Determination of the chemical forms of dissolved cadmium, lead and copper in seawater

The chemical forms of Cd, Pb and Cu in seawater have been examined using a novel scheme which permits the quantification of up to seven different species of one metal. The concentration of each species was calculated from measurements using anodic stripping voltammetry of labile and total metal in samples which were (a) untreated, (b) UV irradiated, (c) passed through a chelating resin column, and (d) UV irradiated then passed through a chelating resin column. In the sample studied, the major proportion of Cd, Pb and Cu was found to be associated with organic and inorganic colloidal species. Less than half of the bound Pb and Cu was readily exchangeable with added ²¹⁰Pb and ⁶⁴Cu.     

Stoichiometry among bioactive trace metals in seawater on the Bering Sea shelf

The distribution of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in seawater was investigated on the Bering Sea shelf (56–64°N, 165–169°W) in September 2000. The unfiltered and filtered seawater samples were used for determination of total dissolvable (TD) and dissolved (D) metals (M), respectively. The TD-M concentrations were generally higher than in the Pacific Ocean. TD-Cd was highest in deep water of the outer shelf domain and dominated by dissolved species. The other TD-M were highest at stations close to the Yukon River delta and had higher fractions of labile particulate (LP) species that were obtained as the difference between TD-M and D-M. Dissolved Al, Ni, and Cu were characterized by input from the Yukon River. Dissolved Mn and Co showed maximums on the bottom of the coastal domain, suggesting influence of sedimentary Mn reduction. The correlations of D-Zn, D-Cd, and macronutrients indicated their distributions were largely controlled through uptake by microorganisms and remineralization from settling particles. All these three processes (river input, sedimentary reduction, and biogeochemical cycle) had an influence on the distribution of D-Fe. D-Pb was fairly uniformly distributed in the study area. The stoichiometry of D-M in the Bering Sea shelf showed enrichment of Co and Pb and depletion of Ni, Cu, Zn, and Cd compared with that in the North Pacific. The LP-M/LP-Al ratio revealed significant enrichment of the other eight metals relative to their crustal abundance, suggesting importance of formation of Fe–Mn oxides and adsorption of trace metals on the oxides.     

Speciation, distribution, and potential ecological risk assessment of heavy metals in Xiamen Bay surface sediment

Based on the survey of surface sediment in Xiamen Bay in October 2011, the speciation, distribution, and potential ecological risk assessment of heavy metals （Cu, Pb, Zn, Cd, and Cr） in this area were studied us-ing the sequential extraction method and ecological risk assessment method. The results indicated：（1） the total concentrations of these heavy metals were influenced by runoff, industrial wastewater, and sewage, and were all higher in the coastal area than the offshore area while the highest area of Pb was a little far-ther away from the coastal water due to atmosphere deposition;（2） sequential extractions suggested that Cu was mainly composed with residual and Fe/Mn-oxide bound fractions, Pb was bound to Fe/Mn-oxide, Zn and Cr were dominated by residual, and Cd bound to exchangeable and carbonate fractions; （3） the order of migration and transformation sequence was Cd＆gt;Pb＆gt;Cu＆gt;Zn＆gt;Cr and the degree of pollution was Cd＆gt;Pb＆gt;Cu＆gt;Zn＆gt;Cr;and （4） the ratios of the secondary and primary phases showed that Zn and Cr were both clean, Cu may be polluted, Pb was moderately polluted, while Cd was heavily polluted.     

Mechanisms for trace metal enrichment at the surface microlayer in an estuarine salt marsh

The relative contributions of adsorption to particulate surfaces, complexation with surface-active organic ligands and uptake by micro-organisms were evaluated with respect to their importance in the surface microlayer enrichment (‘partitioning’) of Cd, Pb and Cu. The contributions of each process were inferred from field data in which partitioning of the dissolved and particulate forms of Cd, Pb and Cu, total and dissolved organic carbon, particles and total bacteria were observed. In the South San Francisco Bay estuary, particle enrichment appears to control trace metal partitioning. Trace metal association with the particulate phase and the levels of partitioning observed were in the order Pb > Cu > Cd and reflect the calculated equilibrium chemical speciation of these metals in computer-simulated seawater matrices.     

胶州湾海水痕量金属?溶解有机质分配特征及其影响因素探讨

采集胶州湾表层和底层海水样品,分析了Cu、Cr、Cd、Pb、Ni、Co等痕量金属在海水中的空间分布特征及其在不同分子量溶解有机质中的分配特征,并探讨了痕量金属?溶解有机质分配机理及浮游生物活动与盐度等环境因素对该分配过程的影响。结果表明,胶州湾海水中痕量金属呈近岸浓度较高的分布特征,在湾东北部出现高值区,Cd和Pb还分别在湾口与湾中部出现高值区。胶州湾海水中痕量金属平均有70.1%分配于低分子量(<1 kDa)组分中,其中Cu和Cd低分子量组分所占平均比例分别达79.0%与77.6%,Cr、Ni和Co稍低,分别为71.5%、67.3%及66.9%,Pb则仅为58.2%。海水中的溶解有机碳也以低分子量组分为主,所占比例平均达73.1%,且光谱特征显示低分子量溶解有机质中类腐殖质含量更高,含有丰富的羧基和羟基,金属配合能力较高,导致痕量金属多分配于低分子量溶解有机质中。高分子量溶解有机质(>1 kDa)所占比例与叶绿素a浓度呈显著正相关,表明浮游植物初级生产通过释放高分子量溶解有机质影响海水痕量金属?溶解有机质的分配过程。胶州湾湾顶盐度较低海域痕量金属高分子量组分略高,可能是生物活动及陆源输入(产生更多高分子量溶解有机质)与盐度(低盐有利于高分子量有机质的稳定性)共同作用的结果。     

Effect of sample pretreatment on the reliability of solid speciation data of heavy metals — implications sesfor the study of early diagenetic processes

Experimental data on anoxic freshwater sediments from the Hamburg harbor indicate that commonly performed storage and pretreatment methods including aeration by drying strongly change the original associations of heavy metals with different sediment components. Oven-drying as well as freeze-drying under ‘vacuum’ affects metals originally bound to carbonate (Fe, Mn) and to the sulfidic/organic fraction (Zn, Cd, Cu, Pb), as indicated by sequential chemical extractions. While the easily oxidizable Cu and Pb portions are transferred mainly into the moderately reducible fraction, those of Zn and especially Cd are found in easily reducible and labile exchangeable fractions upon aeration of the sediment. Metals from only the latter fractions are potentially mobilizable via pore-water fluxes. Useful information on solid speciation influencing the mobility of contaminants in biogeochemically reactive sediments by the chemical leaching approach requires, therefore, proper and careful handling of the anoxic sediment samples.     

常见重金属在翅碱蓬(Suaeda heteroptera)根际沉积物系统季节迁移变化

应用原子吸收光谱法(AAS)和电感耦合等离子体原子发射光谱法(ICP-AES)对翅碱蓬-根际沉积物系统常见重金属(Cu、Pb、Zn和Cd)总量和不同化学形态含量进行了季节跟踪测定。结果表明,系统中Cu、Zn、Pb和Cd环境化学行为呈现显著季节变化。从化学形态上看,根际沉积物中Cu和Pb在生理周期内均以残渣态为主,有机结合态在夏季和秋季达较高值。Zn在生理周期内均以交换态为主且随季节变化明显,碳酸结合态和铁锰结合态随季节变化不明显。Cd以残渣态为主,交换态在春季达最高。从总量上看,根际沉积物中的Cu、Zn、Pb的总量在夏季和秋季具有较高值。从系统迁移情况看,植物对Cu和Pb吸收量均为冬季春季秋季夏季,且大部分限制于地下;其体内分布除秋季Pb为根叶茎外,其它时期均为根茎叶。Zn吸收量为秋季夏季冬季春季,且绝大部分被吸收至地上。Zn吸收和分布取决于根际沉积物生物有效含量;总之,春季植物体重金属向根际沉积物迁移。夏季和秋季,Cu、Pb和Cd由根际沉积物向植物体迁移变化并不明显,而Zn正好相反。4种元素在冬季均为根际沉积物向植物体内迁移。     

Mobilization of metals from riverine suspended matter in seawater

Suspended matter from rivers in the Russian Far East was leached by seawater to assess the extent of Zn, Cd, Pb, and Cu release from the land-derived solids to estuarine and coastal waters. The concentration of solids in the leaching experiments was 0.25 g/l. The suspended matter used varied in metal content from background levels to heavily contaminated.The concentration of Zn, Cd, Pb, and Cu in the leaching solution after 1, 4, 24, 48, and 96 h was determined by anodic stripping voltammetry. Measurable Cd was transferred from river suspended matter to seawater with both background and elevated Cd concentrations, though the amount of Cd released was different. The increase in Zn and Pb in solution was observed only at the enriched concentration of metals in the suspended solids. The Cu transfer into solution was more pronounced from material with elevated Cu concentration, but the amount of degradable organic matter in the solid phase was more important.The losses of metals from the riverine solids varied from 60% to 80% of total concentration for Cd to negligible for Pb, independent of contamination. The Zn loss depended on the initial concentration in the solids and decreased from 11–16% for the heavily contaminated suspended matter to 3–8% for the moderately enriched ones and to negligible for the pristine solids. Cu loss varied from 1% to 30% of total content, with no clear dependence on concentration in the suspended matter.The significance of additional input of dissolved metals to estuarine and coastal waters from remobilization was assessed by comparison with the initial concentration of dissolved metals in river water. Such experiments could be used to assess the water quality impact of atmospheric fallout of contaminated solids and storm drainage from the urbanized areas, in addition to river suspended matter studies.     

广西廉州湾贝类养殖区重金属的含量变化及潜在生态风险评价

根据2012—2017年每年8月廉州湾贝类养殖区现场监测资料,探讨了重金属(Hg、Cu、Pb、Cd)在其海水和表层沉积物中的含量变化,评价了2种介质中重金属的污染状况和沉积物重金属的潜在危害状况.结果表明:海水中重金属平均含量为Cu Pb Cd Hg,除Cu外,Hg、Pb、Cd的年际变化均呈明显上升趋势,其污染程度顺序为Cu Hg Pb Cd,整体水质状况基本属于本底水平;表层沉积物中重金属平均含量为Pb Cu Cd Hg,除Hg外,Cu、Pb、Cd的年际变化趋势和水相中的变化基本一致,其污染程度排序为Cu Pb Hg Cd,整体处于中等污染水平;表层沉积物中重金属的潜在生态风险程度顺序依次为Hg Cd Cu Pb,6次调查结果的综合潜在生态风险指数RI值均低于140,平均值为76. 98,表明该海域属于低潜在生态风险水平.     

Seasonal variability in the kinetics of Cu,Pb, Cd and Hg accumulation by macroalgae

Here it is demonstrated that both Porphyra spp. and Enteromorpha spp. of macro-algae display similar and very marked seasonal variations in their concentration factor (CF) of Cu, Pb, Cd and Hg in field conditions. The CF variations are specific for each metal and reproducible over several years. The way variations in the biological activity affect the equilibrium and kinetics of the interaction between trace metals and live algae was studied in vitro. Natural seawater was used as the culture medium. Voltammetry was used for the determination of natural organic ligands and trace metals except Hg, which was determined by mercury cold vapour after on-line pre-concentration. Titrations with the relevant metal demonstrated that the maximum binding capacity of the algae was not significantly dependent on the season for Pb (ca. 100 μmol g_{dry algae}⁻¹), Cd (ca. 50 μmol g⁻¹) and Hg (80–100 μmol g⁻¹). Marked seasonal variations were observed for Cu (ca. 40 μmol g⁻¹ in January; 70 μmol g⁻¹ in May; and 100 μmol g⁻¹ in August). The conditional stability constants of metal–algae complexation sites were seasonally independent and similar for both algae: logK_MS′=8.5±0.3 (Cu), 5.6±0.2 (Pb), 5.3±0.2 (Cd) and 18.0±0.3 (Hg). Exudates with a strong Cu complexing capacity (logK′_CuL=12.47±0.06) were determined in cultures with added Cu, Pb or Cd concentrations, and identified by cathodic stripping voltammetry (CSV) as cysteine or glutathione. All the tested metals promoted the liberation of exudates, both cysteine- and glutathione-like ligands were exuded in the presence of Cu, only cysteine-like ligands in the presence of Pb, and only glutathione-like ligands in the presence of Cd, the rise depending of the season of the year, particularly for Cu. Highest levels were produced in the presence of added Pb. When exposed to either 1- or 100-μM total dissolved metal concentrations, the metal uptake, and its rate, varied with the season and the algae.     

Geochemistry of suspended matter from the Baltic Sea 2. Results of bulk trace metal analysis by AAS

In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g⁻¹), Cu (1330 μg g⁻¹) and Cd (12 μg g⁻¹) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (K_d) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.     

Monitoring trace metals in seawater using a diffusive gradient in thin film probe in Ulsan Bay,East Sea,Korea: Comparison with transplanted mussels

To evaluate the applicability of a diffusive gradient in thin film (DGT) probe for monitoring dissolved metals in coastal seawater, DGT-labile metal concentrations were compared with total dissolved metal concentrations using spiked and natural seawater samples in the laboratory and transplanted mussels (Mytilus galloprovincialis). This was achieved through the simultaneous deployment of DGT probes and transplanted mussels in Ulsan Bay during winter and summer. DGT-labile metal concentrations were 45% (Cu) ~ 90% (Zn) of total dissolved concentrations, and the order of non-labile concentrations was Cu > Pb > Co ~ Ni > Cd ~ Zn in both metal-contaminated and non-contaminated seawater samples, which was similar to the order of stability of metal complexes in the Irving–Williams series. The overall variability of the DGT probe results within and between tanks was less than 10% (relative standard deviation: RSD) for all the metals tested during a 48-h deployment. The accumulation of metals, as determined by DGT probes, represented the spatial gradients better than the transplanted mussels did for all of the metals tested, and the extent of metal accumulation in mussels differed depending on the metal. The comparison of results for the DGT probe and the transplanted mussels in two seasons (winter and summer) suggested that metal accumulation in mussels was controlled by the physiological factors of mussels and partly by their diet (particulate metal loadings). The DGT probe could be used as a monitoring tool for dissolved metals in coastal seawater because its results explained only labile species. When using the DGT probe, slightly more than half of the total dissolved concentration in seawater samples for all the metals investigated displayed timeintegrated properties and distinct spatial gradients from pristine to metal-contaminated seawater.     

基于生物可利用性评估城市道路沉积物重金属生态风险

城市道路沉积物重金属风险评价是表征城市环境质量的有效途径.采用重金属化学形态和生物可利用性来评估其生态风险更合理,越来越受到人们的关注.本文采集山东省青岛市崂山区10条次干道沉积物样品,分析不同粒径沉积物中Zn、Cd、Cu、Pb的含量、化学形态和生物可利用性,采用地累积指数(Igeo)和改进的生态风险指数(RIm)评价...     

RESEARCH ON THE DETERMINATION OF Pb, Cd, Cu AND Zn IN SEAWATER BY STRIPPING VOLTAMMETRY

In this paper, a comparison viral made between the two results of determining Pb, Cd, Cu and Zn in seawater by direct current (tripping voltammetry (DCS) with rotating glass carbon electrode and by differential pulse stripping voltammetry (DPS) with hanging mercury drop electrode (HMDE). By DCS, the range of linear calibration curves obtained was 4×10-3 M-2×10-7M for Cu, Zn and Cd, and 4× 10-9M-2×10-3M for Pb. By using DPS, the range of linear calibration curve was as follows: Cu 0.65-1.9 ppb; Pb 1.0-10 ppb; Zn 0.65-2.0 ppb; Cd 0.02-0.14 ppb. It was found that DCS could be used for determining Pb, Cu, Zn in coastal waters, but it is necessary to add gallium ion to it to eliminate the interference of Cu-Zn inter-metallic compound for determining Zn. The DPS is better for determinig Cd.     

海水养殖池沉积物中重金属形态和生物酶活性的关系研究

以连云港市对虾养殖池表层沉积物为研究对象,采用Tessier连续萃取法,研究了表层沉积物中重金属(Cu、Zn、Pb、Cd、Cr、As、Mn)的赋存形态和酶(脲酶、碱性磷酸酶、过氧化氢酶、转化酶)活性的相关性。结果表明,重金属Cu和Zn以有机-硫化物结合态为主要的赋存形态,Pb以铁锰氧化物态为主要的赋存形态,Cd以可交换态(平均33.47%)和碳酸盐结合态(平均31.16%)为主要存在形态,Cr和As主要以残渣态存在,Mn的铁锰氧化物态比例最高。脲酶的活性范围为0.45—8.96mg/(g·24h),碱性磷酸酶活性范围为2.45—6.69mg/(g·24h),过氧化氢酶活性范围为0.14—2.36m L/(g·min),转化酶活性范围为0.45—10.45mg/(g·24h)。脲酶活性与Cd、As的可交换态、Cd的碳酸盐结合态、Cu、As的铁锰氧化物态、Zn、Pb、Cd、Mn的有机硫化物态之间显著相关;碱性磷酸酶活性与Zn、Cd的铁锰氧化物态显著相关;过氧化氢酶活性与Cd的可交换态、碳酸盐结合态及残渣态、Cu、Cd、As的铁锰氧化物态、Zn、Pb、Cd、Mn的有机硫结合态之间显著相关;转化酶活性与Cu、Cd、As的可交换态、Cd的碳酸盐结合态、Cu、Cd、As的铁锰氧化物态、Zn、Pb、Cd、Mn的有机硫化物态、Cd、As的残渣态之间显著相关。酶活性可以用来指示海水养殖池沉积物中重金属的形态转化过程。     

珠江口荷包岛近岸海域沉积物重金属分布及其潜在生态危害评价

本文采用2008年在珠江口荷包岛近岸海域的调查数据,对表层沉积物重金属的分布特征及重金属与TOC的相关性进行了分析,并采用Hakanson潜在生态危害指数法对其生态危害程度进行了评价。结果表明:重金属Cd,Hg,Cr和As四种元素分布基本呈现荷包岛近岸海域较高的特点,重金属Zn,Pb和Cu的分布没有明显规律;重金属富集顺序为Cd＞Zn＞Cu＞Hg＞As＞Cr＞Pb。相关性研究表明,重金属Cu与Zn显著相关,Hg,Cr,Cd和As极显著相关;有机质是影响沉积物重金属迁移和转化的重要因素。潜在生态危害评价结果表明,荷包岛近岸海域表层沉积物重金属总体潜在生态危害轻微;各重金属生态危害程度顺序为Cd＞Hg＞As＞Pb＞Cu＞Cr＞Zn;对荷包岛近岸海域生态环境具有潜在生态危害的重金属主要是Cd和Hg。     

九龙江口表层沉积物重金属的污染特征与来源分析

为了解九龙江口表层沉积物重金属的污染特征,作者于2013年9月在九龙江口进行了表层沉积物采样调查分析,结果表明：沉积物中Cu、Pb、Zn和Cd的空间分布较为相似,高值区均分布在南溪入海口和海门岛下游海域,Cr含量的高值区也分布在南溪入海口附近。聚类分析将采样点位分为4类：第一类主要分布在河口区外侧,沉积物中油类含量较高;第二类主要分布在南溪出海口,硫化物、Zn和Cr的含量较高;第三类分布在河口区中北部,污染物含量处于中等水平;第四类主要分布在海门岛下游海域,硫化物、TOC、Cu、Pb和Zn含量较高。地质累积系数评价显示：Hg、Cu、Pb、Zn、Cr、As处于未污染到轻度污染水平,Cd为轻度污染到重度污染水平;Zn、Cr、Cd的I_geo指数相对较高,第二类和第四类站位的I_geo指数相对较高。相关分析表明,硫化物与Cu、Zn、Cd正相关性较高,Cu与Zn、Cd、Cr正相关性较高,Pb与Zn、Cd正相关性较高,Zn与Cd、Cr正相关性较高。主成分分析表明,河口沉积物重金属主要有以下几个可能来源：流域和河口的工农业活动和采矿活动、流域水土流失、流域自然风化。针对河口沉积物重金属污染,流域-河口污染控制与生态修复需采取以下措施：工业污染的控制、农业污染控制、养殖污染的控制、植树造林与河岸带绿化和矿山生态恢复。     

Distribution Characteristics of Heavy Metals and Grain Size of Sediments from Hailing Bay, China

Introduction Hailing Bay located in western Guangdong province is an important marine aquaculture base and a famous scenic spot. Moyang River which flows across Yangjiang is the major runoff and polluted source in the sea area of Hailing Bay. Hailing Bank ( approximately 5 000 m ) which was built to connect Hailing Island and the continent in 1964 has blocked the natural circulation of suspended sand and pollutants in seawater. Water flux through the Yangjiang harbor extensively decreases …     

湛江南柳河入海排污口邻近海域沉积物重金属污染评价

对南柳河排污口邻近海域表层沉积物中重金属的含量分布、富集状况进行分析,并采用潜在生态危害指数法进行评价。结果表明:Cu,Pb,Zn,Cd,Hg含量分布呈现由西北到东南递减的变化特点;5种重金属元素的富集程度均较重,且程度由大到小依次为Pb>Zn>Cu>Hg>Cd;生态危害评价显示,Pb,Cu,Zn等元素属于轻微生态危害,Hg,Cd等元素属于中等生态危害,5种元素生态危害程度由重到轻依次为Hg>Cd>Pb>Cu>Zn。     

东海陆扰海域铜、铅、锌、镉重金属排海通量及海洋环境容量估算

汇总并分析了20世纪80年代初以来东海陆扰海域重金属排海通量年变化规律及主要来源,应用多介质海洋环境中重金属迁移-转化模型,估算了东海陆扰海域重金属海洋环境容量。20世纪80年代初以来,东海陆扰海域铜、铅、锌、镉排海总量整体上呈不对称的倒"U"形变化趋势,基本符合"环境库兹涅茨曲线",20世纪90年代达到最大值,当前排海总量仍高于20世纪80年代初期的水平。东海陆扰海域铜、铅、锌、镉污染物主要来源于以河流为主的陆源排放,其中88.0%左右来源于河流排放,7.5%左右来源于排污口,只有4.5%左右来源于大气沉降。长江流域排海通量占东海陆扰海域排海总量的比例最大,平均为92.4%左右,钱塘江流域平均只有3.9%左右,闽江流域平均只有3.7%左右。东海陆扰海域铜、铅、锌、镉污染物海洋环境容量分别约为17.0,4.7,113.1,0.71 kt/a。当前铅、锌、镉污染物排海总量没有超过东海陆扰海域海洋环境容量,但铜的排海总量超过其海洋环境容量大约8%。