乐安江河滩表层土中重金属的分布和残留分析

流经亚洲最大露天铜矿(德兴铜矿)的乐安江,其三条支流被由采矿行为而产生的酸性矿山废水AMD和一个活性炭厂排出的废液所污染,以至其河滩表层土中有高浓度的Cd、Cu、Pb、Zn。根据中国土壤环境质量标准判断,乐安江河滩表层土有4个地方被Cu所污染,3个地方被Pb和Zn所污染。而对于Cd、Cr、Ni来讲,所有采样点的浓度都比较低。4个高浓度金属离子的采样点表层土表明了它们受到了人为活动的污染。计算出的污染指数也表明受到污染的表层土呈局部分布,与4个污染源(德兴铜矿、银山铅锌矿、火力发电站和捕鱼区、金属高炉)的位置相对应。尽管4个污染源中的后面两个被清理有十几年了,但历史遗留下来的污染物仍残留在表层土中。     

Integrating geochemical (surface waters, stream sediments) and biological (diatoms) approaches to assess AMD environmental impact in a pyritic mining area: Aljustrel (Alentejo, Portugal)

Aljustrel mines were classified as having high environmental hazard due to their large tailings volume and high metal concentrations in waters and sediments.To assess acid mine drainage impacted systems whose environmental conditions change quickly,the use of biological indicators with short generation time such as diatoms is advantageous.This study combined geochemical and diatom data,whose results were highlighted in 3 groups:Group 1,with low p H(1.9–5.1)and high metal/metalloid(Al,As,Cd,Co,Cu,Fe,Mn,Ni,Pb,Zn;0.65–1032 mg/L)and SO_4(405–39124 mg/L)concentrations.An acidophilic species,Pinnularia aljustrelica,was perfectly adapted to the adverse conditions;in contrast,teratological forms of Eunotia exigua were found,showing that metal toxicity affected this species.The low availability of metals/metalloids in sediments of this group indicates that metals/metalloids of the exchangeable fractions had been solubilized,which in fact enables metal/metalloid diatom uptake and consequently the occurrence of teratologies;Group 2,with sites of near neutral p H(5.0–6.8)and intermediate metal/metalloid(0.002–6 mg/L)and SO_4(302–2179 mg/L)concentrations;this enabled the existence of typical species of uncontaminated streams(Brachysira neglectissima,Achnanthidium minutissimum);Group 3,with samples from unimpacted sites,showing low metal/metalloid(0–0.8 mg/L)and SO_4(10–315 mg/L)concentrations,high pH(7.0–8.4)and Cl contents(10–2119 mg/L)and the presence of brackish to marine species(Entomoneis paludosa).For similar conditions of acidity,differences in diversity,abundance and teratologies of diatoms can be explained by the levels of metals/metalloids.     

Hydrogeochemical and mineralogical characteristics related to heavy metal attenuation in a stream polluted by acid mine drainage: A case study in Dabaoshan Mine, China

Dabaoshan Mine, the largest mine in south China, has been developed since the 1970s. Acid mine drainage (AMD) discharged from the mine has caused severe environmental pollution and human health problems. In this article, chemical characteristics, mineralogy of ocher precipitations and heavy metal attenuation in the AMD are discussed based on physicochemical analysis, mineral analysis, sequential extraction experiments and hydrogeochemistry. The AMD chemical characteristics were determined from the initial water composition, water-rock interactions and dissolved sulfide minerals in the mine tailings. The waters, affected and unaffected by AMD, were Ca-SO₄ and Ca-HCO₃ types, respectively. The affected water had a low pH, high SO₄^2- and high heavy metal content and oxidation as determined by the Fe²⁺/Fe³⁺ couple. Heavy metal and SO₄^2- contents of Hengshi River water decreased, while pH increased, downstream. Schwertmannite was the major mineral at the waste dump, while goethite and quartz were dominant at the tailings dam and streambed. Schwertmannite was transformed into goethite at the tailings dam and streambed. The sulfate ions of the secondary minerals changed from bidentate- to monodentate-complexes downstream. Fe-Mn oxide phases of Zn, Cd and Pb in sediments increased downstream. However, organic matter complexes of Cu in sediments increased further away from the tailings. Fe³⁺ mineral precipitates and transformations controlled the AMD water chemistry.     

乐安江河水和沉积物中Cu，Pb，Zn的时空变化特征及来源分析

德兴铜矿是亚洲最大的露天铜矿,其酸性矿山废水(AMD)对乐安江的影响在20世纪80—90年代曾得到了系统的评价. 然而,相比10年前,该矿山的产量已经增加4倍,但乐安江重金属污染变化情况目前尚不了解. 研究表明:乐安江河水、悬浮颗粒物和沉积物中重金属的空间分布主要与德兴铜矿和银山铅锌矿的AMD输入有关. 与10年前相比,如今由于乐安江上下游的几个重金属污染源被清理掉了,所采集到的样品中Cu,Pb和Zn的含量都比较低;而且由于贫铜矿石(w(Cu)<0.3%)得到了充分利用,乐安江沉积物中Cu含量明显下降.      

北京市密云水库上游金铁矿区土壤重金属污染特征及对比研究

不同金属矿山选冶活动造成的矿区及周边土壤中重金属的分布累积特征不同.为了解密云水库上游金矿和铁矿矿区土壤中重金属地球化学特征的异同及污染状况,对区域内典型的金矿和铁矿矿区进行土壤样品采集,应用地球化学方法研究了2种土壤中重金属的污染特征,并应用地累积指数法评价了其污染状况.结果表明,2种土壤中除As外的其它重金属含量明显高于北京市土壤重金属背景值,金矿矿区土壤重金属含量普遍高于铁矿矿区.相关性分析表明,金矿矿区土壤中Cu含量与Pb、Zn(p<0.01)及Cr、有机质(OM)含量(p<0.05)之间显著相关,pH值与Pb含量(p<0.01)及Hg含量(p<0.05)呈显著负相关,而铁矿矿区土壤中重金属含量之间的相关性不显著.金矿尾砂中重金属含量明显高于铁矿尾砂,与矿区土壤污染状况一致.地累积指数法评价结果显示,金铁矿区土壤中重金属的污染程度均已十分严重,金矿矿区土壤污染程度高于铁矿,金矿矿区土壤重金属的污染程度由高到低依次为:Pb>Hg>Cd>Cr>Cu>Zn>Co>As;铁矿矿区土壤重金属的污染程度由高到低依次为:Pb>Cd>Cr>Co>Cu>Zn>Hg>As.该研究数据可为同一区域内不同金属矿区重金属污染的有效监控与治理提供科学依据.     

酸缓冲容量对污泥屏障重金属再溶出控制研究

借助污泥中的厌氧微生物活动,污泥屏障可用来固定尾矿堆场的重金属.针对尾矿风化淋滤形成的酸性采矿废水(acidmine drainage,AMD)与污泥屏障相互作用,可能会引起已固定重金属再次溶出问题,通过酸滴定实验,研究了不同厌氧培养时间的污泥悬液的酸缓冲容量及其对重金属再溶出的影响.结果表明,污泥悬液酸缓冲容量与悬液固液比成正比,并随着厌氧还原程度的加深而增加.碳酸盐缓冲体系和有机质缓冲体系对污泥悬液酸缓冲有重要意义.酸滴定实验发现,随着pH降至6.2以下,重金属Zn、Pb和Cu开始快速溶解释放,且释放量符合ZnCuPb.基于实验结果,建立了污泥屏障在AMD渗透条件下酸缓冲容量消耗的数学模型.模拟计算结果表明,对于厚度2.0 m的污泥屏障,即使在10.0 m水头的AMD渗透酸化条件下,有效酸缓冲容量经历666 a之后才能被耗尽,在此时间内污泥屏障具备对重金属的生物化学固定能力.     

煤矿周围土壤中铜、锌污染状况及特征分析

以陕西省神木县西沟乡六道沟流域作为研究区域,对六道沟煤矿周围的土壤中的铜、锌的含量进行了研究,着重分析了煤矿开采是否对周围土壤造成重金属污染以及重金属在煤矿周围土壤中的分布特征。结果表明该区域仅有部分土壤遭受铜、锌的轻度污染,即煤矿开采会对周围土壤造成不同程度的污染,且铜、锌含量随着距煤矿距离的增大而递减,并随采样深度增加而递减。     

污泥屏障氧化缓冲容量与重金属再溶出关系研究

借助微生物厌氧活动特别是硫酸盐还原反应,污泥屏障可用来固定尾矿堆场重金属.针对尾矿风化淋滤形成的酸性采矿废水(AMD)与污泥之间发生的氧化还原反应导致的重金属溶出问题,通过氧化滴定实验研究了不同污泥悬液的氧化缓冲容量及其与重金属浓度的关系.结果表明,污泥悬液的氧化缓冲容量随着悬液固液比的增大略有减小,但随着悬液厌氧培养时间的延长而增加.污泥的氧化缓冲容量主要来自Eh≤-150mV的强烈还原区间,可达氧化缓冲容量的50%以上.氧化滴定过程中发现,当Eh≥-150mV时,Zn首先明显溶出;当Eh≥150mV时,Cu和Pb明显溶出.基于实验结果,建立了污泥屏障在AMD渗流条件下氧化缓冲容量消耗的数学模型.模拟计算结果表明,当AMD水头高度为10m时,厚度2m的污泥屏障经历AMD溶液38787a的渗透氧化,仍可保持原有的强烈还原状态,具备对重金属的固定效果.     

高砷煤矿废水对表层岩溶水水质的影响

矿业开发过程对水环境的影响是严重的,而表层岩溶水是喀斯特地区居民的主要水源之一,具有典型的脆弱性. 因此,研究酸性矿山水对岩溶水质的影响尤为重要. 以兴仁县交乐高砷煤矿区为例,从水化学角度研究高砷煤矿废水对矿区周边表层岩溶水水质的影响. 结果表明:酸性矿山排水中ρ(SO₄2-)和溶解态金属中ρ(Cd),ρ(Cu),ρ(Zn),ρ(Mn)和ρ(Fe)高,pH低;矿山废水主要影响下游溪流地表水及其流经的岩溶管道水体的水质,对当地居民的正常使用影响较大;pH沿溪流方向逐渐升高,而水体中主要离子浓度呈不同程度的降低趋势;与酸性矿山排水没有水力联系的周边支流及泉点目前尚未受到影响.      

Cu(II), Fe(III) and Mn(II) combinations as environmental stress factors have distinguishing effects on Enterococcus hirae

Pollution by various heavy metals as environmental stress factors might affect bacteria. It was established that iron (Fe(III)), manganese (Mn(II)) and copper (Cu(II)) ion combinations caused effects on Enterococcus hirae that differed from the sum of the effects when the metals were added separately. It was shown that the Cu^2 +–Fe^3 + combination decreased the growth and ATPase activity of membrane vesicles of wild-type E. hirae ATCC9790 and atpD mutant (with defective F_oF₁-ATPase) MS116. Addition of Mn^2 +–Fe^3 + combinations within the same concentration range had no effects on growth compared to control (without heavy metals). ATPase activity was increased in the presence of Mn^2 +–Fe^3 +, while together with 0.2 mmol/L N,N′-dicyclohexylcarbodiimide (DCCD), ATPase activity was decreased compared to control (when only 0.2 mmol/L DCCD was present). These results indicate that heavy metals ion combinations probably affect the F_OF₁-ATPase, leading to conformational changes. Moreover the action may be direct or be mediated by environment redox potential. The effects observed when Fe^3 + was added separately disappeared in both cases, which might be a result of competing processes between Fe^3 + and other heavy metals. These findings are novel and improve the understanding of heavy metals ions effects on bacteria, and could be applied for regulation of stress response patterns in the environment.     

酸性矿山废水区域废矿石中真核生物多样性分析

采集安徽某铁矿酸性矿山废水库周边的废矿石样品,分析了样品的主要物化参数,进而利用分子生物学方法,构建真核生物18S rDNA克隆文库,对样品中的真核生物多样性和群落结构进行了研究.结果表明,该区域呈现强酸性,pH均在3以下,Fe、SO2-4、P、NO-3-N含量都显示同一个趋势,即裸露的废矿石样品PD和1M的含量高于有植被覆盖的样品LW和XC.4个样品含有子囊菌门(Ascomycota)、担子菌门(Basidiomycota)、球囊菌门(Glomeromycota)和节肢动物门(Arthropoda)这4类真核生物.其中球囊菌门可以与植物形成绝对共生关系,是早期植物适应陆地环境的关键.包含球囊菌门的样品LW和XC,有植被保护,其生物多样性比裸露的废矿石样品PD和1M的生物多样性更丰富.此外,还发现样品中存在很多对极低pH、重金属有耐受力的菌种,如Penicillium purpurogenum、Chaetothyriales sp.、Staninwardia suttonii等.     

乐安江沉积物重金属污染及生态风险性评价

对１９８７－１９９５年期间所采集的乐安江表层沉积物中的重金属含量进行了统计分析和生态风险性评价。结果表明,德兴铜矿的矿山酸性废水和洎水河河水,使乐安江沉积物受到重金属的严重污染。     

粤北大宝山AMD水-表层沉积物的重金属分布特征及其影响因素

粤北大宝山铁铜多金属矿床的尾矿富含硫化物矿物,在化学和生物氧化作用下,产生pH5的酸性矿山废水(AMD).本文对大宝山槽对坑、铁龙AMD的10个采样点的表层沉积物进行物相和微观形貌分析,测定水样和表层沉积物中Pb、Cu、Mn、Cr等重金属离子的含量,讨论pH与次生矿物对重金属元素在水-表层沉积物分布差异的影响.结果表明:AMD的表层沉积物的次生矿物主要由铁、锰的氢氧化物、铁矾类矿物、羟氧硫铅矿和偏砷酸氢铁矿组成,其中含铁次生矿物具有一定的空间演化特征.水-表层沉积物的重金属浓度空间分布差异主要受pH和次生矿物组合控制.水的重金属含量总体是随着pH的降低而增大,且Pb、Cu、Mn具有显著相关性.羟氧硫铅矿是Pb的主要沉淀方式;水钠锰矿的析出沉淀影响Mn、Pb、Cu的沉降率;水铁矿、针铁矿、施威特曼石控制低pH环境中Cu的沉降行为;针铁矿、黄钾铁矾、施威特曼石是水溶液中Cr的强力清除剂.     

Effect of periphyton community structure on heavy metal accumulation in mystery snail (Cipangopaludina chinensis):A case study of the Bai River, China

The ratio of metal:P stoichiometry was used to identify the accumulation pathways of heavy metals (V, Cr, Co, Ni, Cu, Cd, and Pb) from periphyton to snails Cipangopaludina chinensis Gray (C. chinensis) in the Bai River watershed. The results showed that periphyton communities were mainly composed of two types of algae, filamentous green algae and unicellular diatoms. The proportion of unicellular diatoms in the periphyton community is a key factor that influences metal accumulation in C. chinensis. The V, Cr, Co, Ni, and Cd content of C. chinensis increased steadily as the corresponding metal content of periphyton increased, but Cu and Pb in the snail did not increase in the periphyton. Mechanisms of V, Cr, and Ni accumulation were found to be related to the proportion of diatoms, while Cd and Pb accumulation were dependent on the physiological characteristics of C. chinensis. The accumulation of Cu in C. chinensis was closely related to their grazing behavior. The metal:P stoichiometry revealed that Cr, Ni, and Cd can reduce the potential ecological risks associated with increased P inputs to the ecosystem. V and Co were considered to be relatively safe, regardless of the periphyton P content. Finally, Pb may not be prone to transfer to higher trophic levels, and may pose the lowest ecological risks of the studied heavy metals, but Cu can cause potential ecological risks when eutrophication has occurred.     

湖南采矿区和冶炼区水稻土重金属污染及其潜在风险评价

对湖南省9个县市采矿区和冶炼区附近的水稻土中重金属Cd、As、Cu、Zn和Pb进行了调查和分析.结果表明,采矿区和冶炼区周围的水稻土中重金属Cd、As、Cu、Zn和Pb的含量呈对数正态分布.单因子污染指数法评价表明,在所调查的区域中,有6个县市矿区和冶炼区附近的水稻土受到Cd的严重污染,其它地区的水稻土分别受到Cd、As、Cu、Zn和Pb不同程度的污染,其中衡阳常宁市水口山铅锌矿区和株洲清水塘冶炼区附近的水稻土受到重金属的严重污染.潜在风险评价表明,采矿区和冶炼区周围的水稻土中Cd潜在风险参数最高,其次是Pb和As.衡阳常宁水口山铅锌矿、株洲清水塘冶炼区、娄底冷水江锡矿和湘潭锰矿附近的水稻土中重金属的潜在生态风险参数很高,具有很高潜在风险程度;永州道县冶炼区水稻土中重金属的潜在生态风险程度为较高程度;郴州柿竹园铅锌矿.常德石门雄磺矿、益阳赫山区金矿区和岳阳临湘铅锌矿区附近的水稻土的重金属潜在生态风险为中等程度.     

基于悬铃木叶片重金属累积特性的大气污染分析和评价

以悬铃木叶片为监测器官,对淮南市6种大气环境20个样区Cd等6种重金属的累积量进行了测量和聚类,并分析了叶片富集重金属的EF值.结果表明,不同样区悬铃木叶片累积的6种重金属含量不同,平均值大小表现为Zn>Cu>Cr>Ni>Pb>Cd;环境不同,叶片累积同种重金属的量也存在差异,水泥厂周边环境悬铃木叶片累积的Cd和矿区Cu以及交通主干道大气环境中Cr、Ni、Pb和Zn显著高于其他环境;除风景区、自然村Cr外,其他采样环境中被测重金属EF平均值全部超过1,矿区、电厂、交通主干道及水泥厂周边环境中的6种重金属的EF值全部大于3,淮南市总体大气环境重金属污染为Cd>Cu>Zn>Ni>Pb>Cr.     

窟野河矿区河段表层沉积物重金属污染特征及风险评价

对窟野河上游煤矿区和中下游非煤矿区的河流表层沉积物重金属As、Cu、Pb、Zn、Cd、Cr、Co和Mn含量污染特征进行了分析比较,并采用地积累指数法和潜在生态危害指数法评价其污染程度。结果表明:重金属含量均高于陕北地区土壤背景值,煤矿区和非煤矿区重金属含量有一定的差异性,其中Cr-Cu、Cr-Cd、Mn-Cu-Zn、Co-Pb、As-Cd和As-Pb元素间有一定的同源性。煤矿区和非煤矿区均受到不同程度的重金属污染,全水域处在强的潜在生态危害级别,Cd的影响占主导地位,后期应重点监控治理。     

三峡澎溪河回水区消落带岸边土壤重金属污染分布特征

在对澎溪河回水区消落带及岸边土样品中重金属含量和样品理化性质测定的基础上,重点分析了该区域内重金属分布特征,并对重金属元素间的相关性展开研究.同时,应用地累积指数对研究区域污染现状进行评价.结果表明,消落带样品中Cu、Cr、Zn、As、Cd、Pb、Hg的平均含量分别为28.17、59.21、108.98、4.77、2.02、28.85、0.52mg·kg-1;岸边土样品中重金属的含量范围分别为22.32、54.90、98.05、7.87、0.77、22.97、0.94mg·kg-1.Cd是三峡库区污染较严重的重金属元素.相关性分析表明：在消落带样品中,Cd与Zn显著相关（p〈0.01）,Pb、Hg和Cu、As都存在显著的正相关关系,说明这4种重金属元素在接受外来污染时可能存在相似性;在岸边土样品中,Cd与Zn、Cr与Cu、As与Hg显著相关（p〈0.01）,Pb与Cu、Cr、Zn、Cd显著正相关,表明这几种重金属可能有着相似的来源.消落带样品重金属污染程度评价结果为：Cd〉Hg〉Zn〉Pb〉Cu〉As〉Cr,岸边土样品重金属污染程度评价结果为：Hg〉Cd〉Zn〉As〉Pb〉Cu〉Cr,Cd和Hg在个别站位达到了严重污染水平.消落带土壤受人为扰动后会成为水体的二次污染源,因此,消落带土壤重金属对水体的潜在影响不容忽视.     

酸性矿山废水天然中和形成的富铁沉淀及其环境属性

采集了云南王家滩铁矿的酸性矿山排水及其与溪流中和后的溪水与沉积物, 运用谱学及电子显微分析等方法,对采集样品的化学及矿物学等方面的特征进行了分析. 结果表明, 王家滩铁矿的酸性矿山排水在与未污染溪水中和时, 酸度和电导率均显著降低, 但元素的浓度变化不很一致, 沿水流方向,除Fe3+、SO2-4、 Ca2+等少数元素, 大多数元素的浓度都未发生明显的降低. 中和成因沉淀物具有富铁的特征,矿物组成以水铁矿为主, 此外在下游沉积物中还见有少量针铁矿及纤铁矾. 其中上游中和区水铁矿以2线水铁矿为主, 下游以6线水铁矿为主. 而各处沉积均具有明显的分层特征,且均为外层以2线水铁矿为主, 内层以6线水铁矿及针铁矿为主. 以水铁矿为主要矿物的中和沉积物对各种有毒有害元素具有较强的吸持作用. 对这些结果的进一步分析表明, 在成因上,pH值和SO2-4的浓度共同控制了水铁矿的形成;在重(类)金属吸持方面,水铁矿的迁移及相应的对AMD中重(类)金属的自净化作用受中和区域的水动力条件影响较大.     

赤水河流域表层沉积物重金属的污染特征及生态风险评价

赤水河是长江水系唯一一条主河道没有筑坝的一级支流,对长江流域珍稀鱼类繁殖具有重要的生态意义.为了解赤水河流域沉积物中重金属的污染特征,采集32个样品,并对7种重金属(Cu、Zn、Cd、Mn、Ni、Hg、As)含量分别进行测定.结果表明,赤水河沉积物中7种重金属含量全部高于赤水河沉积物背景值,但与我国其他河流相比,赤水河重金属含量较低,污染较少.地累积指数评估结果表明,7种重金属的平均Igeo值由高到低依次为CdMnNiAsCuZnHg,其中90.62%的采样点存在不同程度的Cd污染.污染负荷指数计算表明,上、中、下游的污染负荷指数分别为1.49、1.14、1.03,均属中等污染.Hakanson潜在生态风险指数法评价结果表明,各重金属单因子生态危害程度由强至弱依次为CdHgAsNiCuMnZn,各采样点7种重金属的潜在生态风险指数(RI)介于32.34~930.07之间,总体潜在生态风险较低.