水稻籽实对不同形态重金属的累积差异及其影响因素分析

在分析成都平原核心区土壤重金属（Cd、Cr、Pb、Cu、Zn）全量、各形态含量及相应点位种植的水稻籽实重金属含量的基础上，通过统计分析、空间插值及线性回归方程的模拟，研究了土壤Cd、Cr、Pb、Cu、Zn全量的空间分布状况、各形态重金属含量统计特征，以及水稻籽实对重金属各形态的累积差异及其影响因素。结果表明，成都平原水稻土重金属污染较轻，除Cd外，均低于国家土壤环境质量二级标准。土壤中重金属的可交换态含量均较低，Cd主要以铁锰氧化态存在，Cr、Cu、Zn、Pb主要以残渣态存在。水稻籽实对5种重金属的累积效应顺序为：Cd＞Zn＞Cu＞Pb＞Cr。与水稻重金属累积关系密切的重金属活性形态（可交换态、碳酸盐结合态、铁锰氧化物结合态和有机物结合态）主要有：Cd的碳酸盐结合态、Cr的可交换态、Pb的有机物结合态和Cu的碳酸盐结合态含量；Zn各活性形态对水稻籽实含量的影响不明显。土壤理化性质对不同活性形态重金属元素的影响效应各不相同。活性态Cd主要受有机质、pH和容重的影响；活性态Cr与pH、有机质、CEC和容重密切相关；活性态Pb与有机质、容重、中细粉粒、砂粒等均有密切的关系；Cu的活性主要受粘粒、有机质含量的影响；Zn的有效性主要受pH、有机质、砂粒、容重的影响。总的看来，对土壤Cd、Cr、Pb、Cu、Zn各活性形态含量影响效应较强的是有机质、pH、容重，而与土壤吸附性能密切相关的颗粒组成、CEC的影响不甚明显。     

泉州走马埭典型土壤重金属的赋存形态分析

采用改进的Tessier连续萃取方法研究了泉州走马埭国家农田示范保护区典型土壤中重金属(Cr、Ni、Cu、Zn、Cd、Pb)的化学形态分布,通过土壤重金属的赋存形态分析比较了6种重金属的生物可利用性。研究结果表明,土壤中不同重金属元素化学形态分布具有不同的特点:Cr和Ni主要以残渣态存在,其余形态所占的比例很小;Cu以残渣态含量最高,碳酸盐结合态含量最低;Zn以残渣态为主,可交换态含量最低;Cd以可交换态和碳酸盐结合态为主,水溶态含量最低;Pb以残渣态和铁锰氧化物结合态为主,水溶态含量最低。土壤中除Cd外,Zn、Cu、Cr、Pb、Ni在正常自然条件下相对比较稳定。     

苏南经济快速发展区土壤Cu、Ni、Pb、Zn形态及其有效性定量分析——以昆山市为例

研究了江苏省昆山市农田土壤有效态Cu、Ni、Pb、Zn各形态含量及其有效性。结果表明,土壤重金属Cu、Ni、Pb、Zn各形态含量以残渣态有机质结合态铁锰氧化物结合态碳酸盐结合态、可交换态,残渣态含量明显高于其他形态。Cu和Pb有机质结合态所占比例相对也较高,分别达36.09%和28.30%。土壤可交换态含量、碳酸盐结合态含量、Fe-Mn氧化物结合态含量及残渣态含量均以Zn最高;土壤有机质结合态含量以Cu最高;土壤可交换态含量变异系数、土壤碳酸盐结合态含量变异系数及土壤Fe-Mn氧化物结合态含量变异系数以Ni为最大;土壤有机质结合态含量变异系数以Zn最大;土壤残渣态含量变异系数以Pb最大。土壤铁锰氧化物结合态铜和可交换态铜对土壤有效态铜含量影响最大;土壤可交换态镍含量对土壤有效态镍含量最大;土壤铁锰氧化物结合态铅和有机质结合态铅对土壤有效态铅含量影响最大;土壤可交换态锌和碳酸盐结合态锌对土壤有效态锌含量影响最大。     

长春市城区土壤中Pb、Cu、Zn、Cd及Cr化学形态特征

为弄清长春市城市土壤中Pb、Cu、Zn、Cr及Cd的化学形态分布特征,系统采集了26件城市表层(0~20 cm)土壤样品,采用连续提取法对重金属各化学形态含量进行了测定。结果表明:Pb、Zn、Cu及Cr主要以残渣态存在,其次是铁锰氧化物结合态、腐殖酸结合态和强有机结合态占有次要地位,离子交换态和水溶态所占比例均较低;Cd则主要以碳酸盐结合态存在,同时,水溶态和离子交换态所占比例较高。残渣态Pb和Zn在城区表层土壤中所占比例较近郊土壤中略有下降,但幅度不大,除Cu外,其余各元素易迁移、高生物有效性的水溶态在城区表层土壤中所占比例略有上升。Pearson相关分析结果表明,各元素残渣态与全量均呈极显著正相关,其它各活性态与全量间的相关程度与重金属种类有关。土壤pH值和Fe、Mn含量对重金属的化学形态的影响也与重金属种类有关,而且,同一重金属的不同存在形态受土壤pH值和Fe、Mn含量的影响程度也不同。     

海南岛砖红壤中铅、镉的化学形态与转化

采用土培实验和连续提取.原子吸收分光光度法,研究了重金属Pb、Cd在海南岛花岗岩砖红壤中的形态组成、外源Pb、Cd污染及化学修复剂磷、钙、硫对土壤重金属形态的影响.结果表明:在供试原土壤中,重金属Pb的化学形态以结合态和残余态为主,土壤有效态Pb含量较低,其中残余态Pb>有机质结合态Pb>铁锰氧化物结合态Pb>碳酸盐结合态Pb>交换态Pb>水溶态Pb,说明土壤Pb的环境风险较低;重金属Cd的化学形态以铁锰氧化物结合态和碳酸盐结合态为主,土壤中交换态Cd含量较高,其中铁锰氧化物结合态Cd>碳酸盐结合态Cd>交换态Cd>有机结合态Cd>残余态Cd>水溶态Cd,说明土壤Cd的环境风险较高.当外源Pb、Cd污染土壤时,有铁锰结合态Pb>残余态Pb>有机态Pb>碳酸盐结合态Pb>交换态Pb>水溶态Pb,交换态Cd>铁锰氧化物结合态Cd>碳酸盐结合态Cd>残余态Cd>有机态Cd>水溶态Cd的趋势.向污染土壤施加化学改良剂过磷酸钙、硫化钠和石灰,能显著降低水溶态Pb、Cd和交换态Pb、Cd的含量,并使有机结合态Pb、碳酸盐结合态Pb和铁锰氧化物结合态Pb含量下降,但残余态Pb、碳酸盐结合态Cd、铁锰氧化物结合态Cd和有机态Cd有增加的趋势,残余态Cd的含量基本稳定.     

长期施用畜禽养殖废弃物下潮土重金属的累积特征

通过田间试验研究了畜禽养殖废弃物长期施用(2001—2013年)对重金属(Cr、Cu、Zn、Pb、Cd、As)在潮土中累积、形态转化及迁移行为的影响。试验设置畜禽养殖废弃物(猪粪,OM)和化肥氮磷钾(NPK)两个处理,每处理设置3个重复。结果显示,畜禽养殖废弃物的长期施用造成Cu、Zn在OM处理土壤中的含量明显高于NPK处理,并主要累积于耕层土壤(0~20 cm),但总体含量(Cu:38.71 mg/kg;Zn:83.26 mg/kg)较低,对农田生态安全的影响较小。形态分析结果显示,OM处理土壤中DTPA络合态、弱酸结合态和铁锰结合态Cu、Zn、As的含量均显著高于NPK处理,但不同形态Cr、Pb、Cd在两种处理土壤中的差异相对较小。其中,Cr主要以非提取态的形式存在(Cr95%)。外源性Cu易累积于非提取态(52%),而Zn则以弱酸溶解态(40%)和铁锰结合态(60%)为主。畜禽养殖废弃物的农田施用不仅是土壤重金属的重要来源,也是土壤重金属活性提高的重要原因,并造成部分重金属在剖面土壤中发生明显迁移行为,累积于更深层土壤中。     

基于区间线性规划理论的水稻土重金属Cd形态限量标准研究

应用生态环境效应法,借助区间线性规划理论,以稻谷Cd与活性形态(可交换态、碳酸盐结合态、铁锰氧化物结合态和有机物结合态)Cd含量间的线性回归模拟方程为目标函数,以稻谷Cd限量卫生标准为限制条件,筛选各约束条件下的最大最优值为各活性形态Cd含量的限量标准,为成都平原土壤重金属污染控制提供参考,为深入研究基于生物有效性的土壤重金属限量标准的制定提供科学依据。结果表明,土壤Cd活性形态限量标准分别为:可交换态Cd≤0.0865 mg/kg,碳酸盐结合态Cd≤0.2641 mg/kg,铁锰氧化物结合态Cd≤0.2461 mg/kg,有机物结合态Cd≤0.0760 mg/kg。     

新乡市环宇大道工业区周边土壤重金属的污染特征和评价

通过实地采样及室内化学分析的方法,研究了新乡市环宇大道工业区周边土壤Pb、Cd、Ni、Zn、Cu和Cr 6种重金属污染特征和风险评价,并应用Tessier五步连续萃取的方法对土壤中超标的Cd,Ni和Zn进行形态分析。结果表明:(1)土壤中Pb、Cd、Ni、Zn、Cu和Cr的平均含量分别是63.08 mg kg-1、176.85 mg kg-1、307.2 mg kg-1、485.6 mg kg-1,38.7 mg kg-1和47.9 mg kg-1,Pb、Cu、Cr平均含量达标,Cd、Ni、Zn平均含量均超标,分别是国家土壤环境质量二级标准的176.85、5.12、1.62倍。(2)Ni和Zn主要以铁锰氧化物结合态和残渣态存在,Cd主要以铁锰氧化物结合态存在,其次为碳酸盐结合态,3种重金属的迁移能力依次为:Cd>Zn>Ni。(3)每种重金属都存在不同程度的潜在生态风险,Cd的潜在生态风险最大并构成了很强的危害。     

安徽主要水稻土中重金属形态分布与土壤酶活性研究

通过野外调查和实验分析,对安徽几类不同地貌下的水稻土中重金属Cu、Zn、Pb的化学形态特征及其与4种土壤酶活性间的关系进行了研究.结果表明:3种不同地区水稻土中,残留态和有机态Cu、Zn、Pb含量在总量中所占比例最高.平原和丘陵地区水稻土中有机结合态Cu、Zn、Pb明显高于山区;而山区水稻土中Fe-Mn氧化物结合态Cu、Zn、Pb相对含量高于平原和丘陵地区.在水稻土中,碳酸盐结合态Cu、Zn对过氧化氢酶活性的抑制作用最大,交换态Pb对脲酶活性的抑制作用最大.反映水稻土Cu、Zn污染用碳酸盐结合态Cu、Zn和过氧化氢酶活性指标,而反映Pb污染用交换态Pb和脲酶活性指标是可行的.     

皖南茶园土壤重金属化学形态及其生物有效性

以皖南茶园为研究对象,通过Tessier连续提取分级法对茶园土壤重金属(Zn,Cu,Pb,Ni)全量及其化学形态进行了分析,利用活性态重金属占全量之比来评价其生物有效性。结果表明,皖南茶园土壤中Zn,Cu,Pb,Ni含量均未超过国家标准;除Zn外,其他元素均高出背景值,存在较明显的富集现象;土壤中4种重金属在5种形态上表现出不同的分布规律,Zn,Cu,Ni以残渣态为主,分别占总量的72.55%,90.00%和81.79%,而Pb以铁锰氧化物结合态为主,占总量的70.09%;Zn,Cu,Pb,Ni的活性态部分占全量比例分别为5.04%,1.51%,0.97%和0.23%,土壤重金属活性态部分与茶叶中重金属含量之间呈现正相关关系,且皖南茶区的茶叶重金属含量在限量值的安全范围内。     

Relationship Between Extractable Metals in Acid Soils and Metals Taken Up by Tea Plants

Abstract

The accumulation of heavy metals in plants is related to concentrations andchemical fractions of the metals in soils. Understanding chemical fractions and availabilities of the metals in soils is necessary for management of the soils. In this study, the concentrations of copper (Cu), cadmium (Cd), lead (Pb), and zinc (Zn) in tea leaves were compared with the total and extractable contents of these heavy metals in 32 surface soil samples collected from different tea plantations in Zhejiang province, China. The five chemical fractions (exchangeable, carbonate‐bound, organic matter‐bound, oxides‐bound, and residual forms) of the metals in the soils were characterized. Five different extraction methods were also used to extract soil labile metals. Total heavy metal contents of the soils ranged from 17.0 to 84.0 mgCukg^?1, 0.03 to 1.09 mg Cd kg^?1, 3.43 to 31.2 mg Pb kg^?1, and 31.0 to 132.0 mg Zn kg^?1. The concentrations of exchangeable and carbonate‐bound fractions of the metals depended mainly on the pH, and those of organic matter‐bound, oxides‐bound, and residual forms of the metals were clearly controlled by their total concentrations in the soils. Extractable fractions may be preferable to total metal content as a predictor of bioconcentrations of the metals in both old and mature tea leaves. The metals in the tea leaves appeared to be mostly from the exchangeable fractions. The amount of available metals extracted by 0.01 mol L^?1 CaCl₂, NH₄OAc, and DTPA‐TEA is appropriate extractants for the prediction of metals uptake into tea plants. The results indicate that long‐term plantation of tea can cause sol acidification and elevated concentrations of bioavailable heavy metals in the soil and, hence, aggravate the risk of heavy metals to tea plants.     

Tea Plantation–Induced Activation of Soil Heavy Metals

Abstract

The accumulation of heavy metals in tea leaves is of concern because of its impact on tea quality. This study characterized long‐term changes of soil properties and heavy‐metal fractions in tea gardens and their effect on the uptake of metals from soils by the plants. Soil and tea leaf samples were collected from five plantations with a history of 2–70 years in Jinghua, Zhejiang Province, southeast China. The six chemical fractions (water‐soluble, exchangeable, carbonate‐bound, organic‐matterbound, oxide‐bound, and residual forms) of cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), nickel (Ni), manganese (Mn), lead (Pb), and zinc (Zn) in the soils were characterized. Dissolved organic‐matter accumulation in the soils and effects of low‐molecular‐weight organic acids on solubility of soil heavy metals were also tested. Long‐term tea plantation use resulted in accumulation of dissolved organic matter, decrease of soil pH, and elevation of water‐soluble and exchangeable metal fractions, thereby increasing metal contents in leaves. The influence was more significant when soil pH was less than 4.4. The results indicated that both acidification and accumulation of dissolved organic matter induced by tea plantations were also important causes of increased accumulation of the metals in the tea leaves. This was particularly true for the soils polluted with low concentration of heavy metals, because availability of the metals in these soils was mainly controlled by pH and dissolved organic matter.     

污染水稻土中重金属的形态分布及其影响因素

通过BCR3步提取法研究了江西省贵溪铜冶炼厂污染区水稻土中重金属的形态分布。研究表明,废渣场渗滤液污染区域(渣场区)的污染较污水灌溉污染区(污灌区)严重,渣场区土壤中Cu、Pb、Cd的含量高于污灌区,而污灌区土壤Ni含量较高。在表层(0～20cm)水稻土中,Cu以可氧化态为主,Pb以可还原态和可氧化态为主,Cd以酸溶态为主,Ni以残渣态为主,不同重金属元素的有效态所占总量百分比大小顺序是Cd>Cu>Pb>Ni。土壤重金属不同形态之间也呈现一定的相关性,说明Cu与Pb、Cd、Ni之间具有同源性。土壤pH主要影响了污灌区中Cu的形态分布,以及渣场区土壤酸溶态Ni的分布。土壤有机质含量对各重金属形态分布的影响不明显。     

大宝山矿区农田土壤重金属污染及其植物累积特征

对金属矿山选冶活动影响的农田土壤,不同灌溉水源会影响重金属的分布累积特征。根据实际情况将大宝山矿区农田土壤分为污水灌溉区、清水灌溉区、自然修复区和对照区,并进行土壤和植物样品采集,调查研究了土壤的基本理化性质,Cd、Pb、Cu、Zn、Mn 5种重金属的含量和化学形态分布,以及不同区域植物中重金属的含量。结果表明:污灌区Cd、Pb、Cu、Zn的含量最高,是自然修复区和清水灌溉区的1.75倍~10.51倍,对照区最低;Mn在各采样点的含量无显著差别。土壤Cd、Cu、Zn、Pb含量两两之间显著正相关,Mn与Cu、Zn、Cd、Pb呈负相关关系;土壤pH与重金属环境有效态关系密切。残渣态是5种重金属的主要存在形态,有机态含量也较高;Cd的环境有效态含量占总量的比例是其他4种重金属的2倍左右。稻米中5种重金属在清水灌溉区的含量均比污水灌溉区低,其中Cu和Zn的含量在两区域均未超标(NY861-2004),而Pb和Cd的含量严重超标。重金属在自然修复区和清水灌溉区呈现较低的土壤污染和人体健康风险,该研究数据可为金属矿区土壤污染控制提供科学的依据。     

Effect of Water Quality on Heavy Metal Redistribution and Mobility in Polluted Agricultural Soils in a Semi-Arid Region

Mornag Plain is a coastal area of the Mediterranean basin, which has undergone an agricultural industrial boom. The aim of this study was to investigate the different water qualities used for irrigation on heavy metal mobility in these polluted agricultural soils. The geo-accumulation indices for heavy metals (Ni, Cr, Pb, Cd, Cu, and Zn) revealed that industrial activities and used treated wastewater (TWW) contributed to soil pollution, and water irrigation always decreased this contamination. After long-term use of different water types, high perturbation of heavy metal redistribution has occurred. Groundwater use altered all heavy metal redistributions in the irrigated soil among various soil-solid and soil-solution fractions, as compared to the unirrigated soil. Slight acid water use transferred some metals from different solid phase components into water-soluble and exchangeable fractions. However, TWW use transformed some Ni, Cr, Cd, Cu, and Zn from water-soluble and exchangeable fractions to less labile fractions, particularly into organically bound fractions. Reuse of conventional water within the same soil decreased the whole soil redistribution index values, indicating tendency to return to the pattern of distribution of groundwater-irrigated soil.     

工业和农业污染稻田土壤重金属的赋存形态及水稻吸收运移比较

[目的]稻田土壤重金属污染是当前农产品安全生产关注的重要问题.本文比较分析工业和农业污染源稻田土壤重金属的赋存形态及水稻吸收运移,以期为稻田土壤重金属污染控制提供参考.[方法]在长江中下游地区调查选取工业源和农业源重金属污染稻田各27块,在水稻成熟期使用抖根法采集根际土壤及水稻根系和籽粒样品,采用Tessier七步提取...     

天水苹果园土壤重金属富集状况评价及来源分析

对天水果园表层（0~20 cm）219件土壤样品进行研究,测定5种重金属（Zn、Cu、Pb、Cr和Cd）及有机质含量,以天水小陇山土壤为对照,运用相关分析和主成分分析方法区分土壤中重金属的来源。结果表明,①Zn、Cu、Pb、Cr和Cd含量分别为77.39、23.03、23.62、61.49 mg.kg-1和0.07 mg.kg-1,其中Cd极显著（P〈0.01）高于小陇山土壤,其余4种重金属虽高于小陇山土壤但无显著差异性（P〉0.05）;②研究区土壤Cu、Pb、Cr三者间在0.01或0.001水平上具有显著正相关性,且这3种重金属与土壤有机质具有显著正相关性,其余重金属间不存在显著相关性;③主成分分析显示Cu、Pb和Cr来源相似,主要来自于成土母质,Cd来源于人为施肥因素,Zn的富集受多种因素影响。研究评价结果显示,天水地区果园土壤Cd受人为施肥影响较大,具有一定程度的富集。     

DISTRIBUTION AND SEQUENTIAL EXTRACTION OF SOME HEAVY METALS FROM SOILS IRRIGATED WITH WASTEWATER FROM MEXICO CITY

A sequential extraction procedure was used to fractionate Cu, Cd, Pb and Zn in 4 soil profiles into the designated forms of water soluble + exchangeable, organically bound, carbonate and Mn oxides bound. Soil profiles were obtained from the Rural Development District 063, State of Hidalgo, which have been irrigated with wastewater coming out of the basin of Mexico. The total heavy metal contents range as follows: Cu, 8.9 to 86.5 mg kg^-1 Cd, 0.86 to 5.07 mg kg^-1 Pb, 18.1 to 131.7 mg kg^-1 and Zn, 101 to 235.5 mg kg^-1. The highest concentrations of total heavy metals were found in the surface layers at all soil profiles. Sequential chemical fractionation indicated that the four metals were predominantly associated with the organic fraction at most soil samples. The contents in all fractions of the four metals showed a decrease with depth which has been explained by the variations in the organic matter and CaCO₃ contents in the different layers of soils. These soil properties were also the most important variables in the biological availability of the metals in these soils.     

Long-Term Transformation and Redistribution of Potentially Toxic Heavy Metals in Arid-Zone Soils: II. Incubation at the Field Capacity Moisture Content

Solid-phase transformation of added Cd, Cu, Cr, Ni, Pb and Zn, in two arid-zone soils incubated in the field capacity moisture regime for one year, were studied. The heavy metals were fractionated into six empirically defined fractions using a selective sequential dissolution (SSD) protocol optimized for arid-zone soils. Each of these fractions was named based on the major soil component targeted for dissolution during the specific SSD step, but it is not assumed that they are mineralogically and chemically totally specific. The transformations of the metals in the two soils incubated at the field capacity regime were compared with those at the moisture saturation regime (Han and Banin, 1997). An initial fast stage of transformation of the soluble metals from the exchangeable (EXC) fraction to the less labile fractions (the carbonate (CARB) fraction for Cd, Pb, Zn, Ni and Cu, and the organic matter (OM) fraction for Cr, and to some extent Cu and Ni) occurred during the fractionation and within one hour after addition. This was followed by a second stage, involving long-term transformation processes of all metals: added Cd was transferred from the EXC into the CARB fraction; added Cr was transferred from the CARB to the OM fraction and Pb was transferred very slowly to the easily reducible oxide (ERO) fraction. Added Cu, Ni and Zn were transferred from the EXC and CARB fractions into the ERO fraction and to some extent OM and RO fractions. In Part I of this series, we reported that during incubation in the saturated moisture regime, Zn and Ni were transferred mainly into the RO and OM fractions. Cadmium, Cr and Pb underwent the same transformation pathways during the slow long-term process, with slightly different rates, in both water regimes. At low levels of addition, the incubated soils moved over one year towards a distribution similar to that of the native soil. At higher levels, the soils still remained removed from the quasi-equilibrium which characterized the native soil, even at the end of one year of incubation.     

香港土壤研究Ⅶ.BCR提取法研究重金属的形态及其潜在环境风险

基于类型土壤的重金属元素形态分析研究相对较少,本研究以香港地区7个亚纲的土壤剖面为例,利用欧共体参比司(BCR)制定的三步连续提取法研究了类型土壤中重金属Cd、Cu、Pb和Zn的化学形态及其潜在环境风险。结果表明,Pb、Cd和Zn元素除残留态外,HOAc溶解态的比例也相对较高,但不同类型的土壤有所差别,而Cu元素则以残留态和可氧化态为主。在这7种类型土壤中,正常潜育土和湿润淋溶土中的重金属潜在环境风险相对较高,而在这4种重金属元素中,又以Pb元素的潜在环境风险最大。