土壤中铜、铅、锌相对浓度比的恒定性及其环境地球化学意义

土壤中的铜、铅、锌是引人关注的重金属元素,它们的含量、存在形态和迁移转化对环境质量和生态效应都产生重要的影响。铜、铅、锌同属于戈尔德斯密特地球化学分类中的亲铜元素,由于与硫亲合力强这一共同的地球化学特性,使得它们的迁移形式、赋存状态和沉     

恬矿库周围土壤中重金属存在形态特征研究

通过对大冶铜绿山铜铁矿尾矿库周围土壤中重金属形态分析实验,研究了重金属各种形态在土壤中的分布特征。由对比实验可知,尾矿库周围土壤中Ｃｕ、Ｐｂ、Ｚｎ、Ｃｄ等重金属含量都显著地高于对照样品,书经受到重金属的严重污染。土壤中重金属形态分布征为：ｗ（Ｃｒ、Ｚｎ、Ｆｅ）;可变换态〈碳酸盐态〈有机态〈铁锰氧化态〈残渣态;ｗ（Ｃｕ、Ｐｂ）：可变换态〈碳酸盐态〈有机态〈残渣态〈铁锰氧化态;ｗ（Ｃｄ）：残渣态,有机     

长江口海域表层沉积物重金属元素赋存形态特征

通过长江河口地区水下表层沉积物样品多种化学元素的赋存形态分析测试数据,综合分析重金属元素的赋存形态特征。研究结果显示：镉、汞、铅残渣态所占比例均小于50%,锌、砷、铬、铜、镍残渣态占比均大于50%;8个元素的残渣态与全量呈显著正相关关系。沉积环境和沉积物粒径对重金属元素赋存形态具有重要影响。沉积物的物质来源、矿物组成特征、水动力作用与沉积物粒度和物理化学条件等是长江口地区表层沉积物重金属元素赋存形态的主要控制因素。     

长江武汉段冲积土壤中重金属的环境地球化学特征

长江沿江全流域的重金属元素镉异常带引发了人们对沿长江流域城市的镉及其他重金属元素的环境地球化学特征及生态效应的关注。本文以长江流域具有重要的经济发展战略意义的武汉为研究区,对长江武汉段沿岸的冲积土壤中主要重金属元素镉、铜、铅、镍、铬的含量和以BCR法分步提取的弱酸提取态、可还原态、可氧化态和残渣态等4种形态的分量进行了较系统的分析,同时,配套分析了蔬菜样品中的重金属元素镉、铜、铅、镍、铬的含量,以便了解重金属元素的环境地球化学特征。结果显示,长江武汉段沿岸的冲积土壤中,重金属镉含量超标;铅、铜、镍元素含量接近国家土壤环境质量标准二级指标,基本上对植物和环境不造成危害和污染,满足一般农田、蔬菜地、茶园、果园、牧场等土壤环境标准;铬元素含量较低,接近其背景值。长江武汉段沿岸的冲积土壤中重金属元素的含量和活动性强的弱酸提取态分量随着采样点位置距离武汉钢铁厂越近而增大,显示重金属污染的部分原因可能是工业生产造成的。重金属元素在表层土壤中存在积累效应,表现为表层土壤中重金属元素含量高于对应深层的含量。重金属元素的形态分布特征与各自的地球化学性质有关,活动性强的弱酸提取态镉和铅分量高,具有潜在的环境危害。这些土壤中种植的蔬菜中,重金属元素镉含量普遍明显超标,部分蔬菜中铅元素含量超标,铜、镍、铬元素含量正常。     

干旱区绿洲土壤共存重金属元素形态变化及生物有效性实验分析——以Cd、Zn、Ni元素为例

采用盆栽试验,初步研究了干旱区绿洲土壤—胡萝卜系统中镉、锌、镍3种重金属的形态变化特征及其生物有效性问题。结果表明:供试绿洲土壤原状土中,Cd、Zn、Ni均以稳定的残渣态形式存在,而处理土壤中重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Zn、Ni则主要以铁锰氧化态为主;3种元素的活性大小依次为Cd>Ni>Zn。根据回归分析,元素Zn对胡萝卜块茎和茎叶吸收Zn量贡献最大的分别是Zn的碳酸盐结合态和铁锰氧化态;元素Ni对胡萝卜各部位吸收贡献最大的均为Ni的铁锰氧化态。     

北京平原区两年内土壤中五种重金属元素化学形态变化及生物有效性

为了监测北京市平原区2015年和2016年土壤中5种重金属As、Cd、Hg、Pb、Zn化学形态的变化趋势,运用Tessier连续提取法对土壤重金属进行了形态分析,并对影响重金属元素生物有效性的因素进行研究。结果表明,2年内研究区表层土壤重金属元素的形态变化微弱,有效态含量以Cd元素最高,达到45.67%,故潜在生态危害性最大;其次为Zn元素,达12.16%,其中碳酸盐结合态占比虽大,但由于研究区土壤呈偏碱性,Zn元素的迁移能力较弱,潜在危害性较小;As、Hg、Pb均以难迁移态存在,故潜在危害性也较小。土壤重金属元素的生物活性系数及迁移系数分别为:CdZnPbAsHg和CdAsZnPb=Hg,其中Cd元素2年的生物活性系数和迁移系数最高,展现出较强的生物活性和迁移能力,其余重金属元素的活性系数和迁移系数较低,潜在危害性较弱。影响重金属元素生物有效性的因素较复杂,以重金属元素全量为主,p H、有机质、CEC等理化性质次之。     

干旱区绿洲土壤共存重金属元素形态变化及生物有效性实验分析

采用盆栽试验,初步研究了干旱区绿洲土壤—胡萝卜系统中镉、锌、镍3种重金属的形态变化特征及其生物有效性问题。结果表明：供试绿洲土壤原状土中,Cd、Zn、Ni均以稳定的残渣态形式存在,而处理土壤中重金属被钝化的量有限,Cd的存在形式主要以碳酸盐态为主,Zn、Ni则主要以铁锰氧化态为主;3种元素的活性大小依次为Cd＞Ni＞Zn。根据回归分析,元素Zn对胡萝卜块茎和茎叶吸收Zn量贡献最大的分别是Zn的碳酸盐结合态和铁锰氧化态;元素Ni对胡萝卜各部位吸收贡献最大的均为Ni的铁锰氧化态。     

印染污泥中重金属形态分析及生物有效性

选取上海某印染厂的印染废水处理后的活性污泥样品,通过盆栽土培试验,用黑麦草对印染污泥进行修复,运用Tessier A连续提取法研究修复后黑麦草根际和非根际印染污泥中铅、铜、镍、锌、镉5种重金属形态的变化,以及重金属的生物有效性与植物中有效态含量之间的关系。结果表明,栽培后根际与非根际环境中各重金属元素具有典型的形态分布特征:铅主要以离子交换态和残渣态存在;铜主要以碳酸盐结合态和残渣态存在;镍由紧结合态(铁锰氧化物结合态+有机结合态)向离子交换态转移;锌的有机结合态和碳酸盐结合态有所增加;镉主要以离子交换态和铁锰氧化物结合态为主,说明镉元素较活泼,具有潜在的环境影响能力,应该给予更多的关注。印染污泥中重金属的生物有效性与重金属元素的性质有关,铜、锌的生物有效性较高,其次是铅,最低是镍、镉。     

金昌市铜镍矿区周围土壤中重金属的迁移特征

对金昌矿区不同区域土壤5~20 cm层中重金属各化学形态及活性态的迁移行为进行了研究,结果表明：土壤中重金属不同化学形态迁移率不同,弱酸提取态、可还原态、可氧化态和残渣态平均迁移率分别为0.13、0.51、0.30和0.54。重金属总量和活性态（包括弱酸提取态、可还原态、可氧化态）迁移率也表现出很大差异,尾矿区土壤Cr总量迁移率较高为0.65,而其活性态迁移率较低为0.26,Ni与Cr迁移特征完全相反,总量迁移率为0.26,而活性态迁移率为0.67;农田土壤中Pb总量迁移率低而活性态迁移率高,Ni与Zn特征相似,总量迁移率高而活性态迁移率相对较低;大棚地土壤中重金属迁移率均较低,Cu和Ni活性态几乎未发生向下迁移。可见,重金属的迁移与其化学形态分布关系密切,与重金属总量的迁移率相比,活性态迁移率能够更有效地反映出土壤中重金属的迁移特征和潜在危害性。     

铜陵矿山酸性排水及固体废弃物中的重金属元素

在调查中国铜陵凤凰山铜矿和新桥硫铁矿两种不同类型矿山固体废弃物特征的基础上,研究了矿山尾矿和废石产生酸性排水的可能性及其差异以及矿山固体废弃物中重金属元素的赋存形式。结果表明,凤凰山铜矿的尾矿基本不产生矿山酸性排水,而新桥硫铁矿采矿废石产生矿山酸性排水,并且凤凰山铜矿的尾矿和新桥硫铁矿采矿废石中重金属元素的赋存形式也有差异,前者重金属Cu、Pb、Zn、Cd、As、Hg主要赋存于硅酸盐态中,而后者在还原态中有较高的含量,这反映了在地表条件下尾矿中大量重金属元素已经发生了迁移,而采矿废石已经开始氧化,且酸性排水的存在更有利于废石中重金属元素的迁移和扩散,进而导致矿区周围环境的污染。     

内蒙古废弃钨钼矿区周围土壤重金属污染生态环境评价及成因分析

为研究内蒙古赤峰市废弃钨钼矿区周围土壤重金属污染特征、潜在生态风险及成因分析，共采集83份表层土壤样品和6个土壤钻孔。采用ArcGIS空间插值分析方法研究As、Cd、Cr、Cu、Ni、Pb、Mo和Zn的空间分布，构建重金属扰动指数函数研究重金属受人类活动的污染程度，利用地累积指数法验证矿区周围土壤重金属污染程度，通过相关性分析判断重金属来源并讨论污染成因。结果表明：矿区周围土壤As、Cd、Cu、Pb、Zn和Mo平均含量明显高于矿区周边背景值，高含量主要分布尾矿库周围，主要来源为矿山采选活动；Cr和Ni基本无污染，主要来源为母岩风化。通过重金属扰动指数函数计算发现：采用区域背景值对矿区周围进行重金属污染评价夸大了矿山采选活动对矿区周围土壤重金属的污染，矿区周围土壤重金属污染是由于天然重金属富集和采矿活动共同作用下的“双驱动模式”导致，尾矿库周围土壤重金属污染程度随着与尾矿库水平距离的增加和深度的加大而逐渐降低。降水量丰富程度是影响重金属迁移能力的关键因素，该矿处于降水量匮乏地区，尾矿库对周围土壤重金属污染范围有限，对生态环境影响轻微。     

Mineralogical and geochemical alteration of Hitura sulphide mine tailings with emphasis on nickel mobility and retention

Weathering of Hitura (W Finland) nickel sulphide mine tailings and release of heavy metals into pore water was studied with mineralogical (optical and electron microscopy, X-ray diffraction) and geochemical methods (selective extractions). Tailings were composed largely of serpentine, micas and amphiboles with only minor carbonates and sulphides. Sulphides, especially pyrrhotite, have oxidized intensively in the shallow tailings in 10–15 years, but a majority of the tailings have remained unchanged. Oxidation has resulted in depletion of carbonates, slightly decreased pH, and heavy metal (Ni, Zn) release in pore water as well as in the precipitation of secondary Fe precipitates. Nevertheless, in the middle of the tailings area, where the oxidation front moves primarily downward, released heavy metals have been adsorbed and immobilized with these precipitates deeper in the oxidation zone. In contrast to what was seen in pore water pH, but in accordance with static tests of the previous studies, the neutralisation potential ratio (NPR) calculated based on the mineralogical composition and the total sulphur content suggested that tailings are ‘not potentially acid mine drainage (AMD) generating’. However, the calculated buffering capacity of the tailings resulted largely from the abundant serpentine because of the low carbonate content. Despite its slow weathering rate, serpentine may buffer the acidity to some extent through ion exchange processes in fine ground tailings. Nevertheless, in practice, acid production capacity of the tailings depends primarily on the balance between Ca–Mg carbonates and iron sulphides. NPR calculation based on carbonate and sulphur contents suggested, that the Hitura tailings are ‘likely AMD generating’. The study shows that sulphide oxidation can be significant in mobilisation of heavy metals even in apparently non-acid producing, low sulphide tailings. Therefore, prevention of oxygen diffusion into tailings is also essential in this type of sulphide tailings.     

安徽铜陵林冲尾矿库重金属元素分布与迁移及其环境影响

通过对铜陵凤凰山矿林冲尾矿库中重金属元素的空间分布特征及相关土壤、水系沉积物和植物中重金属元素含量变化的研究，初步了解尾矿重金属元素的空间变化和迁移规律，分析了其对周围环境的影响及潜在危害性，并指出了尾矿库土地综合开发利用的方向。     

Characteristics of distribution and chemical speciation of heavy metals in environmental mediums around Jinchang mining city,Northwest China

Heavy metal contamination was the main environmental problem around the Jinchang Ni–Cu mine area of Gansu, Northwest China. The concentration of heavy metals (Cr, Cu, Ni, Pb, and Zn) in various environmental mediums around the Jinchang Ni–Cu mine area were analyzed using atomic absorption spectrometry (AAS). The different chemical speciation of heavy metals was extracted using BCR (European Community Bureau of Reference) sequential extraction procedure, and the concentration of chemical speciation of each heavy metal was measured by inductively coupled plasma-atomic emission spectrometry. The results showed that Cu and Ni were the most important heavy metal pollutants in various mediums including cultivated soils, dust on slagheap surfaces, tailings, and sediments in waste water drains. In the tailings and sediments, the concentrations of Ni were obviously higher than those of Cu, whereas, in the soil and dust, the concentrations of Cu were higher than those of Ni. Analysis of chemical speciation indicated that Cr and Zn were mainly in residual fraction; Cu was mainly in oxidizable fraction; Ni was mainly in reducible fraction and acid soluble fraction; and Pb was mainly in reducible fraction and residual fraction. The extent of contamination of various environmental mediums was different because the heavy metals were derived from different sources. Furthermore, the mobility of various heavy metals was different because of the different distribution of chemical speciation.     

缓冲期碳酸盐型尾矿重金属释放机制——柱淋滤实验研究

碳酸盐型尾矿在缓冲期/中性矿山废水(NMD)释放期的重金属污染问题易被忽视。本文以广西大厂锡石-硫化物尾矿作为研究对象,采用柱淋滤实验方法,探讨碳酸盐型尾矿在缓冲期重金属的释放机制,为此类型尾矿重金属污染的防治提供依据。实验结果表明,大厂尾矿在缓冲期(约7年,pH值为6. 6～8. 0)存在Sb、Zn、Cd、As(Pb)释放污染问题。在尾矿堆放初期(0. 5年,pH值由7. 6降至7. 2),Zn、Sb、Cd快速、大量释出;中期(0. 5～2. 5年,pH值由7. 2波动升高至8. 0),Sb较平稳释出;后期(2. 5～7年,pH值变化范围为8. 0～6. 6,呈降低趋势),受气温及pH值影响,As、Sb(Pb)呈波动或间歇振荡释出,即在夏季高温、pH值较高时,释出元素浓度较高,反之,在冬季低温、pH值较低时,释出元素浓度较低。重金属的释放与尾矿中硫化物的氧化程度高低及氧化先后顺序有关。这些矿物的氧化顺序大致为:闪锌矿(Zn、Cd)、辉锑锡铅矿(Sb)→脆硫锑铅矿(Sb)→毒砂(As)、方铅矿(Pb)。因此,对于(广西大厂)碳酸盐型尾矿在缓冲期的重金属污染应分阶段、季节(夏季),采取有针对性的防治措施;在缓冲期(7年)后应注意尾矿酸性矿山废水(AMD)+重金属(如As、Sb)复合污染的防治。     

Geological impact of some tailings dams in Sardinia,Italy

This article deals with the results of a survey carried out in Sardinia on both active and abandoned tailings dams, and we also discuss the geological impact of tailings dams of two mines: the Masua mine, a large syngenetic Pb-Zn deposit located in Cambrian limestones, and the Montevecchio mine, a Pb-Zn vein deposit near a Hercynian granite intrusion. The characteristics and metal content of material in the dams were analyzed. A high contamination of heavy metals (Pb, Zn, Cd, Cu) was found both in the soils and water of Rio Montevecchio, a stream draining the tailings dams and other mining operations in the area.The study indicates that a control plan to minimize heavy metal pollution must be drawn up for all mines of the area, whether active or abandoned.     

陕西潼关金矿区太峪河底泥重金属元素的含量及污染评价

通过对潼关金矿区太峪河和太峪水库底泥中重金属元素总量的调查,探讨了金矿开发活动中重金属元素对河流底泥的污染程度。研究结果表明,除As外,河流底泥中重金属元素的含量与尾矿渣中重金属元素的含量变化一致,表明其主要来源于尾矿渣,但又明显高于尾矿渣。在同一地点河流底泥中重金属元素的含量平均高出河水中的1048.61～666030.08倍,呈显著富集。以邻近地区不受工矿活动影响的河流底泥重金属元素的含量均值作为评价参比值,太峪河底泥受到了Hg、Pb、Cd、Cu、Zn元素的极度污染,单项污染超标倍数及综合污染指数法评价结果表明,Hg、Pb、Cd平均污染超标倍数达366.90、217.42和149.97,是底泥中最主要的污染元素。河流底泥重金属元素的综合污染指数高达278.97,表明河流的复合污染亦呈极度状态。太峪河底泥受重金属元素极度污染的现实提示,矿区的环境防治工作已刻不容缓。     

Source analysis and risk evaluation of heavy metal in the river sediment of polymetallic mining area: Taking the Tonglüshan skarn type Cu-Fe-Au deposit as an example,Hubei section of the Yangtze River Basin,China

In this paper, 25 sampling points of overlying deposits in Tonglushan mining area, Daye City, Hubei Province, China were tested for heavy metal content to explore pollution characteristics, pollution sources and ecological risks of heavy metals in sediments. A geo-accumulation index method was used to evaluate the degree of heavy metal pollution in the sediment. The mean sediment quality guideline quotient was used for evaluating the ecological risk level of heavy metal in the sediment. And a method of correlation analysis, clustering analysis, and principal component analysis was used for preliminary analysis on the source of heavy metal in the sediment. It was indicated that there was extremely heavy metal pollution in the sediment, among which Cd was extremely polluted, Cu strongly contaminated, Zn, As, and Hg moderately contaminated, and Pb, Cr, and Ni were slightly contaminated. It was also indicated by the mean sediment quality guideline-quotient result that there was a high ecological risk of heavy metals in the sediment, and 64% of the sample sites had extremely high hidden biotoxic effects. For distribution, the contamination of branches was worse than that of the main channel of Daye Dagang, and the deposition of each heavy metal was mainly influenced by the distance from this sample site to the sewage draining exit of a tailings pond. The source analysis showed that the heavy metals in the sediment come from pollution discharging of mining and beneficiation companies, tailings ponds, smelting companies, and transport vehicles. In the study area, due to the influence of heavy metal discharging from these sources, the ecotoxicity of heavy metals in the sediment was extremely high, and Cd was the most toxic pollutant. The research figured out the key restoration area and elements for ecological restoration in the sediment of the Tonglüshan mining area, which could be referenced by monitoring and governance of heavy metal pollution in the sediment of the polymetallic mining area.©2022 China Geology Editorial Office.     

Estimation of potential pollution from mine tailings in the San Pedro River (1993–2005), Mexico–US border

The San Pedro River (SPR) is located in northern Sonora (Mexico) and southeastern Arizona (USA). SPR is a transboundary river that develops along the Sonora (Mexico) and Arizona (USA) border, and is considered the main source of water for a variety of users (human settlements, agriculture, livestock, and industry). The SPR originates in the historic Cananea mining area, which hosts some of the most important copper mineralizations in Mexico. Acid mine drainage derived from mine tailings is currently reaching a tributary of the SPR near Cananea City, resulting in the contamination of the SPR with heavy metals and sulfates in water and sediments. This study documents the accumulation and distribution of heavy metals in surface water along a segment of the SPR from 1993 to 2005. Total concentrations of Cd, Cu, Fe, Mn, Pb, and Zn in surface waters are above maximum permissible levels in sampling sites near mine tailing deposits. Nevertheless, a significant decrease in the Fe and SO₄ ²⁻ in surface water (SO₄ ²⁻: 7,180–460.39 mg/L; Fe: 1,600–9.51 mg/L) as well as a gradual decrease in the heavy and transition metal content were observed during the period from 1994 to 2005. Approximately 2.3 km downstream of the mine tailings, the heavy metal content of the water drops quickly following an increase in pH values due to the discharging of wastewater into the river. The attenuation of the heavy metal content in surface waters is related to stream sediment precipitation (accompanied by metal coprecipitation and sorption) and water dilution. Determining the heavy metal concentration led to the conclusion that the Cananea mining area and the San Pedro River are ecosystems that are impacted by the mining industry and by untreated wastewater discharges arising from the city of Cananea (Sonora, Mexico).