根瘤菌对土壤铜、锌和镉形态分配的影响

以湖南郴州红壤和河北巩义褐土为供试土壤。制备Cu、Zn、Cd污染土壤。接种大豆根瘤菌(Rhi-zobium fredii)HN01,用连续提取法浸提土壤中不同形态的重金属．结果表明。褐土接种根瘤菌后固相结合态Zn总量降低10％。专性吸附态、氧化锰结合态和有机结合态Zn减少达9％～26％．红壤中结合态Zn的总量变化不显著,但专性吸附态和氧化锰结合态Zn含量显著减少。交换态Zn含量显著增加．褐土中接种根瘤菌抑制了Cu向土壤溶液的释放,固相结合态Cu总量增加18％,可交换态、专性吸附态、氧化锰结合态和有机结合态的Cu增加20％～54％．接种根瘤菌对土壤中Cd的溶解没有明显的抑制或促进作用,但改变了红壤中各形态Cd的含量高低顺序．Cd污染红壤中可交换态和有机结合态Cd含量分别增加22％和11％,专性吸附态和氧化锰结合态Cd分别减少14％和29％．根瘤菌对不同类型重金属及不同土壤中重金属形态影响的差异主要与土壤pH降低有关．     

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.     

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.     

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。     

利用乙二胺四乙酸淋洗修复重金属污染的土壤及其动力学

通过室内模拟试验,采用振荡淋洗的方法研究了乙二胺四乙酸(EDTA)浓度、pH、淋洗时间对重金属去除效果的影响.利用一级反应动力学模型对试验数据进行拟合,并测定了EDTA处理前后土壤中重金属形态的变化.结果表明,EDTA溶液在浓度为0.1 mol·L^-1、pH 7、淋洗时间1 d的条件下能达到对污染土壤重金属的最大去除率,去除率分别为Cd 89.14%、Pb 34.78%、Cu 14.96%、Zn 45.14%.模型拟合结果表明,Cd的质量转移系数最大,其次是Zn、Pb和Cu.说明在土壤淋洗过程中,Cd和Zn最先达到质量转移的平衡状态,然后是Pb和Cu.形态分级结果表明,EDTA能有效地去除交换态、碳酸盐结合态和氧化物结合态重金属,而对有机态和残余态部分重金属作用效果不明显.     

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.     

海口城市土壤重金属污染特征与生态风险评估

对海口城市土壤重金属含量、空间分布特征与赋存形态进行了研究,并评估了其生态风险。结果表明,海口城市土壤重金属Hg、As、Cd、Cu、Cr、Ni、Pb、Zn的平均含量分别为0.073、3.82、0.25、26.7、92.4、52.5、29.1和84.1 mg·kg-1。与海口土壤背景值相比,海口城市土壤明显富集重金属Hg、As、Cd、Cu、Cr、Ni、Pb和Zn,受到一定程度重金属污染。Cr、Ni、Cu、Cd和Zn元素主要在郊区富集,Pb主要在路边绿化带中富集,Hg主要在生活区富集。海口城市土壤中Zn、As、Cr、Cu和Ni以残渣态为主,Hg主要以强有机态和残渣态存在,Pb主要以铁锰氧化态和残渣态存在,而Cd则主要以生物可利用态为主。生态风险评价结果显示,海口城市土壤重金属综合生态风险属于微弱水平,但Cd和Hg污染应引起重视。     

好氧高温猪粪堆肥中重金属砷、铜、锌的形态变化及钝化剂的影响

采用连续提取法研究了猪粪好氧堆肥处理中重金属浓度和形态的变化以及添加不同比例的重金属钝化剂对其浓度和形态的影响.结果表明：经过堆肥处理后,猪粪中重金属As、Cu和Zn的总浓度均有所增加.从重金属结合形态的变化来看,可交换态As和Zn含量降低,残渣态As和Zn含量升高,表明As和Zn存在着向有效性相对较低的形态转化的趋势;重金属Cu则表现出不同的变化趋势,即可交换态与残渣态Cu含量下降,而碳酸盐结合态、铁锰结合态及有机结合态Cu含量有所增加,在今后的堆肥利用中应注意其可能带来的环境风险;3种重金属钝化剂及不同添加比例的处理中,5.0%的海泡石和2.5%的膨润土分别对重金属As、Zn表现出较好的钝化效果,堆肥后残渣态As和Zn的增幅分别达到79.8%和158.6%,均高于不加钝化剂处理.与对照相比,堆肥后7.5%的海泡石对残渣态Cu的降低幅度最小,为39.3%.猪粪堆肥中添加适量的重金属钝化剂,可以在一定程度上降低重金属的有效性以及猪粪堆肥利用中重金属污染的风险.     

强还原过程对设施菜地土壤重金属形态转化的影响

设施菜地由于污水灌溉、粪肥施用等导致重金属污染.本文通过土柱淹水同时添加玉米秸秆培养和后期通水淋洗,研究强还原法对设施土壤重金属(Cd、Cu、Pb和Zn)形态转化的影响.结果表明: 强还原处理使土壤pH显著降低,玉米秸秆处理变化更显著;土壤氧化还原电位(Eh)迅速下降至-280 mV左右.玉米秸秆处理可以促进土壤中Cd、Cu、Pb和Zn活化,第9天土壤中有机物及硫化物结合态和残渣态Cd、Cu、Pb和Zn含量比重下降;至15 d培养结束,土壤中4种重金属含量较对照分别减少18.1%、19.0%、16.1%和15.7%.玉米秸秆处理可以增加土壤中Cd和Zn的溶出量,但是Cu的溶出量减少;胶体结合态Cd和Pb含量较对照增加、Cu较对照显著减少、Zn没有显著变化.强还原可以引起设施土壤重金属活化,提高蔬菜积累重金属的风险,而且其随土壤水分的运移可能导致水体的污染.     

Heavy metals in human hair and teeth

Biological samples were collected simultaneously with environmental quality investigations. Studies of metal levels in biological (hair and teeth) and environmental (soil and air) samples were performed in Zwardoń during 1991/1992. Zwardoń is a small mountain resort village, situated on the border pass of Zwardoń, in the close proximity of the southwestern border of Poland. Heavy metal levels in soil, air, and chemical metals forms in the soil were examined. Pearson’s product correlation in soil (for total concentration of heavy metals and each chemical form) in hair and in teeth was calculated to investigate bioavailability of heavy metals in human organism. We received essential correlations simultaneously between: Pb vs Mn in exchangeable form of metal in soil, in teeth and in soil (total); Cd vs Zn and Mn vs Co in organically bound form in soil and in teeth and soil (total); and Cu vs Zn in all investigated samples (teeth, hair, soil total, and organically bound form in soil); Mn vs Co and Cr vs Mn in residual form in soil, in teeth, and in soil (total) and between Co vs Ni for hair, soil (total), and residual form in soil.     

Assessment of Heavy Metal Pollution in Water and Sediments from the Ghalechay River,Baychebagh Copper Mine Area,Iran

The concentrations of selected heavy metals in sediments and waters in Baychebagh copper mine were determined using ICP-OES. Except for Co, the average concentrations of Cd, Cu, Pb, and Zn in sediments from the Ghalechay River in the district exceed the world-average shale and continental upper crust value. Enrichment factors for Pb, Cu, and Cd were significantly enriched in sediments, indicating environmental contamination. Geoaccumulation index calculated for different sampling stations indicates that the sediments are unpolluted with respect to Co and Zn while unpolluted to moderately polluted with Cu and highly polluted with Pb and Cd. The Sediment Quality Guidelines (SQGs) suggest that Cd and Pb may pose the highest risk for the environment. Sequential extraction analyses of sediments revealed that Cu, Co, Pb, and Zn bound to extractable, carbonate, reducible and oxidizable fractions are lower than residual fraction. About 10% of the total Pb was associated with the exchangeable fraction, indicating remobilization, while Cd (89%), Pb (73%) Co (58%), Cu (76%), and Zn (68%) closely associated with the residual and oxidizable fractions, resulting in their environmental immobility. The residual forms are not expected to be released under normal conditions in the river and could be considered an inert phase.     

Effect of phosphorus application on transformation of zinc fraction in soil and on the zinc nutrition of lowland rice

We have studied in the laboratory the effect of different levels of P application on the transformation on native as well as of applied zinc in a rice-growing soil under two moisture regimes viz., flooded and nonflooded. Application of P caused a decrease in the water soluble plus exchangeable and organic complexed with a concomitant increase in the amorphous and crystalline sesquioxide bound forms of native soil zinc. Application of P also caused a decrease in the transformation of applied Zn into the water soluble plus exchangeable and organically complexed and an increase in the amorphous and crystalline sesquioxide bound forms of zinc. The above effects of P were more pronounced in soil under flooded than under nonflooded moisture regimes. The water soluble plus exchangeable and the organically complexed forms of Zn are considered to play an important role in Zn nutrition of lowland rice, while the role of the amorphous and crystalline sesquioxide bound forms are less important in this regard.The results of greenhouse experiments showed that P application caused a progressive decrease in the Zn concentration in shoot and root. This was attributed at least partly to the decrease in the water soluble plus exchangeable and organically complexed forms of Zn and an increase in the amorphous and crystalline sesquioxide bound forms in soil due to P application.     

Sequential extraction and speciation of Ba,Cu, Ni,Pb and Zn in soil contaminated with automotive industry waste

Abstract

Sequential extraction or fractionation of heavy metals in the solid phase and their speciation in soil solution are important tools for assessing changes resulting from land use and/or pollution. The distribution of the various forms of Ba, Cu, Ni, Pb and Zn was evaluated in soil samples taken from a polluted area, and the speciation of cations and anions in a soil solution contaminated with automotive industry waste. We evaluated the sequential extraction and speciation of Ba, Cu, Ni, Pb and Zn in a Leptosol associated with a Cambisol and contaminated with automotive industry waste. Soil samples were collected at 0-0.2 m (a mix of soil and waste); 0.2-0.4 m (waste only), and 0.4-0.6 m (soil only) both in the polluted area and in two contiguous unpolluted areas: a sugarcane plantation and a forest fragment. Total concentrations of metals in the polluted area were above limits for intervention established by European Community regulations. Cu was mostly distributed in the residual and in the oxide-bonded fractions, except for the waste-only sample, in which the carbonate-bonded fraction was significant. Zn was concentrated in the residual and carbonate-bonded fractions, while Ba, Ni and Pb predominated in the residual fraction of the contaminated samples. Metals in the soil solution were predominantly in the hydroxyl forms, except for Ba, which was mostly in the ionic form (Ba²⁺).     

铜尾矿库区狗牙根根际土壤铜的形态变化

通过野外调查和室内分析,对安徽省铜陵市铜尾矿库区狗牙根根际土壤Cu的形态进行了研究．结果表明,尾矿库区狗牙根根际与非根际土壤Cu大部分为矿物态Cu,交换态Cu含量偏低．与非根际土壤相比,狗牙根根际土壤pH值下降,有机质含量显著增加．随着狗牙根的生长,根际土壤有机结合态Cu和交换态Cu含量显著增加,其占土壤总Cu量的比例分别增加7．89％和超过5％,碳酸盐结合态Cu和铁锰氧化物结合态Cu含量则有所下降．狗牙根生长促进了根际土壤Cu形态的转化,提高了Cu在土壤中的迁移能力,加之狗牙根的吸收作用,其根际土壤Cu含量显著降低．     

Operationally determined chemical speciation of barium and chromium in drilling fluid wastes by sequential extraction

ABSTRACT

A study has been conducted to determine the influence of pH on the speciation and distribution of barium and chromium in drilling mud. Samples in equilibrium under controlled conditions were subjected to sequential extraction procedure to fractionate the heavy metals into the designated forms of exchangeable, adsorbed, organically bound, carbonate and residual phases. This provides an insight into the potential availability of the heavy metals for possible release into groundwaters and/or surface waters. The major portion of both the metals studied was found in the carbonate and residual forms with the relative distribution depending on the pH. Generally, decreasing pH caused a shift from the residual form towards the carbonate or organic forms of metals. The occurrence of metals in more stable organic, carbonate and residual forms in drilling mud, coupled with no significant release to the aqueous phase upon varying the pH indicates the resistance of these metals to remobilisation from drilling mud.     

Heavy Metal Partitioning in Bottom Sediments of the Matanza-Riachuelo River and Main Tributary Streams

This study provides geochemical partitioning, potential bioavailability, and enrichment of Cd, Cu, Pb, and Zn in bottom sediments collected from the Matanza-Riachuelo River and its main tributary streams. A modified Tessier sequential extraction procedure, complemented with acid volatile sulfide (AVS) and simultaneous extracted metals (SEM) measurements, was applied to determine the partitioning of metals into four fractions (metals bound to amorphous sulfide, carbonate, and exchangeable), bound to Fe/Mn oxides (reducible), bound to organic matter/sulfide (oxidizable) and residual. Spatial and vertical distributions of metals were studied. The core sediments show a decreasing concentration of metals with depth. In top sediments, non-residual Cu was mainly associated with oxidizable phase, whereas Pb, Cd, and Zn were mainly associated with amorphous sulfide. Pb exhibited the highest enrichment in all sites. The ratio AVS/SEM was greater than one at sediment sections close to the water column, indicating that metals extracted with hydrochloric acid were mainly associated with the amorphous sulfide. The strong influence of amorphous sulfide in the retention of Cd, Pb, and Zn in anoxic sediments of Matanza-Riachuelo river system suggests that dredging and aeration could lead to the remobilization of metals from sediments to the water column, hence making the metals more available to the biota.