Distribution of heavy metals and nutrients in rainwater in coastal regions between the southern Yellow Sea and East China Sea

Rainwater samples were collected in series in Qianliyan Island (southern Yellow Sea) and Shengsi Archipelago (East China Sea) between May 2000 and May 2002, chemical analysis for pH values, concentrations of heavy metals (Cu, Pb, Zn and Cd) and nutrients (NH4+, NO3-, PO43-, SiO32-) were performed. Results indicate that concentrations of most of the heavy metals and nutrients in rainwater show clear seasonal variation, i.e. high level in winter and low level in summer. Regionally, concentrations are higher in the southern Yellow Sea than in the East China Sea, but the annual input of heavy metals into oceans by wet deposition is similar in both stations. However, the input of nutrients by wet deposition in the East China Sea is 2–3 times higher than that in the southern Yellow Sea. In individual, Pb and PO43- are input to the sea mainly by dry deposition; whereas Cu, Zn, Cd and N compounds are input dominantly by wet deposition, the N/P ratios in the rainwater from two stations are much higher than those in seawater, showing a significant impact of atmospheric wet deposition on marine production and biogeochemical circulation of nutrients in these sea regions.

Heavy metals in sediments of Yellow Sea and East China Sea: Chemical speciation,distribution,influence factor,and contamination

Metal species and the degree of environmental pollution are related to the hydrogen sulfide(H_(2)S),an important product of early diagenesis that can react with metals to form stable compounds.To investigate the eff ects of H_(2)S to metals and evaluate metal environment eff ect in the sediments of the East China Sea(ECS)and Yellow Sea(YS),geochemical characteristic and spatial distribution of nine heavy metals and H_(2)S profile were studied.Higher H_(2)S content and lower metal content was observed in the sediments 10 cm in depth in the North Yellow Sea and the west coast of South Korea.The pollution load index(I_(pl))indicates that the southern coast of Shandong Peninsula underwent moderate pollution(I_(pl)=1)of heavy metals and no heavy metal pollution appeared in other areas(I_(pl)<1).To some extents,the ecological risk of Cd and As enrichment was moderately severe in all stations.The chance of heavy metal combination to be toxic in ECS and YS during summer was 21%.In addition,correlation between H_(2)S content and metals in both solid and porewater phases was obvious,corroborating important eff ect of H_(2)S on metal distribution.Moreover,H_(2)S could aff ect the spatial distributions of heavy metals in porewater directly and be indicative of potential biological eff ects of combined toxicant groups in the study region.

Distribution of eight heavy metals in the inner shelf sediments of East China Sea:Risk assessments and sources analysis

Although numerous studies on heavy metals(HMs)in sediments have been carried out in the East China Sea(ECS),the knowledge on the recent pollution levels of HMs in coastal region remains not well understood due to the rapid developments of urbanization in eastern China.In this study,23 surface samples and 4 core samples are collected in the inner shelf of the ECS.The average dry-weight concentrations follow the descending order of Zn,Cr,Ni,Pb,Cu,As,Cd,and Hg(103.6±26.0,42.8±12.4,37.0±9.1,34.7±11.1,19.5±10.3,15.7±11.6,0.056±0.017,and 0.041±0.017μg g^(−1),respectively).HMs concentrations share a similar spatial distribution pattern of TOC content with a decreasing trend from coastline to outer sea.Additionally,HMs concentrations exhibit a decreasing trend from top to bottom sediments,especially for Hg at the open sites due to the wet and dry deposition of atmospheric Hg besides the riverine inputs.The potential ecological risk indices(PERI)values in coastal sediments were about 2-4 times higher than those in open sea.Although the Hg and Cd concentrations were lower by 2-3 orders of magnitude than those of other six metals,the PERI values of Hg(65.5)and Cd(52.1)were 3-40 times higher than those of others.The hierarchical cluster result is consistent with the PCA result,suggesting that Hg,Cd,and As have similar sources and probably mainly originated from anthropogenic emissions.

ANALYSIS OF Cu, Cd, Co AND Ni IN SURFACE WATER OF THE KUROSHIO AREA IN THE EAST CHINA SEA

Study of 1986 and 1987 heavy metal distribution in surface water of the Kuroshio area in the East China Sea showed regional and slight seasonal variations in distribution and concentration . Heavy metal levels in Taiwan Strait, the sea area north of Taiwan and the continental shelf are higher than those in the main axis of the Kuroshio . Dissolved Cu in summer and winter decreases with the increase of salinity , but dissolved Cd has no obvious change with salinity .

Analysis of Cu,Co,V and Zn in Coastal Waters of the East China Sea by Inductively Coupled Plasma Mass Spectrometry(ICP-MS)

In this study, a simple method for the simultaneous determination of trace metals(Cu, V, Co, Zn) in coastal seawater using the Mg(OH)2 coprecipitation inductively coupled plasma mass spectrometry(ICP-MS) was developed. This multi-element method enables the simultaneous extraction of four metals, particularly Co and V. The recoveries of Cu, Co, V and Zn after Mg(OH)2 coprecipitation were 73%, 96%, 94% and 92%, which means that our procedure was well-suited to the determination of these four trace metals. The detection limits were 3.81, 0.18, 6.09 and 1.91 nmol L-1, respectively. Then, applying this method to the simultaneous determination of these four metals in coastal water samples from the East China Sea revealed that the concentrations of Cu, Zn, Co and V were higher in bottom waters compared to water at other depths, and higher concentrations were generally observed at the Yangtze River estuary. Additionally, example vertical profiles of dissolved trace metal concentrations for the East China Sea in spring and autumn are compared. These findings indicate that Zn had the greatest seasonal variation followed by Cu, V and Co. For Zn and Co, the concentrations were higher during spring than during autumn. For Cu and V, the seasonal variation in the concentrations was opposite.

Temporal and spatial distribution of dissolved copper,lead,zinc and cadmium in the Changjiang Estuary and its adjacent waters

Heavy metal concentrations were measured in the Changjiang Estuary and its adjacent waters. Results from a systematic survey in April 2002 to March 2003 indicate that the ranges of the concentrations of dissolved copper, lead, zinc and cadmium in the study waters are 1.01 - 6.86, 0. 10 - 0.39,3.17 - 9.12 and 0.011 - 0. 049 μg/dm^3 , respectively. Similar to zinc, the behavior of dissolved copper was essentially conservative, but high scatter has been observed for high salinity samples, which can be attributed to the decomposition or mineralization of organic matter by bacteria. Dissolved lead may have active behavior with an addition at high salinity. Overall concentrations of dissolved cadmium increase with salinity. The mean values of these dissolved metals calculated for the surface waters were higher than those for the middle and bottom ones. External inputs of dissolved heavy metals to the surface waters were the likely explanation for these higher values. The maximum seasonal average values of dissolved copper and zinc were found in summer, reflecting higher amounts of riverine input in this season. In contrast, the maximum seasonal average values of dissolved lead and copper were found in winter and the lowest ones in summer, respectively, which might be asso- ciated with a combination of low concentration with heterogeneous scavenging. Concentrations of these dissolved metals found for the Changjiang Estuary fall in the range observed for the other estuaries but are noticeably higher than those from uncontaminated rivers, except for cadmium. Compared with observations for the Changjiang Estuary in the last two decades, it is clear that the Changjiang estuarine waters has been contaminated with copper, lead, zinc and cadmium during China＇ s industrialization, but concentrations of them have decreased in the last few years.

黄海及东海海域大气降水中的重金属

于2000年5月至2002年5月在黄海的千里岩岛和东海的嵊泗群岛两个采样点共采集了120多个降水样品 ,测定了pH值和重金属Cu、Pb、Zn、Cd的含量。结果表明 ,两个采样点的降水样品中重金属的浓度有明显的季节变化 ,冬季的浓度高于夏季。千里岩岛降水中的重金属的浓度明显高于嵊泗群岛 ,尽管其降雨量小于嵊泗群岛 ,千里岩岛大气降水中重金属的沉降通量仍大于嵊泗群岛。在千里岩岛 ,Pb以干沉降为主 ,而Cu、Zn、Cd的湿沉降占明显优势 。

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%。

东海沿岸海域牡蛎体内的重金属含量及其污染评价

利用火焰原子吸收光谱法、石墨炉原子吸收光谱法、冷原子吸收光度法对2007年6月份在东海沿岸海域采集的牡蛎(Ostreasp.)样品中的Cu、Zn、Pb、Cd、As、Cr、Hg、Ni共8种重金属进行了分析。结果表明:牡蛎体内重金属含量之间存在明显差异,Cu和Zn的含量显著高于其它重金属的含量,且两者之间存在有显著的正相关关系。与海洋贝类的生物质量标准相比,牡蛎体内的重金属含量基本上都还没有超过各自的第二和第三类评价标准,这说明当前东海沿岸海域牡蛎的生物质量总体上尚较好。各类重金属在东海沿岸海域的空间分布基本上以长江口含量为最高,其余海域含量较低,各海域重金属污染程度可分为三类,第一类环境质量较好,第二类环境质量一般,第三类海域环境污染程度较严重,人类活动是污染的主要来源。

Cu、Pb、Zn和Cd对东海原甲藻的生态毒性效应

采用现场调查、现场培养实验和模型分析的方法,研究长江口及邻近海域重金属Cu、Pb、Zn、Cd对东海原甲藻的生态毒性效应.结果表明,东海原甲藻在重金属浓度较低时处于非检测毒性生长状态,在重金属浓度较高时处于毒性生长状态,毒性效应随重金属浓度的升高而增大,重金属离子与生物活性离子的竞争吸附是造成2种不同生长状态的原因.建立非检测毒性效应模型,获得Cu、Pb、Zn、Cd对东海原甲藻的非检测毒性浓度（NDEC）分别为4.1,45.2,131.7,138.9μg/L.2003年5月调查海区溶解态Cu、Pb、Zn、Cd浓度范围分别为1.0～5.8,0.10～0.57,3.8～7.5,0.01～0.05μg/L,Cu浓度超过其NDEC的面积达49%,估计造成东海原甲藻生物量降低5%,浓度最高的海区降低24%,Pb、Zn、Cd等对东海原甲藻的NDEC高于调查海区的浓度,不会对其生长造成影响.

中国东部海域底质沉积物中重金属研究现状

中国东部海域(渤海、黄海和东海)底质沉积物接受了巨量的重金属(As、Cd、Cu、Cr、Hg、Ni、Pb、Zn和V),从而使得底质环境质量可能面临严重的重金属污染。这些重金属来源复杂,其中既有自然源重金属又有不同人为来源。其中自然源可能主要包括长江流域、黄河流域的泥沙和中国西部沙漠的粉尘,人为来源可能主要包括煤炭和燃油消耗、钢铁冶炼和有色金属冶炼,其中煤炭消耗和有色金属冶炼可能是中国东部海域沉积物铅和汞的最主要的来源。这些重金属主要通过河流输入的方式进入到中国东部海域,尽管鉴定沉积物中重金属具体人为来源的方法较多,但在中国东部海域应用最为成功的是铅稳定同位素。尽管巨量的重金属输入到中国东部海域,但绝大部分海域底质沉积物质量良好,仅在锦州湾海域重金属含量严重超标。

东海三个倾倒区表层沉积物重金属富积特征及其潜在生态风险评价

根据2003年东海吴淞口北倾倒区、椒江口倾倒区和闽江口倾倒区表层沉积物中重金属的监测资料,采用富积系数法和Hakanson潜在生态危害系数法对其富积程度和潜在生态危害程度进行了分析和评价。结果表明:在三个倾倒区表层沉积物所监测的重金属中,Cu和Pb元素的富积程度相对最高,As次之,Hg和Cd元素的富积程度较低。从空间上看,Cu和As元素的富积程度呈现吴淞口北倾倒区<闽江口倾倒区<椒江口倾倒区的特征;而Pb,Cd和Hg元素的富积程度呈现由北向南递增的趋势,即:吴淞口北倾倒区<椒江口倾倒区<闽江口倾倒区。潜在生态危害系数评价结果显示,东海三个倾倒区表层沉积物中的重金属对海洋生态系统的潜在生态危害非常轻微,均属于轻微潜在生态危害范畴,其中轻微潜在生态危害程度相对较重的是As,Cd和Hg元素,Cu和Pb元素的轻微生态危害程度较轻。

长江口及邻近海域细颗粒沉积物中重金属的空间分布及沉积通量

长江每年输送大量的泥沙进入东海,其中细颗粒沉积物具有搬运距离远、扩散范围大的特点,成为示踪河口及近海沉积物源汇过程的良好载体。本文基于采自长江口及邻近海域的44个表层沉积物样品,分析了细颗粒组分中重金属的空间分布和沉积通量,探讨了重金属来源和搬运沉积过程。研究表明:长江口及邻近海域细颗粒沉积物中Cu、Cr、Ni、V和Zn含量、沉积通量的空间分布具有高度的相似性,总体表现为长江口及浙闽沿岸高,向外急剧降低;该区细颗粒沉积物中的重金属主要来自长江,入海后向两个方向扩散,其一为向西南方向扩散,沉积于内陆架泥质区;其二是向东的跨陆架输送,沉积于长江冲淡水影响的海域。从长江口向西南方向的输送和沉积是长江入海重金属最重要的汇。

东海陆架沉积物中重金属地球化学研究

研究了东海陆架表层沉积物中的重金属含量分布特征,基本服从“粒度律”,即随着沉积物的粒度变细而含量增高;区域分布的基本特征是高值区分布于中国台湾岛东侧和大陆近岸区域,低值区分布于东部及北部浅海大沙滩区;分析该区沉积物中重金属的地球化学特征及其分布规律采用无量纲分析,提出了重金属集散规律的多因子控制关系式,采用最小二乘法求得系数α、b及相关系数r:rZn=0.82,rCu=0.91,rPb=0.90,rCd=0.89,rHg=0.80,rC r=0.87。

东海主要重金属生态基准浓度初步研究

采用现场培养实验的方法,研究了Cu、Pb、Zn和Cd重金属对东海原甲藻(Prorocentrum donghaiense Lu)的生态毒性效应。计算结果表明:重金属Cu、Pb、Zn、Cd对东海原甲藻生长的非观察效应浓度(NOEC)分别为3.7、32.6、133.2和128.0μg/L;生长抑制效应浓度EC05分别为4.6、56.3、142.8和151.3μg/L。估算了我国东海海水中重金属Cu、Pb、Zn和Cd的生态基准浓度分别为4.6、0.1、28和0.3μg/L。我国Cu、Pb和Cd的一类海水水质标准高于东海海水生态基准。

黄、东海表层沉积物重金属赋存形态及风险评价

利用Teissier 5步连续提取法分析了黄、东海6个表层沉积物样品中重金属Zn、Pb、Ni、V、Fe和Mn的赋存形态,并基于富集因子评价法、地质累积指数评价法和酸提取态比重风险评价法对6种重金属的污染现状和潜在生态风险进行了初步评价。各重金属的含量分布依次为:Fe>Mn>Zn>V>Ni>Pb。Ni、Zn、V和Fe两两之间均呈现很好的正相关,表明这些元素污染具有同源性。赋存形态分析表明,V、Fe、Zn和Ni主要以残渣态存在,Pb和Mn在可提取态和残渣态比例相当。铁锰氧化物结合态和碳酸盐结合态是非残渣态Pb和Mn的主要存在形式。富集因子评价法和地质累积指数评价法结果显示,Pb、V、Fe和Mn主要受自然来源影响,未受到人类活动的影响。Ni和Zn受到轻微人类活动影响。酸提取态比重风险评价结果显示,Pb和Mn风险评价为中风险,易从沉积物重新释放进入水体形成二次污染。

东海北部表层沉积物重金属地球化学研究

为了解东海北部海域表层沉积物重金属元素空间分布特征,地球化学分区及其产生原因,搜集了近期研究区沉积物调查资料,经过分析讨论,结果表明:研究区各重金属元素空间分布类似,有近岸高、远岸低的特点,有3个重金属含量高值区,1个低值区;研究区可划分为11个地球化学分区,包括钱塘江、长江口两个河口区,江苏至浙江近海的6个近岸海区,以及邻近的3个陆架分区;物源及水动力条件对重金属元素的分布具有控制作用,而沉积物的粒度和有机质含量对其有重要影响。

东海海洋大气颗粒物中重金属的来源及入海通量

2006～2007年,对杭州湾以南的东海海域进行了春、夏、秋、冬4个航次的海洋大气调查,分析了大气颗粒物中重金属元素(Cu、Pb、Zn、Cd)的含量,根据调查结果,采用富集系数法对重金属的来源进行了初步分析,对干沉降入海通量进行了估算.结果表明,调查海域海洋大气颗粒物中的Cu、Pb、Zn、Cd含量相对于地壳和海水均表现为强富集,富集系数远远大于10,属于污染元素,主要来自人类活动污染.重金属元素的大气干沉降通量大小顺序为Zn[10.92 mg/(m2.a)]>Pb[2.299mg/(m2.a)]>Cu[1.611 mg/(m2.a)]>Cd[0.017 mg/(m2.a)].各种金属元素月通量均为冬季最高,夏季或秋季最低,且季节差异十分显著.按调查区域覆盖面积(160 000 km2)估算,每年Cu、Pb、Zn、Cd大气干沉降总量为2 376 t,约为长江重金属年入海通量的13%,因此大气输入也是重金属进入东海的重要途径之一.

东海表层沉积物中重金属集散特征及变化规律

为研究重金属集散特征及在海洋沉积物中的变化规律,采用π定理建立准则,分别对表征重金属集散特征多因子中的中值粒径、细粒平均粒径及其含量、有机质和粘土含量做了数理统计与分析,建立多元集散控制方程,并运用最小二乘法求解方程中的相关系数.结果表明,该方程能够很好地表征海洋沉积物中重金属元素富集规律及其在海底环境中动态变化过程.

百年来东海内陆架沉积物中重金属的累积过程及生态风险变化

研究了东海内陆架两个沉积岩芯DH33和KP04中重金属的含量,分析了重金属的累积过程及影响因素,并对不同重金属间的相关性进行了比较,最后利用潜在生态危害指数表征了百年来的生态风险变化。结果表明:东海内陆架沉积物中重金属主要来源于长江的入海携带,因地理位置差异,两岩芯重金属含量变化与长江径流量变化响应程度不同,DH33靠近长江口,响应较好,径流量大的年份重金属含量高;KP04远离长江口,响应较差,浙闽沿岸流和台湾暖流均会对KP04有物源供应。重金属V与Cr、Cr与Ni间相关性良好;As、Hg、Cd 3者与其它金属相关性较差,KP04重金属的含量总体大于DH33,与"粒度律"相矛盾,初步推测KP04站位重金属含量的变化受物源供应和沉积速率共同作用的影响,台湾暖流可能是重要的物源供应途径。生态风险评价结果显示,仅岩芯KP04在1990s和1930s处于"中度污染"级别,且主要是由Hg、Cd、As引起。