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.     

海水中铀与碱式碳酸锌的反应级数及活化能

目前国外对碱式碳酸锌吸附海水中铀的报导较少,对其吸附海水中铀的反应级数及活化能测定的报导尚未见到。本文试图用三颈瓶反应器及分光光度法,测定海水中铀与碱式碳酸锌的反应级数及活化能,并获得较满意的实验结果。     

胶州湾海水中一氧化碳光致生成影响因素的研究

海水中的一氧化碳(CO)主要由溶解有色有机物(CDOM)光降解产生,且CO的光致生成量受到环境因素的影响。采集了胶州湾及其河口表层水样,通过实验室模拟实验开展了不同的环境条件(辐射强度、光照时间、温度、pH和盐度)以及水体中CDOM的来源对CO光致生成的影响研究。结果表明胶州湾海水中CO的光致生成速率随辐射强度的增强、水温的升高和水体pH的增大而增大;随着光照时间的延长、水体盐度的增大而逐渐减小;不同来源的CDOM对水体中CO的光致生成速率产生了不同的影响。     

胶州湾海水中一氧化碳光致生成影响因素的研究

海水中的一氧化碳(CO)主要由溶解有色有机物(CDOM)光降解产生,且CO的光致生成量受到环境因素的影响。采集了胶州湾及其河口表层水样,通过实验室模拟实验开展了不同的环境条件(辐射强度、光照时间、温度、pH和盐度)以及水体中CDOM的来源对CO光致生成的影响研究。结果表明胶州湾海水中CO的光致生成速率随辐射强度的增强、水温的升高和水体pH的增大而增大;随着光照时间的延长、水体盐度的增大而逐渐减小;不同来源的CDOM对水体中CO的光致生成速率产生了不同的影响。     

The non-biological oxidative degradation of dissolved xanthopterin and 2, 4, 6-trihydroxypteridine by the pH or salt content of seawater

The degree of chemical instability of xanthopterin and related pteridines in seawater was studied with a view to assessing its role in the ecological turnover of these compounds in the marine environment. Solutions of these compounds in natural and synthetic seawater, brines containing one or more component salts of seawater, and buffers covering a wide pH range were incubated aseptically at 22–25°C in complete darkness and the chemical changes were spectrophotometrically monitored.Pterin, lumazine, and isoxanthopterin were completely stable in seawater, while the other pteridines degraded in the order dioxylumazine < leucopterin < xanthopterin <<< oxylumazine (the trivial names oxylumazine and dioxylumazine are used to denote 2, 4, 6-trihydroxy- and 2, 4, 6, 7-tetrahydroxy-pteridine, respectively). Apart from oxylumazine, the chemical instability of the other pteridines was correlated with pH corresponding to that of seawater. The high instability of oxylumazine was shown to be due to the salt content of seawater and not its pH; this pteridine required minimal concentrations of salt and traces of heavy-metal ions (such as Cu²⁺) to show significant chemical change. When the salt present was NaCl or KCl only, oxylumazine showed 1:1 oxidative conversion to dioxylumazine, but with the total salts of seawater the conversion was 2:1 with half of the oxylumazine being degraded, apparently by ring-cleavage, to unidentified non-pteridine products; this latter degradation is attributed to the total complex of ions present in seawater. In contrast to oxylumazine, xanthopterin gave evidence of 1:1 oxidative degradation via leucopterin in seawater, and this degradation appeared to be independent of trace metal ions. Chemical mechanisms are suggested for the observed degradations, and the ecological implications of the latter are discussed.     

Photochemical production of molecular hydrogen in lake water and coastal seawater

Samples of lake water and coastal seawater from Nova Scotia, Canada, were irradiated with natural or artificial sunlight to investigate the potential for photochemical hydrogen production. Hydrogen photo-production was observed in all natural water samples. Rates of hydrogen formation were highest in coloured lake water (range: 98–163 pmol L^− 1h^− 1) and lower in seawater (range: 19–45 pmol L^− 1 h ^− 1). Dilutions of the most highly coloured lake sample (Kejimkujik Lake) showed a positive linear relationship between H₂ production rates and CDOM concentration. Photo-production rates normalised to UV absorption coefficients at 350 nm indicated that the photochemical efficiency of hydrogen formation varied between samples, perhaps due to differences in the CDOM composition. Photochemical hydrogen formation was also seen in solutions of syringic acid and acetaldehyde: two low-molecular-weight carbonyl compounds found in natural waters. Photochemistry may therefore offer least a partial explanation for the persistently high levels of hydrogen observed in the low-latitude surface ocean.     

海水冷却技术

城市用水中约 5 0 %是工业冷却水。海水代替淡水作为工业冷却用水——海水冷却 ,是解决我国沿海城市和地区淡水资源危机问题的重要途径之一。海水冷却技术包括海水直流冷却技术和海水循环冷却技术 ,目前我国基本具备了具有自主知识产权的海水(直流、循环 )冷却关键技术。寻求政府在资金、政策等方面的大力支持 ,加强有关行业、院所、企业的“强强联合”,适时借鉴国外先进的海水冷却塔技术 ,加快产业化技术示范 ,是推进海水循环冷却技术快速发展的必由之路     

Photochemical formation of glyoxylic and pyruvic acids in seawater

Glyoxylic and pyruvic acids were formed when filter-sterilized seawater was exposed to solar radiation. Production rates varied from samples collected from distinctly different regions of the sea. Humic-rich seawater from the Florida Bay exhibited net photochemical production rates (glyoxylate, 27.5 nM/W-h m⁻²; pyruvate, 12.9 nM/W-h m⁻²) that were significantly greater than net production rates for humic-poor water (glyoxylate, 3.1 nM/W-h m⁻²; pyruvate, 1.8 nM/W-h m⁻²) collected in the Gulf Stream. When seawater was not filtered, the concentrations of glyoxylate and pyruvate were found to undergo diurnal variations resulting from an imbalance between biological and photochemical processes.A depth profile of the glyoxylate concentration from several oceanic stations showed a pronounced daytime maximum in the upper 10 m; this finding is consistent with laboratory results that demonstrated that glyoxylate is formed photochemically in seawater. Pyruvate, in contrast, showed no clear trend with depth; its distribution in the water column may be primarily controlled by biological processes rather than by photochemical processes.Biological processes are generally thought to control the spatial and temporal distribution of simple organic metabolites in seawater. Our results show that photochemical processes may also be important in the marine cycling of some biochemical compounds.     

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.     

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.     

海水中锰的光化学反应研究

对海水中锰的光化学反应及其影响因素进行了研究.实验结果表明,锰的光化学反应主要通过有机物为媒介进行,反应液中加入的有机物种类和浓度的改变会导致锰的光化学反应速率的改变.增加光强,有利于锰的光还原反应的进行.降低体系的pH值,可提高锰的光反应速率.锰在不同介质中光反应速率从大到小的顺序为:去离子水、人工海水、天然海水.此外,搅拌有利于锰的光反应的进行,但在体系分布已达均匀的前提下,搅拌速率的大小对锰的光反应速率几乎无影响.研究表明,通过光化学反应,海水中的锰会由四价的颗粒态转化为二价的可溶态,从而有利于浮游植物的吸收和生长.     

Long lifetimes of β-glucosidase,leucine aminopeptidase,and phosphatase in Arctic seawater

The active lifetime of extracellular enzymes is a critical determinant of the effectiveness of enzyme production as a means for heterotrophic marine microbes to obtain organic substrates. Here, we report lifetimes of three classes of extracellular enzyme in Arctic seawater. We also investigated the relative importance of photochemical processes and particle-associated processes in inactivating extracellular enzymes. Enzyme inactivation in filtered seawater was slow, with apparent half-lives of enzyme activities on the order of hundreds of hours. The presence of particles (including cells) did not significantly change inactivation rates, suggesting that the long half-lives observed in filtered seawater were realistic for enzymes in unfiltered seawater. Phosphatase and leucine aminopeptidase were susceptible to photoinactivation, but only under high intensity UV-B and UV-C illumination; there was no evidence for increased inactivation rates under natural illumination at our study site in Ny Ålesund, Svalbard. Comparison of inactivation rates of commercially-obtained enzymes from non-marine sources with the extracellular enzymes naturally present in Arctic seawater suggests that the natural enzymes contain structural features that confer longer lifetimes, consistent with observations reported by others from a range of field sites that cell-free enzymes can contribute a substantial fraction of total hydrolytic activity in the water column.     

Identification of estrogen-like alkylphenols in produced water from offshore oil installations

Produced water released into the sea from oil installations contains a vast number of organic compounds. This work focuses on the analysis and identification of phenols in produced water, in particular long-chain para-substituted alkylphenols, which act as endocrine disruptors for marine biota. Some alkylphenol standards, unavailable commercially, have been synthesised and some compounds of interest identified. However, a complete identification is not possible since conventional GC techniques cannot achieve the desired degree of separation. An overview of the levels of the 52 known alkylphenols in produced water from nine oil installations in the North and Norwegian Seas has been made. The previously unidentified alkylphenols in produced water have been characterised by means of alkylphenol retention indices (APRI) and mass spectrometry, and their total amounts estimated for the same nine locations. Our results confirm the presence of naphthols and other as yet unidentified compounds in produced water, while thiophenols were not detected by the used technique.     

Dissolved uranyl complexed species in artificial seawater

The distribution of dissolved uranyl species was calculated on the basis of the stability constants published elsewhere and compared with the results obtained from the experiments performed in artificial seawater. According to the distributions calculated and electrochemical and spectrophoto-metrical measurements performed in model electrolytes and artificial seawater (pH=8.2) in the presence of sufficient hydrogen peroxide, uranium most probably predominates in the form of a mixed uranyl-dicarbonato-hydrogenperoxo complex. The results obtained could be applied to the natural marine photic zone.The mixed complex has to be taken into account as an additional form of dissolved uranium species influencing their cycle in natural water systems. Recent discovery of the presence of hydrogen peroxide in the surface waters of seas has challenged a long-held notion of the prevalence of uranyl-carbonato complexes in seawater.     

缓解水源紧缺的最佳选择——谈青岛市的海水直接利用

简要介绍了青岛淡水资源紧缺形势，论述了解决“水困扰”的最佳选择，重点阐明海水直接利用的领域极其广阔，建议居民生活的洗涤，冲厕用水尽量“以海代淡”；最后提出了海水利用的关键技术问题和建议。     

Influence of m-cresol purple indicator additions on the pH of seawater samples: correction factors evaluated from a chemical speciation model

The perturbation of the indicator m-cresol purple on the pH in seawater is illustrated in diagrams, representing measurements in 1-cm and 5-cm cells. The diagrams apply to a measured pH interval of 7.4–8.4 using a 2-mM stock solution of m-cresol purple sodium salt dissolved in seawater. The magnitude of the perturbation is described as correction values, i.e., the change in seawater pH caused by the indicator. The diagrams are based on calculations made by using the equilibrium speciation programme, MARINHALT. From these calculations, and least squares fitting methods, pH correction values are described in terms of the pH difference between each seawater sample and the pH of an indicator stock solution. Calculations are performed for a typical high latitude water and a north Pacific deep water. Diagrams are presented for a salinity of 35 and a temperature of 15°C. Responses to salinities between 32 and 36 and temperatures 15–25°C are illustrated as well. A ±0.05 pH difference between a seawater sample and an indicator stock solution gives a correction of less than 0.001 pH unit for a 1-cm cell. For a 5-cm cell, pH differences between the indicator stock solution and a seawater sample as large as ±0.3 cause corrections smaller than ±0.001 pH unit. Calculations demonstrate that the five-fold lower indicator concentration used with 5-cm cells decreases the perturbation effect by approximately a factor of five relative to 1-cm cells.     

Centropages typicus (Crustacea,Copepoda) reacts to volatile compounds produced by planktonic algae

Volatile organic compounds (VOCs) may play the role of infochemicals and trigger chemotaxis and ecologically relevant responses in freshwater and marine invertebrates. Aquatic grazers use these signals as chemical cues to trace the presence of their food or to detect their predators. However, detailed data are still needed to fully understand the role of these relationships in marine plankton. We investigated the ability of the copepod Centropages typicus to perceive the odour of three planktonic diatoms (Skeletonema marinoi, Pseudonitzschia delicatissima and Chaetoceros affinis) and a dinoflagellate (Prorocentrum minimum). This information is ecologically relevant for orientation, habitat selection, predator avoidance and communication. In addition, as the pH of the medium influences the perception of chemical cues in aquatic environments, we tested the effect of seawater acidification resulting from increasing levels of CO₂, and its influences on the olfactory reactions of copepods. For this reason, our tests were repeated in normal (pH 8.10) and acidified (pH 7.76) seawater in order to simulate future ocean acidification scenarios. Using replicated chemokinetic assays we demonstrated that VOCs produced by Ps. delicatissima and Pr. minimum attract copepods at normal pH, but this effect is lowered in acidified water. By contrast, the odour of S. marinoi mainly induces a reaction of repulsion, but in acidified water and at higher concentrations this toxic diatom becomes attractive for copepods. Our experiments demonstrate, for the first time, that copepods are sensitive to the volatile compounds contained in various microalgae; VOCs prompt chemokinesis according to algal species and odour concentrations. However, seawater acidification induces changes in copepods' perception of odours. These findings highlight the sensitivity of chemically mediated interactions to global changes     

Disruption of magnesium regulation in the crab Cancer productus exposed to chlorinated seawater

Exposure of the crab Cancer productus to chlorinated seawater resulted in alterations in haemolymph sodium and magnesium concentrations. At the highest chlorination levels, which approached the 96-h LC₅₀, regulation of both ions was essentially abolished. Reciprocal changes in the sodium and magnesium levels suggested an effect on the activity of the bladder wall, which has been implicated in the regulation of haemolymph magnesium in crustaceans.Additionally, exposure to 1·19 μg/ml applied Cl (0·68 μg/ml TRO) for 96 h resulted in a fourfold increase in the ammonia excretion rate. Crabs also contributed considerable chlorine demand to the exposure seawater. Measurements of TRO in the inhalant seawater and water exiting the crabs' branchial chambers indicated a reduction in TRO equivalent to 57% of that initially present in the inhalant water (0·51 μg/ml TRO).Measurements of ammonia concentrations in the exposure water indicated that ammonia in seawater was consumed in reactions with oxidants. This was especially evident at higher levels of chlorination. At 0·58 μg/ml applied Cl and above, chlorination resulted in near disappearance of ammonia from the water.     

胶州湾海水中溶解有色物质的光脱色对光致生成一氧化碳速率的影响

利用在胶州湾中不同位置取得的3个水样,对溶解有色物质进行了不同时间的光脱色,探讨了有机物含量随脱色时间的变化趋势,得出有机物吸光系数和溶解有机碳随脱色时间的增长而呈指数减小,说明光脱色可以明显降低溶解有机物的含量。对不同光脱色程度的水样进行了光化学降解,测定了其主要产物一氧化碳的光致生成速率,发现在8个不同波段下一氧化碳光致生成速率与350 nm的吸光系数和溶解有机碳之间均有良好的线性关系。350 nm的吸光系数和溶解有机碳含量在一定程度上均可较好地表示海水中CDOM的含量。     

Collection and detection of natural iron-binding ligands from seawater

Iron (Fe) is an essential element for the biochemical and physiological functioning of terrestrial and oceanic organisms, including phytoplankton, which are responsible for the primary productivity in the world's oceans. However, due to the low solubility of Fe in seawater, phytoplankton are often limited by their inability to incorporate enough Fe to allow for optimal growth rates in regions with dissolved Fe concentrations below 1 nM. It has been postulated that certain phytoplankton may produce compounds to facilitate the uptake of Fe from seawater to overcome this limitation. Dissolved Fe in the oceans is overwhelmingly complexed (>99%) by strong organic ligands that may control the uptake of Fe by microbiota; however, the identity, origin, and chemical characteristics of these organic chelates are largely unknown. Although it has been implied that some components of natural Fe-binding ligands are siderophores, no direct analyses of such compounds from natural seawater have been conducted. Here, we present a simple solid-phase extraction technique employing Biobeads SM-2 and Amberlite XAD-16 resins for concentrating naturally occurring dissolved iron-binding compounds from large volumes (>200 l) of seawater. Additionally, we report on the first successful determination of molecular weight size classes and preliminary iron-binding functional group characterization within those size classes for isolates collected from the surface and below the photic zone (150 m) in the central California coastal upwelling system. Electrochemical analyses using competitive ligand equilibration/adsorptive cathodic stripping voltammetry (CLE-ACSV) showed that isolated compounds had conditional Fe-binding affinities (with respect to inorganic iron—Fe′) of K_FeL,Fe′^cond=10^11.5–10^11.9 M⁻¹, similar to purified marine siderophores produced in laboratory cultures and to the ambient Fe-binding ligands observed in seawater. In addition, 63% of the extracted compounds from surface-collected samples fall within the defined size range of siderophores (300–1000 Da). Hydroxamate or catecholate Fe-binding functional groups were present in each compound for which Fe binding was detected. These results illustrate that the functional groups previously shown to be present in marine and terrestrial siderophores extracted and purified from laboratory cultures are also present in the natural marine environment. These data provide evidence that a significant fraction of the organic Fe-binding compounds we collected contain Fe-binding functional groups consistent with biologically produced siderophores. These results provide further insight into characteristics of the Fe-binding ligands that are thought to be important in controlling the biological availability of Fe in the oceans.