Heavy metals in soils and crops in Southeast Asia

In a reconnaissance soil geochemical and plant survey undertaken to study the heavy metal uptake by major food crops in Malaysia, 241 soils were analysed for cation exchange capacity (CEC), organic carbon (C), pH, electrical conductivity (EC) and available phosphorus (P) using appropriate procedures. These soils were also analysed for arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), nickel (Ni), lead (Pb) and zinc (Zn) using aqua regia digestion, together with 180 plant samples using nitric acid digestion. Regression analysis between the edible plant part and aqua regia soluble soil As, Cd, Cr, Cu, Hg, Ni, Pb and Zn concentrations sampled throughout Peninsular Malaysia, indicated a positive relationship for Pb in all the plants sampled in the survey (R ² = 0.195, p < 0.001), for Ni in corn (R ² = 0.649, p < 0.005), for Cu in chilli (R ² = 0.344, p < 0.010) and for Zn in chilli (R ² = 0.501, p < 0.001). Principal component analysis of the soil data suggested that concentrations of Co, Ni, Pb and Zn were strongly correlated with concentrations of Al and Fe, which is suggestive of evidence of background variations due to changes in soil mineralogy. Thus the evidence for widespread contamination of soils by these elements through agricultural activities is not strong. Chromium was correlated with soil pH and EC, Na, S, and Ca while Hg was not correlated with any of these components, suggesting diffuse pollution by aerial deposition. However As, Cd, Cu were strongly associated with organic matter and available and aqua regia soluble soil P, which we attribute to inputs in agricultural fertilisers and soil organic amendments (e.g. manures, composts).     

矿区周围土壤中重金属危害性评估研究

分别用总量法和连续萃取法对广东大宝山矿周围土壤、植物和沉积物中重金属的总量和化学形态进行了详细分析。结果发现，矿山废水流入的横石河沉积物中Pb、Zn、Cu和Cd的质量分数分别为1841．02、2326．28、1522．61和10.33mg／kg；经此河水灌溉的稻田中重金属(Cu、Cd、Pb和Zn)的质量分数也远远超出了土壤环境二级标准值，其中Cu、Cd超标倍数分别为14．01和4．17倍。结果还表明，生长在矿区周围的植物也受到不同程度重金属的污染且不同植物吸收和积累重金属的能力相差很大。用Tessier连续法对土壤中重金属进行萃取发现，虽然重金属主要存在于残余态中，但在Fe-Mn氧化态、有机结合态中的质量分数也很高．说明这些土壤确实受到了有毒有害重金属元素的严重污染。     

风险评价代码法对农田土壤重金属生态风险的评价

为揭示矿区周边农田土壤中重金属分布特征及其潜在生态风险,于2013年在云南省某铅锌矿周边的农田土壤共布设68个采样点,分析土壤中Cd、Hg、As、Pb、Cr、Cu和Zn的含量及污染程度,并采用改进的BCR法测定了各重金属形态分布特征,在此基础上运用风险评价代码法评价了重金属的潜在风险程度.结果表明,7种重金属都存在不同程度的超标,其中超标最严重的是Cd和Zn,超标率分别达到92.6%和75%.7种重金属化学形态也不尽相同:在重金属有效态中,Cd的水溶态和可提取态较高(平均值达到31.2%);Pb、Cu和Zn可还原态、可氧化态这两部分含量较高,两部分之和的平均值分别可达到27.9%、30%和29.2%;Hg、As和Cr的残渣态含量较高,平均值分别为90.4%、72.9%和76.8%.风险评价代码评价结果表明,54.4%的样点Cd为高生态风险,45.6%的样点Cd为中度生态风险;100%的样点Zn为中度生态风险;Cu有41.2%的点位属于低生态风险,58.8%的点位属于中度生态风险;As和Pb主要以低生态风险为主(所占比例分别为92.6%和91.8%);Hg主要以无生态风险为主(所占97.1%).综上,该矿区周边农田土壤受到了严重的重金属污染,其中土壤中Cd的生态风险最高,同时,Zn和Cu的生态风险也不容忽视.     

Geographical distribution and risk assessment of heavy metals: a case study of mine tailings pond

ABSTRACT

In China, a large number of tailings deposited on natural surfaces, the potential risk of tailings attracts people’s attention. In this study, heavy metals distribution, geo-accumulation index, ecological risk index, microbial diversity and community were examined to evaluate the risks of a tailings pond. Results indicated the tailings pH is about 8.17, and the redox potential was lower than zero. Heavy metals could be leached and migrate from the tailings. The tailings pond had more influence on the distribution of Pb, Zn, As, Cu, and S. The influence distance of Pb, Zn, and Cu was less than 10?m, and the influence distance of As and S was less than 50?m. S and As had stronger migration capability than other elements in the soil. The biggest potential ecological risk resulted from Pb, and the distances more than 100?m had low ecological risk. The tailings decreased microbial richness and diversity of the surrounding environment. Oxidising bacteria and reducing bacteria existed in both the tailings and the surrounding soils; however, there were more oxidising and reducing microbes in the tailings than in the surrounding soils. The tailings pond currently has little impact on the environment, but the potential risk still exists.     

工业城市不同功能区土壤和蔬菜中重金属污染及其健康风险评价

为了研究和评价工业城市不同功能区的土壤和蔬菜中重金属污染和健康风险状况,以株洲市为例,在工业区（石峰区）、农业区（芦淞区）和旅游区（大京风景区）分别采集土壤和蔬菜样品,分析重金属Cd、As、Pb、Hg、Zn、Cr和Cu的质量分数,并采用地质累积指数法（Igeo）和健康风险评价模型分别对土壤和蔬菜中重金属进行评价。结果表明：工业区、农业区和旅游区土壤中Cd、As、Pb、Hg、Zn、Cr和Cu的平均质量分数都超出湖南省土壤背景值,部分重金属甚至超出国家土壤环境质量二级标准。不同功能区土壤中重金属的地质累积指数（Igeo）表明：工业区、农业区和旅游区土壤受到不同程度的重金属污染,其中Cd和Hg的污染最为严重,污染程度依次是工业区〉农业区〉旅游区。不同功能区蔬菜中Cd、As、Pb和Zn的危害商（HQ）值都大于1.0,而Cu和Cr的危害商（HQ）都小于1.0。不同功能区蔬菜中重金属危害指数（HI）都大于10.0,尤其是工业区蔬菜的危害指数（HI）〉100.0,当地成年人食用受到重金属污染的蔬菜会导致严重的健康危害,其中Cd和As,是危害指数（HI）的主要贡献者,两者贡献率之和的范围为75%~89%,而Cr的贡献率几乎为0。     

Heavy metals in Jamaican surface soils

A regional survey of Jamaican surface soils has been conducted in which more than 200 samples were collected at a sample density of 1 per 64 km² across the island and analysed for total concentrations of 31 elements by instrumental neutron activation analysis (INAA), energy dispersive X-ray fluorescence (EDXRF) analysis and atomic absorption spectrophotometry (AAS). The aim of the survey was to begin the construction of a high-precision geochemical database to provide information on elemental levels in soils for application to environmental studies, agriculture, and human and animal health. Results on the regional scale are presented for As, Cd, Cu, Hg and Pb. Although Jamaican surface soils are enriched in several heavy metals compared with world soil means and crustal abundances, lead is of particular importance at this stage because of its occurrence in residential areas. Except for Cu, the distribution maps of these elements are highly correlated with bauxite which in Jamaica is associated with white limestone geology and residualterra rossa soils.     

污染土壤中有机质结合态重金属的研究

用物理与化学相结合的方法研究了2个污染土壤剖面中有机质结合重金属（Cd、Cu、Pb和Zn）的分布，把有机质相结合态重金属分为颗粒状有机质（POM）结合的重金属和与细土腐殖质结合的重金属。结果表明，土壤POM对重金属有明品的富集作用，其中〉2mmPOM重金属Cd、Cu、Pb和Zn的富集系数分别在1．4～3．2、2．5～2．6、2．8—3．9和3．0～3．9之间；而0．05～2mmPOM重金属Cd、Cu、Pb和Zn的富集系数分别在2．7～7．8、3．2～6．4、3．2～9．3和3．2～5．6之间，0．05～2mmPOM组分中重金属的平均富集高于〉2mmPOM组分。POM中重金属的富集程度与土壤重金属的积累呈正相关。有机质结合态重金属占土壤重金属总最的比例随土壤有机质积累而增高，表土层约40％以上的重金属以有机质结合态存在。     

Heavy metals fraction and ecological risk evaluation in municipal solid waste gasification slag non-burnt bricks

The heavy metals in non-burnt bricks made from municipal solid waste (MSW) gasification slags with a modified European Bureau Community of Reference procedure were studied. Heavy metals were present in the form of oxidizable and residual fractions, which were stable and not easy to dissolve. The preparation process of non-burnt bricks displayed prominent solidification effect for some heavy metals in the gasification slag. The solidified rate for metals, such as As, Cd, Cr, Ni, and Zn reached 89.82%, 79.57%, 73.64%, 66.73%, and 88.05%, respectively. Moreover, the leaching concentrations of eight heavy metals were all below 8 mg/kg. On the basis of these observations, the risk of exposure to heavy metals in non-burnt bricks was evaluated using the solidification formula and the leaching concentration of heavy metals combined with the assessments of the Hakanson potential ecological risk and pollution ratio of secondary phase and primary phase. Results showed that the preparation of MSW gasification slag non-burnt bricks was not harmful to the environment, but attention is warranted for possible migration of heavy metal cadmium (Cd) in the long term, which may result in an impact on the ecological environment.     

贵屿电子垃圾处理对河流底泥及土壤重金属污染

以广东省汕头市贵屿镇电子垃圾处理场为对象,主要研究了电子垃圾场附近河流的底泥和农田土壤中重金属形态分布特征。结果表明,底泥中Cd、Cr、Cu、Pb、Zn质量分数分别为52.9-67.1、309-359、79.2-1485、391-449、37.5-111 mg.kg^-1;土壤中Cd、Cr、Cu、Pb、Zn的平均质量分数分别是54.1-57.1、278-320、93.5-116、382-415、46.2-68.1 mg.kg^-1。底泥和土壤中Cd、Cr、Cu、Pb均超过《土壤环境质量标准》（GB15618—1995）二级标准,其中以Cd和Cu污染最为严重。底泥及土壤中重金属的地球化学形态分布规律基本一致。重金属具有较高迁移性,重金属的迁移性为Cd〉Cr〉Pb〉Zn〉Cu。     

湖南某植烟土壤重金属含量及其生态风险评价

采集了湖南某植烟区表层土壤样品112份,测定了土壤中6种重金属元素的含量,并采用单因子污染指数法、综合污染指数法和潜在生态危害指数法对其污染状况进行评价.结果表明,植烟区土壤重金属平均含量分别为36.25(Cu)、69.78(Zn)、37.66(Pb)、0.36(Cd)、12.71(As)、0.27(Hg)mg·kg-1.6个元素的变异系数在32.57%—59.03%之间,属于中等变异,元素分布不均.污染评价结果表明,植烟区土壤重金属Cu、Zn、Pb、As的单因子污染指数平均值小于1,其污染较轻.而重金属Cd和Hg的超标率为54.46%和58.04%,土壤受到Cd和Hg污染.潜在生态风险指数评价结果显示植烟区土壤重金属属于轻度污染.相关性分析结果表明Cu、Zn、Pb和Cd之间呈显著相关性,As和Hg相关性显著,说明其同源性较高.来源分析表明,研究区Cu、Zn、Pb和Cd污染来源东北部主要为矿区污染,西南部主要是人为源,As主要来源为成土母质和生活源,Hg主要为大气污染源.     

Distribution and mobility of metals in agricultural soils near a copper smelter in South China

The distribution and mobility of heavy metals in the paddy soils surrounding a copper smelting plant in south China was investigated. We assessed the degree of metal contamination using an index of geoaccumulation. The metals were divided into two groups: (1) Cu, Zn, Pb and Cd, whose concentrations were heavily affected by anthropogenic inputs, and (2) Ni, Co and Cr, which were mainly of geochemical origin. Concentrations of Cu, Cd, Zn, and Pb in the polluted soils were higher than the Chinese soil quality criteria. The chemical partitioning patterns of Pb, Zn and Cu indicated that Pb was largely associated with the residual and NH₂OH HCl extractable fractions. In contrast, Cd was predominantly associated with the MgCl₂ extractable fraction. A large proportion of Cu was bound to the acidic H₂O₂ extractable fractions, while Zn was predominantly found in the residual phase. The fraction of mobile species, which potentially is the most harmful to the environment, was found to be elevated compared to unpolluted soils in which heavy metals are more strongly bound to the matrix. The mobility of the metals was studied by water extraction using a modification of Tessier’s procedure, and the order of mobility was Zn > Cd > Cu  > Pb.     

珠海近岸海域表层沉积物中的重金属及生态危害评价

为了研究珠江口近海海域重金属的污染状况,2009年8—12月对珠海珠江口4个站点的表层沉积物进行了6次采样,测定了表层沉积物中重金属Cd、Cr、Pb、Hg、Cu、Zn、Mn、Ni、Fe和金属Al的质量分数,分析了它们质量分数间的相关性,依据Lars Hakanson提出的沉积物中金属污染物评价方法,对Cd、Cr、Pb、Hg、Cu和Zn等6种典型重金属的潜在危害进行了评价。结果表明,Cd、Cu和Zn是该调查区域的主要重金属污染物,应该予以优先控制和治理。位于马骝洲水道入海口的S1位点上,金属元素（Cd除外）质量分数的季节特征是秋季（丰水期）〈冬季（枯水期）,重金属危害指数（RT）为轻微级,重金属潜在生态危害系数（Eir）顺序为Cd〉Hg〉Pb〉Cu〉Zn〉Cr;在S2位点,Cd、Cu、Hg、Ni和Fe的平均质量分数为秋季〉冬季,其它5种金属则为秋季〈冬季,RT为强级;在S3、S4位点上,8种金属元素（Hg、Mn除外）的质量分数呈现秋季〉冬季的现象,RT为很强级;S2、S3和S4站点的Eir均表现为Cd〉Hg〉Cu〉Pb〉Zn〉Cr的顺序。     

广州市菜园土主要蔬菜重金属背景含量的研究

研究了广州市几个主要的蔬菜生产基地种植的白菜、芥蓝、芥菜、菜薹、萝卜、大白菜、豆瓣菜、结球甘蓝、芹菜、菜豆、豌豆、结球莴苣、尖叶莴苣、菠菜、番茄等15种蔬菜中Pb、Hg、Cd、Cr和As等5种重金属的背景质量分数。其背景质量分数为：Pb 0．002～0．148mg/kg；Hg ND-0．006mg/kg；Cd 0．001～0．034mg/kg；Cr 0．002～0．150mg/kg；As 0.001～0．070mg／kg。由于不同种类蔬菜的吸收特性和遗传特性有所不同，其重金属背景质量分数也有很大差异。蔬菜中元素水平还与土壤条件等因素有关。     

神木煤矿区土壤重金属污染特征研究

通过对神府煤田开采区3个煤矿区周围土壤Cu、Cd、Cr、Mn、Ni质量分数进行测定及分析,评价了煤田开采对周围土壤的污染程度。结果表明,长期的煤炭资源开发、运输等活动,已导致周围土壤受到重金属不同程度的累积性污染,土壤中Cd、Ni质量分数高于陕西省土壤背景值,且Cd污染程度较高,Ni污染程度较低,而Cu、Cr、Mn基本不受污染。3个煤矿表层土壤各重金属元素质量分数均表现出污染区大于对照区,但这种变化幅度存在一定差异;Cu、Cr、Mn 3种重金属元素虽没有超出背景值,但已表现出一定程度的累积;煤矿周围土壤重金属污染受到开采年限、土壤质地、风向等因素的影响。3个煤矿污染区土壤剖面样品中,5种重金属元素质量分数基本上随着土壤深度的增加呈现降低的趋势,且这种趋势具有波动性。     

龙塘镇电子垃圾拆解区土壤和河流底泥重金属赋存形态及生态风险

龙塘镇是珠三角电子垃圾拆解区之一,采用AAS方法对该地土壤和河流底泥沉积物中5种重金属(Cd、Cr、Cu、Zn和Pb)含量进行测定分析,结果显示周围农田土壤中Cd含量是《国家土壤质量标准》二级标准的3倍左右,是广东省土壤背景值的20倍左右;拆解区土壤Cd超标最为严重,最高达5.67倍,超过广东省土壤背景值达36.17倍;拆解区下游0—1500 m河流底泥中Cd、Cr、Cu、Zn和Pb含量大幅增加且部分金属超标,Cd在0—40 cm深度内含量总体逐渐降低,仍远超背景值,Cu含量采样深度内递减规律最显著且在0—10 cm内含量超标,Cr、Zn和Pb除部分点位在表层积累较多外,其余与背景值相差不大且未超标.采用BCR(the Community Bureau of Reference)法提取重金属不同形态可知,底泥中Cd主要以弱酸溶态和可还原态为主,Cu主要以可氧化态存在,Cr主要以残渣态存在,而Zn和Pb则以可还原态为主;其中Cd的可提取态比例较高(60%),容易释放出来形成"二次污染".潜在生态风险结果表明,河流底泥中Cd生态危害程度属于极强(Ei320);其他金属Cr、Cu、Zn和Pb危害风险程度属于轻微(Ei40);金属Cd对整个RI值贡献最大(88%),应重点加强对Cd污染的防控.     

有色矿业区耕作土壤、蔬菜和大米中重金属污染

有色金属矿业区周边土壤重金属污染严重,对我国生态环境质量、食品安全和人体健康构成了一定威胁,研究典型矿业区周边复合污染地带的土壤环境质量及其食物安全对促进其可持续发展具有深远的意义。从湖南省的长沙、株洲、衡阳、郴州等有色金属矿业区收集耕作土壤、蔬菜和大米样品,结合主成分分析、聚类分析和相关分析,研究其中重金属元素的累积和迁移特征,评估蔬菜和大米中重金属元素对人体健康的潜在危害程度。研究结果表明,耕作土壤中主要重金属污染元素为Cd、As、Pb、Cu、Zn等;主成分分析表明,菜地土中第一主成分主要反映了Pb、Zn、Cd、As的复合污染信息以及与土壤pH的相关关系;水稻土中第一主成分主要反映了Cu、Zn、Pb、Cd的复合污染信息;聚类分析进一步阐明耕作土壤以Cd、Pb、As、Cu、Zn为主的复合污染特征。研究区蔬菜中Cd、Pb、As、Cu、Zn、Cr含量,大米中Cd、Pb和Zn含量均明显超过我国食品卫生标准;蔬菜中Cd、Pb、As和大米中Cd、Pb对人体健康的潜在危害较大。     

土壤重金属污染的植物修复中转基因技术的应用

重金属污染的植物修复技术以其费用低廉、不污染环境等优点一度成为环境科学界研究的热点。为了克服植物修复技术中超积累植物生长缓慢和地上部生物量小等带来的限制，近年来研究者通过大量试验研究发展，外源基因在植物体内的高效表达可以提高植物吸收、运输、降解污染物的能力和修复的效率。本文首先对目前国内外重金属污染土壤植物修复的研究动态进行综述，重点论述了PCs、MTs、MerA、MerB、ArsC、γ-ECS等转基因在土壤重金属污染植物修复中的应用，最后指出在充分考虑到转基因植物给生态环境带来潜在威胁的前提下，转基因技术的研究与开发不仅可以促进多学科的交叉研究和丰富环境科学的研究领域，更重要的是在很大程度上有效地克服了目前土壤重金属污染植物修复中存在并急需解决的棘手问题，为土壤重金属污染的植物修复提供了更加广阔的应用和发展前景。     

神木煤矿区土壤重金属污染特征研究

通过对神府煤田开采区3个煤矿区周围土壤Cu、Cd、Cr、Mn、Ni质量分数进行测定及分析,评价了煤田开采对周围土壤的污染程度。结果表明,长期的煤炭资源开发、运输等活动,已导致周围土壤受到重金属不同程度的累积性污染,土壤中Cd、Ni质量分数高于陕西省土壤背景值,且Cd污染程度较高,Ni污染程度较低,而Cu、Cr、Mn基本不受污染。3个煤矿表层土壤各重金属元素质量分数均表现出污染区大于对照区,但这种变化幅度存在一定差异;Cu、Cr、Mn 3种重金属元素虽没有超出背景值,但已表现出一定程度的累积;煤矿周围土壤重金属污染受到开采年限、土壤质地、风向等因素的影响。3个煤矿污染区土壤剖面样品中,5种重金属元素质量分数基本上随着土壤深度的增加呈现降低的趋势,且这种趋势具有波动性。     

几种沼渣中Cu和Zn的含量及其形态分布

通过CaCl2、EDTA、HOAc一步提取法和改进的BCR三步法对6种沼渣中的重金属Cu和Zn的形态进行了研究.结果表明,沼渣中重金属的形态组成与重金属的种类和沼渣的类型有关;单一提取剂对沼渣中Cu、Zn的提取效率顺序为：EDTA〉HOAc〉CaCl2,其中EDTA的提取效率可达70%以上,HOAc提取效率在11%和62%之间,中性盐CaCl2的提取效果最差,其提取效果最高不到0.6%;沼渣中Zn的可移动性大于Cu的可移动性,若原沼渣中含有高浓度的Zn,施入土壤中可能使得植物吸收过多的Zn,从而产生农用风险.     

An evaluation of heavy metals contamination in soils from Ganzhou navel orange orchards by geoaccumulation indexes and statistical analysis

Heavy metal pollution in orchard soils is of increasing concern owing to the potential health risk via the food chain. The evaluations of the degree of heavy metal contamination and the potential sources in soils from navel orange orchards in the Ganzhou district were investigated in the present study with the geoaccumulation index and hierarchical cluster analysis. The soil samples were collected from 280 navel orange orchards located in the 18 counties of the Ganzhou district. The concentrations of heavy metals in the samples were determined using atomic fluorescence spectrometry and inductively coupled plasma atomic emission spectrometry with sample preparation by microwave digestion system. The results of the geoaccumulation index showed that the Ganzhou navel orange orchards were practically uncontaminated with Hg, As, Pb, Cd, Cr, Zn, and Cu, while uncontaminated to moderately contaminated with Ni. The results of cluster analysis indicated that four distinct clusters emerged for 18 sampling counties, and the considerable differences between clusters were derived from the different kinds of polluted substances. Results of the assessment of geoaccumulation index of heavy metals in soils will be helpful for the formulation of strategic sustainable agriculture in Ganzhou navel orchards and improvement of the navel orange yield and quality.