炼锌废渣中重金属 Pb、Zn的矿物学特征

利用X射线衍射（XRD）和带能谱的电子显微镜（TEM／SEM）等方法研究土法炼锌固体废物的矿物组成，特别是重金属Pb和Zn的矿物学赋存特征。结果表明：固体废物是一种高度不均匀的复杂集合体。废渣主要是由石英、长石、碳酸盐矿物、铁质和铝质的非晶质玻璃以及少量风化次生矿物相组成。Pb在废渣中主要以金属Pb形式存在，或呈纳米金属Pb颗粒包裹或吸附于其它矿物表面及玻璃质集合体中。废渣中Zn的存在形式比Pb复杂得多，有硅锌矿、 锰硅锌矿、丝锌铝石等矿物存在形式，在其它矿物表面或玻璃质集体体中也能见到少量纳米级金属Zn。     

典型铜镍矿区周围环境介质中重金属及其化学形态分布特征

重金属污染是金属矿山开采和冶炼所引起的主要环境问题。对甘肃省典型矿业城市金昌市周围农田土壤、废渣堆表面风化物及降尘、尾矿坝尾矿砂和尾矿坝旁排污沟沉积物中Cr、Cu、Ni、Pb、Zn含量及其化学形态进行分析。结果表明:不同区域环境中重金属呈现不同程度累积,其中以Cu、Ni最为显著,含量由高到低依次为尾矿坝排污沟>尾矿坝>废渣堆>农田土壤;尾矿砂和沉积物中重金属分布以Ni含量显著高于Cu含量为特征;而农田土壤和风化物及降尘中重金属分布以Cu含量高于Ni含量为特征,前者Cu、Ni主要来源于尾矿,后者与冶炼烟尘排放有很大关系;样品中除Cr、Zn以残渣态为主外,Cu、Ni、Pb化学形态分布有较大差异,Cu以可氧化态和残渣态为主,Ni以可还原态为主,其次为弱酸提取态,Pb以可还原态为主,其次为残渣态。土壤理化性质是影响重金属化学形态分布的重要因素。     

贵州赫章土法炼锌导致的重金属积累

贵州省赫章县的土法炼锌不仅导致植被的破坏,而且使附近土壤和溪流沉积物中重金属有不同程度的积累,土壤中w(Pb)达到37.24×10~(-6)～30100×10~(6),w(Zn)为162.23×10~(-6)～31625×10~(-6),w(Cd)为0.50×10~(-6)～113×10~(-6),大大超过了当地的土壤背景值;沉积物中w(Pb)达到325.00×10~(-6)～21850×10~(-6),w(Zn)为1250.00×10~(-6)～30425×10~(-6),w(Cd)为25×10~(-6)～97×10~(-6)。土壤和沉积物中Pb、Zn含量与Fe_2O_3有极显著的正相关性;土壤中重金属Pb、Zn含量与Al_2O_3有极显著的正相关性,而沉积物中Pb、Zn含量与Al_2O_3则没有相关性。土壤和沉积物中铁矿物(铁氧化物和氢氧化物)对重金属的强烈固定作用。连续提取法对化学形态研究表明,Pb、Zn在土壤中主要表现为铁锰氧化物结合态与残渣态,而在沉积物中则主要为碳酸盐结合态、残渣态和铁锰氧化物结合态。土壤中可交换态Pb、Zn所占的比例很小,但其绝对含量变化较大,w(Pb)从最低2.75×10~(-6)到最高310.41×10~(-6),w(Zn)4.94×10~(-6)～321.10×10~(-6)。沉积物中w(Pb)7.42×10~(-6)～98.91×10~(-6);w(Zn)9.97×10~(-6)～72.67×10~(-6)。土壤中重金属Pb、Zn的有效性程度明显高于溪流沉积物,对生态环境的潜在危害更大。     

大型金属矿山不同环境介质中重金属元素化学形态分布特征——以甘肃金昌市和白银市为例

重金属元素在环境介质中的存在形态及各形态比例是决定其迁移性和生物可利用性的重要因素.采用BCR法连续提取过程对大型金属矿山周围土壤和水体沉积物中Cd、Cr、Cu、Ni、Pb和Zn化学形态的分析结果表明,土壤和水体沉积物中不同重金属元素化学形态分布有很大差异.总体而言,Cd以弱酸提取态为主(约占60%),Cr以残渣态为主,占90%以上,Cu以可氧化态为主(约占60%),Ni和Pb以可还原态为主,分别约占50%和60%,Zn以残渣态为主,约占45%.不同区域土壤中重金属元素各形态质量分数之和依次为厂区外围>尾矿坝旁>农田,各形态分布也与总量具有相似的变化趋势.金昌市矿山环境介质中重金属以Cu和Ni为主,白银市以Cd、Cu和Pb为主,重金属元素的生物可利用态和潜在可利用态质量分数高,平均约占各金属,总量的60%～90%,对周围环境具有很大的潜在生态危害性.     

基于形态学分析铅锌矿不同功能区土壤重金属元素的分布特征及污染评价

为掌握尤溪铅锌矿区土壤重金属元素分布特征和污染现状,通过采集尤溪铅锌矿不同功能区0~20cm表层土壤样品,测定土壤中Pb、Zn、Cd、Cu、Cr 5种重金属元素的总量及其化学形态,分析不同功能区土壤重金属污染及分布特征,同时采用次生相与原生相比值法(RSP)进行污染评价。结果表明,尤溪铅锌矿不同功能区土壤中Pb、Zn、Cd含量均超过国家土壤环境质量三级标准,废弃冶炼区土壤Cd、Cu、Pb、Zn含量均最高,分别为标准值的14.78、1.13、3.73、1.34倍,采矿区Cr含量最高,但未超过标准限值。重金属形态结果表明,相比其他元素,Cd弱酸提取态所占比例最高,Cu可交换态比例最高,Pb、Zn、Cr以残渣态为主。RSP法评价表明,不同重金属的污染程度表现为:Cu(1.15)Cd(0.80)Pb(0.59)Zn(0.57)Cr(0.54);不同功能区土壤重金属污染表现为:尾矿库区冶炼区废弃冶炼区采矿区。SPEF法评价表明,尤溪铅锌矿区受人为污染明显,采矿区和尾矿库区Zn污染最为严重,冶炼区和废弃冶炼区Pb污染最为严重,功能区污染顺序为:尾矿库区冶炼区废弃冶炼区采矿区。     

安徽铜陵水木冲尾矿重金属赋存状态及污染特征研究

为探讨富硫化物尾矿酸化及重金属污染特征,选择安徽铜陵水木冲尾矿库浅层(0～90 cm)剖面为研究对象,对其结构特点、矿物组成、重金属(Pb、Cd、Zn、Ni、Cr、Mn、Cu和As)含量及赋存形态进行研究。结果表明,该尾矿库浅层出现分层现象,即表层为强硬化层,向下依次为弱硬化层和松散层,且呈酸性;矿物主要以辉石、长石、云母和石膏为主,由浅及深,金属硫化物及碳酸盐型矿物特征峰呈现增强的趋势;重金属呈现两种富集类型:表层(0～30cm,As、Pb)富集和中部(40～60 cm,Cd、Cu、Mn、Ni、Zn和Cr)富集型,其中Cu、Cd、As污染较为严重。由相关性分析可知,部分金属之间存在一定的伴生性,且p H值是影响重金属迁移的重要因素之一。该尾矿重金属主要以残渣态为主,其中Pb的潜在迁移能力最强,As最弱,顺序为Pb Cd Zn Ni Cr Mn Cu As。     

铅锌矿山开发导致的重金属在环境介质中的积累

以连续提取法和相关性分析研究了土法冶炼锌、铅锌和矿山开采导致的重金属在废渣及环境介质土壤、溪流沉积物中的积累，并分析了其环境危害性。结果显示，贵州赫章土法炼锌导致的重金属Pb、Zn、Cd在环境介质中的积累相当高。水城杉树林铅锌矿山开采引起的重金属积累则相对较低，但也明显高于背景值；土壤和沉积物中的铁矿物对重金属有强烈的固定作用。除残渣态外，Pb、Zn在土壤、炼锌废渣中主要呈铁锰氧化物结合态，沉积物中则为碳酸盐结合态。可交换态Pb、Zn含量变异较大，但在炼锌废渣、土壤中含量明显高于河流沉积物，暗示铅锌矿开发对土壤环境的潜在危害更大。     

大亚湾表层沉积物重金属元素形态特征、控制因素及风险评价分析

为了解大亚湾表层沉积物中重金属的污染状况,对大亚湾海域23个点位表层沉积物中7种重金属元素（Cr、Ni、Cu、Pb、Zn、Cd、As）的质量分数、形态特征、来源控制因素以及潜在生态风险进行了研究。采用优化BCR提取法分析重金属元素赋存形态,并依据各种重金属元素的形态特征与沉积物基质属性进行了相关因子分析,了解其分布的控制因素。结果表明：大亚湾沉积物重金属元素呈现环带状分布特征,从岸向湾内逐渐减小;重金属元素质量分数的高值区主要分布于大鹏澳、哑铃湾及范和港附近;重金属元素赋存形态中Cr、Ni、Cu、Zn、As主要以残渣态存在,Pb主要以可还原态存在,Cd主要以酸提取态存在;7种重金属元素各自非残渣态所占比率从大到小为Pb(78.83%)、Cd(78.65%)、Cu(48.54%)、Zn(48.10%)、Ni(38.31%)、Cr(28.43%)、As(27.76%),即Pb最高,As最低,表明Pb的迁移性最强;通过因子分析,大亚湾重金属主要为沿岸自然风化产物的输入,其次为工业废水及养殖污水。运用酸提取态风险评估法对重金属元素潜在生态风险进行评价,发现研究区所选重金属元素综合风险评价Cd为高风险,其余重金属为中-低风险等级。     

贵阳城市土壤重金属元素形态分析

选取贵阳市62个代表性的表层土壤样品,分析了其重金属元素的含量和存在形态.结果表明,贵阳城市土壤中5种重金属元素(Cr、Cu、Pb、Zn和Cd)的含量较高,且变化较大.表层土壤中Cr、Cu、Zn主要以残渣态形式存在,Pb主要以可氧化态形式存在.Cd可还原态含量高达47.5%,残渣态含量最低,说明Cd较活泼,具有潜在的环境影响能力.     

北京城区土壤中Hg、Pb、Cd、Cu及Zn化学形态及环境效应

为弄清北京城区土壤中Hg、Pb、Cd、Cu及Zn五种重金属元素的化学形态分布特征,系统采集了126件城区表层土壤样品,采用连续提取法对重金属元素各化学形态含量进行了测定。结果表明:土壤中土壤中Hg、Pb、Cd、Cu、Zn含量差异显著。Hg元素以残渣态和强有机结合态为主,Cd元素离子交换态、碳酸盐结合态、残渣态、铁锰氧化物结合态含量较高,Pb、Cu、Zn元素以残渣态、铁锰氧化物结合态为主。Hg元素的有效态含量最低(不足1%),现情况下不会对环境造成污染;Cd元素的有效态含量最高(40%),生物有效性和潜在生态危害性较大,运用植物修复技术对其治理为经济有效的方法;Pb、Cu、Zn有效态含量较低(约10%),生物有效性和潜在生态危害性均有限。各元素形态与全量之间相关程度虽有差别,但基本呈正相关关系。     

Isotopic exchange of Zn with stable Zn adsorbed on reference clay minerals

For reference clays of low organic content, Zn adsorbed on the clay minerals is in kinetic equilibrium with ⁶⁵Zn in solution. Thus the specific activity approach applied to the transport of ⁶⁵Zn(II) at the water-reference clay interface is intrinsically valid.     

Local coordination of Zn in hydroxy-interlayered minerals and implications for Zn retention in soils

The objective of this study was to determine the local coordination of Zn in hydroxy-interlayered smectite (HIS) as a function of Zn loading and synthesis conditions and to assess the importance of hydroxy-interlayered minerals (HIM) for Zn retention in contaminated soils. Published and newly collected extended X-ray absorption fine structure (EXAFS) spectra of HIS reacted with Zn at molar Zn/hydroxy-Al ratios from 0.013 to 0.087 (corresponding to final Zn contents of 1615-8600 mg/kg Zn) were evaluated by shell fitting. In Zn-HIS, Zn was octahedrally coordinated to oxygen at 2.06-2.08 Å and surrounded by Al atoms at 3.03-3.06 Å in the second-shell. With increasing molar Zn/hydroxy-Al ratio, the coordination number of second-shell Al decreased from 6.6 to 2.1. These results were interpreted as a progressive shift from Zn incorporation in the vacancies of gibbsitic Al-polymers to Zn adsorption to incomplete Al-polymers and finally uptake by cation exchange in the polymer-free interlayer space of HIS with increasing Zn loadings. In a second part, we determined the speciation of Zn in eight contaminated soils (251-1039 mg/kg Zn) with acidic to neutral pH (pH 4.1-6.9) using EXAFS spectroscopy. All soils contained hydroxy-Al interlayered vermiculite (HIV). The analysis of EXAFS spectra by linear combination fitting (LCF) showed that a substantial fraction of total Zn (29-84%) was contained in HIM with high Zn loading. The remaining Zn was adsorbed to organic and inorganic soil components and incorporated into phyllosilicates. In sequential extractions of Zn-HIS spiked into quartz powder and the Zn contaminated soils, Zn was mainly released in the two most resistant fractions, in qualitative agreement with the findings from LCF. Our results suggest that formation of Zn-HIM may strongly retain Zn in pristine and moderately contaminated acidic to neutral soils. Due to their limited sorption capacity, however, HIM do not allow for the accumulation of high levels of Zn in response to continued Zn input into soils.     

锌稳定同位素地球化学综述

锌是生物生命必需的微量元素和与人类活动息息相关的金属元素。随着样品纯化技术的提高和新一代质谱仪的开发应用,锌同位素体系已成为近年发展起来的金属(非传统)稳定同位素地球化学的一个热点领域,得到国内外学者的广泛研究。对最新的锌稳定同位素研究结果进行了系统总结,分别从分析方法、分馏理论、储库同位素组成以及应用等方面进行了论述。锌同位素已被广泛应用到天体化学、海洋、大气以及地球深部等诸多地球科学研究领域,大大提高人们对全球锌及其他重金属元素生物地球化学循环的认识。锌同位素在宇宙化学、环境地球化学、古气候环境重建以及健康及生物医学领域将具有非常大的应用前景。     

Stable Cu and Zn isotope ratios as tracers of sources and transport of Cu and Zn in contaminated soil

Copper and Zn metals are produced in large quantities for different applications. During Cu production, large amounts of Cu and Zn can be released to the environment. Therefore, the surroundings of Cu smelters are frequently metal-polluted. We determined Cu and Zn concentrations and Cu and Zn stable isotope ratios (δ⁶⁵Cu, δ⁶⁶Zn) in three soils at distances of 1.1, 3.8, and 5.3 km from a Slovak Cu smelter and in smelter wastes (slag, sludge, ash) to trace sources and transport of Cu and Zn in soils. Stable isotope ratios were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) in total digests. Soils were heavily contaminated with concentrations up to 8087 μg g⁻¹ Cu and 2084 μg g⁻¹ Zn in the organic horizons. The δ⁶⁵Cu values varied little (−0.12‰ to 0.36‰) in soils and most wastes and therefore no source identification was possible. In soils, Cu became isotopically lighter with increasing depth down to 0.4 m, likely because of equilibrium reactions between dissolved and adsorbed Cu species during transport of smelter-derived Cu through the soil. The δ⁶⁶Zn_IRMM values were isotopically lighter in ash (−0.41‰) and organic horizons (−0.85‰ to −0.47‰) than in bedrock (−0.28‰) and slag (0.18‰) likely mainly because of kinetic fractionation during evaporation and thus allowed for separation of smelter-Zn from native Zn in soil. In particular in the organic horizons large variations in δ⁶⁶Zn values occur, probably caused by biogeochemical fractionation in the soil-plant system. In the mineral horizons, Zn isotopes showed only minor shifts to heavier δ⁶⁶Zn values with depth mainly because of the mixing of smelter-derived Zn and native Zn in the soils. In contrast to Cu, Zn isotope fractionation between dissolved and adsorbed species was probably only a minor driver in producing the observed variations in δ⁶⁶Zn values. Our results demonstrate that metal stable isotope ratios may serve as tracer of sources, vertical dislocation, and biogeochemical behavior in contaminated soil.     

Biological fractionation of Zn isotopes in aquatic invertebrates

Recent advances in analytical instrumentation have made it more feasible to measure isotope ratios of many elements. In particular, modem multicollector-inductively coupled plasma mass spectrometers can measure isotope ratios of many elements with extremely high precision. As a consequence, we can begin to explore biological fractionation in a systematic way and hence develop isotope ratio measurements as a tool to explore the environmental geochemistry of trace metals. In this presentation we will discuss the problems and potential of measuring isotope ratios of zinc in biological samples from systems with non-specific contamination. This will include such issues as the importance of matrix removal to the measurement of valid isotope ratios, mass bias correction and the availability of standard reference materials. Recent data on isotope ratios of Zn in the aquatic invertebrate Mysis relicta will be presented. These animals are of particular interest because they changed their feeding pattern from juveniles to adults. Thus they can be used to test the hypothesis that differences in the isotopic signature of food sources may determine receptor signatures. The data indicate that there are significant differences in signatures at the different life stages. However, the continual uptake and loss of metals over an organism＇s life span may also lead to fractionation.     

掺Zn球形氢氧化镍的研究

采用化学沉淀法制备球形氢氧化镍,通过对制备条件pH值、添加剂量、搅拌强度的研究,探讨了其对掺Zn球形氢氧化镍     

多接收器等离子体质谱仪Zn同位素测定方法研究

该研究建立了Zn同位素比值的MC-ICPMS高精度测定方法.研究内容包括:对干扰信号、介质影响、基质效应和仪器稳定性的评估等方面.重复性测定中,66Zn/64Zn、67Zn/64Zn、68Zn/64Zn外精度分别为0.1‰(2SD)、0.23‰(2sD)、0.22‰(2SD),达到国际先进水准.     

The origin of Zn isotope fractionation in sulfides

Isotope fractionation of Zn between aqueous sulfide, chloride, and carbonate species (Zn²⁺, Zn(HS)₂, , , ZnS(HS)⁻, ZnCl⁺, ZnCl₂, , and ZnCO₃) was investigated using ab initio methods. Only little fractionation is found between the sulfide species, whereas carbonates are up to 1‰ heavier than the parent solution. At pH > 3 and under atmospheric-like CO₂ pressures, isotope fractionation of Zn sulfides precipitated from sulfidic solutions is affected by aqueous sulfide species and the δ⁶⁶Zn of sulfides reflect these in the parent solutions. Under high P_CO2 conditions, carbonate species become abundant. In high P_CO2 conditions of hydrothermal solutions, Zn precipitated as sulfides is isotopically nearly unfractionated with respect to a low-pH parent fluid. In contrast, negative δ⁶⁶Zn down to at least −0.6‰ can be expected in sulfides precipitated from solutions with pH > 9. Zinc isotopes in sulfides and rocks therefore represent a potential indicator of mid to high pH in ancient hydrothermal fluids.     

The influence of hydrous Mn–Zn oxides on diel cycling of Zn in an alkaline stream draining abandoned mine lands

Many mining-impacted streams in western Montana with pH near or above neutrality display large (up to 500%) diel cycles in dissolved Zn concentrations. The streams in question typically contain boulders coated with a thin biofilm, as well as black mineral crusts composed of hydrous Mn–Zn oxides. Laboratory mesocosm experiments simulating diel behavior in High Ore Creek (one of the Montana streams with particularly high Zn concentrations) show that the Zn cycles are not caused by 24-h changes in streamflow or hyporheic exchange, but rather to reversible in-stream processes that are driven by the solar cycle and its attendant influence on pH and water temperature (T). Laboratory experiments using natural Mn–Zn precipitates from the creek show that the mobilities of Zn and Mn increase nearly an order of magnitude for each unit decrease in pH, and decrease 2.4-fold for an increase in T from 5 to 20 °C. The response of dissolved metal concentration to small changes in either pH or T was rapid and reversible, and dissolved Zn concentrations were roughly an order of magnitude higher than Mn. These observations are best explained by sorption of Zn²⁺ and Mn²⁺ onto the secondary Mn–Zn oxide surfaces. From the T-dependence of residual metal concentrations in solution, approximate adsorption enthalpies of +50 kJ/mol (Zn) and +46 kJ/mol (Mn) were obtained, which are within the range of enthalpy values reported in the literature for sorption of divalent metal cations onto hydrous metal oxides. Using the derived pH- and T-dependencies from the experiments, good agreement is shown between predicted and observed diel Zn cycles for several historical data sets collected from High Ore Creek.