近中性溶液条件下富镉铅锌矿矿石的风化淋滤实验研究

在近中性溶液条件下对富镉锌矿石进行了风化淋滤实验研究,发现淋滤液中产生大量以石膏为主要成分的沉淀物.淋滤液呈碱性,淋滤出来的Zn、Cd以水溶态和沉淀态形式存在,而以后者为主.淋滤50天后,黄铁矿闪锌矿石中Zn、Cd的淋滤率为0.03％和0.01％,而半氧化闪锌矿石Zn、Cd的淋滤率则高得多,分别0.10％和0.60％.     

抚顺西舍场油页岩的淋滤行为及其对周围水体的影响

为研究抚顺市区南部地表堆积的油页岩中微量元素的淋滤作用对水体的影响,本文分别进行了抚顺西露天矿采场和西舍场油页岩pH为4.0、6.5和8.0的动态淋滤实验,以ICP-MS测试了淋滤液及水体中的微量元素。结果表明,高、低品位油页岩中Cu、Zn、Pb、Ni、Rb、Bi、Ba、Ti、Co、Cr、Cu和Mn等淋出率较高;水体中Pb、Cd、Co、Cr、Ni、Zn、Mn等元素超标,表明抚顺西舍场油页岩的堆积已对周围地表水体和地下水体造成了污染。     

大宝山尾矿重金属风化淋滤实验研究

广东大宝山尾矿造成的重金属污染严重影响了矿区的生态环境。对矿区不同采样点的尾矿进行了风化淋滤实验,结果表明,淋滤液的pH值很低(2.5~4.8)并随着淋滤的进行继续降低;淋滤液的电导率不断升高;淋滤液中的SO42-浓度有波动,但变化不大。淋滤液中有次生矿物沉淀生成,吸附了部分重金属离子。经过30d的淋滤,重金属Mn的淋滤率最大且可迁移性最强,Pb的淋滤率最小且沉积性最强;拦泥坝泥浆释放的重金属总量最大。     

铅锌矿床中闪锌矿Cd含量及Zn/Cd值的地质意义

以5个典型铅锌矿床为研究对象,测试了其闪锌矿中的Zn和Cd含量,发现同一标本上深色闪锌矿比晚期的浅色闪锌矿更富集Cd,其原因可能与流体中Zn/Cd值变化相关;而对比不同矿床不同颜色闪锌矿之间Cd的富集规律是没有意义的。同时,与岩浆作用相关的铅锌矿床,其闪锌矿中的Zn/Cd值与相关岩浆岩的Zn/Cd值相似,暗示闪锌矿中的Zn/Cd值可指示成矿物质来源。同时,川滇黔地区铅锌矿床显示出2组不同的Zn/Cd值:1高Zn/Cd值型(300~800),以会泽矿床为代表,其Zn/Cd值介于峨眉山玄武岩和该区地层之间,暗示该类型矿床的成矿物质可能主要来源于峨眉山玄武岩和地层。2低Zn/Cd值型(20~70),以富乐矿床为代表,其Zn/Cd值基本与地层相似,暗示该矿床的成矿物质可能主要来源于地层。而对比川滇黔地区铅锌矿床和与岩浆作用相关矿床的Cd含量及Zn/C值发现,成因不同的矿床,其Cd含量和Zn/Cd值具有较大差异。因此,铅锌矿床闪锌矿中的Cd含量及Zn/Cd值对于判别成矿物质来源和矿床成因具有指示意义。     

不同酸度淋溶条件下石煤中Cd、Pb释放速率

模拟天然降雨成分在三种酸度(pH 3.5、5.5和7.5)下对浙江省下寒武统荷塘组含钒石煤进行了淋溶作用实验,利用ICP-OES、ICP-MS等技术分析了滤出液中的Cd、Pb含量,研究了它们在不同酸碱度的淋溶条件下的释放特征.结果表明,石煤滤出液中Cd含量高低与淋滤液pH值的大小呈反比关系,在强酸性淋滤条件下滤出率为1...     

扬子地块西南缘铅锌矿床Cd、Ge与Ga富集规律初步研究

扬子地块西南缘分布着大量富含Cd、Ge与Ga的铅锌矿床，已成为我国Pb、Zn及Cd、Ge与Ga矿产资源的重要生产基地。对代表性铅锌矿床进行野外地质调查和系统采样鉴定后．应用电子探针微区分析手段，研究主要矿石矿物闪锌矿、方铅矿和黄铁矿中分散元素的富集特征。结果显示．各类矿床中闪锌矿均相对富集Cd，方铅矿富集Ge与Ga，而黄铁矿中Cd、Ge与Ga的富集系数均相对较低．未呈现出选择性富集的趋势；赋存于震旦纪一寒武纪地层且以脉状、网脉状产出的矿体中闪锌矿的Cd含量明显高于赋存于晚古生代并以层状产出的矿体中闪锌矿的Cd含量。     

基于土柱淋滤实验的煤矸石饱和状态下溶质释放过程研究

针对煤矸石山在降水淋滤作用下对矿区周边地下水造成污染的严重问题,用实验模拟法对包头石拐区一废弃煤矿进行饱和状态下煤矸石的淋滤实验研究。结果表明:煤矸石中Ca、Mg、Fe、Cu、Zn、NO₃-、SO₄2-、Cl-的淋滤过程都遵循浓度先升高再降低到稳定值的基本规律,只是NO₃-、SO₄2-、Cl-的淋出速率明显大于重金属的淋出速率,Ca和Mg、SO₄2-和Cl-、Pb和Cr、Cd有相似的淋出机制;重金属最强淋出率从大到小的顺序是Mg>Cd>Ca>Cu>Zn>Cr>Fe>Pb;Hg和As等含量甚微,均未检出。      

闪锌矿的Fe、Cd关系随其颜色变化而变化

闪锌矿是自然界常见的重要金属矿物,含有很多种杂质元素,其中Fe、Cd是闪锌矿最常见,也是最重要的杂质元素。普遍认为,闪锌矿中的Cd、Fe是类质同象取代了Zn。但是,笔者研究发现闪锌矿的Cd与Zn往往成正相关,与Fe呈负消长。说明闪锌矿的Cd类质同象置换主要不是Zn,而是Fe。而且,闪锌矿Cd与Fe的相关性随其颜色的改变而变化。深色闪锌矿的Cd与Fe呈负相关,褐色闪锌矿Cd与Fe既有负消长关系,又有正消长关系。浅色闪锌矿的Cd与Fe呈正相关的数量大增。暗色闪锌矿多形成于高温,Fe具有强烈置换Zn能力。随着形成温度下降,Fe交代Zn的能力不仅逐渐减弱,而且,闪锌矿晶格的Fe变得不稳定,而被释放出来,主要由Cd替代。浅色闪锌矿形成于低温,矿液结晶的后期。矿液中的Zn可能不能满足闪锌矿结晶对Zn的需求,就由离子参数相似的Cd2+和Fe2+替代。致使闪锌矿的Cd与Fe呈正相关,Cd和Fe与Zn负消长。     

大吉山稀有金属花岗岩中富镉闪锌矿的矿物学特征

电子探针研究表明江西大吉山矿床二云母花岗岩和白云母花岗岩中副矿物闪锌矿为富镉闪锌矿(Cd,4.34—19.89％,wt％,下同),铁含量低(Fe,1.03—4.24),尤以具W、Be、Ta、Nb矿化的白云母花岗岩中闪锌矿镉含量为高,并随岩体由下到上(标高的增大)而增高。矿物中Cd+Fe与Zn之间存在良好的线性负相关关系,指示了主要类质同象替代发生在Cd、Fe与Zn之间。矿物中可能存在不等位替代现象和四面体空位。富镉闪锌矿晶胞参数为0.54250—0.54440nm,随矿物中Cd含量的增加而增大。对照表明,当矿物中镉含量特别高时,Skinner(1961)晶胞参数计算公式估计值偏大,需作重新修正。最后,文章对富镉闪锌矿的成因意义进行了讨论。     

青海虎头崖铅锌矿床闪锌矿化学成分特征研究

青海虎头崖铅锌矿床是祁漫塔格成矿带矽卡岩型多金属矿的典型代表之一,该矿区岩浆活动强烈,具有Fe、Cu、Mo、Pb、Zn等多金属成矿元素组合。本文通过电子探针对该矿床中闪锌矿化学成分标型特征进行了详细研究,探讨其中Fe、Cd等元素的分布状态和富集规律。研究表明,矿床中闪锌矿可分为3个世代,从早到晚闪锌矿颜色由黑色逐渐变为浅黄色,矿物组合由闪锌矿-(方铅矿-黄铜矿)-黄铁矿-磁黄铁矿→闪锌矿-方铅矿-黄铜矿-黄铁矿-(磁黄铁矿) →闪锌矿-方铅矿-方解石或石英。早阶段形成的闪锌矿以富Fe贫Zn和Cd为特征,而晚阶段形成的闪锌矿相对贫Fe,富Zn和Cd。通过闪锌矿中的FeS含量估算获得成矿温度范围为148～262℃。随着成矿阶段的演化,3个世代闪锌矿中FeS含量逐渐降低,表明对应成矿温度的不断降低,分别为262～258、260～200、248～148℃。结合Zn/Cd含量比值变化范围,认为虎头崖铅锌矿床应属于中温热液矿床。在空间分布上,沿着热液流动方向,闪锌矿中Zn含量逐渐增加,Fe含量逐渐减少,Zn/Cd变化范围增大,指示矿床中热液流动方向为由北西西到南东东,由深部到浅部,与矿体走向一致。通过与国内其他不同类型铅锌矿床的对比,发现虎头崖铅锌矿床闪锌矿中Zn、Fe、Mn、Cd等化学成分具有典型中温矽卡岩型矿床中闪锌矿化学成分的特征,明显不同于层控型矿床、喷流沉积型矿床等其他类型矿床闪锌矿。结合该矿床地质特征和成矿作用过程,我们认为虎头崖铅锌矿床为矽卡岩型矿床。     

Sodium-cadmium and sodium-zinc exchangeability in montmorillonite

A sodium montmorillonite from Ivan?ice (Czech Republic) was treated with solutions containing various molar concentrations of Zn and Cd for the purpose of determining ion exchange equilibria. The sorption isotherms for Zn and Cd exhibit a rather similar shape, which depends on pH; the maxima for Zn and Cd sorbed on Na-montmorillonite are very close to each other (e.g., 0.419?mmol/1?g and 0.440?mmol/1?g, respectively, for pH=5). It is a characteristic of both elements that a high level of sorption is reached at low concentration in solution. The leachability of Zn and Cd in deionized water from fully saturated montmorillonites is very similar, but a different results were observed for Na leached from fully saturated Na-montmorillonite. The total amount of leached Na was 21.7% (after four consecutive leaching runs). However, only 2.1% and 1.6% were found for Cd and Zn, respectively. Different quantities of Cd and Zn exchanged in Na-montmorillonite influence significantly the shape and position of maximum of the 001 XRD profile. Experimental XRD profiles of montmorillonites, fully saturated with Na, Cd and Zn, corrected for instrumental and physical factors exhibit maxima at 12.59, 14.86, and 14.77?Å, respectively. When the d ₀₀₁ spacing is determined from a corrected profile, it varies systematically with the percentage of exchanged Zn and Cd and the relationships seem to be linear for both elements. For montmorillonites, not fully saturated with one element, the peak shift and peak broadening, characteristic for mixed layered structures with random layer sequences, has been observed.     

An experimental study of heavy metal attenuation and mobility in sandy loam soils

Column flow-through experiments reacting wastewater solutions with sandy loam soil samples were performed to study heavy metal attenuation by two soils with different physical and chemical properties. Reacted soil columns were leached with synthetic acid rain to study the mobility of attenuated heavy metals under leaching conditions. This study demonstrates that cation exchange, surface adsorption, chelation with solid organic material, and precipitation were the important attenuation mechanisms for the heavy metals (Cd, Cr, Cu, Mo, Ph, and Zn). Adsorption on soil hydrous oxide surfaces was the primary attenuation mechanism for Cd and Zn in both soils, and for Cu in a soil with low organic matter content. Wastewater solution pH is also an important factor that influences the retention of heavy metals. Cadmium, Cu, Cr, and Zn became mobile after prolonged application of spiked wastewater solution, either through saturation of soil adsorption sites or due to decreasing pH. Only Cr, Pb, and Mo, which are attenuated primarily through precipitation, show significant net retention by soil. Acid rain water removed heavy metals left in the column residual pore solution and weakly sorbed heavy metals in the soils, and has the ability to mobilize some strongly attenuated heavy metals, especially when the soil organic matter content is high. The results have important applications in predicting heavy metal mobility in contaminated soil, the disposal of acid mine drainage, and assessing the risks of landfall leachate leakage.     

Microbial effects on geochemical behavior of arsenic in As-contaminated sediments

The purpose of this study is to investigate the contamination level and chemical speciation of As in sediments from the Hwachon Au mine area, and to study the effects of indigenous bacteria on geochemical behavior of As in As-contaminated sediments from the mine. Concentrations of heavy metal and metalloids in one composite sample of 9 Hwachon sediments were 24.9 As mg/kg, 16.6 Cd mg/kg, 230 Pb mg/kg and 1080 Zn mg/kg. This indicates that this area was seriously contaminated with As, Cd and Zn. From the result of sequential extraction analysis, most of As (87.9%) existed as a phase of As which coprecipitated with Fe oxyhydroxides. Under aerobic condition, As concentration leached from sediments were 4 times higher in non-sterile than in sterile condition. This enrichment of As leaching could be caused by increase of pH and exudation secreted during microbial metabolism. On the other hand, under anaerobic condition, As concentration has dramatically increased in non-sterile solution with time. This As leaching has begun on 4–5th days of incubation and the highest concentration of 511 As μg/l was recorded on about 11th day. Arsenic leaching under anaerobic condition was caused by microbial enhancement of Fe leaching. Total Fe concentration increased from the 4th day, and this Fe leaching might cause lixiviation of As which had been coprecipitated with Fe oxyhydroxide.     

土壤样品镉同位素分析中Cd与Sn有效分离方法的改进

保证Cd的高回收率以及彻底的Sn干扰去除是获得精确镉同位素组成的前提,目前报道的多种Cd分离与纯化方法获得的Cd回收率有较大差异(42.6%~99.8%),且去除Sn干扰的效果也不同(去除率在87.8%~97.4%之间),Cd回收率和Sn去除率均不理想。本文对前人报道的分离方法进行对比实验,发现0.1 mol/L氢溴酸-0.5 mol/L硝酸是分离Cd和Sn的有效试剂,增加该组混合酸的用量可淋洗出样品中更多的Sn且不会损失Cd,当混合酸的淋洗用量增加至30 mL时,Sn的淋洗率达到99.8%以上,Cd的回收率亦达到99.0%±0.5%,可满足土壤样品镉同位素的测定要求。本工作为获得高精度的镉同位素组成奠定了基础,为研究土壤环境中镉的污染来源提供了技术手段。     

Leaching behaviour of a simulated nuclear waste glass in groundwater of 50–240°C

A simulated nuclear waste glass, developed by the Power Reactor and Nuclear Fuel Development Corporation of Japan, was leached at 50, 75, 95, 110, 160, 210 and 240°C under saturated vapor pressure in groundwater from a granitic terrain. Depth profiles of insoluble components in reacted glass surface were measured by EPMA, together with time-excursion of the solution composition. Except at 160 and 210°C, B, Na, Mo (as MoO₄²⁻), Li, K, Si and Cs were leached out readily, with increasing rate of leaching in this order, at all other temperatures. At the intermediate temperatures of 160 and 210°C, however, the leaching rates of the soluble components were significantly lowered. Surface layers formed on the reacted glass surface thickened and changed in composition and structure with increasing temperature of reaction. During 312 h leaching at 110°C, a leached layer, about 5 μm thick, formed which is depleted in the soluble components and enriched in immobile metals such as Ni, Mn and Fe, and in precipitated components such as Ca and Mg. At 160 and 210°C, the secondary layer is composed of two sharply defined sublayers: an inner leached layer and an outer KSiAlrich layer, probably formed on the leached layer by precipitation from solution. The 50-μm thick layer formed during 508 h of leaching at 240°C is composed of three broadly defined sublayers, an inner leached layer, an outer precipitation layer and a middle layer of intermediate composition between the former two. The significant suppression in leaching rate at 160 and 210°C is interpreted as a result of rapid formation of the precipitation layer on the glass surface which slowed the diffusive migration of solution species responsible for glass dissolution through the surface layer. At 240°C, the leaching rate of soluble species except for silica increased significantly after an initial stage of slow leaching. At this temperature, coarse crystalline analcime precipitated from solution probably in expense of the surface precipitate, thus preventing the formation of surface precipitation layer as impermeable to solution species migration as that formed at 160 and 210°C.     

Bioavailability and mobility of trace metals in phosphogypsum from Aqaba and Eshidiya,Jordan

As, Cd, Cr, Cu, U, and Zn in Aqaba and Eshidiya phosphogypsum showed relative uniformity in particle size presented by coarse (>0.212 mm); medium (0.212–0.053 mm); and fine (<0.053 mm) in the stacks by age of deposition. Jordan phosphogypsum contains low concentrations of As, Cd, Cr, Cu, U, and Zn compared to those reported worldwide. The bioavailability and mobility of trace metals were estimated using aqua regia leaching experiments. Leaching results have shown that around 3% of the As, 1% of the Cd, 5% of the Cr, 9% of the Cu, 4% of the U, and 3% of the Zn are transferred to the surrounding aquatic environment and/or soils. Mobility of trace metals in phosphogypsum was classified into three degrees: elements with high mobility were Cu and U; those with moderate mobility were As and Zn; and those with low mobility were Cd and Cr. It can be concluded that As, Cd, Cr, Cu, U, and Zn were not only uniformly distributed in the stack, but they are not leached from the phosphogypsum stacks in any significant amount, and then they are not easily transferred to the surrounding aquatic environment and/or soils.     

Biochar application to hardrock mine tailings: Soil quality,microbial activity,and toxic element sorption

Waste rock piles from historic mining activities remain unvegetated as a result of metal toxicity and high acidity. Biochar has been proposed as a low-cost remediation strategy to increase soil pH and reduce leaching of toxic elements, and improve plant establishment. In this laboratory column study, biochar made from beetle-killed pine wood was assessed for utility as a soil amendment by mixing soil material from two mine sites collected near Silverton, Colorado, USA with four application rates of biochar (0%, 10%, 20%, 30% vol:vol). Columns were leached seven times over 65 days and leachate pH and concentration of toxic elements and base cations were measured at each leaching. Nutrient availability and soil physical and biological parameters were determined following the incubation period. We investigated the hypotheses that biochar incorporation into acidic mine materials will (1) reduce toxic element concentrations in leaching solution, (2) improve soil parameters (i.e. increase nutrient and water holding capacity and pH, and decrease compaction), and (3) increase microbial populations and activity. Biochar directly increased soil pH (from 3.33 to 3.63 and from 4.07 to 4.77 in the two materials) and organic matter content, and decreased bulk density and extractable salt content in both mine materials, and increased nitrate availability in one material. No changes in microbial population or activity were detected in either mine material upon biochar application. In leachate solution, biochar increased base cations from both materials and reduced the concentrations of Al, Cd, Cu, Pb, and Zn in leachate solution from one material. However, in the material with greater toxic element content, biochar did not reduce concentrations of any measured dissolved toxic elements in leachate and resulted in a potentially detrimental release of Cd and Zn into solution at concentrations above that of the pure mine material. The length of time of effectiveness and specific sorption by biochar is variable by element and the toxic element concentration and acidity of the initial mine material.     

地浸过程中铀迁移特征及条件的实验研究

通过室内模拟试验，对地浸过程中铀的迁移规律进行了研究。结果表明：①溶浸液中铀浓度值在达到饱和浓度前，随地浸路径延长而逐渐增大；②铀的存在形式及其含量与水文地球化学条件相关，当1．9＜pH＜4．4时，为UO2SO4和UO^2 2；当4．4＜pH＜5．1时，为UO2SO4和(UO2)a(OH)^5 ；②随着水文地球化学条件的变化，铀迁移经历了溶解迁移、水解沉淀、再溶解迁移的多次旋回，即当pH＞4．6、Eh＜420mV时，溶解状态的铀产生沉淀；当2．0＜pH＜4．6，420mV＜Eh＜650mV时，U^6 溶解迁移；当pH＜2．0、Eh＞650mV时，U^4 溶解迁移；④根据溶浸液中铀浓度和pH、Eh临界值，铀地浸路径可划分出充分浸出带、有效浸出带、铀沉降带和未浸出带，不同特征的浸出带随浸出时间的变化而有序移动。     

Comparison of potentially toxic metals leaching from weathered rocks at a closed mine site between laboratory columns and field observation

Potentially toxic metals, such as Cu, Pb and Zn, are leached from weathered rocks at many closed mine sites due to the acidic environments and mineralogical modifications. The mobilized toxic metals may cause contamination of surrounding water bodies. In this study, both laboratory column experiments and field observations at a former mine located in the north of Japan were carried out to compare the leaching behavior of Cu, Pb and Zn. The thickness of the surface weathered rock was varied (10, 20 and 30 cm) for the columns experiments while porous cups for porewater sampling were set up at different depths (GL-15, -45, -70, and -95 cm) for the field observations. Deionized water was added once a week over 75 weeks to the columns to simulate rainfall while porewater was extracted by a vacuum pump in several sampling campaigns (over 18 months). Similar low pH and leaching behavior of potentially toxic metals were observed for column experiments and field observations. A moderate increase in concentration with depth was observed for Cu and Zn. However, no increase in concentration was observed for Pb. This suggests that the leaching of Cu and Zn is enhanced by the length of the flow pathway through the weathered rock layer while Pb concentration is restricted by the precipitation of insoluble Pb sulfate. Thus, the thickness of the weathered rock layer is an important parameter that should be taken into consideration to estimate the loads of some potentially toxic metals, which is important when designing remediation schemes.     

The leaching of trace elements from municipal solid waste incinerator bottom ash at different stages of weathering

For a proper assessment of the environmental impact of the utilisation and disposal of Municipal Solid Waste Incinerator (MSWI) bottom ash it is necessary to understand weathering processes and their effects on (trace) element leaching. The authors have investigated the processes that control the leaching of Cd, Pb, Zn, Cu, and Mo from 3 categories of bottom ash: (A) unweathered bottom ash (grate siftings and unquenched samples), (B) quenched/non-carbonated bottom ash (freshly quenched and 6-week-old samples), and (C) weathered bottom ash (1.5- and 12-year-old samples). Leaching experiments were performed in a pH-stat at a large range of pH values. The speciation code MINTEQA2 was used for subsequent modelling of precipitation/dissolution processes. The speciation of trace elements in weathered bottom ash was also investigated by microanalytical techniques. In A- and B-type bottom ash the general controlling processes are thought to be precipitation/dissolution of relatively soluble minerals or, in the case of Cu in particular, extensive complexation with dissolved organic C. At the “natural” pH of the samples, the leaching of Cd, Pb, Cu, Zn and Mo is generally significantly lower from C-type bottom ash than from less weathered types of bottom ash. This reduction in leaching is due to the neutralisation of bottom ash pH and the formation of less soluble species of these elements as weathering continues. In the more weathered (C-type) bottom ash trace element leaching does not seem to be solubility-controlled; although slow precipitation reactions cannot be totally excluded, it is hypothesised that the controlling mechanism in those samples is sorption to neoformed minerals.