土壤pH对镉存在形态影响的模拟实验研究

通过模拟实验,研究了土壤pH对水稻土、紫色土和黄壤的水溶态、可交换态、碳酸盐态、铁锰氧化态、有机结合态和残渣态Cd含量的影响。结果表明:在中碱性条件下,水溶态Cd质量分数比值小于3%,但pH<6.5时,水溶态Cd含量随着pH 减小迅速增加, pH 为4. 57 时,水稻土水溶态Cd 质量分数比值最高达48 39%;可交换态Cd含量在碱性条件下,随着土壤pH值增大迅速下降,在酸性区域内,可交换态Cd含量随pH增加呈上升趋势;碳酸盐态和铁锰氧化态Cd含量随土壤pH增大而增加;有机结合态Cd含量随土壤pH增加而增大,但变化幅度不大。对Cd污染的土壤进行治理时,控制土壤pH大于6.5以及增施有机肥等是减少Cd对生态系统危害的关键。     

煤矸石中潜在有害微量元素淋溶析出研究

在煤矸石淋溶实验的基础上，研究了有害微量元素从煤矸石中淋溶析出的浓度与其在煤矸石中的含量和赋存状态的关系。结果表明，溶出浓度受淋溶时间，淋溶液温度，酸碱度的影响。淋溶液温度越高，淋溶时间越长，则有害微量元素从煤矸石中析出的浓度越高；不同的有害微量元素受淋溶液pH值大小影响程度也不相同。     

浙西某地石煤矿山周边耕地土壤重金属污染与生态风险评价

以浙西某石煤矿山及周边农田表层土壤为研究对象,运用潜在生态风险指数法综合评价其潜在生态危害程度。结果表明,Cd、Hg、Cu、As、Zn、Ni、Pb、Cr等8种重金属元素平均含量均高于中国土壤背景值,相关性分析表明,除Cd与Cr呈显著的正相关关系,其余元素两两呈极显著正相关关系;潜在生态风险评价表明研究区土壤环境RI平均值为250.38,属强生态危害程度,Cd元素是构成潜在生态风险的主要因素。地表水检测表明矿坑内地表水呈强酸性,Cd、Zn、Cu含量超标,以Cd超标最严重。周边农作物安全评价得出,该区农产品甘蔗Cd严重超标,农产品质量安全存在较大风险;自然修复石煤矿山地表水Cd含量超标程度高,邻近地区土壤及地表水易受影响,存在生态风险。石煤矿山周边土壤及农产品重金属含量超标严重,建议石煤矿山生态环境修复应采用自然恢复和人工修复相结合的办法,做好石煤矿山废水、废渣处理,减少因淋滤作用对地下水、土壤造成的影响。     

铜矿采矿废石重金属环境污染的淋溶实验研究——以安徽铜陵凤凰山矿田药园山铜矿床为例

本文基于凤凰山铜矿田药园山矿床采矿废石的淋溶实验研究,着重探索表生环境下影响重金属淋滤迁移的因素,分析重金属在采矿废石中迁移转化的机制。动态淋滤实验考查了重金属从两种采矿废石中淋出的浓度与淋溶液的pH值、淋滤时间以及淋出液酸度的关系。结果表明,采矿废石中重金属淋滤强度随酸度的增加而逐渐增强,而淋滤出的重金属浓度并不总是随时间的延长而递减,同时实验研究也表明,淋溶采矿废石的排放水不一定都是酸性的。因此,在评价矿山环境污染以及治理过程中要对当地雨水的平均pH值、所排放采矿废石的岩性以及废石的堆放时间进行综合考虑。     

浙西水田土壤镉形态与有效性研究

土壤镉(Cd)的生物有效性受多种因素影响,化学形态分布是决定其有效性的重要因素。为查明浙西水稻土Cd的生物有效性,分析土壤形态Cd与稻谷Cd含量关系,采集了32个田块土壤样及其中15个田块水稻样品,测试了土壤pH值、Cd总含量及各形态Cd含量和稻谷Cd含量,讨论了不同酸碱度及成土母质条件下土壤Cd形态分布特征及其生物有效性,研究了稻谷Cd含量与土壤不同形态Cd含量的相关性。结果表明,研究区水稻土Cd以离子交换态为主(约占全量的35%),水溶态Cd含量最小(约占全量的1%),其他形态Cd介于二者之间。酸性(pH 5.0～6.5)条件下,土壤中离子交换态Cd含量最高,Cd生物有效性也最高。不同母质形成的土壤Cd形态分布特征不同,灰岩类风化物形成的土壤Cd形态分布特征与其他成母质区土壤差异明显,不同母质区的Cd污染应采取不同的治理措施。相关分析表明,稻谷Cd含量与土壤离子交换态Cd含量呈极显著相关性(P0.01),而与其他形态Cd相关性不显著。     

淋溶条件下石英砂柱中铁锰氧化物的形成特点

用不同浓度铁锰离子混合溶液对石英砂柱进行40次淋溶实验,研究砂柱中铁锰氧化物的形成状况.结果表明,淋出液中铁锰离子浓度与其pH值随着淋溶次数的增加呈现先降低后升高的趋势;各处理所形成的铁锰氧化物含量之间存在极显著差异,淋溶液中铁锰离子浓度越大,形成的铁锰氧化物含量越高,当淋溶液中铁锰摩尔浓度比即c(Fe2+)/c(Mn2+)为2∶1时最有利于铁锰氧化物的形成;随着淋溶次数的增加,铁锰氧化物含量的增长逐渐减慢;不同层次铁锰氧化物含量差异显著,下层(20～30 cm)含量明显高于其它层次;各阶段(每淋溶10次为一阶段)不同形态(非晶形态、晶形态)铁锰氧化物含量间的相关性存在差异,铁锰氧化物尤其是非晶形态的相对比例(Fe/Mn)随着淋溶次数的增加逐渐增大.     

模拟酸雨及施磷对水稻土中铅的淋溶特性影响

采用pH=3.0、pH=4.5与对照pH=5.6的3种模拟酸雨淋溶土柱的方法,研究酸雨及含磷酸雨淋溶下合肥市郊水稻土中铅的释放特征与规律。结果表明:经过相当于1 980 mm降水量的淋溶后,铅释放量总体上表现为随着酸雨强度增加累积淋溶量也增加的现象。酸雨作用下,施磷量越多土壤中铅的淋失总量越大。在酸雨及施磷条件下,大兴地区黄褐土中Pb较义城地区水稻土中易于淋失。     

浙西典型石煤矿山周边耕地富硒土壤地球化学特征及影响因素

为系统研究石煤矿山周边耕地富硒土壤地球化学特征及影响因素,在浙江省常山县辉埠石煤矿山周边耕地采集了表层土壤样品144件、农产品甘蔗样20件、土壤垂向剖面土壤样6件、岩石样5件和地表水样3件。通过样品Se、有机质、As、Cd、Cu、Pb、Zn、Ni、Hg、Cr等元素含量指标测定和统计,探究了该区富硒土壤地球化学特征。结果表明:区内表层土壤硒含量主要集中于0.47~1.34 mg/kg之间,平均含量0.87 mg/kg,远高于浙江省平均值,且硒含量高值区与辉埠石煤矿的走向一致;硒含量随着土壤深度增加而逐渐下降;89.58%的土壤样品和65%的甘蔗样品达到富硒标准,但存在土壤和农产品Cd等主要重金属元素含量超标的生态风险。土壤硒含量均值在寒武系下统荷塘组最高(1.31 mg/kg),奥陶系中—下统最低(0.64 mg/kg);旱地硒均值略高于水田,但差异不显著(p>0.05);硒含量均值高低变化为粗骨土>石灰岩土>水稻土>红壤。研究认为,土壤硒含量受地质背景、土壤类型和有机质等因素的影响,含石煤层黑色岩系和碳酸盐岩等富硒地层是形成富硒土壤的主要因素,小部分与矿山开采等人类活动有关。     

陕西潼关金矿区土壤Pb和Cd生物有效性的影响因素及其意义

土壤中重金属形态与其赋存条件之间的关系是评估土壤重金属风险的关键问题。以受金矿开发影响的土壤中Pb、Cd为研究对象,采用动力学方程分析了土壤有机质、粘粒、pH、Eh等对Pb、Cd生物有效性的影响。结果表明,研究区影响Pb、Cd生物有效性的主要因素有土壤有机质、pH及Eh;有机质与土壤中的Pb、Cd总量呈现正相关性;但当有机质含量增加时,Pb、Cd的水溶态和离子交换态含量反而降低;土壤粘粒对Pb、Cd生物有效性的影响不甚明显;虽然较低的土壤pH值会加剧重金属离子的活性,增强其生物有效性,但过高的pH值又会提高Cd碳酸盐态、铁锰氧化态的含量;Pb、Cd生物有效性随着土壤氧化—还原电位的降低而减弱。研究发现,对于Pb、Cd污染的土壤,通过增施有机肥可提高农产品的安全性;保持土壤处于弱酸—弱碱有利于降低农产品风险;在农作物成熟期实施淹水灌溉,降低土壤氧化—还原电位,可抑制Pb、Cd在籽粒中的累积。     

土壤中重金属元素Pb、Cd地球化学行为影响因素研究

通过研究湖南洞庭湖地区水稻土中Pb、Cd与土壤有机质、粘粒和pH值的关系,结果表明,(1)土壤中有机质含量与Cd、Pb有着显著的正相关性,土壤中有机质含量增加可明显降低Cd和Pb的离子态和可交换态含量。(2)随着粘粒含量增加,Pb和Cd离子可交换态占全量的比值略有增加,这说明粘粒表面吸附的Pb和Cd容易进入植物体中,对生态系统安全具有危害的组分。(3)Cd离子交换态与土壤pH值呈显著相关关系,土壤酸化使Cd的离子交换态比例上升,可直接导致农作物中Cd含量增加,防止土壤酸化是控制Cd对生态系统危害的有效途径;Pb的离子交换态与全量的比值与pH值具有显著的相关性,对于Pb污染严重的土壤,保持土壤pH值在弱酸性至弱碱性范围,防止土壤酸化和盐碱化,可以降低Pb危害。土壤有机质含量、pH值等是控制重金属元素地球化学行为的重要因素之一。     

Speciation analysis of metals （Tl, Cd and Pb） in Tl-containing pyrite and its cinder from Yunfu Mine, China, by ICP-MS with sequential extraction

The speciation of heavy metals such as thallium, cadmium and lead existing in pyrite and pyrite cinder was analyzed by ICP-MS with a sequential extraction procedure. The distribution patterns of these metals including exchangeable, reducible, oxidizable and residual fractions were obtained. Tl, Cd and Pb in pyrite and pyrite cinder samples from each extraction step were determined by inductively coupled plasma mass spectrometry (ICP-MS). Under the optimized instrumental conditions, detection limits of Tl, Cd and Pb in different matrices were within the range of 0.006–0.07 μg/L, and the relative standard deviations ranged from 0.8% to 1.2%. The accuracy of Tl, Cd and Pb determination was checked by analyzing two certified reference materials. The results demonstrate that trace Tl, Cd and Pb in the samples can be accurately determined. The sequential extraction results revealed that the percent contents of Tl, Cd and Pb in exchangeable, reducible and oxidizable fractions in pyrite cinder are different from those in pyrite and in pyrite cinder. Tl, Cd and Pb mostly are distributed in residual fraction. Therefore, the mobility of metals in pyrite is higher than that in pyrite cinder. Although distributions of Tl, Cd and Pb in the non-residual fraction are not dominant in pyrite cinder, the total concentrations of them could not be ignored. Consequently, attention must be paid to the risk of potential pollution by pyrite cinder.     

多壁碳纳米管固相萃取快速检测水样中铅镉铜铁

传统的固相萃取填料应用于环境样品的重金属处理过程中,存在pH不稳定和不同极性萃取物共同萃取较为困难等方面的不足,因此寻找新型固相萃取填料显得尤为重要。本文采用多壁碳纳米管填充固相萃取柱,萃取水中金属元素铅、镉、铜和铁,采用石墨炉原子吸收光谱法测定铅和镉,电感耦合等离子体发射光谱法测定铜和铁。实验考察了多壁碳纳米管的性质、溶液pH值、洗脱溶液、样品流速以及基体效应对测定结果的影响。结果显示:溶液pH=9,1 mol/L硝酸为洗脱溶液,样品流速为2 mL/min时,外径8 nm未修饰的多壁碳纳米管有较好的萃取效率,对溶液中铅、镉、铜和铁的最大吸附容量分别为44.91、42.31、54.68和49.07 mg/g,四种元素的吸附容量均衡;钾、钠、钙、镁离子以及苯和甲苯等基质对四种金属元素的萃取影响不大。方法回收率为95.3%~99.5%,精密度(RSD,n=7)为1.2%~3.2%。本方法采用外径8 nm的多壁碳纳米管固相萃取,与传统萃取方法相比,富集效果好、回收率较高,而且操作简便、准确度高;与前人采用外径20~30 nm的多壁碳纳米管的性能相比,镉和铜的吸附容量更高,还可实现对铁的吸附,且铅、镉、铜和铁四种元素的吸附容量均衡,更适合用于检测水样中的金属元素。     

Multivariate analysis of heavy metals in surface sediments from lower reaches of the Xiangjiang River, southern China

The concentrations of heavy metals (Cr, Mn, Co, Ni, Cu, Zn, Cd, and Pb) in 16 samples collected from the lower reach (Changsha–Xiangtan–Zhuzhou section) of the Xiangjiang River in southern China were determined by high-resolution inductively coupled plasma mass spectroscopy (HR-ICPMS). Multivariate analysis, such as principal component analysis and cluster analysis, coupled with correlation coefficient analysis, was used to analyze the analytical data and to identify possible pollution sources of heavy metals. The results showed that the eight studied heavy metals accumulated in the sediments from the lower Xiangjiang River, especially Mn, Cu, Zn, Pb and Cd, which were 2.0–2.6, 1.7–2.6, 3.5–3.8, 3.2–3.6 and 189.5–152.8 times the soil trace element background for Hunan Province and UCC background values, respectively. Principal component analysis and cluster analysis, coupled with correlation coefficient analysis, revealed that the sediments from lower Xiangjiang River were mainly influenced by two sources: Cr, Co, Ni, Cu, Zn, Cd and Pb mainly originated from industrial sources, whereas Mn was derived from both industrial and natural sources, but mainly from natural sources due to weathering and erosion.     

青藏高原南部枪勇冰川雪冰中痕量元素的组成特征及其环境意义

为了认识青藏高原南部雪冰中痕量元素的组成特征、背景含量水平以及人为污染的可能影响,利用高分辨电感耦合等离子体质谱仪首次对2009年4月19日采自枪勇冰川一个40 cm 雪坑中 Al、 Fe、 Ba、 Cd、Co、Cr、Cu、Li、Ni、Zn、Pb、Sb、Sr、U 和 V 共15个痕量元素的浓度进行了测试和研究.分析表明,不同痕量元素之间浓度变化很大,从 Cd 的0.004 ng/g 变化到 Fe 的8628 ng/g;同一痕量元素的浓度变化范围也较大,最大值/最小值从13(Cd)变化到94(Sr).研究表明,不同痕量元素记录反映了人类活动与自然活动的不同影响.对痕量元素地壳富集系数分析表明,岩石和土壤粉尘是 Ba、Fe、Sr、Co、Cr、V 和 U 的主要来源;而人为污染是枪勇冰川中 Pb、Zn、Cu、Li、Ni、Cd 和 Sb 的一个重要来源.对比研究表明,无论是以粉尘源为主要来源的痕量元素,还是以人为源为主要来源的痕量元素,它们的浓度明显高于中亚有关地区冰川中痕量元素的浓度,更远远地高于格陵兰和南极雪冰中的相应浓度,揭示了该地区大气中痕量元素受到粉尘和人为源污染物带来的显著影响     

东昆仑山玉珠峰冰川雪坑中痕量元素的组成特征

为了认识玉珠峰冰川区域大气中痕量元素的组成和来源,利用高分辨电感耦合等离子体质谱仪对2009年10月采自玉珠峰冰川海拔5800m的一个75cm雪坑中15种可溶性痕量元素（A1、Fe、Ba、Cd、Co、Cr、Cu、Li、Ni、Zn、Pb、Sb、Sr、U和V）的浓度进行了测试．结果表明：痕量元素的浓度变化很大,从最小值1．...     

The effect of filtration on analyses of surface water samples. A study from the Salars of Coipasa and Uyuni,Bolivian Altiplano

Analyses by inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS) and cold vapour atomic absorption (for Hg, CVAA) of a wide range of elements in some 300 surface water samples from the Salar de Uyuni and Salar de Coipasa catchments of the Bolivian Altiplano have been undertaken. Comparison of analyses of acidified aliquots of unfiltered sample water with water filtered at 0.45 μm reveals that the following elements are not affected significantly by filtration in this high-pH environment: B, Ca, Li, Mg, K, Si, Na, Sr, S. The following elements appear to experience significantly elevated concentrations in unfiltered samples, relative to filtered: Al, (As to a minor extent), Ba, Be, Cd, Cr, Co, Cu, Fe, Pb, Mn, Hg, Ni, P, Ag, Tl, Ti, V. The effect appears to be related to the presence, and subsequent dissolution in acid preservative, of Fe-, Al-or Mn-oxyhydroxide flocs (or coatings on silicate particles) in unfiltered samples, and their retention or precipitation on filters.     

Contamination levels assessment of potential toxic metals in road dust deposited in different types of urban environment

A total of 42 samples of road dust were collected along ring road, city centre, city side, and freeway in Urumqi, China. Total concentrations of Cd, Cr, Cu, Ni, Pb, Mn, Be, Co, Zn, and U were determined by using the inductively coupled plasma-mass spectrometry in order to assess and to compare road dust contamination levels of metals among the four roads. The results show that, among the four categories of roads, mean concentrations of Co and U vary little. City centre locations show strong enrichments of Cd, Cu, Pb, and Be. Along the ring road, the highest mean concentrations were found for Cr, Ni, Mn, and Co. However, the highest concentrations of Zn and U were found along the freeway. The cluster analysis shows that three main groups can be distinguished. Every group may be associated with different main sources and concentrations of the metals. The results of contamination assessment reveal that, among all of the potential toxic metals, Cd, Cu, and Zn pollution were obviously heavier with moderate or high contamination indices for most road dust samples, while Cr, Ni, and Pb contamination were lower along the four categories of roads. Compared with the city side, Cd, Cu, Pb, Ni, and Zn contamination were heavier along the ring road, the city centre, and the freeway with high traffic density. Low Pb contamination or no contamination in all the road dust samples may be related to the increasing usage of lead-free petrol.     

Carcinogenic and Non-carcinogenic Risk Assessment of Metals in Groundwater via Ingestion and Dermal Absorption Pathways for Children and Adults in Malwa Region of Punjab

The concentration of trace metals was measured in groundwater samples collected from Malwa region of Punjab, India. The samples were analyzed by using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS). The results were compared with permissible limits prescribed by various health and environmental protection agencies. The concentrations of trace metals such as Mn, Se, Mo, Cd, Sb and Pb were higher than their respective permissible limits at some sampling sites. The total hazard index (HI_total) (summing the hazard index through ingestion and dermal routes) at all the sampling sites exceeded or nearing unity, indicating the presence of non-carcinogenic health effects from ingestion of groundwater and dermal contact with groundwater. The results reveal that the total excess lifetime cancer risk (ELCR_total) of metals exposure was in accordance with the acceptable lifetime risks for carcinogens in drinking water.     

The degassing behavior of Au, Tl, As, Pb, Re, Cd and Bi from silicate liquids: Experiments and applications

We investigate the degassing of volatile heavy metals from natural basalt and dacite and synthetic rhyolite melts doped with Bi, Pb, Tl, Au, Re, Sb, Sn, Cd, Mo, As, Cu in Pt capsules over a range of temperatures (1200-1430 °C) exposed to air at 0.1 MPa. We also investigated the effects of ligands on degassing by adding known concentrations of Cl and S. During the experiments concentration gradients normal to the melt/gas interface arose for the trace metals Au, Tl, As, Cd, Re, Bi and Pb, as shown by measurements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the quenched glasses. In contrast, erratic concentration gradients occurred for Cu, Mo, Sn, Sb due to the development of compositional cords in the glass for those elements. The diffusivities for Au, Tl, As, Cd, Re, Bi and Pb (in decreasing order of volatility) followed an Arrhenius relationship with log D at 1260 °C varying from −12 to −17. The addition of Cl and S were shown to increase by two-to five-fold the volatilities of all metals, with S having a more profound effect. Diffusivities from the experiments were applied in a bubble growth model to examine the behavior of Tl and Pb in volcanic gases. The Tl/Pb ratio in gases shows much greater variation than can be explained by partitioning and magma composition alone, with diffusion serving to drastically enrich or deplete the Tl/Pb of gases to values significantly different from that of the melt.     

Risk assessment of heavy metals in topsoil along the banks of theYangtze River in Huangshi,China

High concentrations of heavy metal in farmland threatens food production and human health. Our study assesses soil quality and the distribution of Cd, Cr, Cu, Zn, Pb and Ni, to identify possible sources of heavy metals along the banks of the Yangtze River in Huangshi. Heavy metal concentrations of 22 topsoil samples were measured using the inductively coupled plasma mass spectrometry instrument and data was analyzed by multivariate statistic approaches. Heavy metal contamination risk assessment was performed using a combination of the Nemerow multi-factor index method, the Hakanson potential ecological risk index method and the Muller index of geo-accumulation method. These methods determined similar results indicating that cadmium (Cd) poses a health risk to residents at the study site while Cr, Cu, Zn, Pb and Ni do not. The Nemerow multi-factor index method demonstrated that 18 samples were heavily polluted, three moderately polluted and one lightly polluted. The Muller index of geo-accumulation method found ten samples were moderately to strongly polluted by Cd, five were moderately polluted, six were lightly to moderately polluted and one was lightly polluted. The Hakanson potential ecological risk index method proved six samples were strongly polluted, seven were moderately polluted and nine were lightly polluted. Since our sampling sites were all in agricultural lands, we recommend the potential ecological risk index method as the most effective given it not only considers the range of pollutants contributing to soil pollution but factors in heavy metals toxicity. We are apt that the source of the high concentrations of Cd found in topsoil is derived from alluvial sediments upstream of the Yangtze River with a high percentage of residual speciation and a low percentage of exchangeable speciation distribution of Cd. This in turns indicates that a high concentration of Cd in soil had little impact on the natural environment. However, 31.9% of the iron-manganese oxides bound speciation indicating that such levels of Cd in soil would be potentially hazardous to the crops, particularly if exposed to a reductive condition.