海洋中硼的研究

硼是海水中的常量元素,也是自然水体中重要的生物、地质、化学元素。海洋中的硼含量、Ｂ／Ｃｌ 比常用于指示水团,研究大洋环流。海洋粘土中的硼含量作为古盐度的指标。硼也对海洋浮游生物的生长起重要的作用。本文综述了海洋中硼的研究,讨论了海洋中硼的迁移。     

热带印度-太平洋浮游有孔虫Pulleniatina obliquiloculata的B/Ca和Cd/Ca指标：次表层海水碳化学参数计算的应用

Pulleniatina obliquiloculata shells from 16 core-top samples from the tropical Indo-Pacific Oceans are analyzed for the ratios of boron and cadmium to calcium(B/Ca and Cd/Ca). The B/Ca ratios show a very weak positive relationship with [B(OH)_4~-] and the dissolved carbonate species at the apparent calcification depth of P.obliquiloculata. The boron partition coefficients(K_D) between P. obliquiloculata B/Ca and seawater[B(OH)_4~-]/[HCO_3~-] distribute around 1.1×10~(-3)-1.3×10~(-3) with a mean value of(1.19±0.12)×10~(-3),and are significantly related to the nutrient concentration, especially phosphate. The lack of any clear correlation between the P. obliquiloculata B/Ca and seawater carbonate chemical parameters suggests that the physiochemical controls on boron incorporation are masked by the complexity of natural seawater condition. But the significant dependence of Ku on nutrient may likely be explained by a nutrient related growth-rate effect. Cd/Ca of P.obliquiloculata shows significant correlation with seawater phosphate concentration, and its partition coefficients(D_(cd)) are significantly related to temperature. A first-principle methodology of P. obliquiloculata B/Ca is applied;with the aid of Cd/Ca as a phosphate proxy and a constraint on K_D, to estimating sea water carbonate chemistry(e.g., pH). The results are fairly promising and allow us to propose the possibility to apply the combination of B/Ca and Cd/Ca proxies(and also Mg/Ca and δ~(18)O for estimating temperature and salinity) for the paleoreconstruction of seawater carbonate chemistry.     

Conservative behaviour of boron in the Tamar Estuary

Boron is found to be conservative in the Tamar Estuary in a series of surveys conducted over an 18-month period. Dissolved boron in the estuary derives almost entirely from seawater.     

Modifications of the curcumin method enabling precise and accurate measurement of seawater boron concentration

To achieve greater precision and accuracy in the measurement of seawater boron concentrations, we propose a series of modifications to an established (curcumin) method based on the reaction of boric acid with curcumin. The modifications were derived from a series of experiments evaluating the stability of the curcumin–acetic acid reagent, the dependence of the reaction on temperature and duration, the effect of evaporation during the dehydration process, the interference of water, and the effect of sea salts. Application of the modified method to analysis of seawater samples collected from the Pacific Ocean indicated that it yielded considerably better precision and accuracy for boron concentration measurements than both the conventional curcumin method and other analytical techniques.     

Estimates using fluorescence spectroscopy of the present state of petroleum hydrocarbon contamination in the water column of the northwest Atlantic Ocean

Concentrations of petroleum hydrocarbons in seawater from the general region between Nova Scotia and Bermuda were estimated using fluorescence spectroscopy. Concentrations in surface water (0–3 mm) averaged 20.4 μg/l, and in water from 1 and 5 m they averaged 0.8 and 0.4 μg/l respectively. No significant concentrations could be detected in deeper water. There was considerable variability in the concentrations suggesting that the distribution of oil in seawater is quite patchy, especially in surface waters. Seawater samples for hydrocarbon analysis cannot be collected with conventional sampling equipment. Due to adsorption problems, the inner surface of samplers must come into contact only with the water being sampled and must be rinsed with organic solvent after samples are removed. Because these precautions were not taken in previous investigations, much of the published data of hydrocarbons in seawater is unreliable.     

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.     

阴极溶出伏安法测量海水中溶解态铁

使用阴极溶出伏安法,利用2,3-二羟基苯丙氨酸(DHN)可以与Fe(Ⅲ)结合生成配合物,而BrO3-的加入可以催化该电化学反应的性质,系统研究了海水中溶解态Fe(Ⅲ)的最佳分析条件。结果表明,体系中添加20.0μmol/L DHN即可达到分析要求;添加BrO3-可以使溶出电流线性增大,选择的最终浓度为20.0mmol/L。当沉积电位为-0.20V,扫描速率为50.0mV/s,沉积时间为90s时,即可达到低铁海水的分析要求,在此条件下检测限为0.011nmol/L。紫外消解可以使测量灵敏度比未消解时提高13倍。用此方法测量得到的太平洋某处(158°15′E,22°23′N)海水表层水浓度为0.45nmol/L,75m处浓度为0.14nmol/L,1 500m处浓度为0.86nmol/L。     

The determination of α-amino acids in seawater using a fluorimetric analyser

A method is described for the detection of free α-amino acids in the picomole range in seawater samples of less than 100 ml volume. The modifications made to a standard amino acid analyser to incorporate a fluorimetric detection system are described in detail, together with the methods for desalting the seawater samples on cation exchange resin and the concentration procedures prior to analysis. A complete analysis of up to 30 amino acids requires around 3 h with a detection limit of around 0.05 μg of an individual acid per litre. Twenty samples of seawater from different depths in the open Baltic have been analysed for their FAA contents together with 3 samples taken from the Kiel Fjord. The total FAA content of the samples ranges from 4.5 to 84 μg/l with a mean of around 25 μg/l. Five samples were hydrolysed prior to analysis in order to estimate the CAA content of the seawater. The values lay in the range 438–805 μg/l.     

Fluctuation of dissolved organic carbon in seawater of Sagami Bay during 1971–1972

Fluctuation of dissolved organic carbon (DOC) was studied during 1971–1972 at monthly intervals in surface layers of Sagami Bay. Concentration of DOC varied from 0.8 to 1.7 mgC/l in surface water (0 m). Maximum concentration of 1.7 mgC/l was observed in July 1971 and after then DOC decreased gradually to a minimum of 0.8 mgC/l in May 1972. The fluctuation of DOC during the observation periods seems to have close relations with those of water temperature and salinity. High DOC concentration found in summer months may be associated with bloom of phytoplankton or intrusion of seawater from Tokyo Bay and/or inland water containing high DOC.     

我国氨氮海水质量基准的探讨

我国现行的氨氮海水质量标准参照国外基准与标准制定,未考虑是否能够有效保护中国海洋物种,科学性欠缺。对我国海水氨氮质量基准进行研究,采用美国EPA推荐的物种敏感度排序(SSR)技术,结合美国海水氨氮水质基准数学模型,搜集利用我国15种海水水生生物的非离子氨毒性数据,根据非离子氨氮和总氨氮转换公式,得出水体在不同pH值、温度和盐度条件下的总氨氮水质基准在pH为7.0~9.0、温度为0~30℃的范围内,盐度为10时,基准最大浓度(CMC)和基准连续浓度(CCC)的范围分别为0.089~57.141 mg/L与0.007~4.365 mg/L;盐度为20时,CMC和CCC的范围分别为0.092~61.152 mg/L与0.007~4.671 mg/L;盐度为30时,CMC和CCC的范围分别为0.095~65.446 mg/L与0.007~4.999 mg/L;3个环境因子,对CCC和CMC的影响程度由大到小依次为:pH、温度、盐度。相对于美国,我国急性基准的取值区间收缩了5倍,慢性基准的取值区间收缩了10倍。研究结果认为,现行的非离子氨数值应修正为0.007 mg/L才能有效保护我国海洋生物,同时建议使用总氨氮的基准来管理海水中氨氮变化。为修订我国氨氮海水质量标准提供了科学依据。     

Dissolved free amino acids in coastal seawater using a modified fluorometric method

The method of Parsonset al. (1984) for measuring dissolved free amino acids (DFAA) in coastal seawater was modified. We found considerable interference in DFAA determination from ammonia dissolved in coastal seawater, although the interference of urea could be ignored. For DFAA analysis for coastal seawater samples, ammonia determinations for the same sample are needed to correct DFAA values. For coastal surface seawater samples from all over the Seto Inland Sea, Japan, values of DFAA ranged from undetectable to 1.87 μg-at N/l when corrected for ammonia, while uncorrected values ranged from undetectable to 2.61 μg-at N/l. DFAA, urea, nitrate+nitrite, ammonia and DON concentrations in surface seawater collected in the Seto Inland Sea were analyzed simultaneously. DFAA at four seasons constituted from 1.4 to 10.1% of DON, with a mean value of 6.5%. The concentration of urea was similar to that of DFAA and often higher than that of ammonium, although generally lower than that of nitrate.     

海南岛南岸三亚湾海水Sr/Ca、Mg/Ca变化及对珊瑚微量元素温度计的响应

本文对海南岛南岸三亚湾2008~2009年海水的周间隔取样,用全谱直读等离子体原子发射光谱(ICP-AES)分析方法对其Sr/Ca、Mg/Ca比值进行了测定。结果显示其比值（Sr/Ca=8.558~9.227mmol/mol,Mg/Ca=4.924~5.403 mol/mol）与全球各大洋和主要珊瑚礁区有明显地高异常偏差,而且在春末夏初和秋末冬初两个过渡期,三亚湾海水Sr/Ca比值波动幅度比Mg/Ca相对较大,且体现了一定的差异性。在此基础上,结合海水的Sr/Ca、Mg/Ca比值在时间和地域空间上的变化对珊瑚温度计标定的影响,及对不同站点建立的珊瑚Sr/Ca温度计进行了重新校正,并与分配系数法对比分析,我们认为利用珊瑚的Sr/Ca、Mg/Ca比值重建古SST记录时必须综合考虑包括海水微量元素比值变化在内的各种影响因素对温度计标定的干扰。     

Selenium in sediments, pore waters and benthic infauna of Lake Macquarie, New South Wales, Australia

Measurements of selenium in sediments and benthic infauna of Lake Macquarie, an estuary on the east coast of Australia, indicate that sediments are a significant source of selenium in the lake's food web. Analysis of surficial sediment samples indicated higher selenium concentrations near what are believed to be the main industrial sources of selenium to the lake: a smelter and a power station. Sediment cores taken from sediments in Mannering Bay, near a power station at Vales Point, contained an average of 12 times more selenium in surficial sections than sediment cores from Nord's Wharf, a part of the lake remote from direct inputs of selenium. The highest selenium concentration found in Mannering Bay sediments (17.2 μg/g) was 69 times the apparent background concentration at Nord's Wharf (0.25 μg/g). Pore water concentrations in Mannering Bay were also high, up to 5 μg/l compared to those at Nord's Wharf which were below detection limits (0.2 μg/l). Selenium concentrations in muscle tissues of three benthic-feeding fish species (Mugil cephalus, Platycephalus fuscus, Acanthopagrus australis) were significantly correlated (p<0.05) with surficial sediment selenium concentration. Selenium concentrations in polychaetes and molluscs of Mannering Bay were up to 58 times higher than those from Nord's Wharf. Two benthic organisms, the eunicid polychaete Marphysa sanguinea and the bivalve mollusc Spisula trigonella, were maintained at different densities in selenium-spiked sediments. Both animals accumulated selenium from the spiked sediment, confirming that bioaccumulation from contaminated sediments occurs. Collectively, these data suggest that benthic food webs are important sources of selenium to the fish of Lake Macquarie.     

珠江口表层水中主要常量离子的研究

９９４年９月采集了珠江口表层海水水样,并对其溶解态的Ｋ＋、Ｎａ＋、Ｃａ２＋、Ｍｇ２＋、ＳＯ２－４、Ｃｌ等化学要素进行了测定。结果表明,珠江口调查海域表层水中溶解态的Ｋ＋、Ｎａ＋、Ｃａ２＋、Ｍｇ２＋、ＳＯ２－４主要受陆源淡水与外海水物理混合稀释的影响,与Ｃｌ具有良好的直线正相关;Ｃａ２＋／Ｃｌ、ＳＯ２－４／Ｃｌ明显高于大洋水相应比值,Ｎａ＋／Ｃｌ、Ｍｇ２＋／Ｃｌ略高,而Ｋ＋／Ｃｌ比大洋比值低;在与中国其它各主要河口表层水对应Ｃｌ比较中,珠江口的ＳＯ２－４／Ｃｌ较高,而Ｃａ２＋／Ｃｌ,Ｍｇ２＋／Ｃｌ比值居低;上述各主要常量离子和Ｃｌ的等值线均沿自北向南走向递增。     

从藻类化石的垂直分布探讨杭州西湖的演变历程

于１９９４年春在杭州西湖东北面,西面及湖中心小瀛洲３个钻孔共取了７０号岩芯样,经浮选,筛选,以显微镜检鉴定化石藻种,并分析其垂直分布,从而探讨西湖的形成历史,西湖自晚更新世以来的６个化石藻带由下而上依次为：轮藻带,微藻带,微红金颗藻－近缘针杆藻－条纹小环藻带,圆筛藻带,圆筛藻－近缘针杆藻－微红金颗藻桥穹藻－异极藻－短缝藻带和水花束丝藻带,从而反映了西湖的６个发育时期,淡水古湖沼期,淡咸水过渡期,海     

Behaviour of boron,calcium and magnesium in a polluted estuary

Behaviour of industrially added boron in the well mixed Ambika river estuary of South Gujarat, India has been studied along with that of calcium and magnesium. The ratios of Ca : Cl and Mg : Cl at varying chlorinities were always within the normal ranges found in river water at one end and seawater at the other end. B : Cl exceeded the river water end limit at the ebb tide at an upstream station. Percentage addition or removal of boron, calcium and magnesium was calculated using the concept of the theoretical dilution line. The external input raised the boron concentration by 263% in the vicinity of the industrial discharge. A correlation coefficient of ?0·82 between chlorinity and percentage addition or removal of boron supports the theory of boron incorporation in sediments in amounts proportional to salinity. Inverse relationship between percentage addition or removal of boron and suspended solids was observed. Behaviour of calcium and magnesium was in line with the replacement of Ca²⁺ ions occupying the majority of ion-exchange sites in riverine clays by Mg²⁺, Na⁺ and K⁺ during their first encounter with seawater.     

Spatial distributions of dimethylsulfide in the South China Sea

The concentration of dimethylsulfide (DMS) and supporting parameters were determined in surface seawater and vertical profiles at 26 stations in the South China Sea. The concentrations of DMS in surface seawater ranged from 61 to 148 ng S/l, with a mean of 82 ng S/l. High concentrations of DMS were found in the productive regions. The vertical profiles of DMS were characterized by a maximum at depths typically between 20 and 75 m. The concentrations of DMS were correlated with the levels of chlorophyll a both in the surface seawater and in the vertical distribution. The concentrations of DMS were higher than expected for this chlorophyll-poor tropical sea, as indicated by markedly high DMS (ng S/l)/chlorophyll a (μg/l) ratios ranging from 315 to 3524 with a mean of 1768 for all the surface seawater samples. DMS concentration was significantly correlated with seawater temperature and dissolved oxygen, but it showed an inverse relationship to nutrients (including nitrate, phosphate and silicate). On the basis of sea surface concentrations of DMS and gas exchange calculations, the mean flux of DMS from the South China Sea to the atmosphere was estimated to be 5.5 μmol m⁻² d⁻¹.     

海湾区海水中的溶存甲烷 Ⅱ.浓度、海气交换通量

本文基于日本东京湾、伊势湾和浜名湖的调查资料，详细地比较了这3个海湾海水中的溶存甲烷浓度、饱和度。表层海水中，溶存甲烷浓度以供名湖最高，达95nmol／dm3，伊势湾和东京湾相近，分别为41nmol／dm3和37nmol／dm3；其表层测定浓度是其平衡浓度的13～78倍，并分别计算了这3个海湾中甲烷的海气交换通量；用平均值外推法得出全球海洋环境中总的甲烷海气交换通量为6．3Tg／a。     

海水中氨基酸对Cu（Ⅱ）在r—MnOOH上吸附的影响

实验测定了海水中氨基酸存在下Ｃｕ（Ⅱ）在ｒ－ＭｎＯＯＨ上吸附的等温线、Ｃｕ（Ⅱ）％－－ｐＨ曲线和Ｃｕ（Ⅱ）％－氨基酸深度曲线。结果表明，较低浓度氨基酸对Ｃｕ（Ⅱ）在ｒ－ＭｎＯＯＨ上吸附没有影响，而较高浓度氨基酸却起抑制作用，这主要是由于海水中Ｃｕ（Ⅱ）－氨基酸络合反应与ｒ－ＭｎＯＯＨ竞争Ｃｕ（Ⅱ）所致。此外，海水中较高浓度氨基酸只使Ｃｕ（Ⅱ）在ｒ－ＭｎＯＯＨ上吸附的表面分级离子交换稳定常数Ｋｉ（ｉ     

Methane in the western North Pacific

The concentration of methane in about 400 seawater samples collected in the western North Pacific, mostly from 40°N to 5°S along 165°E was determined. While the concentration of methane in the surface water was slightly greater in the high-latitudes, it did not widely vary with a standard deviation of 0.29 n mol/l for a mean value of 2.49 n mol/l. The 90% confidence limit of the mean was 0.08 n mol/l. The degree of oversaturation in 1991 (31±4%) was not different from that in circa 1970. If we assume that this degree of oversaturation occurs in the entire oceans, the annual flux of methane becomes 6×10¹²g CH₄. Both the concentrations of methane and chlorophylla were higher in the surface 100 m layer. However, the correlation between them was not well in the entire surface waters. This may indicate that the production of methane is not directly related to the photosynthetic process. The concentration of methane decreased gradually with increasing depth down to 1000 m. Its horizontally and vertically uniform concentration in the abyssal water suggests that the turnover time of methane in the oxic pelagic water is in the range between a few years and a few hundred years.