炼锌固体废渣中重金属(Pb、Zn)的存在状态及环境影响

利用XRD、TEM/EDS和连续提取实验研究了土法炼锌固体废渣中重金属的矿物学特征及不同粒度中重金属的相态分布特征。与通常发现的重金属一般富集在小粒径废渣中的情况不同,本工作所研究的废渣样品中大粒径废渣与细粒径废渣相似,甚至有更高的金属含量。化学形态研究表明,冶炼过程形成的矿物(或玻璃质)集合体和堆积后的风化过程形成的次生矿物是废渣中重金属存在的主要化学相。同时发现Pb的残渣态很少(0.39%～15.75%),而Zn的残渣态较高(14.3%～46.2%),这可能与冶炼工艺所形成较多Zn的硅酸盐矿物有关。尽管可交换态Pb、Zn在不同相态中的相对比例非常小(Pb0.03%～1.30%;Zn0.03%～3.30%),但其绝对含量却比一般土壤或沉积物要高(Pb1.5～385μg/g;Zn3～590μg/g)。由于重金属可交换态有比其他化学相态更高的活动性和生物可利用性,因此,对环境有较大的潜在影响。废渣样品的微束分析表明,Pb在废渣中见有金属Pb存在形式或呈纳米金属Pb颗粒包裹于其他矿物或铁合金及熔球集合体中。同时不排除有Pb的碳酸盐矿物存在的可能。而以硅锌矿Zn2(SiO4)、锰硅锌矿(Zn,Mn)2犤SiO4犦和纤维状的丝锌铝石Zn8Al4犤(OH)8(SiO4)5犦·7H2O等矿物形式存在以及Fe、Mn等的铝硅酸盐形式存在的Zn,可能是导致Zn的残渣态较高的原因。与连续提     

贵州牛角塘镉锌矿床中发现原生硫镉矿

在贵州牛角塘镉锌矿床中既有次生硫镉矿的存在，也发现了原生硫镉矿。硫镉矿的产状如下：①呈包裹体形式产于硫化物中；②以不规则晶粒赋存于硫化物粒间：③形成硫镉矿．方铅矿细脉或硫镉矿微脉穿插硫化物；④分布在黄铁矿中方铅矿或闪锌矿周围；⑤被菱锌矿胶结并交代，形成硫镉矿残骸状角砾；⑥组成菱锌矿．硫镉矿疏松集合体或菱锌矿．硫镉矿细脉；⑦呈皮壳状或薄膜状分布在氧化矿石表面或裂隙面上。前五种形式产出的硫镉矿为原生硫镉矿，主要分布在原生矿石或弱氧化的矿石中。后两种产状的硫镉矿为次生硫镉矿，分布于氧化矿石晶洞中或矿石表面和裂隙面上。并从Cd、Zn地球化学特性、热力学和结晶化学性质探讨了原生硫镉矿形成机制。     

西藏扎西康锌多金属矿床地质特征及银的赋存状态研究

扎西康锌多金属矿床位于西藏特提斯喜马拉雅板片的"金锑多金属"成矿带东段。研究显示,矿体主要呈脉状、透镜状产于近南北向的张性断裂中。热液成矿作用主要可划分为早、晚2个成矿阶段,7个成矿亚阶段,早期以铅锌矿化为主,晚期以锑(铅)矿化为主。岩矿石镜下鉴定和电子探针分析表明,扎西康矿床矿石种类繁多,矿物组合和成矿元素均呈现明显的分带现象,由深至浅(W→E)为含锡(铁)闪锌矿+铁锰碳酸盐+少量方铅矿+少量黄铜矿(深部)→(铁)闪锌矿+铁锰碳酸盐+少量方铅矿+黄铁矿+毒砂+少量银黝铜矿+少量石英(中深部)→方铅矿+闪锌矿+脆硫锑铅矿+铁锰碳酸盐+硫锑铅矿+少量银黝铜矿+石英(中部)→辉锑矿+方铅矿+少量闪锌矿+石英+少量铁锰碳酸盐(浅部),对应的元素分带为Zn(Pb+Ag+Cu+Sn)→Zn(Pb+Ag)→Zn+Pb(Sb+Ag)→Pb+Sb+Ag+Zn。矿区银矿化主要集中在Ⅴ号矿体ZK2703-ZK2302、ZK1502-ZK1105和ZK806三个区域,与铅锑矿化关系密切。矿石中银主要以类质同象的形式存在,独立银矿物相对较少。其中,类质同象银主要赋存在方铅矿中,少量赋存在硫锑铅矿、脆硫锑铅矿、毒砂、黄铁矿等金属硫化物中;独立银矿物有少量的银黝铜矿、硫锑铅银矿、银(含银)硫铜锑矿。成矿流体中铅、锌、锑、银的运移和富集沉淀是受体系中温度、压力、浓度、pH值等多种因素综合控制的结果。     

滇西铜多金属硫化矿的工艺矿物学特性

云南西部地区有大量铜多金属硫化矿资源,主要金属矿物之间连生、包裹及嵌布状态复杂,传统的工艺矿物学研究方法难以对矿物的特性参数实现快速自动定量。为此采用现代工艺矿物学研究系统MLA,对滇西铜多金属硫化矿的化学组成、物相组成,矿物组成、元素分布、嵌布粒度、连生及包裹关系等进行分析,结果表明:滇西铜多金属硫化矿含Cu 1.29%,Zn 2.10%,Pb 0.43%,S 24.93%,有价矿物主要为黄铜矿、闪锌矿和黄铁矿,铜矿物和锌矿物主要与黄铁矿相互连生和包裹,有价矿物中有88%以上分布在大于10μm的易选粒级范围,磨矿粒度达到-15.77μm时,铜矿物和锌矿物能实现单体解离,计算得到铜多金属硫化矿中铜、锌、硫的选矿理论回收率分别为88.49%,92.10%和89.20%。研究结果对该矿的选矿工艺流程制定和选别指标的提高提供了依据和指导,有助于该地区矿产资源的综合开发利用。     

云南思茅地区铜锌硫化矿工艺矿物学分析

云南思茅地区有大量难选铜锌多金属硫化矿资源,由于其矿石结构、成分及构造复杂,采用传统的镜下鉴定工艺矿物学分析对铜、锌等有价金属的赋存状态等难以自动准确定量。本文采用化学分析、偏光显微分析及矿物解离度分析(MLA)等多种现代分析测试方法,研究该地区矿石的主要元素组成、矿物种类、嵌布和包裹特性等。分析表明,铜锌硫化矿的主要元素及含量为Cu 3.03%、Zn 3.90%、S 27.44%、Pb 0.13%。金属矿物主要是黄铁矿、黄铜矿和闪锌矿,含少量方铅矿;目的矿物黄铜矿、闪锌矿主要与黄铁矿连生和被其包裹;其次黄铜矿和闪锌矿相互连生和被其包裹,且96%以上的黄铜矿、闪锌矿和黄铁矿均分布在粒度大于9.6μm的易选粒级范围。方铅矿多呈细粒嵌布状,与铜、锌、硫矿物之间的磨矿解离有一定困难。根据工艺矿物学研究结果,本文提出,思茅地区的铜锌硫化矿矿石需磨至约31μm方能实现铜-锌-硫矿物的解离,需磨至约14μm方能实现铅与其他矿物的解离,同时预测了铜锌硫化矿中铜和锌的理论选矿回收率分别为91.22%和84.92%。本文研究成果对该地区难选多金属硫化矿的选矿技术制定和指标选择具有实际的指导意义。     

冲积物覆盖区活动态金属在土壤中的分配规律

以我国山东省北部为例，研究了冲积物覆盖区土壤中金属的存在形式，特别是活动态金属的分配规律。通过研究发现，活动态Au在土壤全量Au中大约占到70％的比例，而Cu、Pb、Zn等元素在土壤中所占的比例相对较小。每种金属在四种活动态中的分配比例也存在较大差别。造成这些差别的主要原因是元素的地球化学性质不同，特别是地球化学性质极为不活泼的Au，反而大部分以活动形式存在，主要是因为Au在表生环境中以纳米或亚微米等超微细颗粒形式存在，使其化学性质发生了很大的变化。     

我国天然锌铜金属互化物的发现和特征

锌、铜金属互化物是罕见的天然合金矿物，由锌、铜两种元素组成。由于形成条件、环境不同及矿物中锌、铜元素含量不同，形成系列锌、铜金属互化物。经过对我国近二十年来发现的各类型天然锌、铜金属互化物产出的地质特征，物理、化学及光学性质进行的系统研究发现，目前我国在不同的地质体中出现多种不同类型的锌、铜金属互化物，该类矿物主要形成于高温、还原且缺硫的条件下，多数与造岩矿物共生，而与多数金属硫化物形成条件不同。     

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。     

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。     

滇东南都龙超大型锡锌多金属矿床黄铁矿LA-ICPMS微量元素组成研究

滇东南马关都龙是一个以锡锌为主,共-伴生铟、铜、铅、钨、铁、银等多种元素的锡锌多金属超大型矿床。虽然前人从矿物学、矿床地球化学、年代学等不同角度开展了较多的研究,该矿床锡锌多金属矿化为燕山晚期岩浆热液活动的产物已是不争的事实,但关于该矿床是否存在热水沉积作用及其与锡锌多金属成矿作用的关系依然存在较大争议。本文选取都龙矿区广泛存在的黄铁矿作为主要研究对象,在矿相学基础上利用LA-ICPMS对不同阶段黄铁矿的微量元素组成开展了系统的研究。野外及显微鉴定结果表明,矿区存在四种类型(期次)的黄铁矿,即:鲕状黄铁矿Py1;穿切或交代Py1的细脉状黄铁矿Py2;与闪锌矿等硫化物共生的自形黄铁矿Py3;包裹早期黄铁矿或闪锌矿等硫化物的他形黄铁矿Py4。LA-ICPMS分析结果表明,该矿床黄铁矿中富集多种微量元素,其中Co、Ni、As、Ge等元素以类质同象的形式存在黄铁矿晶格中,而其余元素多以显微矿物包体形式赋存于黄铁矿中。上述四期黄铁矿微量元素组成存在较大差别,Py1相对富集Zn和As,而其余微量元素含量较低,Co与Ni含量较低,Co/Ni比值远低于1.00,其微量元素组成与典型沉积作用形成黄铁矿基本一致; Py2与Py1具有相似的微量元素组成特征,其Co/Ni比值接近Py1变化范围; Py3和Py4除富集Zn、As外,Mn、Co、Ni、Cu、Sb、Pb、Bi元素含量也相对较高,其Co/Ni比值相对较高,多大于1,与典型岩浆热液型黄铁矿微量元素组成相似,而与沉积型黄铁矿差异明显。结合各阶段黄铁矿产出地质特征,对比不同类型黄铁矿微量元素组成,本研究认为:Py1鲕状黄铁矿为热水沉积作用形成; Py2为Py1变质改造形成的细脉状黄铁矿,其微量元素继承了Py1; Py3为岩浆热液活动形成的自形黄铁矿; Py4为岩浆热液活动晚期形成的他形黄铁矿,Ag和Bi组成作为区分不同成因类型黄铁矿的化学指标的潜力。矿区早期沉积作用形成鲕状黄铁矿过程可能为后期成矿作用提供了部分硫源及少量Zn等成矿物质,海西-印支期区域变质改造作用对矿区成矿作用影响不大,而燕山晚期岩浆热液活动才是矿区锡多金属大规模成矿作用的主导因素。     

Heavy Metal Distribution in Soils near the Almalyk Mining and Smelting Industrial Area,Uzbekistan

Abstract: The present study demonstrates distribution and chemical forms of heavy metals in soils of the Almalyk mining and smelting industrial area along five transects. The study area is located in Almalyk, Uzbekistan, where the intensification of industrial enterprises negatively impacts the environment. The distribution of 17 heavy metals (Cu, Zn, Pb, Sc, V, Cr, Co, Ni, Ga, Rb, Sr, Y, Zr, Nb, Ba, Th, and U) were studied in 21 sampling locations (21×3=63 soil samples) along five radial transects with a total length of 60?km downwind deposition gradient. Soil samples were collected from the upper layer (0–10?cm) at 4–6?km intervals. As a result of X-ray fluorescence spectrometry analyses by using X-ray fluorescence spectroscopy (XRF, Philips Analytical Ink, USA ), a significant decrease in heavy metal (Cu, Zn, Pb) deposition was found going from the source in a downwind direction. Soil samples taken from the first location (near the pollution sources) showed higher concentrations of Cu, Zn and Pb, and lower concentrations with increasing distance from the source. Obtained data showed different impact of pollution sources to heavy metal deposition and distribution in soils. The Almalyk mining and smelting complex is the major source of Pb, Zn and Cu enrichment in soils. Distribution of other trace elements does not exceed background content and suggests lithogenic background. This allowed us to divide these elements into two groups: (1) technogenic (Cu, Zn and Pb); and (2) lithogenic (Sc, V, Cr, Co, Ni, Ga, Rb, Sr, Y, Zr, Nb, Ba, Th and U) origins.     

Post-depositional redistribution of trace metals in reservoir sediments of a mining/smelting-impacted watershed (the Lot River,SW France)

Mining/smelting wastes and reservoir sediment cores from the Lot River watershed were studied using mineralogical (XRD, SEM–EDS, EMPA) and geochemical (redox dynamics, selective extractions) approaches to characterize the main carrier phases of trace metals. These two approaches permitted determining the role of post-depositional redistribution processes in sediments and their effects on the fate and mobility of trace metals. The mining/smelting wastes showed heterogeneous mineral compositions with highly variable contents of trace metals. The main trace metal-bearing phases include spinels affected by secondary processes, silicates and sulfates. The results indicate a clear change in the chemical partitioning of trace metals between the reservoir sediments upstream and downstream of the mining/smelting activities, with the downstream sediments showing a 2-fold to 5-fold greater contribution of the oxidizable fraction. This increase was ascribed to stronger post-depositional redistribution of trace metals related to intense early diagenetic processes, including dissolution of trace metal-bearing phases and precipitation of authigenic sulfide phases through organic matter (OM) mineralization. This redistribution is due to high inputs (derived from mining/smelting waste weathering) at the water–sediment interface of (i) dissolved SO₄ promoting more efficient OM mineralization, and (ii) highly reactive trace metal-bearing particles. As a result, the main trace metal-bearing phases in the downstream sediments are represented by Zn- and Fe-sulfides, with minor occurrence of detrital zincian spinels, sulfates and Fe-oxyhydroxides. Sequestration of trace metals in sulfides at depth in reservoir sediments does not represent long term sequestration owing to possible resuspension of anoxic sediments by natural (floods) and/or anthropogenic (dredging, dam flush) events that might promote trace metal mobilization through sulfide oxidation. It is estimated that, during a major flood event, about 870 t of Zn, 18 t of Cd, 25 t of Pb and 17 t of Cu could be mobilized from the downstream reservoir sediments along the Lot River by resuspension-induced oxidation of sulfide phases. These amounts are equivalent to 13-fold (Cd), ∼6-fold (Zn), 4-fold (Pb) the mean annual inputs of the respective dissolved trace metals into the Gironde estuary.     

Chemical partitioning of trace and major elements in soils contaminated by mining and smelting activities

Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii) bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, particularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indicates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in the carbonate fraction (CaCO₃), while the exchangeable and residual phases are the main fractions for Ca at the smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.     

Primary minerals of Zn-Pb mining and metallurgical dumps and their environmental behavior at Plombières,Belgium

The primary phases and minerals of the Plombières dumps include typical smelting furnace products such as metallic Fe, Pb, Cu, Zn, Fe-Zn alloys, carbides, phosphides, sulfides of Fe, Zn, Pb, Cu, Mn (alabandite), and FeAs. Spinels, mainly of Fe and Al, are common constituents of the primary assemblage; substitution by Zn, V, Cr, Ti, Mg, and Ca occurs. Primary phases also include the most common Zn-rich fayalite, Zn-rich Ca-Fe silicates, melilite, corundum, and apatite. Most of the Zn is incorporated in iron silicates, ZnO and ZnS. Lead occurs mainly as PbS, metallic lead, and is also present in coal residues. Cadmium is found mainly in metallic zinc and its alloys and in ZnO. The dumps also contain mining wastes composed of pyrite, melnikovite, and iron oxides produced by natural weathering of Zn-Pb ores. Melnikovite and iron oxides are rich in As, Pb, and Zn and possess an increased content of Tl. Leaching tests carried out on the surfaces of polished sections indicate that acid rain (solutions I and II) will mobilize mainly Zn and Cd and, to a much smaller extent, Pb and Sb. Leaching of metals by sulfate-chloride fluids present in the pore network of dumps (solutions III, IV, and V) depends on the pH, which in the dumps is controlled by the proportion of carbonates to sulfides. The more acid fluids leach both sulfides and silicates.     

Simulation of sedimentary Ore-Forming processes: Concentration of Pb and Zn from brines into organic and Fe-bearing carbonate sediments

An experimental sedimentary system comprising a tank of 4 m³ capacity equipped for monitoring chemical, mineralogical, and biological changes has been used to investigate the mechanisms by which Pb and Zn may be removed from solution in sulphide-deficient brines and concentrated in sediments. In the experimental system, Pb and Zn together with ferric hydroxides (probably lepidocrosite), organic matter, and a variety of calcium and magnesium carbonate phases, were deposited from an aerobic, highly saline, Pb and Zn-rich brine supporting a vigorous growth of the green alga Chlorococcus sp. The resultant organic and Febearing carbonate sediments contained Pb up to 0.5% and Zn up to 1.0%. Overall concentration factors compared with the overlying brine were in the range 200 to 300. Pb was removed from solution mainly by coprecipitation with carbonate phases; the Pb content of the two major carbonate phases decreasing in the order aragonite to monohydrocalcite. Zn was deposited in association with the Fe-bearing minerals. Complexing of Pb and Zn by organic matter, and the direct precipitation of Pb and Zn carbonates and/or hydroxides made, at most, a secondary contribution to the overall concentration process.     

Application of Zn isotopes in environmental impact assessment of Zn–Pb metallurgical industries: A mini review

Zn and Pb smelters are the major contributors to Zn and Pb emissions among all anthropogenic sources, thus, it is essential to understand Zn isotopic variations within the context of metallurgical industries, as well as its fractionation in different environments impacted by smelting activities. This mini review outlines the current state of knowledge on Zn isotopic fractionation during the high-temperature roasting process in Zn and Pb refineries; δ⁶⁶Zn values variations in air emissions, slags and effluents from the smelters in comparison to the geogenic Zn isotopic signature of ores formation and weathering. In order to assess the environmental impact of these smelters, the available and measured δ⁶⁶Zn values are compiled for smelter impacted natural water bodies (groundwater, stream and river water), sediments (lake and reservoir) and soils (peat bog soil, inland soil). Finally, the discussion is extended to the fractionation induced during numerous physicochemical reactions and transformations, i.e. adsorption, precipitation as well as both inorganic and organic surface complexation.     

铭溪龙凤场铅锌混合矿选矿工艺的探讨

福建省大田县硫铁矿利用原有设备，部分进行技改配置生产铅锌混合矿；并采用铅锌混合优先浮选流程，经过一年多生产实践，混合矿质量均达到国家标准；但铅、锌回收率低。通过改造选矿工艺流程、增加精选槽数、稳定原矿和加强磨矿细度控制等试验表明，铅、锌回收率可稳定在９２％以上     

铅锌在花岗质硅酸盐熔体和共存含水流体间分配机理的实验研究

本文利用作者首次设计改进的固液制样术、金管处理术及测试分析程序完成了铅、锌在花岗质硅酸盐熔体和共存含水流体间的分配实验,确定了一系列铅锌流-熔分配系数;并从分配模型和熔体地球化学等方面探讨了铅锌的流-熔分配规律和机理。实验结果和理论分析均表明,在含水花岗质岩浆体系中,氯(钠)有利于铅、锌的流-熔分离,而氟(钾)则相对地阻碍了这种分离。     

Risk of metal mobility in soils from a Pb/Zn depleted mine (Lugo,Spain)

The risk of Pb, Zn and Cd mobility is evaluated in soils from a depleted mine at Rubiais (Lugo, Spain). This area is under special protection because of its outstanding natural value. Soils from nine different areas were selected: at the mining zone (R1, R2, R3), at minespoils (R4, R5, R6) and soils developed on the settling pond (R7, R8, R9). A control soil (RC) was sampled outside the mine. The objectives are (i) to study the characteristics of soils with high influence on metal retention, (ii) to determine the content of Pb, Zn and Cd comparing it with the generic reference levels, and (iii) to evaluate the distribution and the interactions between the metals and the soil geochemical phases by means of sequential chemical extraction, X-ray diffraction, field emission scanning electron microscopy/energy-dispersive X-ray spectroscopy (FE-SEM/EDS) and time of flight secondary ion mass spectrometry (TOF–SIMS). The concentration of Pb, Zn and Cd ranges 850–6,761, 1,754–32,287 and 1.8–43.7 mg kg^?1, respectively, and the highest proportion is in the residual fraction. The Mn oxides highly influence the retention of Cd while Pb retention is mainly influenced by Fe oxides. Zn is uniformly distributed amongst the residual fraction and the Fe and Mn oxides. TOF–SIMS and SEM/EDS techniques confirm the fractionation results, showing how Pb and Zn are as sulphide and associated with Fe and Mn oxides. Nevertheless, care should be taken since oxides and sulphides could suffer sulphide oxidation processes or alteration of the oxides causing leaching and the contamination of the protected ecosystem.     

Effects of Soil Composition on Zn Speciation in Drainage Waters from Agricultural Soils

The influence of Zn speciation on Zn transport by drainage from different soils to surface water is examined in a stream catchment in an agricultural area. Drainage waters were collected from two types of soils, a mineral soil (MS) and a soil rich in organic matter (OS) by means of artificial drainage pipes. The speciation of dissolved Zn in the stream and the drainage waters was determined using ligand-exchange and voltammetry. About 50–95% of dissolved Zn is bound in strong complexes, and the free Zn²⁺ ion concentration is in the range of 1–16% of dissolved Zn. A substantial part of Zn is present in weaker organic or inorganic complexes. The simulated Zn speciation using the WHAM VI model is compared to the determined speciation. Free Zn²⁺ concentrations predicted by the WHAM VI model are generally higher than the analytically determined free Zn²⁺, but are mostly within the same order of magnitude. Effects of different soil organic matter content on Zn speciation and transport are discussed. Zn speciation in the drainage at the OS site is influenced by the distribution of organic matter between the solid and solution phase. The abundant organic Zn complexes in solution contribute to facilitate Zn transport from soil into surface waters, through the drainage at the OS site. Drainage from the OS site contributes about twice as much Zn input to the receiving water as the MS soil, as related to specific area. The mineral soil contains much lower organic matter, and a part of Zn bound with inorganic phases can hardly be released by dissolved organic ligands, leading to much higher Zn retention at the MS site.