河流沉积物重金属污染质量控制基准的研究 Ⅱ.相平衡分配方法(EqP)

以重金属污染严重的江西乐安江表层沉积物为对象，利用热力学相平衡分配法（ＥｑＰ）和相关基础数据库，研究探讨了该流域沉积物中重金属污染的数值型质量控制基准（ＳＱＣ）。结果表明，铜矿采矿活动导致某些江段沉积物中铜实际污染程度远高于相应的ＳＱＣ水平。另外，由于沿江中、小工矿企业废水的随意排放，同样造成附近沉积物中铅、锌、铬等重金属含量不同程度地超出各自的基准数值。此ＳＱＣ的建立为制订该流域沉积物质量管理标     

重金属污染沉积物质量评价研究—以太湖为例

以太湖的表层沉积物为研究对象,运用相平衡分配法(EqP)探讨了沉积物中4种重金属(Cu, Pb, Zn, Cd)的沉积物质量基准(CSQC)值;根据美国国家环境保护局(US EPA)基于水生生物对重金属的最终慢性毒理水平的淡水水质基准,制定了太湖4种重金属(Cu, Pb, Zn,和Cd)的沉积物质量基准值分别为145.2,308.72,293.01,0.46mg/kg.以此CSQC为参比值,参考潜在生态危害指数法对各元素赋予不同的权重值,运用综合污染指数法对太湖沉积物重金属的环境质量进行评价,结果显示,2010年8~9月太湖沉积物质量基本为良.这一结果与沉积物重金属总量分析结果一致.     

应用相平衡分配法建立污染物的沉积物质量基准

以污染较为严重的天津某污水库的表层沉积物为对象,应用热力学相平衡分配(EqP)法,初步探讨了该水体沉积物中4种重金属(Cd,Cu,As,Hg)和2种有机氯农药〔滴滴涕(DDT)、六六六(HCH)〕的沉积物质量基准(SQC)推荐值. 其中,基于我国地表水水质基准的4种重金属Cd,Cu,As和Hg的SQC推荐值分别为4.3,86,218和0.45 mg/kg;基于美国环境保护署(US EPA)的保护水生生物水质基准的2种有机氯农药(DDT和HCH)的SQC推荐值分别为18.0和0.27 μg/kg. 通过与不同国家制订的SQC值进行比较发现,地区间的SQC值相差较大,说明在SQC值的确定过程中存在诸多不确定因素. 所推算出的几种污染物的SQC值均接近所有数据的中间值,表明其可为该水体沉积物的风险评估提供依据.      

黄河包头段水-沉积物系统中重金属的污染特征

以系统的形态分析实验研究为基础 ,结合上覆水、悬浮物、沉积物及孔隙水中重金属的分布特征 ,评价了黄河包头段水体中重金属 (Cu、Pb、Zn、Cd)的潜在危害程度 .结果表明 ,黄河包头段干流沉积物中Pb、Cd等重金属具有较大的潜在生态危害性 ,更易造成污染 ;包头市工业废水对黄河干流水体重金属污染有明显的迭加作用 .此外 ,分层位 (按深度 )计算的SQC值结果揭示 ,用表层沉积物或不同层位 (深度 )的混合沉积物所得沉积物重金属质量基准代表某一区域或河段沉积物重金属质量基准有一定的风险性 .     

河流沉积物重金属污染质量控制基准的研究 Ⅰ.C-B-T质量三合一方法(Triad)

在综合数据库ＣＥＲＰ－ＤＢＭＳ支持下，利用水体沉积物质量三合一工具，初步建立江西乐安江表层沉积物中重金属污染的质量控制基准。通过将化学分析、毒性鉴定２和底栖群落结构变化三基元集成为一体的三轴图和相应的响应信息判断矩阵，基于现场生物响应的重金属污染的剂量－响应关系。     

河流沉积物重金属污染质量控制基准的研究Ⅰ.C-B-T质量三合一方法(Triad)

在综合数据库ＣＥＲＰＤＢＭＳ支持下，利用水体沉积物质量三合一工具（Ｔｒｉａｄ），初步建立江西乐安江表层沉积物中重金属污染的质量控制基准（ＳＱＣ）．通过将化学分析（Ｃ）、毒性鉴定（Ｔ）和底栖群落结构变化（Ｂ）三基元集成为一体的三轴图和相应的响应信息判断矩阵，基于现场生物响应的沉积物质量基准能较为清晰地指示乐安江流域表层沉积物中重金属污染的相对程度和分布模式，体现底栖生物对沉积物重金属污染的剂量响应关系，为进一步制订该区域沉积质量管理标准（ＳＱＳ）、开展后续的污染治理与恢复工程提供技术保证和科学依据．     

区域沉积物质量基准常用建立方法的改进与优化

建立区域沉积物质量基准（SQC）具有重大的社会、经济和环境价值。本文选择两种当前流行的基准建立方法,相平衡分配法（EqP）和质量三合一法（Triad）,重点阐述在指标选择与定量、误差模拟校正、模式拟和运算等实施操作方面各自的改进与优化。同时探讨了SQC的发展趋势以及在污染沉积物治理与恢复决策中的作用。     

太湖和辽河沉积物重金属质量基准及生态风险评估

以太湖、辽河的表层沉积物为研究对象,运用相平衡分配法（EqP）初步探讨了两流域沉积物中4种重金属（Cd,Cu,Pb,Zn）的沉积物质量基准（C_SQC）推荐值,并对两流域沉积物中的重金属进行了生态风险评估. 根据美国国家环境保护局（US EPA）基于水生生物对重金属的最终慢性毒理水平的淡水水质基准,制定了太湖及辽河4种重金属（Cd,Cu,Pb和Zn）的沉积物质量基准推荐值分别为6.42,55.3,20.6和201.5 mg/kg及5.42,52.8,18.9和177.7 mg/kg. 通过与不同国家及地区制定的C_SQC值进行比较,推算出4种重金属的C_SQC值大都接近所有数据的中间值. 从沉积物固相和间隙水相2个不同的角度对沉积物中重金属进行的生态风险评估表明,两流域的大部分区域同步可提取重金属（SEM）与酸可挥发性硫化物（AVS）含量的差值大于0,而_i［C_Ti］/［C_SQC,i］值与_i［C_IW,i］/［CCC_i］值均大于1,说明在整体上两流域沉积物中的重金属存一定的生态风险. 由于未考虑各金属元素之间的拮抗或协同等作用以及底栖生物敏感性的问题,所使用的生态风险方法在评价生态风险方面可能会相对有所偏差.      

林丹的吸附解吸行为对其沉积物基准的影响

研究了林丹在3种沉积物上的吸附/解吸行为.结果表明,在3种沉积物上的吸附等温线都符合Freundlich模型,其吸附性能受有机碳含量和颗粒分布的影响.而解吸等温线明显地偏离吸附等温线,存在显著的解吸滞后现象,解吸用二元平衡解吸(DED)模型进行拟合,效果良好.解吸不可逆程度随着沉积物中林丹初始浓度增大而增大.由DED模型推算的沉积物基准值比用线性模型推算的基准值高46倍以上.     

湘江沉积物镉和汞质量基准的建立及其应用

沉积物质量基准是保护底栖生物免受污染物危害的保护性临界水平,可用来评估与沉积物结合的污染物的影响,并为底栖生物保护和沉积物的科学管理提供依据.分析了湘江43个采样点沉积物、上覆水、间隙水和植物中Cd和Hg含量,选取钩虾做沉积物毒理实验,利用相平衡分配法、加标毒理实验法和背景值法确定湘江沉积物Cd和Hg质量基准低值(SQC-L)分别为1.89 mg·kg-1和0.13 mg·kg-1,基准高值(SQC-H)分别为28.32 mg·kg-1和0.79 mg·kg-1.经与国内外基准值比较,并与底栖生物监测数据和植物监测数据对比分析,表明确定的基准值合理.应用该基准值评价湘江沉积物质量现状发现,湘江沉积物Cd和Hg含量低于SQC-L和高于SQC-H的采样点所占比例较低,74.4%和76.7%的采样点沉积物Cd和Hg含量在SQC-L和SQC-H之间.     

The biotic ligand model: a model of the acute toxicity of metals to aquatic life

The United States Environmental Protection Agency (USEPA) has established nationally applicable water quality criteria (WQC) for metals that are designed to be protective of aquatic life. However, in some instances these criteria may be over-protective as a result of natural, site-specific differences in water quality characteristics. These differences affect metal speciation and bioavailability, fundamental considerations in assessing toxicity. Laboratory studies completed during recent years have advanced the current understanding of metal chemistry in aquatic systems, including the formation of organic and inorganic metal complexes and sorption to particulate organic matter. Parallel investigations have led to an improved understanding of the physiological basis of why metals are toxic to aquatic organisms. These studies have, in combination, led to an improved understanding of how site-specific water chemistry affects bioavailability, and how metals exert toxicity at the organism site of action, at the biotic ligand in the context of the model to be described. The biotic ligand model provides a quantitative framework for assessing metal toxicity over a range of hardness, pH and dissolved organic carbon (DOC) levels. The chemical equilibrium sub-model incorporates metal-biotic ligand interactions to compute metal accumulation at the site of action (e.g., the gill of a fish) as a function of water quality. The toxicity sub-model uses this computed accumulation level as the basis for successfully predicting observed variations in toxicity associated with changes in water quality. The results highlight the potential utility of this approach to provide an alternative means of developing site-specific permit limits and WQC. The ability of the model framework to quantitatively assess the effects of hardness, pH and DOC on toxicity, in comparison to current WQC for metals that typically vary with hardness alone, is a significant advance in understanding how site-specific conditions affect the toxicity of metals.     

Fractionation of heavy metals in runoff and discharge of a stormwater management system and its implications for treatment

A stormwater management system utilizing the mechanisms of sedimentation and filtration/infiltration was developed and constructed for the immobilization of suspended solids and heavy metal constituents （Fe, Zn, Pb, Cr, Cu, Cd, Ni） in runoff. Monitoring took place between May 2010 and November 2012 on a total of 24 storm events. This research on the fractionation of heavy metals in runoff and discharge of a stormwater system provided insight on the actual efficiency of the system and determined the implications for treatment of the particulate-bound and dissolved heavy metals in runoff. Results revealed that the partitioning of heavy metal load in runoff in either dissolved or particulate-bound were influenced by flow rate and total suspended solids load, and evident in high-intensity storm （rainfall-runoff event）. On the other hand, the partitioning of heavy metal load discharge from the stormwater system was more apparent during the early period of discharge having higher variability in dissolved than particulate-bound heavy metal. Findings revealed that fractionation of heavy metals played an important role in the performance of the stormwater system; thus, must be considered in designing stormwater systems. For the stormwater system to be effective, it is recommended to design the system treating not only the early period of a storm （first flush criteria） rather until the peak part of the hydrograph （high flow rate where partitioning was greatest） from a load basis.     

“三门六科”水质基准最少毒性数据需求原则

MTDR(最少毒性数据需求)是水质基准推算中数据应用的重要原则. 以重金属Pb2+、Cd2+、Cu2+、Zn2+、Hg2+、Cr6+为例,在广泛搜集物种毒性数据的基础上,通过数据比较分析,初步研究了我国水生生物基准的MTDR. 结果表明:Hg2+、Pb2+和Cu2+基于“三门六科”推导的急性基准值与基于美国“三门八科”MTDR的推算结果相近,分别相差20.5%、25.2%和33.3%;Cd2+、Zn2+和Cr6+的计算结果差别较为明显,表明相对于美国“三门八科”MTDR,在我国生物毒性数据缺乏的情况下,“三门六科”MTDR对于部分污染物基本可行,但仍具有一定的不确定性. “三门六科”包括鲤科、除鲤科外的另一科鱼类(冷水鱼优先)、两栖类、浮游甲壳类、昆虫类和环节动物类.      

New approach to studies of heavy metal redistribution in soil

The bioavailability and mobility of heavy metals in soils is dependent upon redistribution processes between solution and solid phases and among solid-phase components. This paper reviews the definitions and applications of two newly developed parameters, the redistribution index and the reduced partitioning parameter, in quantifying redistribution processes of heavy metals in contaminated soils. The redistribution index depicts the removal/attainment of metal-contaminated soils from/to the fractional distribution pattern characteristic of non-amended soils, while the reduced partitioning parameter quantifies the relative binding intensity of heavy metals in soils. Over time, metal salt-spiked and sludge-amended soils approached the fractional distribution pattern of non-amended soils. The rates of redistribution of metals and their binding intensity in soils were affected by the metal species, loading levels and soil properties. Metals in contaminated soils at low loading levels approach the fractional distribution pattern of non-amended soil more rapidly than those at high loading levels. The sequence order of approach by metals to the fractional distribution pattern of non-amended soil was: Cd>Cu>Ni=Zn>Cr. In both non-amended and contaminated soils, Cr had the highest binding intensity, Cd the lowest, and Cu, Ni and Zn, intermediate values. In addition to our own data, primarily on metal salt-spiked soils, these two indices are also used to evaluate redistribution processes of heavy metals in sewage sludge-amended soils from other published reports.     

南京城市边缘带化工园区土壤重金属污染评价

为揭示城市边缘带强烈人为活动对土壤环境质量的影响,以南京化工园附近20km^2区域为研究区,网格化精确布点,采集表层土壤样品共计54个,并对其重金属Cu、Zn、Pb、Cr、Cd、Hg、As含量进行了测定分析.结果表明,研究区表层土壤中除Hg外的其它6种重金属含量均未超过国家二级标准;Hg是本区表层土壤重金属污染的主要因子.另外,应用地统计学的克里格方法对研究区内表层土壤污染的空间变异特征进行了分析,并讨论了研究区域的潜在污染源及其污染途径.结果表明,研究区内局部土壤重金属污染主要由蔬菜土壤高强度利用及农化产品投入所致,同时不排除污染水灌溉的影响.     

Heavy metal pollution in intertidal sediments from Quanzhou Bay, China

The concentrations of eight heavy metals （Cu, Zn, Pb, Cd, Cr, Ni, Hg, and As） in the intertidal surface sediments from Quanzhou Bay were determined to evaluate their levels and spatial distribution due to urbanization and economic development of Quanzhou region, southeast China. The ranges of the measured concentrations in the sediments are as follows： 24.8-119.7 mg/kg for Cu, 105.5-241.9 mg/kg for Zn, 34.3-100. 9 mg/kg for Pb, 0.28-0. 89 mg/kg for Cd, 51.1-121.7 mg/kg for Cr, 16.1-45.7 mg/kg for Ni, 0.17-0.74 mg/kg for Hg, and 17.7-30.2 mg/kg for As. The overall average concentrations of above metals exceed the primary standard criteria but meet the secondary standard criteria of the Chinese National Standard of Marine Sediment Quality. Several contents of Cu and Hg exceed the secondary standard criteria at some stations. The results of geoaccumulation index （Igeo） show that Cd causes strong pollution in most of the study area. There are no significant correlations among most of these heavy metals, indicating they have different anthropogenic and natural sources. Some locations present severe pollution by heavy metals depending on the sources, of which sewage outlets, aquatic breeding, and commercial ports are the main sources of contaminants to the area.     

水质基准两栖类受试生物筛选

两栖动物是水生生态系统的重要生物群落,是水生生物基准的重要保护对象. 参照美国水生生物基准技术指南,搜集、筛选了12种本土代表性两栖动物的生物毒性数据,通过毒性数据分析,筛选出对两栖动物毒性最大的污染物,主要包括农药、重金属和杀虫剂三大类,以及4属基准研究受试生物. 在4属(5种)受试生物中,黑眶蟾蜍对硝酸银的累积概率为15%,六趾蛙对马拉硫磷的累积概率为1%,牛蛙对五氯酚的累积概率为8%,棘胸蛙对丙溴磷的累积概率为27%,虎纹蛙对硫丹的累积概率为29%. 结果表明:蛙属(六趾蛙)对农药、蛙属(牛蛙)对杀虫剂、蟾蜍属(黑框蟾蜍)对重金属均为敏感物种,虎纹蛙属(虎纹蛙)对农药、棘蛙属(棘胸蛙)对杀虫剂均为较敏感物种. 这4属(5种)两栖动物可以作为相关污染物的水质基准研究的受试物种.      

水质基准本土环节动物与水生昆虫受试生物筛选

作为水环境质量评价体系中重要的指示生物类别,水生环节动物和水生昆虫是水生生物基准研究中不可或缺的基准受试生物.参照美国水生生物基准技术指南, 选择我国广泛分布的10种本土环节动物和水生昆虫,搜集、筛选对各水生物种毒性最大的3种污染物,并进行水生生物敏感性分析. 在污染物毒性数据的物种敏感度分布中,若物种的累积概率小于30%则为较敏感,该物种可作为基准研究受试生物. 结果表明:不同生物对污染物敏感性存在差异,颤蚓对有机锡化合物、重金属,苏氏尾鳃蚓对重金属均较敏感;仙女虫、黄翅蜻、四节蜉、扁蜉对各类农药均较敏感;尾盘虫能够在一定程度上指示表面活性剂污染状况. 因此,环节动物颤蚓属、尾鳃蚓属、尾盘虫属、仙女虫属,水生昆虫黄翅蜻属、四节蜉属及扁蜉属均可作为水质基准研究中的受试生物.      

pH对沉积物中五氯酚毒性的影响及其质量基准值推导

PCP（pentachlorophenol,五氯酚）是一种可电离有机化合物,pH会影响水体中PCP的毒性.为准确评估沉积物中PCP的生态风险,通过研究不同pH下沉积物中PCP对河蚬（Corbicula fluminea）、泥鳅（Misgurnus anguillicaudatus）、伸展摇蚊（Chironomus riparius）等底栖生物的毒性效应,探讨沉积物中PCP生物毒性与pH的关系.基于毒性试验结果和搜集筛选文献中报道的PCP生物毒性数据,利用物种敏感度分布法推导PCP沉积物质量基准,进而对我国淡水水体沉积物中PCP风险进行评估.结果表明:①沉积物中PCP对底栖生物的毒性均随pH的升高而降低,pH为6.5~8.5时,沉积物中PCP对河蚬、泥鳅、伸展摇蚊的96 h-LC₅₀值分别为2.99~7.64、8.05~8.76、10.50~22.30 μg/g;对泥鳅的30 d-LC₁₀值为0.26~0.80 μg/g,对伸展摇蚊的21 d-EC₁₀值为0.28~0.54 μg/g.②推导获得PCP依赖于pH的沉积物质量基准函数,即CMC_sed（急性基准值）=e0.204pH-2.96、CCC_sed（慢性基准值）=e0.204pH-5.85,当pH为7.0时,CMC_sed、CCC_sed分别为0.217、0.012 μg/g.③我国主要淡水河流、湖泊沉积物中99.0%的采样点w（PCP）低于该研究推导的CCC_sed,仅有1.0%的采样点w（PCP）介于CCC_sed与CMC_sed之间.研究显示,我国主要淡水水体沉积物中PCP总体风险较低,个别地区沉积物中PCP可能存在潜在的生态风险,需要引起重视.      

Influence of metal-contamination on distribution in subcellular fractions of the earthworm (Metaphire californica) from Hunan Province, China

Earthworms have the ability to accumulate of heavy metals,however,there was few studies that addressed the metals in earthworm at subcellular levels in fields.The distributions of metals(Cd,Cu,Zn,and Pb) in subcellular fractions(cytosol,debris,and granules) of earthworm Metaphire californica were investigated.The relationship between soil metals and earthworms were analyzed to explain its high plasticity to inhabit in situ contaminated soil of Hunan Province,south China.The concentration of Cd in subcellular compartments showed the same pattern as Cu in the order of cytosol debris granules.The distribution of Zn and Pb in earthworms indicated a similar propensity for different subcellular fractions that ranked as granules debris cytosol for Zn,and granules cytosol debris for Pb.The internal metal concentrations in earthworms increased with the soil metals(p 0.05).Significant positive correlations were found between soil Cd and Cd concentrations in cytosol and debris(p 0.01).Moreover,the soil Pb concentration significantly influenced the Pb concentrations in cytosol and debris(p 0.01),similar to that of Cd.The soil Cu concentrations was only associated with the Cu in granules(p 0.05).Soil Zn concentrations correlated with the Zn concentrations in each subcellular fraction(p 0.05).Our results provide insights into the variations of metals partitioning in earthworms at subcellular levels and the relationships of soil metals,which could be one of the detoxification strategies to adapt the long-term contaminated environment.