Chemical forms of heavy metal contaminants in sediments of Miyun reservoir

The chemical forms, spatial distribution and sources of As, Hg, Cd, Pb and Zn in sediments of the Miyun reservoir were studied. The results of sequential extraction demonstrate that most of As, Pb and Zn were bound to the residual fraction, Hg was associated with the sulfide fraction while Cd was associated with the carbonate fraction and the residual fraction. On the vertical profiles the concentrations of the heavy metals in total and each fractions mostly decreased with increasing depths in sediments, suggesting that the heavy metals input from the upstream watershed increases yearly. Summation of the residual fraction, the sulfide fraction and the carbonate fraction accounts for 60.03%―85.60% of the total heavy metal contents in the sediments, which represent the geochemical background values of the elements and relate closely to soil erosion. Results of the main factor analysis show that most sediments of the reservoir come from the upstream soil erosion, the point source pollution and domestic waste. Moreover, the microbial activities taking place on the sediment-water interface are also one of the major factors to cause the increasing content of the organic matter fraction and the iron-manganese oxide fraction. Environmental change of the reservoir water could make the removability of the heavy metals increase, leading to the increase of their concentrations in pore water in sediments, and imperiling water quality of the reservoir.     

富硫型水库沉积物AVS和SEM空间分布特征及重金属风险评价

随着湖库外源性污染的有效控制,沉积物污染特征成为影响湖库水环境质量的关键因素。本文以富硫型水库——汤河水库为研究对象,分析探讨水库沉积物的理化性质、重金属总量、酸可挥发性硫化物(acid volatile sulfide,AVS)和同步提取重金属(simultaneously extracted metals,SEM)的空间分布特征,采用沉积物基准法(sediment quality guidelines, SQGs)和AVS与SEM关系法对重金属可能诱发的生态风险和毒性效应进行评估。结果表明:汤河水库沉积物中AVS含量在0.03~51.75 μmol/g之间,并呈现坝前深水区>东支流库区>西支流库区的空间分布特征。根据Pearson相关性分析可知,汤河水库沉积物AVS含量与间隙水中SO₄^2-浓度、沉积物烧失量(LOI)含量呈显著正相关,与沉积物间隙水中NO₃^-浓度和沉积物pH呈现显著负相关。间隙水中SO₄^2-浓度和沉积物LOI含量是控制AVS产量的重要因素。水库沉积物中ΣSEM变化范围为0.52~2.75 μmol/g,呈现出东支流库区>坝前深水区>西支流库区的分布规律。水库沉积物中ΣSEM/AVS和ΣSEM-AVS的变化范围分别为0.06~22.73和-49.18~2.44 μmol/g,显示出水库坝前深水区表层0~10 cm沉积物不具有生态风险,而东、西支流库区沉积物中的SEM因为不能完全被AVS所固定而存在潜在生态风险。就单一重金属而言,汤河水库坝前深水区和东西支流中部区域沉积物Ni、Cu、Pb和Zn含量均介于临界效应含量(threshold effects level, TEL)值和可能效应含量(probable effect level, PEL)值之间,可产生低级风险毒性效应,但Ni的毒性效应风险接近中级,今后应予以重点关注。富硫型水库沉积物中容易出现高含量AVS,沉积物间隙水中SO₄^2-和NO₃^-的浓度是决定沉积物AVS净产量的重要因素。流域内重金属土壤背景值以及工业、采矿产业排放的废水类型直接影响着诱发生态风险的重金属种类。     

High resolution time series of lead and zinc in sediments of Lake Constance

Sediments in Lake Constance have been dated by radiometric methods and lamination counting. Investigations into the concentrations of lead and zinc in the sediments were carried out to get detailed information about environmental history. Maximum concentrations were found at the beginning of the 1960's. The lead maximum contamination occurred 3 years before the zinc maximum and has an unidentified source. The use of coal, leaded gasoline or the remobilization within the sediment could be excluded to result in the lead maximum. The fluctuations in zinc contamination could be explained with increasing and decreasing pollution (industry, coal burning, building of sewage plants). The greatest fluctuations of both metals occur during periods of great change in the economic history of Germany.     

白洋淀沉积物重金属潜在生态风险及生物可利用性分析

沉积物是湖泊水体重金属的主要汇集场所,也是湖泊重金属污染研究及整治的重点.本文分析了白洋淀多个淀区沉积物中16种重金属含量水平及垂向分布特征,解析了其中典型有害重金属潜在生态风险,并基于酸可挥发性硫（AVS）及同步可提取金属（SEM）、间隙水溶解态金属、可转化态金属形态分级等研究,对重金属生物可利用性进行了分析.结果表明：沉积物重金属含量均值高低依次为Fe （29630.50 mg/kg）>Ti （3213.07 mg/kg）>Mn （539.44 mg/kg）>Zn （104.01 mg/kg）>V （76.63 mg/kg）>Cr （52.60 mg/kg）>Cu （43.49 mg/kg）>Ni （35.83 mg/kg）>Pb （26.75 mg/kg）>Co （10.32 mg/kg）>As （8.96 mg/kg）>Mo （2.06 mg/kg）>Sb （1.57 mg/kg）>Tl （0.43 mg/kg）>Cd （0.31 mg/kg）>Hg （0.16 mg/kg）;其中,10种重金属在各淀区沉积物中呈现出自北往南逐渐降低的趋势,各金属在不同淀区分布差异性主要由污染输入所致.除北部烧车淀区域外,其余区域重金属潜在生态风险总体处于较低水平.重金属污染主要来源于该区域周边河道,但近10年来污染输入及在沉积物中的富集总体趋于稳定并呈逐渐降低的趋势.入淀污染不仅增加了该区域沉积物中重金属总量,也使得其中可转化态重金属比例较高,大多在30%~90%之间,提升了重金属生物可利用潜力.水生植物等内生性有机质的大量富集导致沉积物还原性较强,AVS含量较高,沉积物中AVS和ΣSEM均值分别为（10.59±6.37）和（2.23±1.53）μmol/g （dw）.Cd、Cu、Ni、Pb、Zn等金属由于高含量还原态硫的固定而生物可利用性较低.然而,As和Hg在这样的高有机质和强还原环境下更容易溶解和释放,是潜在生物可利用性相对较高的金属,在间隙水中的浓度分别达到（17.07±0.23）和（2.39±0.94）μg/L,未来研究及整治中应给予更多关注.     

Heavy metal transport in large river systems: heavy metal emissions and loads in the Rhine and Elbe river basins

Pollutant transport and management in the Rhine and Elbe basins is still of international concern, since certain target levels set by the international committees for protection of both rivers have not been reached. The analysis of the chain of emissions of point and diffuse sources to river loads will provide policy makers with a tool for effective management of river basins. The analysis of large river basins such as the Elbe and Rhine requires information on the spatial and temporal characteristics of both emissions and physical information of the entire river basin. In this paper, an analysis has been made of heavy metal emissions from various point and diffuse sources in the Rhine and Elbe drainage areas. Different point and diffuse pathways are considered in the model, such as inputs from industry, wastewater treatment plants, urban areas, erosion, groundwater, atmospheric deposition, tile drainage, and runoff. In most cases the measured heavy metal loads at monitoring stations are lower than the sum of the heavy metal emissions. This behaviour in large river systems can largely be explained by retention processes (e.g. sedimentation) and is dependent on the specific runoff of a catchment. Independent of the method used to estimate emissions, the source apportionment analysis of observed loads was used to determine the share of point and diffuse sources in the heavy metal load at a monitoring station by establishing a discharge dependency. The results from both the emission analysis and the source apportionment analysis of observed loads were compared and gave similar results. Between 51% (for Hg) and 74% (for Pb) of the total transport in the Elbe basin is supplied by inputs from diffuse sources. In the Rhine basin diffuse source inputs dominate the total transport and deliver more than 70% of the total transport. The diffuse hydrological pathways with the highest share are erosion and urban areas. Copyright © 2002 John Wiley & Sons, Ltd.     

典型小型水库表层沉积物重金属分布特征及生态风险

以典型乡镇水库通济桥水库表层沉积物为研究对象,在分析其中As、Cd、Cr、Cu、Hg、Ni、Pb和Zn等有毒、有害重金属分布特征的基础上,分析重金属来源,评价重金属污染程度及其潜在生态危害.结果表明:通济桥水库表层沉积物中,上述8种重金属均存在一定程度的污染,坝前和入库区污染物蓄积更为明显.其中,Hg和Cd的污染范围较广、污染程度较严重.受重金属Hg和Cd的影响,水库表层沉积物存在中等程度的重金属生态危害风险,其中坝前区域已处于强风险等级.为保障水库水体水质安全,防范重金属污染应提到当前水库管理工作的重要位置.     

首钢工业区土壤剖面重金属含量及其结合态的磁指示作用的研究

对取自首都钢铁厂附近的土壤样芯进行了重金属含量、形态分析和的磁学测量.探讨了利用磁参数追踪和指示重金属污染和有机结合态和铁锰氧化结合态重金属的可行性.结果表明:土壤样芯中Cu、Pb、Zn、Fe和Mn的含量与χ、SIRM和ARM存在着十分相似的垂向变化特征,且相关关系显著(0.98>R>0.86).进一步对磁化率和Cu、Pb、Zn、Fe和Mn各结合态进行相关分析表明:五种元素的有机结合态与铁锰结合态和磁化率呈显著相关关系(0.98>R>0.56),而交换态和残渣态重金属与磁化率基本不存在相关关系.反映了磁性矿物和和重金属在赋存状态的本质联系.表明了磁性测量可作为工业区土壤重金属污染及有机结合态与铁锰结合态重金属记录信息提取的辅助手段.     

阳澄湖近代沉积物的古湖泊学研究

对阳澄湖两上短柱状样进行了地上代以及各种环境指标分析。结果表明,湖底沉积物由被长期沉积间断所分割的３个岩性层组成：下部层Ｃ属再沉积的更新世晚硬土层;中部层Ｂ为全新世沉积;上部层Ａ为近１００年以来的表层沉积。对层Ａ的详细分析显示,本世纪以来,特别是７０－８０年代以来,金属元素,营养元素和色素的沉积通量明显提高,说明湖泊重金属污染和富营养化程度的不断加重。     

Heavy metal pollution and assessment in the tidal flat sediments of Haizhou Bay,China

The heavy metal inventory and the ecological risk of the tidal flat sediments in Haizhou Bay were investigated. Results show that the average concentrations of heavy metals in the surface sediments exceeded the environment background values of Jiangsu Province coastal soil, suggesting that the surface sediments were mainly polluted by heavy metals (Cd, Cr, Cu, Mn, Pb and Zn). In addition, the profiles of heavy metals fluxes can reflect the socio-economic development of Lianyungang City, and heavy metals inputs were attributed to anthropogenic activities. Cr, Cu, Pb and Zn were mainly present in the non-bioavailable residual form in surface sediments, whereas Cd and Mn were predominantly in the highly mobile acid soluble and reducible fractions. The ecological risk of the polluted sediments stemmed mainly from Cd and Pb. According to the Sediment quality guidelines (SQGs), however, the adverse biological effects caused by the heavy metals occasionally occurred in tidal flat.     

The distribution of acid-volatile sulfide and simultaneously extracted metals in sediments from a mangrove forest and adjacent mudflat in Zhangjiang Estuary, China

The distribution of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM) were studied in sediments collected from mangrove forest, forest fringe and adjacent mudflat in the Zhangjiang Estuary, China. The aim was to examine the spatial distribution of AVS and SEM in sediments of the Estuary and determine the influence of mangrove trees on AVS and SEM concentrations in the sediments. The results indicated that AVS concentrations in forest sediments were significantly lower than those in mudflat sediments. There was a significant positive correlation between AVS values and moisture contents in forest sediments, while LOI played an important role in AVS concentrations of mudflat sediments. In the forest sediment core, the peak value of AVS appeared deeper in the sediment profile compared to it appeared in the mudflat core. The distribution of SEM showed different trends from that of AVS, and potential toxicity existed in the upriver forest sediments.     

高温高压实验中重金属在硅酸盐熔体中溶解度研究及进展

本文对高温高压重金属溶解度研究的目的、内容进行了概述,并对国内外这一领域研究的历史、现状及有关实验技术方法进行了综述,重点在于对目前国内外研究的进展和方法的初步改进以及讨论高温高压实验对地质找矿的解释应用.     

40 年来江苏石梁河水库重金属污染的沉积记录

根据石梁河水库沉积物粒度和重金属元素(Cu,Cr,Zn,As和Pb)含量的分析,结合137Cs放射性比活度精确定年,研究了石梁河水库沉积速率和重金属的污染变化特征,并利用地累积指数法评价了重金属的污染程度.结果表明:石梁河水库 40年来平均淤积速率为3.85cm/a,Cu,Cr和zn地累积指数一直小于1,处于轻微污染;As污染水平变化较大.现处于低水平的轻度污染;Pb污染水平自柱底始持续恶化,目前地累积指数大于1,且有污染加剧趋势.     

Influence of mangrove reforestation on heavy metal accumulation and speciation in intertidal sediments

To investigate the influence of mangrove reforestation on heavy metal accumulation and speciation in intertidal sediments, core sediments from a restored mangrove forest and adjacent mud flat in Yifeng Estuary (southeastern China) were analyzed. The chemical speciation of heavy metals (Pb, Zn, Cu, Cr and Ni) was determined according to a sequential extraction procedure. Special attention was paid to the upper 20 cm of sediment, in which metal accumulation was enhanced and speciation was obviously modified. Mangrove reforestation decreased the concentrations of all metals in the acid-soluble fraction and increased metal concentrations in the oxidizable fraction. Increased Pb, Zn and Cu concentrations and decreased Ni and Cr concentrations were observed in the reducible fraction. These results suggest that mangrove reforestation facilitated the accumulation of heavy metals in the upper sediment layers but decreased their bioavailability and mobility.     

Effects of environmental regulations on heavy metal pollution decline in core sediments from Manila Bay

We investigated the high-resolution heavy metal pollution history of Manila Bay using heavy metal concentrations and Pb isotope ratios together with ²¹⁰Pb dating to find out the effects of environmental regulations after the 1990s. Our results suggested that the rate of decline in heavy metal pollution increased dramatically from the end of the 1990s due to stricter environmental regulations, Administrative Order No. 42, being enforced by the Philippines government. The presented data and methodology should form the basis for future monitoring, leading to pollution control, and to the generation of preventive measures at the pollution source for the maintenance of environmental quality in the coastal metropolitan city of Manila. Although this is the first report of a reduction in pollution in Asian developing country, our results suggest that we can expect to find similar signs of pollution decline in other parts of the world as well.     

云南错恰湖两百年来气候环境变化与重金属污染

高海拔地区由于特殊的自然环境对气候变化和营养输入的响应十分敏感.在人类活动逐渐加强的背景下,高山湖泊高分辨率的沉积物记录了人与自然相互作用的演变过程.选取云南西北部典型高山湖泊——错恰湖,获取长度37 cm的连续湖泊沉积序列,基于铅铯测年法得到年代深度模型,并对湖芯样品进行总有机碳、总氮及正构烷烃的多指标测定和元素测量,结合气象监测数据探讨分析错恰湖的有机质来源和流域环境演化特征.根据气候代用指标的变化,两百年来错恰湖泊环境及区域气候演化可以分成4个主要阶段：1807-1900年：湖泊水位上升、湖面扩大,有机质丰度下降,有机质以外源贡献为主,内源比例上升;1900-1950年：湖泊水位开始下降、湖面收缩,有机质丰度下降,外源有机质来源增加;1950-1982年：湖泊水位下降、湖面进一步收缩,有机质丰度下降,外源输入比例继续增加;1982-2007年：湖泊水位下降、湖面收缩,有机质含量上升且以陆源输入为主,同时内源贡献比例开始增加.在元素测定结果中,人类活动对应了湖泊沉积重金属含量变化的3个阶段：1950年以前,重金属含量低且稳定,可视作自然背景阶段,人类影响忽略不计;1950年以后,湖泊流域工农业逐渐发展,人为干扰凸显;直到1982年以后,冶炼工业的进步加强了重金属的污染态势,并通过大气传输沉降被湖泊沉积物记录.错恰湖沉积记录的分析讨论在总结该区域气候环境演化历史的同时,加深了对气候人类活动湖泊生态系统相互作用过程的理解,为高山湖泊响应人类活动影响提供了证据.     

鄱阳湖河湖交错带重金属污染对微生物群落与多样性的影响

鄱阳湖河湖交错带是鄱阳湖流域内河流生态系统与湖泊生态系统之间的界面区域,该区域物种多样性丰富,承接了五大河流的来水,是重要的污染缓冲区和净化区.本文研究了鄱阳湖河湖交错带重金属污染对微生物群落结构和微生物多样性的影响,结果表明,已测的重金属(汞、铜、锌、铅和镉)均有不同程度的污染,其中,铅、汞污染最严重,水质标准为Ⅳ类以上,其他重金属均为Ⅱ类;高通量测序结果表明,鄱阳湖河湖交错带微生物群落主要有变形菌门、放线菌门、拟杆菌门和疣微菌门4类,平均含量分别为58.31%、13.63%、9.69%和1.33%.多样性指数分析结果表明,昌江与乐安河交汇处(R9点位)与鄱阳湖出长江口(H11点位)的微生物多样性指数(Chao 1、Shannon和Simpson指数)最高,万家桥(N2点位)与赣江入湖口(W6点位)微生物多样性指数最低.研究表明,受重金属污染严重的区域通常会使微生物群落丰度降低,然而R9和H11点位重金属污染严重,但微生物多样性却较丰富,说明微生物多样性不仅仅受单一因子影响,而是多重因子共同影响.     

Heavy metal concentrations during storm events in a rehabilitated industrialized catchment

Water quality data collected on a fortnightly or monthly basis are inadequate for assessment and modelling of many water quality problems as storm event samples are underrepresented or missed. This paper examines the stormflow dynamics of heavy metals (Pb, Cu, Cd and Zn) in the Nant‐y‐Fendrod stream, South Wales, which has been affected by 250 years of metal smelting, followed by 35 years of landscape rehabilitation measures. For storm events of contrasting (very dry and very wet) antecedent conditions in May 2000 and February 2001, respectively, temporal changes in streamwater heavy metal concentrations above and below an in‐line flood detention lake are analysed. At the upstream site, peaks in total metal concentration were recorded on the rising limb for Pb (0·150 mg l^?1) and Cu (0·038 mg l^?1) but on the falling limb for Zn (1·660 mg l^?1) and Cd (0·006 mg l^?1) in the summer 2000 storm event, yielding clockwise and anticlockwise hysteretic loops respectively. In contrast, metal concentrations, although high throughout the winter storm event, were diluted somewhat during the storm peak itself. The Pb and Cu appear to be supplied by quickflow processes and transported in close association with fine sediment, whereas Zn and Cd are delivered to the channel and lake by slower subsurface seepage in dissolved form. In the winter 2001 event, antecedent soil moisture and shallow groundwater levels were anomalously high and seepage sources of dissolved metals dominated. Downstream of the lake, Pb and Cu levels and suspended sediment were high in the summer storm, but low in the winter storm, suggesting retention with deposition of fine sediment in the lake during the latter. In the winter storm, Zn and Cd levels were higher downstream than upstream of the lake, perhaps because of additional seepage inputs from the surrounding slopes, which failed to have an impact during summer. An understanding of the complex interplay of antecedent soil moisture and the dynamics of subsurface seepage pathways in relation to the three‐dimensional distribution of sources is important in modelling heavy metal fluxes and levels in contaminated urban catchments. Copyright © 2003 John Wiley & Sons, Ltd.     

苏州河网区河道沉积物重金属的污染特征

分析测定了苏州河网区河道底泥十个剖面样点60个样品中Cu、Pb、Zn、Cr、Al、Fe、K、Mn、有机质、TP、TN、粒度、pH及含水量,采用地累积指数、生态风险指数和相关分析等方法研究其重金属污染特征.结果表明:Cu和Zn处于中或中-强度污染,Pb处于无-中污染,没有Cr污染;垂直分布特征显示:Cu和Zn污染逐年变化较为一致,Pb污染有逐年加重趋势;重金属潜在生态风险处于轻微污染状态;相关性分析显示,有机质是影响其分布的重要因素,Mn、Cr、Cu、Zn、Pb五种重金属相关性显著;通过与国内外河流、水库和湖泊沉积物中重金属含量比较,苏州河网区河道重金属的累积受多种因素影响.     

云南阳宗海沉积物重金属污染时空特征及潜在生态风险

分析了阳宗海柱状及表层沉积物中Al、Fe、Mn、Zn、Cr、Co、Ni、Cu、As、Cd、Pb等金属元素的含量,结合沉积年代学,研究了沉积物重金属污染的时空变化和潜在生态风险特征.结果表明,表层沉积物中重金属含量具有一定的空间差异性,As、Cd、Cu、Pb和Zn在中东部湖区含量较高,而Cr、Co、Ni含量高值位于南、北湖区的近岸区域;柱状沉积物中,1990s之前As、Cd、Cu、Pb和Zn含量较为稳定,1990s中后期以来,其含量逐渐增加,并在2009-2010年前后达到最大值,此后逐渐下降;而柱状沉积物中Cr、Co、Ni含量变化趋势与Al、Fe相似,总体上由下向上逐渐降低,这主要与沉积物质地(粒度)逐渐变粗有关.重金属富集系数表明,阳宗海沉积物中主要污染元素为As、Cd、Cu、Pb和Zn,1990s中后期污染程度快速增加,2009-2010年前后达到峰值,此后污染程度逐渐降低;表层沉积物中Cu为未污染至"弱"污染水平;Zn、Pb为"弱-中等"污染水平,As为"中等-强"污染水平,Cd为"弱-强"污染水平,中东部湖区污染程度高于其他湖区,这可能与该湖区缺少入湖径流、自然碎屑物质沉积速率较低以及砷污染事件等人为源的重金属贡献影响更为显著有关.生态风险评价结果表明,在2002-2010年前后沉积物重金属达到"中等-强"潜在生态危害,主要贡献因子是Cd和As,近年来其生态风险等级逐渐降低;表层沉积物中重金属在中东部湖区具有"中等"程度潜在生态危害,而其他湖区表层沉积物重金属具有较低程度的潜在生态风险.     

Heavy metal contamination and ecological risk in Spartina alterniflora marsh in intertidal sediments of Bohai Bay,China

To investigate the effects of Spartina alterniflora on heavy metals pollution of intertidal sediments, sediment cores of a S. alterniflora salt marsh and a mudflat in Bohai Bay, China were analyzed. The results showed that S. alterniflora caused higher total C and P, but lower bulk density and electrical conductivity. The levels of Cd, Cu and Pb were higher in S. alterniflora sediment. Both Cd and Zn were higher than the probable effect level at both sites, indicating their toxicological importance. The geo-accumulation and potential ecological risk indexes revealed higher metal contamination in S. alterniflora sediment. Multivariate analysis implied that anthropogenic activities altered mobility and bioavailability of heavy metals. The percentage of mobile heavy metals was higher in S. alterniflora sediment, indicating improvement of conversion from the immobilized fraction to the mobilized fraction. These findings indicate that S. alterniflora may facilitate accumulation of heavy metals and increase their bioavailability and mobility.