synechococcus-PEI), >20 (Synechococcus-PEII) and <1 (Synechococcus-PEIII) whereas phycocyanin-rich (Synechococcus-PC) dominant at lower salinities. Downstream stratification during monsoon caused Synechococcus group segregation in the surface and near-bottom waters. During monsoon-break and non-monsoon period stabilized waters, increased salinity, temperature, solar radiation and low rainfall favored high Synechococcus abundance whereas unstable waters, increased turbidity and low solar radiation during active monsoon lowered abundance. SYN-PC positively co-related with nitrate and phosphate and SYN-PEI with phosphate. Synechococcus contribution to phytoplankton carbon biomass ranged from 9 to 29%. In monsoonal estuaries, rainfall intensity regulates freshwater runoff which modulates the estuarine environment, creating temporal–spatial niche segregation of Synechococcus groups thereby serving as indicator organisms of the estuarine hydrodynamics.     

The relative importance of buffering and brine inputs in controlling the abundance of Na and Ca in sedimentary formation waters

The concentration of Ca in the formation waters of petroleum reservoirs can play a major role in influencing the outcome of a number of processes that are of great significance to the oil industry. For example, formation water Ca concentration affects the risk of carbonate scale formation during production. In order to better understand the concentrations of Ca in formation waters, we have investigated the chemistries of formation waters from a range of onshore and offshore basins worldwide, using published sources, as well as unpublished data held by BP. Although calcium and sodium are the principal cations in almost all formation waters they vary enormously in their relative proportions. We have identified three distinct trends on a plot of X_Ca (Ca/(Na + Ca)) against Cl. Most data lie on a high-Ca trend, here termed Trend 1, and show an increase in X_Ca with salinity. We interpret this as tracking equilibration with Ca and Na-bearing minerals, with the ratio (mol Ca/mol Na²) remaining approximately constant irrespective of salinity for chloride-dominated fluids. At very high salinities, Br-enriched bittern brines that have taken part in dolomitisation lie at the Cl-rich end of this trend. Some brines remain Na-dominated up to very high salinities and define a distinct low-Ca trend, Trend 2. These are associated with dissolution of halite beds and are interpreted to arise when the amount of Na in the pore fluid greatly exceeds the amount of Ca available in minerals. We refer to such brines as mass-limited; the sparsity of Ca in the rock-fluid system constrains X_Ca to a low value. Remarkably few brines lie between these trends. Finally, dilute formation waters show very large variations in X_Ca and may have bicarbonate as the dominant anion. They define a distinct low-Cl trend, Trend 3. We conclude that the behaviour of Na and Ca in most formation waters reflects equilibration with minerals, and concentrations of Ca in solution are sensitive to pH and P_CO2 as well as to chloride concentration. For some brines however, the amount of salts in solution is sufficient to overwhelm the buffering capacity of the wallrocks.     

Laboratory and marine study of photoluminescent sensors of oxygen dissolved in seawater

The laboratory and marine study of photoluminescent sensors developed at the TsAGI has been conducted to create a highly sensitivity gauge of the oxygen dissolved in seawater. The advantages of the photoluminescent gauge over the electrochemical ones are the following: zero sensitivity to electromagnetic fields, the pH of the water, and the hydrogen sulphide and ions of heavy metals in the water; zero oxygen consumption; and no need for the water to be pumped through the device.     

光纤光谱仪的研制及其在海水营养要素检测中的应用

基于交叉非对称的czerny-Turner结构, 研制了一种微型光纤光谱仪, 采用光栅分光、线阵CCD探测光, 基于复杂可编程逻辑器件及PC104设计CCD数据采集电路, 采样结果通过PC104总线上传至PC104工控机, 光谱仪及数据采集电路集成为一光谱仪模块, 约为96mm(宽)×104mm(长)×18mm(高), 该模块与PC104工控机之间通过PC104总线以“针”和“孔”形式层叠连接, 在具有体积小、功耗低、采样速度快等优点的同时还具有极好的抗震性, 非常适合于野外恶劣工作环境下的在线使用。将其应用于海水中铁等痕量元素及营养盐在线检测仪, 试验结果良好。     

青岛市奥帆赛区海域表层海水中微量元素的研究

通过离子色谱离线螯舍和ICP—MS对青岛市汇泉湾、太平湾、浮山湾采集的海水样品进行分析,得到了该海域表层海水中微量元素质量比的可靠数据,并对表层海水中微量元素的分布特征及其影响因素进行了探讨。将分析结果与国家海水标准进行比较表明,该海域海水中微量元素质量比符合国家一级海水标准。对该海域表层海水微量元素的分布特征的研究表明,近岸和远岸表层海水中微量元素的质量比差别很小,而不同于沿岸海区质量比高,离岸远处质量比较低的一般规律。其主要原因是该海域的人为污染程度小,再加上其特殊的海岸地形以及水动力条件,有利于溶解物质的扩散、迁移和稀释。     

X-Ray fluorescence analysis of the principal elements of the seawater salt composition in the tropical Atlantic

This paper reports on the results of determining the chlorine, potassium, calcium and sulphur concentrations obtained by X-ray fluorescence (XRF) during the 37th cruise of the R/VAkademik Vernadsky in the tropical Atlantic. The determination accuracies for the ratios of K/Cl, Ca/Cl, and S/Cl were 0.45, 0.58, and 2.5%, respectively. As follows from the data obtained, the variations of these ratios exceed the accuracy of the measurements at all stations, and they are connected with the structural features of the hydrochemical fields.Translated by Mikhail M. Trufanov.     

Modelling and observations of tidal wave propagation, circulation and residence times in Puttalam Lagoon, Sri Lanka

Tidal measurements and a depth-averaged 2D model are used to examine wave progression and circulation in a long, shallow, micro-tidal lagoon in Sri Lanka. Ranges and phase lags for different tidal constituents are used to calibrate the model. A single drag coefficient, C_d = 0.0032, gives almost perfect agreement with data. Current measurements are used for validation of the model. The lagoon tide consists of a combination of progressive and standing waves, where progressive waves dominate in the outer part and standing waves in the inner. A Lagrangian based particle-tracking method is developed to study tidally and wind induced residence times. If tides were the only factor affecting the residual circulation, the residence time inside the narrowest section would be approximately 100 days. Steady winds (of typical monsoon average) decrease the residence times to 60–90 days. Estuarine forcing due to net freshwater supply is not modelled (due to lack of reliable runoff data), but independent, long-term salinity observations and calculations based on volume and salt conservation during periods of negligible freshwater supply (the lagoon is seasonally hypersaline) indicate residence times ranging from 40 to 80 days. Model derived residence times based on tides alone represent a minimum exchange. Even weak forcing, through winds, excess evaporation or freshwater supply efficiently reduces residence times.     

海水中大分子有机质对铂族元素的吸附动力学研究

Adsorption kinetics of the interaction between Pt, Pd and Rh(defined here as platinum group elements, PGEs)ions and macromolecular organic compounds(MOCs, 10 kDa), including humic acid, carrageenan and bovine serum albumin, and different cutoff fractions of natural organic matter(1 kDa and 3 kDa) obtained from seawater using centrifugal ultrafiltration devices were investigated. For a given element, all the adsorption kinetics did not reach equilibrium except the interaction between Pt and 1 kDa cutoff, and between Pd and humic acid.For all the tested MOCs, the adsorption kinetics could be divided into two stages, a rapid adsorption process in the first 8 h and the desorption stage after the first 8 h until the equilibrium. The change trend of partition coefficient(log_(10)K_d) values with experiment time was consistent with that of the kinetic curves. However, in the interaction between PGE ions and natural dissolved organic matter(NDOM), an obvious difference in the change trends of log_(10)K_d and kinetic curves was observed. It indicated that the partition behavior of PGE ions interacting with NDOM in seawater was a combined effect of different organic constituents. The adsorption and log_(10)K_d of PGEs in the 1 kDa NDOM fraction were higher and more stable than those in the 3 kDa NDOM fraction. The results also indicated that the 1–3 kDa NDOM may dominate the interaction between PGEs ions and NDOM. Moreover, no kinetic model could perfectly simulate the adsorption process. It indicated that the colloidal struction and morphology of MOCs or NDOM in seawater might be inhomogeneous. Hence, the interaction between PGE ions and organic matter in seawater was a complicated process and needs further research.     

一种移动式海水痕量元素洁净采集实验室的设计

痕量元素及其同位素采集、预处理和分析在海洋研究中具有重要的作用，由于含量极低，在采样、样品预处理及分析过程中容易受到外界污染源沾污。通过在一个20尺标准超高集装箱内制作一套移动式海水痕量元素洁净采集实验室，完成对实验室空间设计、空气质量控制，样品快速转移，实现水样上船后快速进入到洁净环境中，减少样品暴露在大气中时间，在洁净环境中高效完成样品取样、过滤和预处理等操作。所有操作满足GEOTRACES组织有关痕量元素采集的规范要求，从源头上保证分析测试结果的可靠性。     

南太平洋富稀土海区海水中的溶解态稀土元素空间分布特征研究

深海富稀土沉积物因其资源潜力巨大,近年来备受关注。一般认为,沉积物中稀土元素和钇（总称REY）的主要来源为上覆海水,但针对富稀土海区上覆海水中REY的研究较少。本研究针对南太平洋富稀土海区采集的3个站位的全水深海水样品,测试出了15种溶解态REY,并对比了邻近海域已发表的数据,分析了该海区REY的空间分布特征。研究区表层水中溶解态REY浓度主要受风尘输入影响,而中层和深层水体中溶解态REY浓度主要受水团控制。经过澳大利亚后太古代页岩（PAAS）和北太平洋深层水（NPDW）归一化后的配分模式可确定REY间的分馏特征,分辨出不同水团。与其他大洋中报道的REY数据比较发现,表层水中REY浓度受风尘和河流输入影响导致差别较大,中层水中REY浓度与印度洋较为接近,深层水中REY浓度与不同大洋的水团年龄表现为正相关趋势,即REY浓度由小到大依次为大西洋、印度洋、南太平洋、北太平洋。     

北黄海表层沉积物常量元素分布特征及其控制因素分析

为探讨北黄海表层沉积物中常量元素分布特征,并进一步分析其控制因素和物质来源,以常量元素为依托,对304个站位表层沉积物常量元素含量分布特征及控制因素进行统计分析,结果表明:沉积物中SiO2、Al2O3、Fe2O3、MgO、K2O、P2O5、TiO2七种元素含量的空间分布具有明显的区域性。其中,SiO2、K2O具有相似的空间分布;Al2O3、Fe2O3、MgO、P2O5、TiO2具有相似的空间分布,但与SiO2、K2O的分布趋势相反;CaO、MnO、Na2O在区域内分布较为均匀,未显示出明显的高低变化趋势。聚类分析显示,表层沉积物的常量元素分布主要受粒度效应的控制。主因子分析提取出3种控制常量元素分布的主成分,分析表明,粒度控制效应、源区风化作用和不同物源输入是影响表层沉积物常量元素空间分布的主要因素,贡献累计方差总和达77.12%。以K2O、CaO、TiO2为指标,通过FD函数识别出北黄海不同海域内的主要物质来源,其主要物源包括黄河、鸭绿江和黄海暖流携带的长江物质。对北黄海沉积物物质来源进行分析,不仅在海洋矿产资源勘探、航道开发、沿岸港口建设与整治等方面具有实际意义,而且在认识海洋环境变迁等方面同样具有理论意义。     

Determination of dissolved oxygen in seawater by direct spectrophotometry of total iodine

A modified procedure has been proposed for the colorimetric determination of dissolved oxygen in seawater to improve its precision and accuracy. When a pickled sample is acidified, iodine liberated in the iodometric reaction is measured by direct spectrophotometry at 456 nm. Loss of molecular iodine by volatilization is eliminated by transferring the sample to a flow cuvette without contact with air. The method was calibrated for oxygen by spiking known amounts of potassium iodate. Precision was found at better than 0.2% r.s.d. (full scale). Evaluation of accuracy was made by comparison with calculated oxygen solubilities, which shows a relative bias of no more than 0.5% for oxic waters. The analytical throughput was much faster than that of the standard titration procedure.     

山东半岛东部海域表层沉积物微量元素分布及物源指示意义

依据山东半岛东部海域79个站位表层沉积物微量元素测试结果,分析了研究区微量元素含量空间分布特征,识别了沉积物来源,探讨了其控制因素和沉积物输运模式。结果表明,研究区表层沉积物微量元素中Ba和Sr平均质量比最高,分别为465μg/g和198μg/g;Ba含量整体呈中间低、四周高的趋势; Sr整体呈近岸高、离岸低的分布特征。除Ba和Sr外, Cr、Cu、Ni、Pb、Co和V含量空间分布特征基本一致,整体呈近岸低、离岸高的分布特征。通过m(Cr)/m(V)-m(Ni)(m表示元素质量比,μg/g)散点图判别,研究区沉积物主要来源于黄河物质,南部可能有少量长江物质输入。微量元素的分布受物源和粒度效应的控制。研究区微量元素除Ba、Sr外,其余元素与平均粒径呈正相关, Sr元素则与平均粒径呈负相关性,Ba与沉积物粒径无明显相关性。黄海沿岸流携带黄河物质绕过成山头后在研究区发生沉积,同时受到北上黄海暖流的阻隔,在研究区南部发生混合扩散后沉积。研究成果对于补充完善山东半岛泥质区的物源和输运机制具有重要意义。     

Significance of oxides and particulate organic matter in controlling trace metal partitioning in a contaminated estuary

The sediment–water partitioning of radiolabelled Cd, Hg and Zn has been investigated along an estuarine salinity gradient using samples from the Mersey Estuary, UK. Partitioning was studied using untreated particles, and particles that had been extracted using either a reducing agent (NH₂OH.HCl–HOAc) or an oxidising agent (H₂O₂) in order to qualitatively evaluate the relative roles of Fe–Mn oxides and particulate organic matter (POM), respectively, on metal uptake. The extent of Cd partitioning between sediment and water, parameterised in terms of the distribution coefficient, K_D, exhibited a reduction with increasing salinity, regardless of whether or not particles had been digested. However, the magnitude of K_D decreased significantly following either chemical treatment, suggesting that both oxides and organic matter are important sorbents for Cd. The K_D for Hg in the presence of untreated particles increased with increasing salinity, and chemical reduction of the particles enhanced the uptake of Hg and reinforced this trend. Particle oxidation led to a significant reduction in the K_D for Hg, and uptake by the particles decreased with increasing salinity. These observations suggest that POM is considerably more important than Fe–Mn oxides in the removal of aqueous Hg, and that its presence is a prerequisite for enhanced sorption (or salting out) at elevated salinities. The salinity dependence of K_D for Zn displayed characteristics of both Cd (below salinities of about 5) and Hg (at greater salinities). However, the magnitude of K_D for Zn uptake was relatively insensitive to either chemical treatment, suggesting that oxides, POM, and residual phases contribute to the overall sorption of Zn by estuarine particles. Regression analyses of the metal partition data suggest that sorption to oxides and POM is nonadditive, and that the salinity dependence of metal partitioning results mainly from salinity-controlled interactions between metal and organic matter. Sequential extraction of metals bound to untreated and chemically treated particles in the partitioning experiments indicated that the exchangeability or lability of all metals increased on removal of either oxides or POM. This implies that sorption sites of relatively high energy are destroyed (or become less accessible), or sorption sites of relatively low energy are created (or become more accessible) on chemical treatment. These observations support a conceptual model for the particle surface whose integrity and binding properties are only maintained by the coexistence of and interaction between oxides and organic matter.