受土壤类型和金属负荷量影响的重金属形态分布

Two series of soil subsamples, by spiking copper(Cu),lead(Pb),zinc(Zn)and cadmium(Cd)in an orthogonal design,were prepared using red soil and brown soil,respectively.The results indicated that heavy metal fractions in these soil subsamples depended not only on soil types,but also on metal loading quantity as well as on interactions among metals in soil.Lead and Cu in red soil appeared mostly in weakly specifically adsorbed(WSA),Fe and Mn oxides bound(OX),and residual(RES)fractions.Zine cxisted in all fractions except organic bound one,and Cd was major in water soluble plus exchangeable(SE)one.Different from the results of red soil,Pb and Cu was present in brown soil in all fractions except organic one,but over 75% of Zn and 90% of Cd existed only in SE fraction.Meanwhile,SE fraction for any metal in red soil was lower than that in brown soil and WSA and OX fractions were higher.It is in agreernent with low cation exchange capacity and large amounts of metal oxides included in red soil.Metal fractions in soil,especially for water soluble plus exchangeable one ,were obviously influenced by other coexisting metals.The SE fraction of heavy metals increased with increasing loading amounts of metals in red soil but not obviously in brown soil,which suggest that metal availability be easily affected by their total amounts spiked in red soil.In addition,more metals in red soil were extracted with 0.20 mol L^-1 NH4Cl（pH5.40）than that with 1.0 mol L^-1 Mg(NO3)2(pH7.0),but the reverse happened in brown soil,implicating significantly different mechanisms of metal desorption from red soil and brown soil.     

Evaluation of four soil test extractants for Zimbabwe soils

Abstract

The objective of this research was to compare the results from anion exchange Resin extraction of P, and the acidified ammonium acetate (AA) extraction of K and Mg with the results obtained using two single extraction procedures, Mehlich 1 (M‐l) and Mehlich 3 (M‐3). Phosphorus extracted from 72 Zimbabwe soils using M‐l and M‐3 was comparable to Resin extracted P in about 80% of the soils. Mehlich 1 extracted about half the amount of P as the Resin method, and M‐3 extracted about one and one‐half times as much. Phosphorus by M‐3 was highly correlated, (r — 0.846), with Resin extracted P from soils having 0.01M CaCl₂ pH values of equal to or greater than 5.9. On soils less than pH 5.9, the r value was 0.502, and for all soils, the r value for M‐3 vs Resin P was 0.615. Mehlich 1 extracted P vs Resin P had a r value of 0.298. Acidified ammonium acetate (AA) extraction of K and Mg was comparable to M‐l and M‐3 extraction of K and Mg in 92% or more of the 72 soils. The K correlation coefficient (r) for AA vs M‐l and AA vs M‐3 was 0.918 and 0.944, respectively. The Mg correlation coefficient (r) for AA vs M‐l and AA vs M‐3 was 0.940 and 0.962, respectively.     

Comparing tests for soil fertility: 1. Conversion equations between olsen and mehlich 3 as phosphorus extractants for 120 soils of south italy

Abstract

The multiple‐element extractant Mehlich 3 (M3) has not been tested extensively in Europe. In this Land, soil‐P test recommendations are based, since decades, on the evaluation of the Olsen‐extractable P, and the optimal soil‐P levels have been established to range between 1.5 and 3.0 mg of Olsen‐P per 100 g of soil. A research programme was started in order to assess the suitability of M3 as routine soil‐P test in European laboratories. As a first approach, we develop conversion equations from Olsen‐P to M3‐P, in order to assess the agreement and the consistency of the measurements under a wide range of chemical and physical soil properties. To this aim, 120 samples with drastically contrasting features were selected within 206 soils collected from all the regions of South Italy. Soil‐P ranges were 0.07–60.53 for M3, and 0.08–21.47 mg/100 g for Olsen. The results showed that M3‐P was a P extractant more efficient than Olsen. The amounts of M3‐P were, on the average, twice as large as the Olsen‐P ones, with mean values of 5.70 and 2.75 mg/100g, respectively. The soil properties exerted a great influence, as well as showed a contrasting effect, on the extraction efficiency of each method. For neutral‐alkaline calcareous soils, the average M3‐P/Olsen‐P ratio increased to 2.52, and the efficiency of M3 poorly varied according to soil pH and CaCO₃ content. On the contrary, in CaCO₃‐free acidic soils, the M3‐P/Olsen‐P ratio decreased to 1.63. In particular, anomalous ratio values less than 1.0 were observed for acidic soils with high content of organo‐mineral complexes with be shifted to 3.7–7.7 for calcareous soils, and to 2.7–4.9 for CaCO₃‐free soils. Field calibrations would give more information to establish the proper values according to either the soil properties and plant requirements. The results encourage the introduction of M3 as routine soil‐P test in our Countries. One must take into account, however, that some soil properties, in particular the CaCO₃ content, migth be considered for a more precise comparative evaluation with existing laboratory data.     

A comparison of Mehlich I and Mehlich III extractants as predictors of manganese,copper and zinc availability in four Delaware soils

Abstract

The relative effectiveness of Mehlich I (.025N H₂SO₄ + .05N HCl) and Mehlich III (0.2N CH₃COOH + 0.25N NH₄NO₃ +.015N NH₄F + .013N HNO₃ + .001M EDTA) extractants as predictors of Mn, Cu and Zn uptake was assessed in a greenhouse experiment with four Delaware soils. The soils were adjusted to eight pH levels by addition of Ca(OH)₂ or elemental S, and received comparable amounts of Mn, Cu and Zn as either (1) MnSO₄ + CuSO₄ + ZnSO₄ or (2) Poultry Manure. Mehlich 1 and III extractable Mn and Zn, but not Cu, were well correlated in most instances. Excellent correlations were obtained between Mn uptake and Mehlich I and Mehlich III extractable Mn, for all soils and sources. In general, however, neither Zn nor Cu was found to correlate well with plant uptake. Based on this study, conversion to Mehlich III, as a routine soil test extractant for micronutrients, would not result in a significant improvement over the currently used Mehlich I extractant.     

Comparison of soil tests to determine micronutrients status in Argentina soils

Abstract

Soil extraction techniques to measure the status of available micronutrients for plants are important in the diagnosis of deficiency or toxicity. Mehlich 3 (M3), EDTA (pH=8.2), DTPA‐TEA, and Soltanpour and Schwab (SS) solutions were confronted for their ability to extract simultaneously copper (Cu), zinc (Zn), manganese (Mn), and iron (Fe). Argentinean soils from different taxonomic orders with widely varying properties were investigated. The values obtained showed that DTPA‐TEA and SS solutions extracted similar amounts of Zn, Fe, and Mn, while EDTA dissolved comparatively higher amounts of Fe and Mn. Mehlich 3 yielded the highest extractions for the four micronutrients. Soil pH not only affected the extraction of Mn by DTPA‐TEA, SS, and EDTA extractions, but also the extraction of Fe by EDTA. The organic carbon affected the determination of Fe and Zn in all cases. The correlations of the different tests for Cu, Zn, Mn, and Fe were significant. The results suggest that for the determination of the bioavailable status of micronutrients, any of the studied tests could be applied using the soil edaphic properties as factors to improve the correlations between them and standardize the methods.     

Comparison of extractants for available sludge-borne metals: A residual study

To study the availability of sludge-borne Zn, Cu, Cd, Ni and Pb over time, a field study was conducted. Anaerobically digested sewage sludge (dried on sandbeds) from Huntsville and Chicago were applied to a Decatur silty clay loam soil (clayey, kaolinitic, thermic, Rhodic Paleudult), pH 6.2, for 5 consecutive yr. The sludges were applied at rates of 0, 20 (annual application for 5 yr) and 100 mt ha^?1 (single application). Corn (Zea mays L.) and sudangrass (Sorghum sudanenses) were grown on the sludge-treated plots as test crops in 1987. Plant tissue samples were collected at different growth stages. Soil samples collected from the sludge-treated plots were extracted for Zn, Cu, Cd, Ni and Pb by 0.1 M HCI, DTPA, Mehlich 1 and Mehlich 3 extractants. Statistically, Mehlich 1, Mehlich 3, DTPA and 0.1M HCI extractants all gave highly significant correlations with the plant accumulation of Zn, Cu, Ni and Cd, with DTPA giving the highest at any growth stage for both corn and sudangrass, but they gave poor correlations for Pb. Zinc removed by four extractants was more highly correlated with Zn accumulation by corn (r=0.72^** to 0.93^** p=0.01) and sudangrass (r=0.50^** to 0.96^**, p=0.01) than other metals. Based on higher significant linear correlation coefficients (r), DTPA would be the extractant of choice for both crops; however the advantage to using the Mehlich 3 extractant is that, with a shorter shaking time of 5 min (compared to 2 hr for DTPA), it may be better suited for routine analysis of large numbers of soil samples.

     

Comparison of methods for measuring heavy metals and total phosphorus in soils contaminated by different sources

The relationships between the concentrations of zinc (Zn), lead (Pb), copper (Cu), nickel (Ni) and chromium (Cr) as measured by X-ray fluorescence analysis (XRF), aqua regia, and HNO₃ pressure digestion were studied in soil samples covering a wide range of heavy metal concentrations. The soils were contaminated by sewage sludge, exhaust depositions, river sediments of mining residues, and dump material. The question was addressed whether the source of heavy metals or other soil properties affect the relationship between these three methods. The aqua regia-digestible fraction of the five heavy metals reached on average 64% of the XRF-detectable content. The pressure accelerated HNO₃-digestible fraction of the five heavy metals was on average 71% of the XRF-detectable content; the respective phosphorus (P) fraction reached a median of 75%. This suggests that HNO₃ pressure digestion can also be used for characterizing the total P content of soils. Aqua regia extraction and HNO₃ pressure digestion gave similar values for Zn, Pb, and Cu, which dominate the heavy metal load of most contamination sources. Significantly higher Cr values were obtained by HNO₃ pressure digestion than by aqua regia extraction. Additionally, the Cr contents were affected by the source, e.g. sewage sludge had relatively high contents of aqua regia and HNO₃ pressure extractable contents in comparison to the XRF values. The element-specific relationships between the three methods were all highly significant. However, the respective multiple linear regression models were in most cases affected by soil organic carbon (C), in some cases by clay or soil pH.     

Standards for the contents of heavy metals and metalloids in soils

In line with the present-day ecological and toxicological data obtained by Dutch ecologists, heavy metals/metalloids form the following succession according to their hazard degree in soils: Se > Tl > Sb > Cd > V > Hg > Ni > Cu > Cr > As > Ba. This sequence substantially differs from the succession of heavy elements presented in the general toxicological GOST (State Norms and Standards) 17.4.1.02-8, which considers As, Cd, Hg, Se, Pb, and Zn to be strongly hazardous elements, whereas Co, Ni, Mo, Sb, and Cr to be moderately hazardous. As compared to the general toxicological approach, the hazard of lead, zinc, and cobalt is lower in soils, and that of vanadium, antimony, and barium is higher. The new sequence also differs from that of the metal hazard in soils according to the Russian standard on the maximal permissible concentration of mobile metal forms (MPC_mob): Cu > Ni > Co > Cr > Zn. Neither an MPC_mob nor an APC_mob has been adopted for strongly hazardous thallium, selenium, and vanadium in Russia. The content of heavy metals in contaminated soils is very unevenly studied: 11 of them, i.e., Cu, Zn, Pb, Ni, Cd, Cr, As, Mn, Co, Hg, and Se, are better known, while the rest, much worse, although there are dangerous elements (Ba, V, Tl) among them.     

Natural and technogenic compounds of heavy metals in soils

The existing geological classification of heavy metals (HMs) is not suitable for their characterization in soils. The carriers of HMs in soils differ from those in the lithosphere. These are clay minerals; iron oxides, whose composition varies between the background and urban soils; various manganese oxides; and different groups of organic substances. The mineral composition of HM carriers can vary significantly. The main iron oxides are ferrihydrite, goethite, feroxyhyte, and lepidocrocite in the background soils and technogenic magnetite in the urban soils. The different structures of manganese oxides determine their affinity for specific HMs. Metallic iron and green rust are very efficient in artificial geochemical barriers, although they act as strong reducers there. HM compounds strongly vary in soils because of the unstable conditions.     

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.     

Accumulation of heavy metals in oil-contaminated peat soils

X-ray fluorescence and X-ray radiometry represent easy and simple methods to determine concentrations of heavy metals in the ash of peat soils contaminated with oil and can be applied for soil monitoring purposes. Oil spills on peat bogs produce two contamination zones differing in the composition of heavy metals. In the zone of primary contamination, the peat surface is covered by a bitumen crust with V, Ni, Sr, Ba, Ce, and La accumulating there. This zone adjoins the zone of secondary peat contamination, where heavy alkaline-earth metals (Sr, Ba) and lanthanides (Ce and La) are accumulated to a lesser extent. Biological preparations recommended for remediation of oil-contaminated peat soils should be tolerant to high concentrations of heavy metals, particularly, V, Ni, and Ba that are present in the oil contaminated soils in relatively high amounts.     

Glyphosate degradation as a soil health indicator for heavy metal polluted soils

Glyphosate is a commonly used herbicide in grassland soils and microorganisms control its degradation. We introduce the concept of using the degradation rate as an indicator for ecosystem health. Testing this concept, we used soils with a long history of heavy metal pollution (Cu, Pb, and Zn). We hypothesized lower degradation rates in metal-polluted compared to less polluted soils. The degradation rates were measured by repeated measurements of the parent compound in spiked soil-water slurries incubated at 20 °C over 21 days. Average rates showed no differences comparing among soils. We observed a positive correlation between glyphosate degradation rates and soil metal pollution. Therefore, we concluded that the expected impact of the metals on the bacteria responsible for the herbicide degradation was not established. We discuss the potential influence on biological degradation rates of soil pH and adsorption and implications using the concept of the soil health indicator.     

Mobility of heavy metals in pine forest soils as influenced by experimental acidification

The mobility of Pb, Zn, Cd and Cu was examined at two adjacent experimental plots at åmli, southern Norway, B-1 and B-2. Both experiments were established on the same glacifluvial deposits, with forest consisting of uniform stands of Pinus sylvestris L. The forest in B-1 was planted between 1968 and 1970, while B-2 consisted of naturally regenerated trees. The experiments included plots supplied with artificial rain of varying acidity over a period of seven and eight years for B-1 and B-2, respectively, in addition to control plots. In experiment B-1, experimental acidification was carried out both in unlimed plots and in plots applied with three different levels of lime. The two experiments showed distinct differences with respect to effects of the acidification on mobilization of heavy metals from the O horizon. In experiment B-1, the amount of Zn and Cd decreased with decreasing pH in artificial rain, while Pb and Cu were not appreciably affected. The reduction in Zn and Cd concentrations ceased after termination of the acidification experiment. Liming reduced the leachability of Zn, but still appreciable amounts of Zn were obviously leached from the O horizon during the experiment. In experiment B-2 a high retention even of Zn and Cd was observed in the O horizon, probably due to microbial uptake and accumulation.     

北京耕地土壤重金属空间自回归模型及影响因素

为了揭示土壤重金属含量与其影响因素间的作用关系,为土壤重金属的污染控制和治理提供参考,该研究以北京市耕作土壤重金属元素为例,采用传统线性回归模型和空间自回归模型分析和比较了土壤重金属含量及其影响因素间的相关关系。结果表明：Cr、Ni、Zn、Hg空间自回归模型的拟合度较传统线性回归模型好,并且残差的空间自相关性消失。因此,空间自回归模型能够很好地解释重金属含量与其影响因素间的相关关系。结果表明：Cr、Ni含量的影响因素主要为土壤母质和土地利用强度,Zn、Hg含量的主要影响因素为道路、工矿企业和土壤母质。     

Assessment of the migration of heavy metals in soils

Qualitative and quantitative studies of the kinetics and dynamics of technogenic migration of heavy metals (HMs) have been performed in laboratory experiments. It is shown that the redistribution of HMs applied into soils in neutral form has an impulsive pattern. Soil texture does not have a decisive influence on the migration capacity of metals. An important feature of the technogenic migration of HMs is the effect of the polymetallic contamination, upon which the migration capacity of a set of heavy metals is higher than that of separate metal compounds. An index characterizing the ratio of absolute values of migration rates of ionic forms of metals estimated from electrical conductivity values to the rate of infiltration of the soil solution (v_m/v_f) is suggested to estimate the kinetics of HM migration in soils.     

典型设施栽培土壤重金属含量变化及其风险评价

采用野外调查采样和室内分析相结合的方法,对典型设施栽培地山东寿光的部分土壤重金属含量进行测定,并根据温室蔬菜产地环境质量评价标准,选取单项污染指数法和尼梅罗综合指数法对土壤的重金属污染状况进行了环境质量评价。结果表明,重金属Cu、C r、Pb在设施栽培土壤耕层(0—20 cm)的含量达最大值,显著高于露地土壤;而设施栽培土壤中Zn和Cd的含量分别在20—40 cm和40—60 cm的土层达到最大值,其中Zn含量在0—20 cm和60—80 cm的土层显著高于露地土壤,Cd含量在0—20 cm,40—60 cm,60—80 cm和80—100 cm的土层显著高于露地土壤。从不同使用年限设施栽培土壤中重金属含量变化看出,重金属在设施栽培24~年的土壤中含量最高。对研究区设施栽培土壤重金属含量进行风险评估及分级发现,山东寿光设施土壤耕层主要受到重金属Cd的污染。     

Comparison of four extractants and chemical fractions for assessing available zinc and copper in soils of India

Abstract

Relative suitability of different extraction procedures for estimating available zinc (Zn) and copper (Cu) in soils was assessed using DTPA, 0.1 N HCl, ammonium acetate+EDTA, and double acid (HCl+ H₂SO₄) as extractants and rice as a test crop in Neubauer experiment. The relationships between Zn concentration and uptake of Zn by rice plants and Zn extracted by the different methods showed that DTPA‐TEA, pH 7.3, could very suitably be used to assess Zn availability in soils. However, 0.1 N HCl was better for assessing the Cu availability in soils to the rice plants. Water‐soluble and exchangeable fractions of Zn and Cu had significant positive correlations with Zn and Cu concentrations, respectively obtained by all the four extractants tested. The results also showed that DTPA and ammonium acetate+EDTA extracted organically bound Zn, whereas DTPA, 0.1 N HCl and ammonium acetate+EDTA extracted organically bound Cu. Water‐soluble, exchangeable and organic matter bound fractions exhibited significant relationships with Zn and Cu concentrations, their uptake and rice dry matter yield.     

Occurrence and infectivity of arbuscular mycorrhizal fungi in some norwegian soils influenced by heavy metals and soil properties

Mycorrhizae are ubiquitous symbiosis which can mediate uptake of some plant nutrients. In polluted soils they could be of great importance in heavy metal availability and toxicity to plants. Mycorrhizae have also been reported to protect plants against toxic metals. We investigated the occurrence and infectivity of arbuscular mycorrhizal (AM) spores as affected by heavy metal levels and other soil properties in Norwegian soils collected from heavy metal polluted, high natural background and non-polluted areas. Spore numbers, mycorrhizal infectivity and spore germination of indigenous mycorrhizal fungi and of a reference strain (Glomus mosseae) in soils showed lower values in two soils with high metal concentrations and in one soil with a low pH. Mycorrhizal infectivity was negatively correlated with extractable metals. Spore number and mycorrhizal infectivity in a soil with naturally high heavy metal content were not different to in non-polluted soils, and indigenous AM fungi appeared more tolerant to metals than those in non-polluted soils. Mycorrhizal infectivity, expressed as MSI₅₀ values, was significantly correlated (r′=0.89, P< 0.05) with the percentage of germinating G. mosseae spores in the soils. However, the number of spores per volume of soil was not significantly correlated with infectivity or spore germination of the reference strain. The spore germination method is discussed as a bioassay of heavy metal toxicity in soil.     

森林土壤重金属的分布和迁移: 一种高密度采样方法的应用

The vertical distribution and migration of Cu, Zn, Pb, and Cd in two forest soil profiles near an industrial emission source were investigated using a high resolution sampling method together with reference element Ti. One-meter soil profile was sectioned horizontally at 2 cm intervals in the first 40 cm, 5 cm intervals in the next 40 cm, and 10 cm intervals in the last 20 cm. The migration distance and rate of heavy metals in the soil profiles were calculated according to their relative concentrations in the profiles, as calibrated by the reference element Ti. The enrichment of heavy metals appeared in the uppermost layer of the forest soil, and the soil heavy metal concentrations decreased down the profile until reaching their background values. The calculated average migration rates of Cd, Cu, Pb, and Zn were 0.70, 0.33, 0.37, and 0.76 cm year^-1, respectively, which were comparable to other methods. A simulation model was proposed, which could well describe the distribution of Cu, Zn, Pb, and Cd in natural forest soils.     

贵阳市主要土壤重金属状况研究

通过对2000～2003年贵阳市的白云区、修文县、开阳县、清镇市、息烽县、乌当区、小河区以及花溪区的多个旱地的表土和底土（53个样品）中重金属元素（汞、砷、铅、镉、铬）含量进行检测，以GB／T18407．1—2001《农产品安全质量无公害蔬菜产地环境要求》为标准，采用单因子指数法及N．L．Nemerow综合指数法进行评价，分析结果表明：贵阳市无公害蔬菜生产基地的大部分土壤中的5种重金属元素的含量基本在GB／T18407．1—2001规定的范围内，但也有个别区域内土样中砷、镉含量达到了警戒线的含量范围，如白云区底土中砷的单因子综合污染指数达到0．7968、乌当区表土中镉的单因子综合污染指数达到0．7542，两者都属于0．7～1．0污染警戒线范围内。总体土壤的表土、底土重金属综合污染指数分别为0．3785、0．4204，小于0．7，污染等级属于安全，污染水平为清洁，土壤环境质量为1级。