外源重金属在珠江河口湿地土壤中的形态转化

采集珠江口湿地土壤,采用室内培养和Tessier化学逐级连续浸提方法研究了外源重金属在珠江河口湿地土壤中的化学形态转化,探讨了盐分变化对重金属形态转化的影响.试验结果表明,外源重金属进入珠江河口湿地土壤后主要以可利用态和潜在可利用态存在,Ni、Zn、Cu、Cr和Pb主要向铁锰氧化物结合态转化,而Cd主要向可交换态和碳酸盐结合态转化.土壤盐分含量递增对重金属Cu、Zn、Ni和Cr的形态分布无显著影响,对重金属Pb和Cd的影响主要体现在可交换态.在土壤盐分添加量不超过80 g·kg-1时,随着土壤含盐量的上升,土壤Cd和Pb的可交换态比例逐步增大.     

金昌市郊农田土壤Cu,Zn,Ni形态分布特征与生物有效性评价

通过野外调查和室内测试分析,研究了金昌市郊农田土壤重金属Cu,Zn和Ni的形态特征,并以麦粒中重金属含量为重点进行了Cu,Zn和Ni的生物有效性评价.结果表明,研究区域土壤重金属Cu和Ni污染严重;Cu的主要存在形态为有机结合态,Zn的主要存在形态为残渣态,而Ni的主要存在形态为潜在可利用态;三种元素的生物有效性大小顺序为NiZnCu.对麦粒中重金属健康风险进行评价反映出麦粒中Ni含量对人体健康风险较大,而Cu和Zn对人体健康风险较小.逐步回归分析结果表明,农田土壤中Cu可交换态和碳酸盐结合态对麦粒中Cu含量贡献最大,而对麦粒吸收Zn和Ni贡献最大的形态分别为Zn的碳酸盐结合态和Ni的可交换态、碳酸盐结合态、铁锰氧化态和有机结合态.土壤重金属Cu,Zn和Ni各形态分配系数较总量和各形态含量更适合表征本研究区域土壤重金属的生物有效性.     

耕地土壤铜、镉、锌形态及生物有效性研究

土壤重金属总量常被用来评估土壤质量安全,但是大量事实说明单纯用土壤重金属总量并不能完全说明土壤重金属的生物有效性及其环境风险。相对于国内外常用的Tessier的五态方法,欧共体标准物质局提出的三步提取法(BCR法),中国地质调查局地质连续提取法的七态标准少见报道。本研究选取河南平原耕地样品,采用中国地质调查局地质连续提取法(DD2005-03)进行耕地中重金属元素(Cu、Cd、Zn)的形态分布,结果表明:Cu、Zn主要以残渣态存在,其残渣态分别占全量的55.80%和67.35%。Cd以离子交换态为主,占全量的27.30%。Cu、Cd、Zn各态含量占全量比例的顺序是,Cu:残渣态弱有机结合交换态铁锰氧化态碳酸盐结合态强有机结合态水溶态离子交换态。Cd:离子交换态弱有机结合交换态强有机结合态残渣态碳酸盐结合态铁锰氧化态水溶态。Zn:残渣态铁锰氧化态弱有机盐结合态离子交换态强有机结合态碳酸盐态水溶态。从生物可利用性系数k来看,Cd主要以活动性较大的状态存在,很容易被作物吸收。     

耕地土壤铜、镉、锌形态及生物有效性研究

土壤重金属总量常被用来评估土壤质量安全,但是大量事实说明单纯用土壤重金属总量并不能完全说明土壤重金属的生物有效性及其环境风险。相对于国内外常用的Tessier的五态方法,欧共体标准物质局提出的三步提取法（BCR法1,中国地质调查局地质连续提取法的七态标准少见报道。本研究选取河南平原耕地样品,采用中国地质调查局地质连续提取法（DD2005．03）进行耕地中重金属元素（Cu、Cd、Zn）的形态分布,结果表明：Cu、Zn主要以残渣态存在,其残渣态分别占全量的55．80％和67．35％。Cd以离子交换态为主,占全量的27．30％。Cu、Cd、Zn各态含量占全量比例的顺序是,Cu：残渣态〉弱有机结合交换态〉铁锰氧化态〉碳酸盐结合态〉强有机结合态〉水溶态〉离子交换态。Cd：离子交换态〉弱有机结合交换态〉强有机结合态〉残渣态〉碳酸盐结合态〉铁锰氧化态〉水溶态。Zn：残渣态〉铁锰氧化态〉弱有机盐结合态〉离子交换态〉强有机结合态〉碳酸盐态〉水溶态。从生物可利用性系数k来看,Cd主要以活动性较大的状态存在,很容易被作物吸收。     

子牙新河下游湿地土壤重金属垂直分布及形态特征

2014年秋季在子牙新河下游湿地采集柱状土壤样品,分析了Cd、Zn、Cu、Pb的垂向分布特征,利用Tessier连续浸提法,分析了典型湿地N1、N3、B3的重金属形态.研究结果表明,Cd、Zn、Cu、Pb含量垂向分布差异性比较大,波动幅度比较大,多数点位Cd、Cu、Zn在11—19 cm深度处出现峰值,可能与过去金属的输入和周期性淹水有关.Zn、Cu、Pb形态分布为残渣态铁锰氧化物结合态有机物结合态可交换态碳酸盐结合态,Cd形态分布为铁锰氧化物结合态可交换态残渣态有机物结合态碳酸盐结合态,Cd的生物有效性较高.湿地淹水条件影响到湿地重金属Cd的交换态和铁锰氧化物结合态的垂直分布.Cd主要以铁锰氧化物结合态的形式存在于湿地土壤中,其百分含量占53.2%,而重金属Zn、Cu、Pb主要以残渣态的形式存在于湿地土壤中,其百分含量均高于60%.根据风险评价编码法(RAC)对重金属的化学形态进行风险评价,风险顺序为:CdZnCuPb,因此重金属Cd应引起足够的重视.     

外源铅铜镉在长三角和珠三角农业土壤中的转化

选择了我国经济发达地区的长江三角洲和珠江三角洲10个代表性农业土壤，采用室内培养和化学分级方法研究了加入外源铅、铜、镉在土壤中的动态变化及转化趋势，探讨了碳酸钙、粉煤灰、猪粪和钢渣等土壤改良剂对土壤重金属形态的影响。结果表明，随着土壤重金属负荷的提高，土壤中交换态重金属的比例增大，残余态比例下降，有效性提高，对环境威胁增大。当重金属加入最较低时，重金属优先向氧化物结合态、有机质结合态转化；而当加入最较高时，向交换态和碳酸盐结合态转化的比例明皿增加。pH和土壤组分对重金属在土壤中的转化有显著的影响，土壤pH下降可使交换态Cd、Cu、Pb的比例递增。加入碳酸钙、粉煤灰、猪粪和钢渣等改良剂可显著地降低土壤中交换态重金属比例，增加其它形态的重金属比例。     

炼金区土壤中汞形态分布及其生物有效性

采用修正的Tessier方法和回归、偏相关等分析技术,研究了某金矿附近土壤中汞的赋存状态及其相互转化关系和生物可利用性.结果显示该区土壤中各形态汞的含量趋势为:有机结合态残渣态可交换态铁锰氧化态碳酸盐结合态,其中有机结合态汞所占比重最大在60%以上,是最重要的赋存形态;土壤中各形态汞不是独立存在的,内部存在一定的转化关系,如碳酸盐结合态汞可以转化成铁锰氧化态、残渣态的汞,而铁锰氧化态的汞与残渣态的汞之间却存在着一定的竞争关系,这种转化关系在外界条件的影响下处于一种动态平衡状态;土壤中的可交换态和有机结合态是较容易被植物吸收利用有效态的汞,其他形态汞被植物吸收较少.     

长春市土壤微生物生化作用与重金属化学形态关系研究

研究了长春市土壤微生物的生化作用强度（氨化作用强度、固氮作用强度,纤维素分解强度和土壤基础呼吸）与重金属（Pb、Cd、Cu、Zn和Ni）化学形态的关系。通过科学采样和实验室测试分析了不同功能区土壤中,重金属含量和化学形态与微生物生化作用强度,并使用相关分析、偏相关分析多种数据统计方法进行数据处理。结果表明：各功能区因土地利用方式的差别和土壤中重金属的各种化学形态对土壤微生物生化作用强度有不同的影响。其中氨化作用与交换态Cd、Zn和Ni含量呈显著正相关;固氮作用与土壤重金属各化学形态相关性均不显著;呼吸作用与铁锰氧化物结合态Pd和交换态Cu呈显著正相关;纤维素分解作用强度与交换态Pd含量呈显著负相关。在土壤理化性质等相关变量受控时,重金属化学形态对微生物生化作用强度的影响有较明显的变化。其中与无控制变量相比,在控制变量作用下,纤维素分解作用强度受交换态Pd影响上升了0.0314,表现为交换态Pd抑制纤维素分解作用强度。呼吸作用与交换态Pd的相关系数在无控制因素情况下为-0.1425,在有控制因素情况下为-0.3230,表明交换态Pd促进呼吸作用强度。而有机结合态Ni表现为抑制固氮作用。因此可利用交换态Pd与纤维素分解作用强度、呼吸作用强度的相互关系,有机结合态Ni与固氮作用的相互关系等相结合来评价城市土壤重金属污染状况。文章为评价长春城市土壤重金属污染提供了微生物学指标的理论依据。     

大气PM_(2.5)中重金属的化学形态分布

运用多级连续提取法,对广州市不同季节不同采样高度大气PM2.5中重金属的化学形态和生物有效性进行分析。研究表明,PM2.5中各重金属元素之间的化学形态分布差异较大,Zn、Cd、As、Mn主要分布在F1(可溶态与可交换态)和F2(碳酸盐态、可氧化态与可还原态),绝大部分的Pb以F2存在,Ni和Mo主要分布在F1和F3(有机质、氧化物与硫化物结合态),Cu主要以F2和F3存在,Cr主要分布在F3和F4(残渣态),Co则4种形态平均分布。采样高度对重金属的化学形态分布影响不大,同一采样期内楼顶与地面样品中同一元素的化学形态分布结果比较一致。两个采样季节重金属的形态百分比存在不同程度的变化,2007年春重金属的不稳定态(F1)比例比2006年秋普遍增加,次稳定态(F2、F3)比例减少。在10种重金属中,Cd、Zn、Pb和As的生物有效性系数高(>0.7),属于生物可利用性元素,在环境中的活动性要明显高于其它元素;Mn、Cu、Mo、Co、Ni和Cr元素的生物有效性系数值在0.2～0.6之间,属于潜在生物有效性元素,在环境中比较稳定。     

大气PM2.5中重金属的化学形态分布

运用多级连续提取法,对广州市不同季节不同采样高度大气PM2.5中重金属的化学形态和生物有效性进行分析。研究表明,PM2.5中各重金属元素之间的化学形态分布差异较大,Zn、Cd、As、Mn主要分布在F1(可溶态与可交换态)和F2(碳酸盐态、可氧化态与可还原态),绝大部分的Pb以F2存在,Ni和Mo主要分布在F1和F3(有机质、氧化物与硫化物结合态),Cu主要以F2和F3存在,Cr主要分布在F3和F4(残渣态),Co则4种形态平均分布。采样高度对重金属的化学形态分布影响不大,同一采样期内楼顶与地面样品中同一元素的化学形态分布结果比较一致。两个采样季节重金属的形态百分比存在不同程度的变化,2007年春重金属的不稳定态(F1)比例比2006年秋普遍增加,次稳定态(F2、F3)比例减少。在10种重金属中,Cd、Zn、Pb和As的生物有效性系数高(>0.7),属于生物可利用性元素,在环境中的活动性要明显高于其它元素;Mn、Cu、Mo、Co、Ni和Cr元素的生物有效性系数值在0.2～0.6之间,属于潜在生物有效性元素,在环境中比较稳定。     

Seasonal Variations and Chemical Forms of Heavy Metals in Soils and Dusts from the Satellite Cities of Seoul, Korea

This research investigated heavy metal pollution of soils and dusts in two representative satellite cities of Seoul, Korea and studied the seasonal variations in metal concentrations through the rainy season and the chemical forms of metals using a sequential extraction analysis. The metal dispersion pattern was illustrated to match with urban structure. Soil and dust samples were collected from the cities of Uijeongbu and Koyang, which are the northern and northwestern satellite cities of Seoul (the capital), before and after rainy season. Concentrations of Cu, Pb and Zn were higher than those of the world averages for soils, and their levels decreased after rain, particularly in highly contaminated samples. Relatively high pH values were found in roadside soils, but no seasonal variation was found after the rainy season. The three metals (Cu, Pb and Zn) in soils and dusts were associated with various chemical fractions of soils and dusts as distinguished by the sequential extraction scheme, and a strong similarity of metal association between soils and dusts was found, which indicates that airborne dust may be a principle source of soil contamination. Copper is uniformly distributed, and Pb is largely associated with the reducible phase. There is an appreciable proportion of total Zn in the exchangeable/water-acid soluble fraction. After the rainy season, the most soluble fractions in soils and dusts were leached away. In terms of mobility and bioavailability of metals in soils and dusts, the order Zn >> Cu > Pb is suggested. Geographical variations of total metals corresponded well with urbanised areas of cities, especially the industrial complex and major motorways.     

农田重金属污染原位钝化修复研究进展

污染土壤重金属原位钝化修复是通过向土壤中施加一些活性钝化修复材料,通过溶解沉淀、离子交换吸附、氧化还原、有机络合等反应来改变重金属在土壤中的赋存状态,降低土壤中重金属的有效浓度、迁移性和生物有效性。这种方法成本较低、操作简单、见效快且适合大面积推广,在重金属污染土壤修复中有着不可替代的作用。尤其对主要由污水灌溉、大气沉降等造成的农田土壤面源污染,一些具有吸附固定土壤中重金属离子特性的天然物质和工业副产品都可运用在实地的钝化修复中,且不同类型的钝化修复剂对重金属污染土壤的钝化修复效果各不相同。采用实验室评价和实地应用评价,一方面可以评估钝化修复材料对污染土壤中重金属离子的固定效率;另一方面可以评估钝化修复材料对土壤理化性状、养分状况和生物活性的影响。对重金属污染土壤原位钝化修复中不同来源的钝化剂进行了分类,目前广泛使用的钝化修复剂主要包括硅钙物质、含磷材料、有机物料、黏土矿物、金属及金属氧化物、生物碳及新型材料等,概述了它们各自对重金属污染土壤的钝化修复效果。从研究方法、评价指标、环境影响因子、钝化机制以及环境风险评价等方面分析了该领域的研究现状以及存在的主要问题,今后应重点关注钝化修复剂对土壤-作物系统的潜在环境风险以及钝化材料修复效果的田间长期稳定性评价。     

湘南某矿区菜园土中典型重金属的形态分析

分别运用Tessier连续提取法和Leleyter连续提取法研究湘南某矿区菜园土中Pb,Zn,Cu和Cd的形态分布特征.结果表明：菜园土中Pb,Zn,Cu和Cd的总浓度严重超过国家土壤环境质量标准.Pb,Zn,Cu和Cd的主要形态是残渣态,水溶态和交换态所占比例较小.重金属生物可利用性的研究表明,Pb,Zn,Cu和Cd生物可利用的含量较少;在Tessier方法中,除Cu之外,生物不可利用态是主要形态,其次是潜在生物可利用态,而在Leleyter方法中,潜在生物可利用态是主要形态,其次是生物不可利用态.     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

Role of plant growth promoting rhizobacteria in the remediation of metal contaminated soils

Pollution of the biosphere by the toxic metals is a global threat that has accelerated dramatically since the beginning of industrial revolution. The primary source of this pollution includes the industrial operations such as mining, smelting, metal forging, combustion of fossil fuels and sewage sludge application in agronomic practices. The metals released from these sources accumulate in soil and in turn, adversely affect the microbial population density and physico-chemical properties of soils, leading to the loss of soil fertility and yield of crops. The heavy metals in general cannot be biologically degraded to more or less toxic products and hence, persist in the environment. Conventional methods used for metal detoxification produce large quantities of toxic products and are cost-effective. The advent of bioremediation technology has provided an alternative to conventional methods for remediating the metal-poisoned soils. In metal-contaminated soils, the natural role of metal-tolerant plant growth promoting rhizobacteria in maintaining soil fertility is more important than in conventional agriculture, where greater use of agrochemicals minimize their significance. Besides their role in metal detoxification/removal, rhizobacteria also promote the growth of plants by other mechanisms such as production of growth promoting substances and siderophores. Phytoremediation is another emerging low-cost in situ technology employed to remove pollutants from the contaminated soils. The efficiency of phytoremediation can be enhanced by the judicious and careful application of appropriate heavy-metal tolerant, plant growth promoting rhizobacteria including symbiotic nitrogen-fixing organisms. This review presents the results of studies on the recent developments in the utilization of plant growth promoting rhizobacteria for direct application in soils contaminated with heavy metals under a wide range of agro-ecological conditions with a view to restore contaminated soils and consequently, promote crop productivity in metal-polluted soils across the globe and their significance in phytoremediation.     

Soil remediation using in situ immobilisation techniques

The main objective of this study was to investigate the efficiency of different substrates to reduce the extraction of heavy metals concentration in a heavily contaminated soil. Two contaminated soils by Cu and Zn were used to evaluate the effectiveness of eight substrates (calcium carbonate, bentonite, kaolinite, charcoal, manganese oxide, iron oxide, zeolite, phosphate) to reduce metal availability and to study the change of metals speciation in different forms using sequential extraction technique (single step). Sequential extraction technique (single step, 0.11 M acetic acid, HONH₃Cl, H₂O₂+NH₄OAc, Aqua regia) was applied on contaminated soils after and before treatment to evaluate metals speciation. Results indicate that the most effective treatments in decreasing available metal concentrations were calcium carbonate, zeolite and manganese or iron oxide. Metal sequential fractionations indicate that the exchangeable fraction of Cu and Zn in contaminated soils can be transformed into unavailable forms after chemical remediation.     

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.     

土壤环境中镉、锌形态转化的探讨

论述了土壤中镉、锌的形态分布，讨论了影响土壤环境中Cd、Zn形态转化的因素和物质，如pH、石灰、有机质和其它一些离子和它们的影响机制，为治理土壤重金属污染提供理论依据。     

植物吸收修复对土壤镍及其主要化学性质的影响

采用室内盆栽试验方法,研究了外源镍污染土壤的植物吸收修复对土壤镍形态和土壤主要化学性质的影响。试验用水稻土添加NiSO4·6H2O(100～1600mgkg-1)经过12周的驯化培养后,种植了镍超累积植物Alyssu mmurale,110 d后收获植物并进行了试验土壤镍的形态和主要化学性质的分析,采用再分配系数和结合强度系数对植物修复效果进行了定量分析。结果表明,根区土壤中DTPA提取态镍的数量明显减少,根区土壤DTPA-Ni与非根区土壤DTPA-Ni之比的范围在0.33～0.61之间。每盆植物提取镍量为6.61～31.18mg,植物提取量随着添加镍量增加而增加,地上部分最大镍含量达到12454.1mgkg-1。根区的再分配系数在2.17～4.19之间,而非根区的再分配系数在6.87～15.91之间,再分配系数随着镍添加量的增加而增大;根区的结合强度系数为0.84～0.39,而非根区的则为0.88～0.26,随着土壤中镍添加量的增加,结合强度系数逐渐减小。植物吸收修复后,根区土壤镍的再分配系数降低、结合强度系数增大,表明土壤镍各形态之间的稳定性增加,因此植物修复可以加快外源镍在土壤中的稳定。试验结果也表明,根区土壤中pH随着镍添加量的增加呈下降趋势、但较非根区土壤的高;根区土壤有机碳亦较非根区的高。