施污土壤与污泥中Cu、Pb、Cd、Zn的形态分布

污泥中的重金属元素是限制其大规模农田利用的重要因素。施污土壤和污泥中重金属的形态研究可以用来评价土壤中重金属的生物有效性以及它们在土壤中的移动性。用修正BCR三步连续提取法进行分步提取研究了污水污泥和施污后的西红柿地土壤中Cu、Pb、Cd、Zn的形态分布状况。施用污泥堆肥10t hm-2后的土壤中Cu、Pb、Cd、Zn的全量与各种形态含量无明显增加,Cu、Pb、Zn含量远低于国家土壤环境质量标准。土壤中Cu的各种形态分布关系是:残渣态>可还原态=可氧化态>可交换态和弱酸溶解态,Cu在土壤中的存在是以最稳定的残渣态为主。堆肥污泥与干化污泥相比,残渣态Cu的比例明显增加。土壤中Pb的各种形态分布关系是以残渣态和可还原态为主,但可氧化态的分布比例最小。土壤中Cd的可交换态、可还原态和残渣态各占据相等的含量,但可氧化态Cd的含量几乎为零。Zn在土壤中的各种形态分布关系是:可交换态和弱酸溶解态>可氧化态>可还原态>残渣态,Zn在土壤中的存在是以最易迁移的可交换态和弱酸溶解态为主。这些金属元素在土壤中的相对稳定性顺序为:Cu>Pb>Cd>Zn。Zn在土壤中的移动性要远高于Cu。     

Fractionation of residual cadmium,copper, nickel,lead, and zinc in previously sludge‐amended soil

Abstract

The fractionation of heavy metals in previously sludge‐amended soil is important to evaluate their behavior in the environment in terms of mobility and availability to crop plants. A surface soil that received two types of sludges at two different rates, plus fertilizer only and no treatment (control), having been fallow for nine years, was used in this study. The contents of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) fractions in previously sludge‐amended soils were governed by the total content of these metals in the sludges applied and by the rate of sludge application. The contents of these metals were higher for soils that received the Chicago sludge as compared to that receiving the Huntsville sludge. Furthermore, soils that received 20 Mg/ha/yr of sludge for five years generally had higher levels of these metals than those receiving a single dose at the 100 Mg/ha application rate. The percentage of the total content in the water soluble and exchangeable forms was very low (≤1%) regardless of sludge application. The application of sludges tended to reduce the residual fraction and to increase the organic and carbonate fractions. Overall, the predominant forms of the metals in the sludges were as the Cd‐, Ni‐, Pb‐, and Zn‐carbonate and Cu‐organic fractions.     

Comparison of routine soil tests and EPA method 3050 as extractants for heavy metals in Delaware soils

Abstract

Agricultural use of sewage sludges can be limited by heavy metal accumulations in soils and crops. Information on background levels of total heavy metals in soils and changes in soil metal content due to sludge application are; therefore, critical aspects of long‐term sludge monitoring programs. As soil testing laboratories routinely, and rapidly, determine, in a wide variety of agricultural soils, the levels of some heavy metals and soil properties related to plant availability of these metals (e.g. Cu, Fe, Mn, Zn, pH, organic matter, texture), these labs could participate actively in the development and monitoring of environmentally sound sludge application programs. Consequently, the objective of this study was to compare three soil tests (Mehlich 1, Mehlich 3, and DTP A) and an USEPA approved method for measuring heavy metals in soils (EPA Method 3050), as extractants for Cd, Cu, Ni, Pb and Zn in representative agricultural soils of Delaware and in soils from five sites involved in a state‐monitored sludge application program.

Soil tests extracted less than 30% of total (EPA 3050) metals from most soils, with average percentages of total metal extracted (across all soils and metals) of 15%, 32%, and 11% for the Mehlich 1, Mehlich 3, and DTPA, respectively. Statistically significant correlations between total and soil test extractable metal content were obtained with all extractants for Cu, Pb, and Zn, but not Cd and Ni. The Mehlich 1 soil test was best correlated with total Cu and Zn (r=0.78***, 0.60***, respectively), while the chelate‐based extractants (DTPA and Mehlich 3) were better correlated with total Pb (r=0.85***, 0.63***). Multiple regression equations for the prediction of total Cu, Ni, Pb, and Zn, from soil test extractable metal in combination with easily measured soil properties (pH, organic matter by loss on ignition, soil volume weight) had R² values ranging from 0.41*** to 0.85***, suggesting that it may be possible to monitor, with reasonable success, heavy metal accumulations in soils using the results of a routine soil test.     

污泥施田后土壤和玉米植株中重金属分布特征

对施污泥剂量分别为10、30和60thm-2的土壤,采用修正的BCR三步连续提取法分步提取并分析Pb、Cd、Cu、Zn的不同形态。利用高压密封消解技术和电感耦合等离子体质谱(ICP-MS)分析Pb、Cd、Cu、Zn在玉米器官中的分布及其转移富集特征。施污泥土壤中重金属主要以残渣态存在。施污泥量为常规用量的6倍时,即相当于连续6年施污泥的土壤中重金属Pb、Cd、Cu、Zn的含量基本未超过我国土壤环境质量标准。4种重金属在弱酸性土壤中残渣态含量比例的高低依次为CuZnCdPb。施污泥土壤上Pb、Cd在玉米各器官中的平均含量顺序为:茎叶根籽粒;Cu为:根茎叶籽粒;Zn为:根籽粒茎叶。玉米对于各元素的EC值按高低顺序依次为CuZnCdPb。     

Speciation of Metals in Sewage Sludge and Sludge-amended Soils

This study is aimed at ascertaining the chemical partitioning ofCu, Zn, Pb, Ni, Cr and Cd in sewage sludge and agricultural soils repeatedly amended with sludge. The operationally determined speciation was investigated by using selective five steps sequential extraction method for partitioning these metals into different chemicalforms, likely to be released in solution under various environmental conditions. It provides qualitative evidence regarding the form of the association of metals and indirectly of their bioavailability. It can help to explain the process by which metals are eliminated from sewagesludge and also indicate the impact of the use of sludge on agriculturalsoils, as amendments. Data obtained by extraction procedure showed different metal distribution trend among the fractions in sewage sludgeand sludge-amended soils. Comparison of distribution pattern of metals in sludge and sludge-applied soils shows that there is possible redistribution of metals among the different phases. The sum of the metal content in the fractions compared well with the total metal content in sewage sludge, the ratios averaging 1.02, 1.04, 1.07, 0.94, 1.06, and 1.12 for Cu, Zn, Pb, Ni, Cr, and Cd, respectively. The metal recovery efficiency in sludge-amended soils was found to be: 108±6%, 102±5%, 115±8%, 111±4%, 104±7%and 124±28% for Cu, Zn, Pb, Ni, Cr and Cd, respectively.     

污泥与施污土壤重金属生物活性及生态风险评价

将城市污泥以不同质量比施于土壤中构成污泥混合土壤,研究各污泥配比土壤中重金属的生物活性,并采用三种重金属评价方法(地累积指数法、潜在生态风险指数法、综合毒性指数模型)和黑麦草对重金属的吸收富集效果来对施污土壤中重金属具有的生态风险性进行评价。结果表明:污泥的添加使土壤中生物活性态Cd、Cu和Zn含量显著增加,对三种重金属具有活化作用,但对Pb却起到钝化作用。生态风险评价结果表明:污泥的添加使土壤中Pb呈现无污染和低生态风险;Cu和Zn呈现中度污染和低生态风险;Cd达到强度污染和重度生态风险,重金属潜在生态风险(RI)总体处于强度生态风险水平。当污泥添加比例大于6:10(污泥S3处理)时,施污土壤中重金属的综合毒性指数高于土壤对照。黑麦草对Cd、Pb、Cu和Zn的富集浓度与施污土壤中对应重金属的生物活性态含量存在显著正幂指数关系,同时黑麦草对施污土壤中Cd、Cu和Pb的富集能力大小与地累积指数法和潜在生态风险指数法对三种重金属具有的生态风险性的评价结果具有一致性。     

Prediction of available heavy metals by six chemical extractants in a sewage sludge‐amended soil

Abstract

In a field experiment conducted during three years in a sandy‐loam, calcareous soil, one aerobically digested sewage sludge (ASL) and another anaerobically digested sewage sludge (ANSL) were applied at rates of 400, 800, and 1,200 kg N/ha/year, and compared with mineral nitrogen fertilizer at rates of 0, 200, 400, and 600 kg N/ha/year in a cropping sequence of potato‐corn, potato‐lettuce, and potato, the first, second, and third year, respectively. Results showed that the highest values of soil extractable metals were obtained with aqua regia, whereas the lowest levels with DTPA. All metal (Zn, Cu, Cd, Ni, Pb, and Cr) gave significant correlations between metal extracted with the different extractants and metal loading applied with the sludges. The metal extractable ion increased over the control for Zn, Cu, Cd, Ni, Pb, and Cr extracted with DTPA, EDTA (pH 8.6) and 0.1 N HC1, for Zn, Cd, Ni, Pb, and Cr extracted with EDTA (pH 4.65) and AB‐DTPA, and for Zn, Cd, Ni, and Cr extracted with aqua regia. The level of metal‐DTPA extractable resulted highly correlated with that obtained by the other methods, except the Ni‐aqua regia extractable. The soil extractable elements which showed significant correlations with metals in plant were: Zn, Cu, Cd, and Ni in potato leaves, Cd, Ni, and Pb in corn grain, and Zn and Cd for lettuce wrapper leaves. In general, all the chelate based extractants (DTPA, EDTA pH 4.6, EDTA pH 8.6, AB‐DTPA) were equally useful as indicator of plant available metals in the soil amended with sludge.     

Behavior of heavy metals from sewage sludge in a Chernozem of the dry belt in Saxony‐Anhalt/Germany

In a small‐plot trial different doses of sewage sludge (equivalent 82‐330 tons of dry matter per hectare) were incorporated in 0—25 cm depth (1982—1985). The aim of the investigations was to study the fate of the heavy metals Zn, Cd, Cu, Ni, Pb, and Cr, to determine their concentration in different soil fractions using a sequential extraction method and to ascertain their uptake by Zea mays L. plants. Eleven years after the last application the metals supplied with the sludge had moved as far as 50 cm in depth. The concentrations of Zn, Cd, Cu, Ni, and Cr in the saturation extract of the sampled soil layers were closely correlated with the concentrations of dissolved organic carbon (DOC). This result suggests that the heavy metal displacement was partly connected with the DOC movement in the soil. Considerable amounts of Zn and Cd coming from sewage sludge were found in the mobile fractions of the soil. Cu, Ni, and Pb were located especially in organic particles, and Cr was obviously bound by Fe‐oxides. Nine years after the last application the binding species of heavy metals were still different compared with those in the untreated soil. The whole withdrawal of heavy metals by plants yielded <1 % of the applied amounts. In the case of Zn the uptake from the sludge amended soil decreased during the experimental period. No similar tendency was observed for the other elements. In any case their annual variations of uptake exceeded the effect of sludge application.     

The transfer of heavy metals to barley plants from soils amended with sewage sludge with different heavy metal burdens

Purpose

Our main aim objective was to evaluate the transfer of Cd, Cr, Cu, Ni, Pb and Zn to barley (Hordeum vulgare) grown in various soils previously amended with two sewage sludges containing different concentrations of heavy metals. This allowed us to examine the transfer of heavv metals to barley roots and shoots and the occurrence of restriction mechanisms as function of soil type and for different heavy metal concentration scenarios.

Material and methods

A greenhouse experiment was performed to evaluate the transfer of heavy metals to barley grown in 36 agricultural soils from different parts of Spain previously amended with a single dose (equivalent to 50 t dry weight ha^?1) of two sewage sludges with contrasting levels of heavy metals (common and spiked sludge: CS and SS).

Results and discussion

In soils amended with CS, heavy metals were transferred to roots in the order (mean values of the bio-concentration ratio in roots, BCF_Roots, in brackets): Cu (2.4)?~?Ni (2.3)?>?Cd (2.1)?>?Zn (1.8)?>?Cr (0.7)?~?Pb (0.6); similar values were found for the soils amended with SS. The mean values of the soil-to-shoot ratio were: Cd (0.44)?~?Zn (0.39)?~?Cu (0.39)?>?Cr (0.20)?>?Ni (0.09)?>?Pb (0.01) for CS-amended soils; Zn (0.24)?>?Cu (0.15)?~?Cd (0.14)?>?Ni (0.05)?~?Cr (0.03)?>?Pb (0.006) for SS-amended soils. Heavy metals were transferred from roots to shoots in the following order (mean values of the ratio concentration of heavy metals in shoots to roots in brackets): Cr (0.33)?>?Zn (0.24)?~?Cd (0.22)?>?Cu (0.19)?>?Ni (0.04)?>?Pb (0.02) for CS-amended soils; Zn (0.14)?>?Cd (0.09)?~?Cu (0.08)?>?Cr (0.05)?>?Ni (0.02)?~?Pb (0.010) for SS-amended soils.

Conclusions

Soils weakly restricted the mobility of heavy metals to roots, plant physiology restricted the transfer of heavy metals from roots to shoots, observing further restriction at high heavy metal loadings, and the transfer of Cd, Cu and Zn from soils to shoots was greater than for Cr, Ni and Pb. Stepwise multiple linear regressions revealed that soils with high sand content allowed greater soil-plant transfer of Cr, Cu, Pb and Zn. For Cd and Ni, soils with low pH and soil organic C, respectively, posed the highest risk.     

Concentrations and forms of heavy metals in Slovak soils

The risk assessment of heavy‐metal contamination in soils requires knowledge of the controls of metal concentrations and speciation. We tested the relationship between soil properties (pH, CEC, C_org, oxide concentrations, texture) and land use (forest, grassland, arable) and the partitioning of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn among the seven fractions of a sequential extraction procedure in 146 A horizons from Slovakia. Using a cluster analysis, we identified 92 soils as representing background metal concentrations while the remaining 54 soils showed anthropogenic contamination. Among the background soils, forest soils had the lowest heavy‐metal concentrations except for Pb (highest), because of the shielding effect of the organic layer. Arable soils had the highest Cr, Cu, and Ni concentrations suggesting metal input with agrochemicals. Grassland soils had the highest Cd and Zn concentrations probably for geogenic reasons. Besides the parent material (highest metal concentrations in soils from carbonatic rock, lowest in quartz‐rich soils with sandy texture), pedogenic eluviation processes controlled metal concentrations with podzols showing depletion of most metals in E horizons. Partitioning among the seven fractions of the sequential extraction procedure was element‐specific. The pH was the overwhelming control of the contributions of the bioavailable fractions (fractions 1–4) of all metals and even influenced the contributions of Fe oxide‐associated metals (fractions 5 and 6) to total metal concentrations. For fractions 5 and 6, Fe concentrations in oxides were the most important control of contributions to total metal concentrations. After statistically separating the pH from land use, we found that the contributions of Cu in fractions 1–4 and of NH₄NO₃‐extractable Al, Cd, Pb, and Zn to total metal concentrations were significantly higher under forest than under grassland and in some cases arable use. Our results confirm that metal speciation in soils is mainly controlled by the pH. Furthermore, land use has a significant effect.     

包头市铜厂周边土壤中重金属垂直分布特征与形态分析

为了解包头市铜厂周边地区土壤剖面中重金属污染状况,采用火焰原子吸收分光光度法和Tessier连续提取法,对土壤中6种重金属（Cu,Zn,Mn,Ni,Pb和Cd）的垂直分布特征、形态及潜在生物可利用性进行了分析。结果表明:研究区土壤剖面各层土壤中6种重金属含量均超过内蒙古土壤背景值,Cu,Pb和Cd为主要污染物。随采样深度的增加,Cu,Zn,Pb和Mn的含量呈现下降趋势,且由相关性系数可知重金属Cu,Zn和Pb可能有相同人为或自然污染源;土壤剖面中6种重金属均主要以残渣态存在,含量均在50%以上,对生物危害较小;潜在生物可利用性分析结果为:Cu（32.61%） > Mn（31.85%） > Ni（24.90%） > Zn（16.60%） > Cd（15.23%） > Pb（14.87%）,Cu和Mn的潜在生物可利用性较大,其次为Ni,Zn,Cd和Pb潜在生物可利用性较小。     

Distribution of different fractions of cadmium,zinc, lead,and copper in unpolluted and polluted soils

McLaren and Crawford's method for fractionating soil Cu was modified, and used to fractionate soil Cd, Zn, Pb, and Cu in 38 soil samples from 11 soil profiles from industrially polluted and nearby unpolluted areas. Pollutant metals, especially Cd and Zn, were more soluble than the native soil metals. On average, approximately 45% of Cd was present in the CaCl₂ soluble (CA) fraction, whereas corresponding values for the other metals were below 10%. The percentages of each metal in the CA fraction followed the order Cd > Zn > Pb > Cu. The same order was observed for the acetic acid soluble (AAC) fraction. Approximately 30% of total Pb and Cu were present in the pyrophosphate soluble (PYR) fraction, and only 10% of total Cd and Zn. Approximately 20% of total Zn or Pb and 10% of Cd or Cu were present in the free oxide (OX) fraction. Only 20% of Cd and between 40–50% of the other 3 metals were present in the residual (RES) fraction. The results show that Cd is more labile than the other 3 metals.     

Extractability and plant uptake of heavy metals in alum shale soils

Abstract

Fifty soil samples (0–20 cm) with corresponding numbers of grain, potatoes, cabbage, and cauliflower crops were collected from soils developed on alum shale materials in Southeastern Norway to investigate the availability of [cadmium (Cd), copper (Cu), zinc (Zn), lead (Pb), nickel (Ni), and manganese (Mn)] in the soil and the uptake of the metals by these crops. Both total (aqua regia soluble) and extractable [ammonium nitrate (NH₄NO₃) and DTPA] concentrations of metals in the soils were studied. The total concentration of all the heavy metals in the soils were higher compared to other soils found in this region. Forty‐four percent of the soil samples had higher Cd concentration than the limit for application of sewage sludge, whereas the corresponding values for Ni, Cu, and Zn were 60%, 38%, and 16%, respectively. About 70% the soil samples had a too high concentration of one or more of the heavy metals in relation to the limit for application of sewage sludge. Cadmium was the most soluble of the heavy metals, implying that it is more bioavailable than the other non‐essential metals, Pb and Ni. The total (aqua regia soluble) concentrations of Cd, Cu, Zn, and Ni and the concentrations of DTPA‐extractable Cd and Ni were significantly higher in the loam soils than in the sandy loam soils. The amount of NH₄NCyextractable metals did not differ between the texture classes. The concentrations of DTPA‐extractable metals were positively and significantly correlated with the total concentrations of the same metals. Ammonium nitrate‐extractable metals, on the other hand, were not related to their total concentrations, but they were negatively and significantly correlated to soil pH. The average concentration of Cd (0.1 mg kg^‐1 d.w.) in the plants was relatively high compared to the concentration previously found in plants grown on the other soils. The concentrations of the other heavy metals Cu, Zn, Mn, Ni, and Pb in the plants were considered to be within the normal range, except for some samples with relatively high concentrations of Ni and Mn (0–11.1 and 3.5 to 167 mg kg‘¹ d.w., respectively). The concentrations of Cd, Cu, Zn, Ni, and Mn in grain were positively correlated to the concentrations of these respective metals in the soil extracted by NH₄NO₃. The plant concentrations were negatively correlated to pH. The DTPA‐extractable levels were not correlated with plant concentration and hence DTPA would not be a good extractant for determining plant availability in these soils.     

Fraction Distributions of Lead,Cadmium, Copper,and Zinc in Metal‐Contaminated Soil before and after Extraction with Disodium Ethylenediaminetetraacetic Acid

Abstract: The fraction distributions of heavy metals have attracted more attention because of the relationship between the toxicity and their speciation. Heavy‐metal fraction distributions in soil contaminated with mine tailings (soil A) and in soil irrigated with mine wastewater (soil B), before and after treatment with disodium ethylenediaminetetraacetic acid (EDTA), were analyzed with Tessier's sequential extraction procedures. The total contents of lead (Pb), cadmium (Cd), copper (Cu), and zinc (Zn) exceeded the maximum permissible levels by 5.1, 33.3, 3.1, and 8.0 times in soil A and by 2.6, 12.0, 0.2, and 1.9 times in soil B, respectively. The results showed that both soils had high levels of heavy‐metal pollution. Although the fractions were found in different distribution before extraction, the residual fraction was found to be the predominant fraction of the four heavy metals. There was a small amount of exchangeable fraction of heavy metals in both contaminated soils. Furthermore, in this study, the extraction efficiencies of Pb, Cd, and Cu were higher than those of Zn. After extraction, the concentrations of exchangeable Pb, Cd, Cu, and Zn increased 84.7 mg·kg^?1, 0.3 mg·kg^?1, 4.1 mg·kg^?1, and 39.9 mg·kg^?1 in soil A and 48.7 mg·kg^?1, 0.6 mg·kg^?1, 2.7 mg·kg^?1, and 44.1 mg·kg^?1 in soil B, respectively. The concentrations of carbonate, iron and manganese oxides, organic matter, and residue of heavy metals decreased. This implies that EDTA increased metal mobility and bioavailability and may lead to groundwater contamination.     

Effect of sewage sludge application on cotton yield and contamination of soils and plant leaves

Abstract

In a two‐year field experiment, dry sewage sludge was applied to fields plots at rates of 0,26,42,58, or 77 tons ha^‐1 year^‐1 on a clay loam soil (calcixerrolic xerochrept), well drained with a pH value of 8.15. Cotton was the cultivated plant (Gossypiumhirsutum variety korina). Sequential extraction was used to separate the different forms of the metals (exchangeable, organically bound, carbonates and residual) in the soil‐sludge mixtures. Cotton yield increased in the second year of experimentation compared with the control treatment (without fertilization and no application of sewage sludge). Most of the metals studied [cadmium (Cd), zinc (Zn), copper (Cu), and nickel (Ni)] were found in the organically bound, carbonate or residual forms. From the elements in the soil fractions, only Zn in the residual form was correlated with the Zn content of cotton leaves. The diethylenetriaminepentaacetic acid (DTPA) extraction of the plant‐available levels of the elements showed only for Cd a simple linear correlation, between concentration in soils and cotton leaves.     

北京市五环内绿地土壤4种重金属的形态特征及其生物有效性

[目的]了解北京市五环内绿地表层(0—20cm)土壤重金属(Cu,Cd,Pb和Zn)的形态特征及其生物有效性,为北京市绿地土壤重金属污染防治提供比较可靠的参考依据。[方法]在建成时间为2~400a的绿化区内共采集表层土壤样品151个,运用改进BCR提取法分析样品中重金属的赋存形态,而后通过风险评价编码法(RAC)和次生相与原生相分布比值法(RSP)对重金属生物有效性进行评估。[结果]样品中重金属Cu,Cd,Pb和Zn的含量分别为31.42,0.29,29.89,76.78 mg/kg,Cu,Zn在中部和东北部含量较高,Pb在中部地区含量较高,Cd在西北部、东北部和南部存在少量高值区。Cu,Cd,Pb和Zn形态分布的总体规律均为:残渣态可氧化态弱酸溶态可还原态,稳定态含量均远高于有效态,有效态含量比例表明重金属生物有效性大小顺序为:CdZnCuPb风险评价编码法(RAC)表明,Cd和Zn环境风险程度为低风险,Cu和Pb无环境风险。次生相与原生相分布比值法(RSP)显示,Cu,Cd,Pb和Zn元素RSP值分别为0.06,0.49,0.18,0.13,土壤整体上未受到重金属污染,但是有少部分地区存在被污染现象。[结论]北京市五环内绿地土壤总体上不存在重金属Cu,Cd,Pb和Zn污染,环境风险较低,但应对重金属赋存形态保持关注。     

Retention of Metals in Agricultural Soils After Amending with MSW and MSW-Biosolids Compost

The goal of this study was to measure the As, Cu, Fe, Pb and Zn contents of soils amended with municipal solid waste (MSW) and MSW-biosolids compost and to determine the long-term transport of these metals to lower soil horizons. Lead, Cu, Cd and Zn contents in the composts were 3–20 times more concentrated in the compost compared to the soil at the Calverton, NY, U.S.A. farm. As a result, Pb, Cd, Cu and Zn were elevated in the upper 5 cm soil layer following compost application and the metal enrichment was proportional to the amount of compost applied (21–62 Mg ha^-1). In addition, Pb, As and Cu contents of the non-compost amended Calverton soils were enriched above the tillage depth (20–25 cm). Cu, Pb and As enrichment was attributed to the historical use of sodium arsenite, lead arsenate and copper sulfate insecticides and fungicides. Results of the metal analyses of soil cores collected 16 and 52 months following compost application showed that Cu, Zn and Pb remained confined to the upper 5 cm soil layer. The low water extractable fraction of these metals in MSW and MSW-biosolids compost was a major factor limiting the transport of these metals to lower soil horizons. In contrast, Cd leaching from the upper 0–5 and 5–10 cm soil layers was continuous over the 52 month study period and was attributed primarily to the presence of soluble Cd in phosphate fertilizer initially applied to the Calverton farm soil.     

Residual heavy metal concentrations in sludge‐amended coastal plain soils ‐ I. Comparison of extractants

Abstract

The purposes for this research were: to examine the long‐term residual effects of farmland applications of municipal sludges from four treatment technologies on the total and extractable Zn, Cu, Mn, Fe, Pb, Ni and Cd concentrations in Coastal Plain soils; to investigate the effects of sludge sources and rates on the effectiveness of soil extractants to remove the various metals; and to determine correlation coefficients for soil extractable versus plant accumulation in tobacco. The extractants evaluated were Mehlich 1 and 3, and DTPA‐pH 7.3. Composite Ap horizon soil samples and tobacco leaf samples were obtained in 1984 from research plots at two sites in Maryland that were established in 1972 and 1976, respectively, using sludge materials from three wastewater treatment facilities in the Washington, D.C. metropolitan region. Similar application rates were used at both sites.

A wide range in soil pH values was found among treatments at each site. Significant (p ≤ 0.05) increases were observed in total Zn, Cu, Fe, Pb, Ni, and Cd for all sludge sources with increased rates; however, values for total soil Mn exhibited high variability in all cases. The rankings among the extractants varied for some elements depending on the sludge sources. For Zn, the rankings were Mehlich 1 > Mechlich 3 > DTPA‐pH 7.3 across all sources and rates. For Cu, Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was found for soils amended with Blue Plains digested (BPD) and Piscataway limeddigested (PLD) sludges but Mehlich 1 ≥ DTPA pH 7.3 > Mehlich 3 for Blue Plains limed compost (BPLC) and Annapolis Fe and heat treated (AFH) sludges. Concerning extractable Mn, Mehlich Mehlich 1 > Mechlich 3 > DTPH pH 7.3 was the order for BPLC and AFH sludges but Mehlich 3 > Mehlich 1 > DTPA‐pH 7.3 was observed for BPD and PLD sludges. The rankings among extractants for Fe (Mehlich 3 > Mehlich 1 > DTPA‐pH7.3), Ni (Mehlich 3 ≥ Mehlich 1 > DTPA‐pH 7.3), Pb (Mehlich 3 > DTPA‐pH 7.3 > Mehlich 1) and Cd (Mehlich 1 > Mehlich 3 > DPTA‐pH7.3) were somewhat similar across all sludge sources. Significant correlation coefficients were obtained for all three extractants for soil extractable vs. plant Zn, Cu, Ni, and Cd at both sites; however, Mehlich 3 was not significant for Mn. Also, neither of the extractants produced significant coefficients for Fe and Pb.     

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.     

Kinetics of Desorption of Heavy Metals from Polluted Soils: Influence of Soil Type and Metal Source

Kinetics of desorption of heavy metal ions (Cd, Cu, Ni and Zn) from the surface (0–15 cm) samples of an acidic soil (Inceptisol) and a neutral soil (Mollisol) spiked with inorganic salts of these metals or through an acidic sludge were studied by the column method. The rate of desorption of soil applied heavy metals was initially rapid and gradually declined with time. In general, the release of heavy metals from soils polluted by inorganic or sludge sources conformed to a multi-site model of first order kinetics; however, the release of Cd and Ni applied through inorganic sources to the neutral soil could be adequately accounted for by single-site model. The double-site model could adequately explain the release of Cd from sludge amended acidic soil and the release of Zn applied though inorganic salt or sludge to the neutral soil. In acidic soil, the apparent desorption rate coefficients of heavy metals applied through inorganic sources were higher than those for the sludge source. In neutral soil, however, the apparent desorption rate coefficients of heavy metals added through sludge were higher than for inorganic sources. Among the heavy metals, the higher apparent desorption coefficient value and percent desorption of Cd indicated a higher potential of this metal for leaching and ground water contamination. The results also suggested that the acidic soil pH might reduce the ability of the soil to naturally sequester heavy metal cations and lead to their leaching.