模拟酸雨对污染土壤中Cd、Cu和Zn释放及其形态转化的影响

研究了模拟酸雨连续浸泡下污染红壤和黄红壤中重金属释放及形态转化．结果表明。随着模拟酸雨pH值下降,污染土壤中重金属释放强度明显增大;Cd、Zn释放量与酸雨pH值呈线性极显著负相关．Cu与酸雨pH值呈线性显著负相关．模拟酸雨作用下,污染红壤和黄红壤中Cd均以交换态为主;Cu则以有机结合态和氧化锰结合态为主;Zn在污染红壤中以残留态和交换态为主．在污染黄红壤中以残留态和有机结合态为主．土壤有机质含量和阳离子交换量对Cd、Cu、Zn的释放产生一定的影响并影响Cd、Zn的形态转化,但对Cu形态转化影响不明显,随着模拟酸雨酸度增大,污染红壤和黄红壤中重金属Cd、Cu的生物可利用态明显增多,但难解吸态Zn向生物有效态转化效应不明显．     

施用污泥对土壤重金属形态分布和生物有效性的影响

采用盆栽技术和BCR连续浸提法研究了污泥的添加对土壤Cd、Pb、Cu和Zn形态分布的影响及重金属在黑麦草-施污泥土壤中迁移转化规律.结果表明:污泥的添加使土壤中生物有效态的Cd和Zn含量显著增加,生物有效态Pb含量显著降低,残渣态Pb的比例较CK增加了33.3％～74.5％,而可交换态和可还原态Cu含量在污泥与土壤添加比为1∶1时,仅占总量的0.7％和0.2％.污泥的添加能促进黑麦草对Cd、Cu和Zn的吸收,抑制对Pb的吸收.多元线性回归分析结果表明,黑麦草体内Cd、Zn和Cu含量分别与土壤中可还原态Cd、Zn和可氧化态Cu含量存在正相关,草体中Pb的含量则受土壤中可交换态和可氧化态Pb含量共同影响.种植黑麦草后根际土中可氧化态Cd和Cu分别向可交换态Cd和残渣态Cu转化,可交换态和可还原态Zn向可氧化态Zn转化,Pb的生物有效性基本未受影响.     

稻麦轮作下水稻土重金属形态特征及其生物有效性

在成都平原稻麦轮作下86个土样中重金属全量和各形态含量分析的基础上,采集分析相应点位上种植的主要粮食作物小麦和水稻籽粒的重金属含量,通过描述性统计分析、相关性分析及线性回归方程的模拟,研究了土壤中重金属的形态分布特征及其生物有效性。统计分析结果表明：土壤中Cr、Cu、Pb、Zn各形态含量的分配顺序为：残渣态〉有机物结合态〉铁锰氧化物结合态〉碳酸盐结合态〉可交换态,而Cd各形态含量的分配顺序为：铁锰氧化物结合态〉残渣态〉碳酸盐结合态〉有机物结合态〉可交换态。若以活性态（非残渣态含量）而论,Cd的活性最高,Cr的活性最低。除Cr外,各元素全量与各活性形态之间的关系较为密切。土壤中全Cd含量与4种活性形态Cd含量间的相关性均达极显著水平;Cu、Zn全量分别与其铁锰氧化物和有机物结合态含量,Pb全量分别与其可交换态和铁锰氧化物含量间的相关系数达显著或极显著水平。用卫生部颁布的食品中重金属限量卫生标准评价稻麦籽粒重金属累积情况,其结果表明,小麦籽粒（旱作）中的Cd、Cr、Cu、Pb分别超标14.71%、8.70%、6.50%和17.40%,而水稻籽粒（水作）仅有Pb和Cd含量超标10.90%和8.70%。不同形态重金属对水稻和小麦籽粒中重金属累积的影响效应不同，从多元线性回归方程的回归系数来看：稻一麦籽粒中Cd含量受到土壤中各活性形态Cd含量的影响。除铁锰氧化态Cd和有机物结合态Cd含量分别对小麦和水稻籽粒中Cd的累积表现出负效应外，其余均为正效应。可交换态Cu含量对稻-麦籽粒Cu累积的效应最大，其次受碳酸盐结合态Cu含量的影响。稻一麦籽粒Pb含量的累积受土壤各活性态Pb含量影响效应的差异不甚明显。稻-麦籽粒Zn含量与土壤各活性态Zn含量间无显著线性关系。     

绿洲土Cd、Pb、Zn、Ni复合污染下重金属的形态特征和生物有效性

通过模拟基于干旱区绿洲土壤Cd-Pb-Zn-Ni复合污染下的油菜盆栽试验,采用Tessier五步连续浸提法探究了重金属复合污染对油菜生长的影响及其各形态的转化归趋和生物有效性.结果显示,随着Cd-Pb-Zn-Ni复合胁迫水平的升高,油菜的干重先增加后减小,根系的生长由促进作用转变为抑制作用;对照土壤中4种重金属元素均以残渣态为主要赋存形态,可交换态的含量均很小;随着外源重金属的添加,油菜种植土壤中4种重金属元素的各形态含量随之增加,Cd、Pb、Zn的可交换态和Ni的碳酸盐结合态对外界胁迫响应强度最大,Cd、Pb、Zn、Ni的活性增加,且Cd、Pb的主要赋存形态迅速转变为碳酸盐结合态和铁锰氧化态,Zn的主要赋存形态由残渣态和碳酸盐结合态过渡到碳酸盐结合态和铁锰氧化态,Ni的主要赋存形态为碳酸盐结合态;Cd、Zn在茎叶中的含量大于根系,Pb、Ni反之,油菜能将Cd、Zn更多的运输至茎叶,Pb、Ni则主要积累在根系;油菜茎叶吸收Cd和油菜各部位吸收Zn的主要贡献形态为可交换态,根吸收Cd的主要贡献形态由可交换态转变为有机结合态,根吸收Pb和油菜各部位吸收Ni的主要贡献形态为碳酸盐结合态.     

鄂尔多斯地区公路沿线土壤重金属形态与生物有效性

采用TessierA连续提取法对鄂尔多斯地区公路沿线土壤重金属（Pb、Zn、Cu、Ni、Cr）化学形态进行了测定。同时对土壤pH值、重金属含量和公路绿化植物重金属（Cd、Hg、Pb、Cu、Zn、Ni、Cr、As和Se）含量进行了分析，对该区域重金属的生物有效性与潜在生态风险进行预测。结果表明：土壤重金属有效态占总量百分比的大小序列为Zn〉Pb〉Ni、Cr〉Cu，与重金属元素在绿化植物中含量大小序列Zn〉Cu〉Ni、Cr、As、Pb〉Cd〉Hg并非完全趋于一致。不同公路段土壤重金属与其不同形态存在较大的变幅。公路沿线表层土壤中重金属的有效态占其总量为G109（东胜-准格尔段）15．7％～46．1％，G210（达拉特-东胜段）8．0％-40．9％，G109（东胜-鄂托克段）9．1％～33．9％，而且以有机态和Fe—Mn氧化结合态的比例较大，为各元素有效态的主要形态特征。Cu在不同植物不同器官中的含量较高，可能在鄂尔多斯地区特定环境条件下随植物的蒸腾拉力、水分和营养盐运移的生理生态作用下使其在植物体中富集。土壤重金属Zn的有效态含量较高，而残渣态含量低，须特别注意其对区域生态系统的潜在影响。     

铜尾矿库区土壤与植物中重金属形态分析

对铜陵铜尾矿区土壤和植物中重金属形态进行了研究.结果表明,尾矿库区种植地极端贫瘠,有机质含量仅2.6～.8 g·kg^-1,而土壤Cu、Cd、Pb、Zn含量皆高于对照土壤,其中Cu含量达809.30～1 39.4 mg·kg^-1,Cd含量达3.2～6.3 mg·kg^-1,达到对照土壤30～60倍.结缕草和三叶草体内重金属含量与土壤重金属交换态及有机结合态含量成正相关,与碳酸盐结合态、铁锰氧化物结合态成显著或极显著负相关,与矿物态含量相关性不显著.在两种优势植物中,Cu、Zn、Pb均以活性较低的醋酸提取态、盐酸提取态和残渣态为主;Zn在根系和茎叶中,NaCl提取态占有较大比例,而Cd均以NaCl提取态为主.     

施污土壤重金属有效态分布及生物有效性

以城市污泥为研究对象,将城市污泥与土壤按照一定的质量比配成污泥混合土壤.采用6种不同性质提取剂(0.05mol/L EDTA、0.1 mol/L CH3 COOH、0.01 mol/L CaC12、1 mol/L CH3COONH4,0.05 mol/L NaHCO3和0.05 mol/L Tris-HCl)分别对污泥混合土壤中重金属(Cd、Pb、Cu和Zn)的螯合态、酸溶态、中性交换态、中性结合态、碱性交换态和蛋白质结合态进行提取,考察污泥的添加对土壤中不同形态重金属的消长规律.通过黑麦草盆栽试验,探究污泥混合土壤中不同形态重金属的植物可利用性.结果表明:污泥混合土壤中重金属螯合态比例较大,占总量的20.3％-40.0％;其次为酸溶态和中性结合态,而中性交换态、碱性交换态和蛋白质结合态的含量较低.污泥的添加促进了黑麦草对Cd、Cu和Zn的吸收,在污泥添加率为44.4％时根部对其吸收量达最大,分别较CK处理增加了0.3、2.3和6.5倍.抑制了对Pb的吸收,在污泥添加率为37.5％时,根部对Pb的吸收较CK处理下降0.4倍.Pearson相关系数分析结果表明:污泥混合土壤中以螯合态、酸溶态和中性结合态存在重金属可被黑麦草吸收利用.     

芜湖钢铁厂周边土壤及油菜籽中镉、铜、锌、铅含量和形态分布研究

研究了污染土壤、油菜籽中Cd、Cu、Zn、Pb含量、形态分布特征和重金属富集状况及可能存在的生物毒性.结果表明,土壤中Cd、Zn、Pb以铁锰氧化物结合态、Cu以残留态占5种形态最高比例,分别为31.1%、39.3%、53.79%、46.24%;Cd、Pb交换态比例较高,为23.47%、16.32%,Cu、Zn的交换态比例较小,为3.14%、0.54%;土壤中不同重金属与各重金属形态相关关系有差别,5种重金属形态转化为有效态重金属难易程度不同;油菜籽和油菜籽壳中不同重金属累积趋势有差异,Cu易在油菜籽壳中累积,Cd、Zn、Pb易在油菜籽中累积;油菜籽中不同重金属累积率不同,Cd累积率最高,为0.56.油菜籽中重金属累积率与土壤中重金属总量呈显著负相关关系(P＜0.05),土壤中重金属的形态、转化差异是此种负相关关系的主要原因;油菜籽中Cd、Cu、Pb以氯化钠态为主,分别为32.50%、22.94%、34.69%,Zn以EDTA态为主,为45.97%.油菜籽中重金属形态可能影响其毒性,但其毒性的人类膳食风险还需进一步研究证实.油菜籽中重金属形态与油菜中重金属总量相关性不好.     

有机物料对滨海盐渍土重金属根际效应的影响 Ⅰ.土壤内源Zn形态分布

研究了排水条件下施用腐熟有机物料、种稻改良滨海盐渍土内源Zn形态分布。结果表明,单淹水使土中各形态Zn一定程度上向生物有效性较低的Zn形态转化,有效态Zn降低。土壤盐分量不同,明显影响无定形氧化铁结合态、紧结有机态以及硅酸盐矿物态Zn变化。种稻不施有机物料,根际交换态和硅酸盐矿物态Zn亏缺;碳酸盐结合态、氧化锰结合态和无定形氧化铁结合态Zn富集。根际Zn形态转化强度大于非根际,其有效态Zn量接近临界值并高于非根际。有机物料利于根际内外土壤中硅酸盐矿物态Zn的转化,低盐土壤根际更强烈。随有机物料用量增加,促使根际硅酸盐矿物态、碳酸盐结合态及氧化锰结合态Zn向交换态、紧结有机态和无定形氧化铁结合态Zn转化,低盐土壤较明显。     

紫色土外源锌、镉形态的生物有效性

通过对7种形态Zn,Cd与有效态Zn,Cd(DTPA提取）的相关分析及各形态Zn,Cd与植株Zn,Cd含量的通径分析,评价各形态Zn,Cd的生物有效性及对植株的相对贡献和途径。结果表明,交换态Zn,Cd与有效态Zn,Cd呈极显著正相关（r=0.954,0.953),交换态Zn,Cd与植株Zn,Cd含量的通径系数为1．267、1．168,交换态Zn,Cd有效性高,具有最大的生物活性,对植株Zn,Cd含量的贡献最大。其它形态如碳酸盐结合态锌、氧化锰结合态Zn、Cd通过交换态作用于植株的通径链系数（间接通径系数）分别为0．856、0．592、0．723,上述形态对植株Zn,Cd含量也有影响,具有一定的生物相对有效性,但通过交换态间接作用。交换态不仅自身具有最大的生物有效性,而且还作为其它形态Zn,Cd生物有效性的中介,为紫色土其它Zn,Cd库流向植株的主要通道。     

Assessment of a heavy metals‐contaminated site using sequential extraction,TCLP, and risk assessment techniques

The mobility of selected heavy metals in contaminated soil at a previous industrial site in Brisbane, Australia, was assessed using a sequential extraction technique. Copper, Pb, Zn, Cr, Fe, and Mn were extracted from the soil solution/exchangeable, carbonate, Fe and Mn oxides, and organic matter fractions. The amounts of metals adsorbed by these fractions were used as an indicator of each metal's mobility in the soil. Copper and Pb were largely adsorbed by the organic and oxide fractions, while a significant amount of Zn was extracted from the carbonate fraction. The potential mobility and biological availability of the metals in these soils is Zn > Cr = Cu ≈ Pb. Soils were also analyzed using the toxicity characteristic leaching procedure (TCLP) to determine whether the contaminated soil could be disposed of by landfilling. The leachability of all metals from the soils was very low, with metal concentrations below the allowable limits. The TCLP also showed that Zn was the most mobile metal in these soils. An environmental and health risk assessment was undertaken, and it was concluded that the site did not represent a risk despite the “total”; concentrations of some metals being up to 40 times the investigation threshold value adopted in Australia.     

The Adsorption Properties of Agricultural and Forest Soils Towards Heavy Metal Ions (Ni,Cu, Zn,and Cd)

Adsorption of Cu, Cd, Ni, and Zn in single and multi-metal solutions by agricultural and forest soils was investigated in batch sorption experiments. The results showed significant differences in sorption capacities of the studied soils. The selectivity order was as follows: agricultural soil? top forest soil > bottom forest soil. The adsorption sequence Cu > Zn > Ni > Cd was established for the agricultural and bottom forest soil, while the order for the top forest soil was Cu > Ni > Zn > Cd. The experimental isotherms for the metal sorption were described satisfactorily by the Freundlich and Langmuir models. The competitive adsorption experiment indicated a reduction in the amount of metals adsorbed by the soils from the multi-metal solution compared to the single metal solution. Properties of the soils, such as pH, content of clay and organic matter, exchangeable bases and hydrolytic acidity, showed a significant influence on adsorption capacities of the studied soils.     

Copper,Lead, Cadmium,and Zinc Sorption By Waterlogged and Air-Dry Soil

Competitive sorption of copper (Cu), lead (Pb), cadmium (Cd), and zinc (Zn) was studied in three soils of contrasting chemical and physical properties under air-dry and waterlogged conditions. Competitive sorption was determined using the standard batch technique using six solutions, each with Cu, Pb, Cd, and Zn concentrations of approximately 0, 2.5, 5, 10, 20, and 50?mg L^?1Waterlogged soils tended to sorb higher amounts of added Cu, Pb, Zn and Cd relative to soils in the air-dry condition; however, this increase in sorption was generally not statistically (p<0.05) significant. The magnitude of sorption under both waterlogged and air-dry conditions was affected by the type and amount of soil materials involved in metal sorption processes, and competition between other metals for the sorption sites. Metal sorption was closely correlated with soil properties such as cation exchange capacity, organic carbon, and Fe and Mn hydrous oxides. Exchangeable Al may have markedly reduced metal sorption due to its strong affinity for the sorption sites, while increases in exchangeable Mn may have enhanced Zn and Cd sorption. Heavy metal sorption was best described as a combination of both specific and nonspecific interactions. The extractability of Cu, Pb, Cd, and Zn under waterlogged and air-dry conditions was also studied. Three solutions containing these metals were mixed with each soil to achieve a final concentration of 0, 50, and 500?mg kg^?1. Each soil was extracted every 7 days using 1?M MgCl₂ (pH 7) to determine metal extractability. Metal extractability initially decreased then increased due to waterlogging. The increased extractability of added metals was closely related to increased solubility of Fe and Mn suggesting that dissolution of Fe and Mn, oxides under reducing conditions caused a release of previously sorbed Cu, Pb, Cd, and Zn.     

碳酸钙对水稻吸收重金属(Pb、Cd、Zn)和As的影响

选用重金属(Pb、Cd、Zn)和As复合污染土壤进行水稻盆栽试验,结果表明,碳酸钙的添加显著提高了土壤pH值,显著降低了土壤中交换态Pb、Cd、Zn和As的含量,与对照相比,交换态Pb、Cd、Zn和As含量分别最多降低了98.35%,93.72%,98.52%和69.48%。碳酸钙对水稻根、稻谷干重和总生物量没有显著影响,添加量过高时显著降低了水稻分蘖数和茎叶干重,说明过量施用碳酸钙对水稻生长会产生负面作用。因为碳酸钙的添加,水稻植株各部位重金属Zn含量显著降低,糙米中Zn含量最多减少了34.95%;根、谷壳中Pb、Cd含量显著降低,但糙米中含量却未显著降低;水稻各部位As含量均没有显著降低。参照《食品中污染物限量》(GB2762—2012),试验糙米中Pb、Cd、无机As含量均未达到限量标准。显然,碳酸钙的添加降低了Pb、Cd、Zn的生物有效性(水稻根系对Pb、Cd、Zn的吸收累积减少),但并未有效地抑制Pb、Cd向糙米转运;碳酸钙显著降低了土壤的交换态As含量,但并未使土壤中As的生物有效性明显降低(水稻植株各部位的As含量并未显著减少)。     

Preliminary study on heavy metals contamination of soil using solid phase speciation and the influence on groundwater in Bozanta–Baia Mare Area,Romania

Abstract

A preliminary study on soil contamination with heavy metals and As based on solid phase speciation according to the Tessier scheme and the influence on groundwater in an area under anthropogenic influence (Bozanta-Baia Mare, Romania) was conducted. The partitioning of Al, As, Cd, Cu, Fe, Mn, Pb and Zn in five fractions is discussed in relation to soil characteristics, pH, organic matter content, mineralogical composition and distribution of the same elements in airborne particulate matter. The airborne particulate matter contains high quantities of As, Cd, Cu, Pb and Zn as exchangeable fraction. The sequential extraction carried out on soil samples revealed the main role of Fe-Mn oxides surface in the immobilization of metals. Organic matter has a specific role in complexation of Cu, Pb, As and Al, since high contents of these metals were recovered in the oxidizable fraction. Cadmium has a high selectivity for carbonate minerals. The amendment of soil with natural fertilizer increases the exchangeable fraction of metals with the highest toxicity. The available fraction for plants (exchangeable + carbonate-bound species) exceeded the alert values in soil, therefore the continuous monitoring of the area is necessary. The soil is unsuitable for agricultural use due to high contamination on surface with toxic elements resulted from anthropogenic activities. Groundwater is contaminated with very toxic elements (As, Cd and Pb) but also with Cu, Mn and Zn and is unsuitable as supply for drinking water.     

Concentrations and chemical forms of heavy metals in agricultural soil near the world’s largest and oldest tungsten mine located in China

Abstract

Tungsten (W) mining has taken place in Ganzhou in China for about 100 years. Such long-term W mining may release large amount of metals to soils and waters around these mines. Twenty soil samples were taken from the area around the W mines and 10 soil samples from an area much farther away. These soil samples were analysed for physicochemical properties, heavy metal content and their chemical forms. Results show that long-term W mining significantly increased both total and labile contents of Cd, Cu, Pb and Zn, but did not, or only slightly, increased the total content of Co, Cr and Ni in the soil near the mine. Average enrichment factor (EF) in the agricultural soils was 4.0, 2.4, 2.2, and 2.0 for Cd, Cu, Pb and Zn, respectively. The labile fraction was dominated by the carbonate-bound fraction for Cd (54.5%) and organic matter-bound fraction for Cu (37.9%), while the major labile fractions for Pb and Zn were associated with carbonates (30.2% and 6.4%), oxides (17.9% and 10.6%) and organic matter (9.2% and 18.8%). Consequently, there is a need to be cautious about Cd in the soils contaminated by W mining.     

Sequestration Enhancement of Metals in Soils by Addition of Iron Oxides Recovered from Coal Mine Drainage Sites

Iron oxides recovered from abandoned coal mine drainage (AMD) sites (Lowber, Scrubgrass, and Horner) as a soil amendment were investigated in this laboratory study for their effectiveness in the stabilization of cadmium, copper, and zinc in two metal-contaminated soils. The adsorption experimental results demonstrated that all three AMD iron oxides possess significant capacity for adsorption of Cd(II), Cu(II), and Zn(II). Horner iron oxide exhibited the highest adsorption capacity. Both the adsorption and the extraction experimental results showed metal sequestration enhancement through addition of Horner iron oxide to soil (5% to 50% by weight). With soil pH of 4.5 to neutral range, AMD iron oxide addition worked best for strongly adsorbed metals such as Cu, not so well for more weakly adsorbed metals such as Cd and Zn. The more AMD iron oxide amendment added, the less the mobility of the cationic target metals. Addition of AMD iron oxide for metal sequestration was more effective for the contaminated soils with low organic content.     

Metal Speciation and Contamination in Dredged Harbor Sediments from Kaohsiung Harbor,Taiwan

The status of metal speciation and contamination of sediments in Kaohsiung Harbor, Taiwan, was evaluated by a five-step sequential extraction procedure (exchangeable, carbonate, Fe–Mn oxides, organic matter, and residual). Eleven dredged sediment samples from various locations in the harbor were characterized in terms of heavy metals, grain size, and total organic carbons. Results showed that Hg, Pb, Cd, Cr, Cu, Zn, Ni, and Mn had different species composition patterns. The degree of sediment contamination was determined for an individual contamination factor (ICF) and a global contamination factor (GCF); results showed that Kaohsiung Harbor had a high potential risk for Pb, Cd, Cr, and Cu. Based on GCF values, the results showed that those stations, located in the vicinity of the river mouth, fish port, and industrial sites, contributed high potential risk to Kaohsiung Harbor. The potential risk of heavy metals to the environment was assessed for risk using the risk assessment code (RAC) and results showed that Pb, Cd, Zn, and Mn generally created a medium to high risk, and Hg, Cr, Cu, and Ni generally created a low to medium risk.     

Fate and Mobility of Copper in Soil of Cocoa Plantations in Two Southwestern States of Nigeria Treated with Copper-Based Fungicides

Soils from cocoa plantations treated with Boudreaux mixture in two southwestern states of Nigeria were collected at different depths, 0–15 cm and 15–30 cm, and subjected to five-stage sequential extraction to obtain the speciation forms of copper: exchangeable, carbonate, manganese and iron oxides, organic and residual fractions. The Cu content in the extracts from the sequential extraction was read with an Atomic Absorption Spectrophotometer (AAS). The total Cu content of the soil and the physicochemical parameters of the soils were also determined. The results from the study showed that the soils had high organic matter and copper is mostly bounded to the more mobile exogenic phase much more than the stable lithogenic phase, indicating higher mobility. Within the exogenic species, carbonate fraction was the highest followed by the organic bound and the exchangeable fraction in decreasing order. Cu was not detected in the Fe/Mn bound fraction. The implication is that the fate of the administered Cu-based pesticide is more in the relatively stable carbonate bound species than the other, more mobile phase. The results showed variation in the distribution of the copper species from one depth to another. The most transported metal from the surface to the lower layer is the exchangeable fraction. The carbonate bound species is less mobile and is not readily transported into the bottom soil layer. The organic bound Cu has nearly equal distribution between the top and bottom soils and there was little or no transport of the residual metal specie from the top to the bottom. The existence of copper in the soil largely in the anthropogenic (exogenous) phase is not the most desirable for the ecosystem. This may increase the availability of Cu in the cocoa plant and bean and may lead to potential exposure risk.