Effect of solid-phase speciation on metal mobility and phytoavailability in sludge-amended soil

Sequential extraction was utilized for partitioning Cd, Cr, Ni, and Zn, in soil and sludge samples into five operationally-defined fractions: exchangeable, bound to carbonates, bound to Fe-Mn oxides, bound to organic matter and residual. The highest amounts of Cd, Ni, and Zn, expressed as per cent of the total, were found in the Fe-Mn oxide fraction of the sewage sludge. Chromium was significantly associated with the organic fraction of the sludge. The residue was the most abundant fraction for all metals studied in the untreated soil, and for Cd and Ni in the sludge-treated soil. The concentration of exchangeable Cd and Cr was relatively low in the untreated soil and did not change much after sludge application, whereas the concentrations of exchangeable Zn increased about 50 times and the concentrations of exchangeable Ni doubled in the sludge-treated soil. The lysimetric experiment revealed an increase in Zn and Ni uptake by ryegrass and in the percentage of metals leached from the soil profile after massive sludge application. In contrast only negligible changes were observed for Cd and Cr. The assumption that mobility and biological availability are related to metal speciation was confirmed by the agreement between the distribution pattern of Cd, Cr, Ni and Zn in the soils, the uptake of the metals by plants and their capacity for leaching out from the soils.     

Effect of pH on chemical forms and plant availability of cadmium,zinc, and lead in polluted soils

The effect of pH on chemical forms and plant availability of heavy metals in three polluted soils was investigated. The soils were adjusted to pH values of 7.0, 6.0, and 4.5, then sequentially extracted so that Cd, Zn, and Pb could be partitioned into five operationally defined chemical fractions: exchangeable, carbonate, Fe-Mn oxide, organic, and residual. Kidney beans were grown in the soils to investigate plant availability of the metals in relation to changes of their levels in chemical forms resulting from alteration of soil pH. Alteration of pH resulted in changes of chemical forms of the metals in the soils, and at lower pH the changes were more significant. When soil pH values were decreased from 7.0 to 4.55, levels of Cd, Zn, and Pb in exchangeable form increased, decreased in carbonates and decreased slightly in Fe-Mn oxide forms. Their levels in organic and residual forms were unchanged. Although concentration of metals in plants increased with reduction in soil pH values, dry matter yields were also restricted, so that the amount of metal uptake were almost similar. The uptake rate of the metals in the exchangeable + carbonate forms was the same for the three elements in all the cases.     

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.     

土壤外源铜形态的动态变化：5年定位试验

土壤铜污染的危害性不仅取决于总量,还与其在土壤中的形态有关。选用未受污染的粘质壤土,设置对照（32mg·kg-1）、200、400mg·kg-1铜处理模拟土壤铜污染,进行持续5年（2006—2010年）的稻/麦轮作土培试验。参照Tessier的方法测定小麦和水稻成熟期土壤中不同形态铜含量,研究耕作层土壤中各种形态铜含量的动态变化。结果表明：（1）试验期内清洁土壤中总铜以及可交换态、碳酸盐结合态、铁锰氧化物结合态、有机物结合态、残渣态铜含量变化均很小,铜处理使上述参数均大幅增加。（2）污染土壤各形态铜含量随时间推移而变化,其中可交换态浓度持续下降最为显著,5年分别累计下降66%（200mg·kg-1）、67%（400mg·kg-1）。（3）土壤处于旱作条件有利于碳酸盐结合态和有机物结合态铜向铁锰氧化物结合态转化,淹水条件下转化方向相反。（4）铜处理改变了土壤中铜元素的形态分布,清洁土壤主要以残渣态存在（平均占57%）,污染土壤中碳酸盐结合态和铁锰氧化物结合态铜所占的比例明显增加（合计平均占58%）。本研究表明,外源铜进入土壤后,易被植物吸收利用的可交换态浓度持续大幅降低,其他形态则因不同年度和不同耕作方式而相互转化。     

浙江省典型水稻产区土壤水稻系统重金属 迁移特征及定量模型

重金属在土壤?水稻系统中迁移转化规律越来越受到人们的关注。本研究采集浙江省3个不同区位(浙北南浔、浙中嵊州、浙南温岭)的水稻主产区土壤、水稻样品,基于水稻品种(杂交水稻和晚粳稻)进行重金属迁移转化的影响因子分析,明确主要驱动因子,建立定量评测模型并进行验证,以此掌握浙江省典型水稻产区重金属的迁移转化规律。研究结果表明,3个研究区土壤的理化性状存在差异,其中嵊州产区土壤的p H(均值为5.52)、有机质(均值为39.4 g?kg?1)、重金属形态含量等均低于其他两个研究区;3个产区土壤和水稻中重金属含量也存在显著性差异,温岭产区土壤重金属(Cd、Cu、Zn)含量显著高于其他两个产区(P0.05),而嵊州产区的水稻重金属含量则显著高于南浔产区(P0.05);Cd和Zn富集系数高于Cu和Ni,嵊州产区的重金属富集系数(0.018~0.521)显著高于其他两个产区(南浔为0.004~0.143,温岭为0.007~0.269)。土壤重金属形态和土壤理化性质均显著影响不同品种的富集系数,其中土壤理化性质的作用相对较大。对数线性迁移模型能够预测实际产地环境中土壤?水稻系统重金属的有效性(富集系数),晚粳稻的预测结果优于杂交水稻,重金属Ni的预测效果(杂交水稻和晚粳稻的回归系数r分别达0.61、0.70,P0.01)好于其他重金属,而杂交水稻重金属Cd的预测效果(r值为0.21,P0.05)偏低,需增加环境变量,并做进一步研究以提高预测精度。     

外生菌根诱导油松根际土壤重金属形态变化

To understand the role of ectomycorrhizas in improving the tolerance of its host to excessive heavy metals in soil, this study was conducted to exam the patterns of four fractions （the exchangeable, the carbonate-bound, the Fe-Mn oxide- bound and the organically bound） of both Cu and Cd in the rhizosphere of Chinese pine （Pinus tabulaeformis） seedlings grown in excessive Cu and Cd environment. The results showed that the speciation of Cu and Cd in the rhizosphere was significantly influenced by inoculation of ectomycorrhizal fungus Boletus edulis. Compared to the rhizosphere, the content of exchangeable Cu slightly decreased in the mycorrhizosphere of the seedlings grown in 166 and 400 mg kg^-1 Cu contaminated soil, whereas the exchangeable Cd in the mycorrhizosphere decreased remarkably to only 33% and to 60% that of the rhizosphere at 0.75 and 1.50 mg kg^-1 Cd levels, respectively. These indicate the potential capacity of mycorrhizas to alleviate the damage of heavy metals to the host plants by reducing the bioavailability of heavy metals in soil. Distribution of the 4 tested fractions of Cu and Cd at different contamination levels showed that there was a strong tendency of changing from loosely associated fractions to strongly associated fractions in the mycorrhizosphere. The most stable Cd fraction, organically bound Cd, was significantly larger in the mycorrhizosphere than in the rhizosphere at different Cd contamination levels. This phenomenon was also observed for Cu but the difference was not statistically significant.     

不同作物根际环境对土壤重金属形态的影响

采用根垫法研究了玉米、大豆和小麦根际环境对污灌土壤中铜、镉、铅、锌形态的影响。研究结果表明：根际土壤中交换态铜含量呈现增加趋势，碳酸盐态和铁锰氧化物态金属则表现为减少趋势，有机态几无变化。形态变化的幅度与植物种类有关，其中大豆根际土壤中金属形态的变化比小麦和玉米显著。     

水稻子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子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,以及水稻子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。水稻子实对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各活性形态对水稻子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。     

Influences of lignin from paper mill sludge on soil properties and metal accumulation in wheat

The influences of lignin application on soil properties of three different soils, Jiangxi soil (Ultisol, Hapludult), Heilongjiang soil (Alfisol, Entioboralf) and Beijing soil (Alfisol, Haplustalf), and metal accumulation in wheat (Triticum aestivum L.) were studied in a pot experiment. By lignin amendment, soil pH, organic matter (OM) and cation exchange capacity (CEC) increased, except for CEC in the Beijing soil. Analysis showed that available P and K in lignin-amended soils were also elevated, except for P in the Jiangxi soil. A three-step sequential extraction procedure proposed by the Standards, Measurements and Testing Programme (formerly BCR) of the European Commission was used to investigate the fraction redistribution of heavy metals in soils with lignin application. The fractions were specified as B1: water soluble, exchangeable and carbonate bound, and weakly adsorbed; B2: Fe-Mn oxide bound; and B3: organic matter and sulfide bound. Generally, the heavy metal content of the B2 fraction decreased whereas that of the B3 fraction increased. Lignin application to arable soils can not only improve plant growth in vitro, but also reduce the accumulation of the heavy metals Cu, Zn, Cd, Pb, Cr and Ni in wheat plants.     

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.     

Distribution and Transport of Residual Lead and Copper Along Soil Pro?les in a Mining Region of North China

Residual heavy metals are commonly considered to be immobile in soils,leading to an underestimation of their environmental risk.This study investigated the distribution and transport of residual heavy metals along soil pro?les,using the Xiaoqinling gold mining region in North China as a case study.Soil samples were collected at three depths from three locations near the tailing heap.The speciation of copper(Cu) and lead(Pb)(exchangeable,carbonate-bound,Fe-Mn oxide-bound,organic matter-bound,and residual fractions) was determined using a sequential extraction procedure.The residual fraction's morphology was observed using scanning electron microscopy(SEM).Results showed that metal fraction distributions along the soil pro?les were in?uenced by each fraction's mobility.Residual fraction with high chemical stability can not be transformed from or into other fractions.This led to the conclusion that the high concentration of residual metals in soils mainly resulted from residual fraction transport.The SEM analysis showed that ?ne particles(submicrons) were mainly attached to large particles and were likely released and transported by water?ow.The more sorptive fractions(non-residual fractions) were mainly retained in the top soil,and the more mobile fractions(residual fraction) were mainly leached to the deep soil.Cu and Pb concentrations in the residual fraction decreased slightly and those in the non-residual fractions decreased signi?cantly with soil depth.These suggest a relatively higher residual metal mobility along the soil pro?les.Therefore,residual metals can be transported in soils and their environmental risk can not be ignored in assessing soil contamination.     

Solubility of heavy metals in a contaminated soil: Effects of redox potential and pH

To assess the mobilities of Pb, Cd, and Zn from a contaminated soil, the effects of redox potential and pH value on metal solubilities were investigated. Both redox potential and pH were found to greatly affect heavy metal solubility in the soil. Results showed that the soil suspension under continuous oxygen aeration for 21 days resulted in increases of redox potential from 290 to 440 mV and pH value from 6.9 to 7.0, respectively. Soluble concentrations of Pb, Cd, and Zn varied with time, and were all lower than 1 mg kg^?1. When the soil suspension was aerated with nitrogen, final redox potential was ?140 mV and pH value of 7.1. The soluble metal concentrations were slightly higher than those aerated with oxygen. The equilibrium solubility experiments were conducted under three different pH values (3.3, 5.0, 8.0) and three redox potential (325, 0, ?100 mV). Results showed that metals were sparingly soluble under alkaline conditions (pH = 8.0). Metal solubilities were higher when under slightly acidic conditions (pH = 5.0), and increased drastically when pH was kept at 3.3. When solubilities were compared under same pH values, it was observed that metal solubilities increased as redox potential decreased. Generally speaking, acidic and reducing conditions were most favorable for metal solubilization, and the effect of pH was more significant than that of redox potential. It was proposed that heavy metals were mostly adsorbed onto Fe-Mn oxyhydroxides. The pH-dependent metal adsorption reaction and the dissolution of Fe-Mn oxyhydroxides under reducing conditions was the mechanism controlling the release of heavy metals from soils.     

上海市区街道灰尘重金属污染研究

对上海市区街道灰尘重金属的分布特征、赋存形态及其生物有效性进行了研究,结果表明,市区街道灰尘中Pb、Cu、Ni和Zn的平均含量分别为264、182、86和673 mg kg-1,远高于上海市土壤环境背景值;重金属含量空间分布差异较大,Cu、Pb和Zn污染中心区主要位于商业区和内环线附近,Ni污染中心区主要位于外环线附近;市区街道灰尘中Pb主要以铁锰氧化物结合态存在,Cu主要以有机物结合态存在,Ni主要以残渣态和铁锰氧化物结合态存在,Zn主要以残渣态存在;其生物有效性表现为:Ni≈Pb>Zn>Cu。     

洛阳城区及郊区土壤中Pb的分布特征及化学形态研究

对洛阳城市不同功能区表土中的Pb含量与化学形态以及工业和交通对土壤Pb污染的影响进行了研究,结果表明洛阳城市表土中Pb的含量分别为工业区(126.94mg kg-1)>城市道路(77.44mg kg-1)>居民区(59.76mg kg-1)>郊区农用地(52.39mg kg-1)>公园(41.43mg kg-1)>高校校园(36.49 mg kg-1)。工业区周围的土壤Pb含量随与工业区距离的增加而下降,应用地积累指数评价,洛阳城市土壤Pb污染处于轻度到中度污染之间,其中工业区和城区道路地积累指数较高,这些区域的土壤已受到Pb的较强污染。公路和铁路沿线两侧土壤中Pb含量分布也随距离的增加而下降,交通沿线两侧最大的Pb浓度在主导风向一侧10米附近。城市土壤Pb的化学形态以残余态和铁锰氧化物结合态为主,各形态比例为残余志>铁锰氧化物结合态>碳酸盐结合态>有机结合态。     

Chemical Speciation of Heavy Metals in the Fractionated Rhizosphere Soils of Sunflower Cultivated in a Humic Andosol

Chemical speciation and bioaccumulation factor of iron (Fe), manganese (Mn), and zinc (Zn) were investigated in the fractionated rhizosphere soils and tissues of sunflower plants grown in a humic Andosol. The experiment was conducted for a period of 35 days in the greenhouse, and at harvest the soil system was differentiated into bulk, rhizosphere, and rhizoplane soils based on the collection of root-attaching soil aggregates. The chemical speciations of heavy metals in the soil samples were determined after extraction sequentially into fractions classified as exchangeable, carbonate bound, metal–organic complex bound, easily reducible metal oxide bound, hydrogen peroxide (H₂O₂)–extractable organically bound, amorphous mineral colloid bound, and crystalline Fe oxide bound. Iron and Zn were predominantly crystalline Fe oxide bound in the initial bulk soils whereas Mn was mainly organically bound. Heavy metals in the exchangeable form accumulated in the rhizosphere and rhizoplane soils, comprising <4% of the total content, suggesting their relatively low availability in humic Andosol. Concentrations of organically bound Fe and Mn in soils decreased with the proximity to roots, suggesting that organic fraction is the main source for plant uptake. Concentrations of Mn and Zn in the metal–organic complex also decreased, indicating a greater ability of sunflower to access Mn from more soil pools. Sunflower showed bioaccumulation factors for Zn, Fe, and Mn as large as 0.39, 0.05, and 0.04 respectively, defining the plant as a metal excluder species. This result suggests that access to multiple metal pools in soil is not necessarily a major factor that governs metal accumulation in the plant.     

Micrometer-scale internal structure and element distribution of Fe-Mn nodules in Quaternary red earth of Eastern China

Purpose

Fe-Mn nodules are the common feature of tropical and subtropical soils and contain abundant information of pedogenic processes, palaeoenvironmental changes, and element geochemistry. The main aim of the present study was to determine the internal structure and spatial distribution of elements in the Fe-Mn nodules to better understand the 3D internal structure, enrichment, and dynamics of heavy metals in nodules and to provide more aspects to explore the possible heavy metal sequestration and pedoenvironmental implications of Fe-Mn nodules in soils.

Materials and methods

The studied Typic Plinthudult was developed on Quaternary red earths in Èastern China. The Fe-Mn nodules in the Bs horizon of soil were separated and classified into four size fractions (5–8, 3–5, 2–3, and 1–2 mm). The 3D microstructure of Fe-Mn nodules was examined by means of synchrotron radiation-based X-ray microcomputed tomography (SR-mCT), and the spatial distribution of Fe and Mn in nodules was studied by scanning electron microscopy (SEM) equipped with an energy-dispersive X-ray spectrometer (EDS). The association of heavy metals with Fe and Mn oxides in nodules was described by selective chemical dissolution, SEM/EDS, and principal component analysis.

Results and discussion

The SR-mCT images indicated that the 5–8, 3–5, and 2–3 mm nodules exhibited well-defined ring structures, while the 1–2 mm nodule exhibited homogeneous fabric. The internal microstructures of nodules could be divided into four parts: Fe-rich ring, Mn-rich ring, Fe and Mn overlapped ring, and the gap between ring structures. The Fe-Mn nodules were significantly enriched in Mn, Pb, Ni, Cu, and Zn relative to the soil matrix. In particular, the concentrations of Mn and Pb in the nodules were 150 and 90 times greater than those in the soil matrix, respectively. A clear partitioning of heavy metals between Mn and Fe oxide phases was observed in the nodules, indicating that Pb was mainly present in Fe oxides, while Ni, Cu, and Zn were mainly associated with Mn oxide phases.

Conclusions

The SR-mCT and SEM-EDS revealed the detailed internal microstructure of the Fe-Mn nodules and geochemical dynamics of heavy metals in the soil system. The Fe-Mn nodules have very high scavenging ability in sequestrating toxic heavy metals in soils, such as Pb and Ni. The microstructure and spatial distribution of Fe and Mn in nodules reflected the cycle of alternating drying and wetting conditions and served as an important basis for inferring the pedogenic processes and pedoenvironmental conditions.

     

Distribution of Aluminum Fractionation in the Acidic Rhizosphere Soils of Masson Pine (Pinus massoniana Lamb)

The modified Tessier’s sequential extraction procedure and rhizobox cultivation were employed to investigate the distribution of aluminum (Al) fractions in the acidic rhizosphere soil of Masson pine (Pinus massoniana lamb) seedlings. The results showed that the Al in soils was fractionated into five operationally defined fractions. Three sets of soil samples used in the rhizoboxes were collected from the three forest sites in the southeast of China: Sichuan, Zhejian, and Jiangsu. At the end of 100-day cultivation, the rhizosphere Al fractions for the original or bulk soils were in the order of residual > iron-manganese (Fe-Mn) oxides > organic > carbonate > exchangeable. However, in rhizosphere soil, the Al fraction follows the order of residual > organic > Fe-Mn oxides > carbonate > exchangeable. On average, the rhizosphere experienced significant increase in organically bound Al and slight decrease in exchangeable Al contents, but had decreases in contents for the other three Al fractions compared to the nonrhizosphere. The correlation analysis indicated that the Al contents accumulated in roots were significantly and positively correlated with exchangeable Al contents in the rhizosphere, and also characterized by the major portion of organically bound Al, which exhibited a bioavailable transformation of Al fractions. Results indicated that decreases in both redox potential and soil pH, as well as increase in dissolved organic carbon (DOC), were observed in the rhizosphere. Exchangeable Al and organic Al fractions were dependent mainly on soil pH (hydrogen ion concentration) and DOC, accordingly. Decreasing rhizosphere pH from 5.93 to 3.42 accelerated the secretion of organic carbon. These data are helpful for understanding the mobility and bioavailability of Al fractions in the acidic rhizosphere soils of Masson pine.     

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。     

Chemical extractability and availability of heavy metals after seven years application of organic wastes to a citrus soil

Abstract. The chemical extractability of heavy metals introduced into the soil during 7 years application of sewage sludge, composted municipal solid waste and sheep manure, and their availability to citrus plants were studied. The total content of metals in the soil (0-20 cm)was increased by the use of sludges and compost, but only the Ni content in the saturation extracts of soil was significantly increased. Total Cd, Cr, Cu, Ni, Pb, and Zn were sequentially fractionated into water-soluble plus exchangeable, organically bound, carbonate-associated, and residual fractions. Most of the heavy metals were present in carbonate and residual fractions, although substantial amounts of water-soluble plus exchangeable Cd, and organically bound Cu and Ni were found. No significant increases in the metal contents in leaves and orange fruits were observed, with the exception of Pb in leaves. Several statistically significant correlations between metal content in plants, metal content in soil fractions, and chemical characteristics of soil were also found.     

Prediction of heavy metal contents and displacement in soils

Under laboratory conditions, the availability of cadmium, lead and copper in an Orthic Luvisol was investigated when applied to the soil at various initial concentrations. The metals were applied separately or concurrently with the other two heavy metal ions in order to bring about competition for the adsorption sites. The presence of competing metals increased the general availability especially of cadmium in the soil. Lead and copper were to a lesser extent also affected by the competition of other ions. On the basis of our ion-competition results we developed a longterm trend model suitable to predict the consequences of regular heavy metal loading (e.g. in the form of sewage sludge). The model takes into consideration the annual precipitation and the water suction profile of the soil. On the basis of the model predictions it has to be concluded that the threshold values for heavy metals in the sewage sludge regulation (Switzerland) are too high.