土壤性质对烟草中镉富集的影响及预测模型研究

利用15个不同性质的土壤进行盆栽试验,研究了土壤性质对烟草中镉(Cd)富集的影响及预测模型。结果表明,影响烟草中Cd的主要土壤因素依次为土壤Cd浓度、pH、有机质含量。酸性土壤中烟草对土壤Cd具有较强的富集作用。外源Cd比土壤中原生Cd更容易被烟草吸收。土壤基本性质与烟草Cd浓度的数量关系为:Log[烟草Cd]=3.04+1.212Log[土壤Cd]-0.270pH-0.264Log[OC],利用此方程能够很好地预测烟草中Cd浓度。通过降低土壤中Cd的浓度或有效性,提高土壤pH等措施可有效降低烟叶中Cd的浓度。     

Modelling trace metal extractability and solubility in French forest soils by using soil properties

Soil/solution partitioning of trace metals (TM: Cd, Co, Cr, Cu, Ni, Sb, Pb and Zn) has been investigated in six French forest sites that have been subjected to TM atmospheric inputs. Soil profiles have been sampled and analysed for major soil properties, and CaCl₂‐extractable and total metal content. Metal concentrations (expressed on a molar basis) in soil (total), in CaCl₂ extracts and soil solution collected monthly from fresh soil by centrifugation, were in the order: Cr > Zn > Ni > Cu > Pb > Co > Sb > Cd , Zn > Cu > Pb = Ni > Co > Cd > Cr and Zn > Ni > Cu > Pb > Co > Cr > Cd > Sb , respectively. Metal extractability and solubility were predicted by using soil properties. Soil pH was the most significant property in predicting metal partitioning, but TM behaviour differed between acid and non‐acid soils. TM extractability was predicted significantly by soil pH for pH < 6, and by soil pH and Fe content for all soil conditions. Total metal concentration in soil solution was predicted well by soil pH and organic carbon content for Cd, Co, Cr, Ni and Zn, by Fe content for Cu, Cr, Ni, Pb and Sb and total soil metal content for Cu, Cr, Ni, Pb and Sb, with a better prediction for acidic conditions (pH < 6). At more alkaline pH conditions, solute concentrations of Cu, Cr, Sb and Pb were larger than predicted by the pH relationship, as a consequence of association with Fe colloids and complexing with dissolved organic carbon. Metal speciation in soil solutions determined by WHAM‐VI indicated that free metal ion (FMI) concentration was significantly related to soil pH for all pH conditions. The FMI concentrations of Cu and Zn were well predicted by pH alone, Pb by pH and Fe content and Cd, Co and Ni by soil pH and organic carbon content. Differences between soluble total metal and FMI concentrations were particularly large for pH < 6. This should be taken into account for risk and critical load assessment in the case of terrestrial ecosystems.     

Solubility,sorption and desorption of native and added cadmium in relation to properties of soils in New Zealand

Solution cadmium (Cd) concentrations and sorption and desorption of native and added Cd were studied in a range of New Zealand soils. The concentration of Cd in solution and the concentrations and patterns of native soil Cd desorbed and added Cd sorbed and desorbed varied greatly between the 29 soils studied. Correlation analysis revealed that pH was the most dominant soil variable affecting solution Cd concentration and sorption and desorption of native and added Cd in these soils. However, organic matter, cation exchange capacity (CEC) and total soil Cd were also found to be important. Multiple regression analysis showed that the log concentration of Cd in solution was strongly related to soil pH, organic matter and total Cd, which in combination explained 76% of the variation between soils. When data from the present study were combined into a single multiple regression with soil data from a previously published study, the equation generated could explain 81% of the variation in log Cd solution concentration. This reinforces the importance of pH, organic matter and total Cd in controlling solution Cd concentrations. Simple linear regression analysis could at best explain 53% of the total variation in Cd sorption or desorption for the soils studied. Multiple regression analysis showed that native Cd desorption was related to pH, organic matter and total Cd, which in combination explained 85% of the variation between soils. For sorption of Cd (from 2 μg Cd g^–1 soil added), pH and organic matter in combination explained 75% of the variation between soils. However, for added Cd desorption (%), pH and CEC explained 77%. It is clear that the combined effects of a range of soil properties control the concentration of Cd in solution, and of sorption and desorption of Cd in soils. The fraction of potentially desorbable added Cd in soils could also be predicted from a soil’s K_d value. This could have value for assessing both the mobility of Cd in soil and its likely availability to plants.     

重金属的土水分配行为研究——根际土壤溶液采样器的应用

采用根际土壤溶液采样器(Rhizon-SMS)原位采集河南平原耕地土壤溶液.用土壤溶液中重金属浓度对数作为因变量、土壤溶液理化性质作为自变量,进行多元线性逐步回归,结果表明:只有有机碳进入Cu的相关方程,pH进入Cd的相关方程.土壤溶液pH和土壤中的Zn都作为自变量进入Zn的相关方程.土壤溶液中的Cu与pH没有线性关系,而Cd和Zn与土壤溶液pH有显著的线性关系(p＜0.01).计算了土壤中Cu、Cd、Zn在土壤与土壤溶液中的分配系数Kd.本研究中,3种重金属的Kd大小顺序为:Cu＞Zn＞Cd.根据Freeze 和Cherry模型,联合log(Kd-Cd)、log(Kd-Zn)与pH的线性关系,估计了Cd和Zn在土壤中的迁移速度.     

根迹土壤根诱导的化学变化对植物吸收重金属的影响

It is increasingly recognized that metal bioavailability is a better indicator of the potential for phytoremediation than the total metal concentration in soils; therefore, an understanding of the inffuence of phytoremediation plants on metal dynamics at the soil-root interface is increasingly vital for the successful implementation of this remediation technique. In this study, we investigated the heavy metal and soil solution chemical changes at field moisture, after growth of either Indian mustard (Brassica juncea) or sunffower (Helianthus annuus L.), in long-term contaminated soils and the subsequent metal uptake by the selected plants. In addition, the fractions of free metal ions in soil solution were determined using the Donnan membrane technique. After plant growth soil solution pH increased by 0.2-1.4 units and dissolved organic carbon (DOC) increased by 1-99 mg L^-1 in all soils examined. Soluble Cd and Zn decreased after Indian mustard growth in all soils examined, and this was attributed to increases in soil solution pH (by 0.9 units) after plant growth. Concentrations of soluble Cu and Pb decreased in acidic soils but increased in alkaline soils. This discrepancy was likely due to a competitive effect between plant-induced pH and DOC changes on the magnitude of metal solubility. The fractions of free Cd and Zn ranged from 7.2% to 32% and 6.4% to 73%, respectively, and they generally decreased as pH and DOC increased after plant growth. Metal uptake by plants was dependant on the soil solution metal concentration, which was governed by changes in pH and DOC induced by plant exudates, rather than on the total metal concentrations. Although plant uptake also varied with metal and soil types, overall soluble metal concentrations in the rhizosphere were mainly inffuenced by root-induced changes in pH and DOC which subsequently affected the metal uptake by plants.     

THE CONTENTS AND SORPTION OF CADMIUM IN SOME AGRICULTURAL SOILS OF ENGLAND AND WALES

Cadmium sorption was measured in 10 agricultural soils with pH ranging from 4.5 to 7.9, and total Cd content from 0.27 to 1.04 μg g^?1 dry soil. With initial Cd concentrations of 0.5 to 100.0 μM, sorption from 0.002 M CaCl₂ was described by the Freundlich adsorption equation but the gradients of the isotherms increased when the initial concentrations were below 0.5 μm. This indicates that there are specific sites of differing sorption energy; differences between soils in the gradients of the isotherms at low initial concentration could largely be accounted for by their contents of ‘free’ Fe₂O₃. When initial concentrations were below 0.5 μm there was a linear relationship between the quantity of Cd sorbed and the final concentration in solution. This relationship held with all soils except that of lowest pH from which there was a net loss of Cd to the solutions. Desorption was measured from three soils with contrasting pH. With the soil of lowest pH, over 80 per cent of sorbed Cd was desorbed to 0.002 m CaCl₂ and up to 30 per cent to 100 or 500 μm solutions of heavy metal chlorides. In contrast, only very small proportions (<1.25 per cent) were desorbed from the other soils with pH 6.7 and 7.8. The results indicate that Cd is strongly sorbed by soils of pH of above 6.0 when added in amounts comparable to additions in sewage sludges or phosphatic fertilizers, and illustrate the importance of liming as a means of reducing the mobility of this metal in soils.     

The UV‐absorbance of dissolved organic matter predicts the fivefold variation in its affinity for mobilizing Cu in an agricultural soil horizon

It is well established that dissolved organic matter (DOM) mobilizes copper (Cu) in soils but it is unknown to what extent variable DOM quality affects this. During a 5 month period, 250 leachates of an uncontaminated agricultural soil were sampled at 45 cm depth using passive capillary wick samplers. The dissolved Cu and organic carbon (DOC) concentrations varied sevenfold and were weakly correlated (r = 0.56). The [Cu] : [DOC] ratio varied fivefold and exhibited a significant positive correlation (r = 0.77) with the specific UV‐absorbance of DOM at 254 nm (SUVA), indicating that the more aromatic DOM had higher Cu affinity. The dissolved Cu concentrations were predicted by an assemblage model in WHAM6 using the composition of the solid phase above the wick samplers and that of the solution, including DOC. The predicted [Cu] : [DOC] ratio was almost constant when assuming default DOM properties with 65% of all DOM active as fulvic acid (%AFA). The %AFA was subsequently varied proportionally to the SUVA of DOM and using the SUVA of pure FA (SUVA_FA) as a fitting parameter. In that case, the variation in the predicted [Cu] : [DOC] ratio was much larger and the predicted Cu concentrations were within a factor of 1.4 of the measured values for 90% of the samples. The fitted SUVA_FA was 38 l g^?1 cm^?1, in excellent agreement with that of Suwannee River FA (SUVA_FA = 37 l g^?1 cm^?1). It is concluded that the DOM quality, e.g. the aromaticity, should be taken into account when estimating Cu mobility in soils.     

Validation of Transfer Functions Predicting Cd and Pb Free Metal Ion Activity in Soil Solution as a Function of Soil Characteristics and Reactive Metal Content

According to recent insight, the toxicity of metals in soils is better related to the free metal ion (FMI) activity in the soil solution than to the total metal concentration in soil. However, the determination of FMI activities in soil solution is a difficult and time-consuming task. An alternative is to use empirical equations (so called transfer functions (TFs)) that relate FMI activity in solution to the reactive metal concentration in the solid phase and to soil properties (pH and organic matter content). Here we test the applicability of two sets of TF for Cd and Pb using independent data from a wide range of soil types and regions that are not represented in the datasets used to derive the TFs. From these soils, soil solution was extracted using four different methods. For all these extracts, FMI activities were calculated from total concentrations in solution using the speciation program WHAM VI. In some of the soils, Cd and Pb FMI activities were also measured using a Donnan membrane technique. Most of these FMI activities deviated from the TF predictions by less than one order of magnitude and were within the 95% confidence interval of the TFs, irrespective of the method used to extract soil solution. Predictability was higher for Pb than for Cd and differed also between the two TF sets.     

A comparative study of Cd,Cr(III), Cr(VI), Hg,and Pb uptake by minerals and soil materials

The pH dependency of Cd, Cr(III), Cr(VI), Hg, and Pb uptake by 14 different types of minerals and soil materials has been studied. The solids were interacted with metal solutions separately in a batch procedure, and the percentage of metal uptake of different metal-solid combinations was compared and evaluated. The results were quantified by the pH values at which 10, 50 and 90% of the metal uptake took place. Physical and chemical characteristics of the solids were correlated with metal uptake. The results verify the importance of geochemical parameters of soils such as organic content, type of clay mineral, presence of complexing ions, and redox-potential for controlling metal uptake. Retention of Cd, Cr(VI), Hg, and Pb was found to be strongly dependent on organic content of the materials studied. Montmorillonite (in bentonite and smectite) showed the highest uptake of Cd, Cr(III) and Pb among all minerals and soil materials, while illite and kaolinite showed lower uptake than the soils. At low pH, the uptake percentage of Cr(VI) by organic soils was higher than that of any of the other metal ions. The uptake of Hg was low in comparison to other cations, which may be explained by formation of soluble Hg(CI)₂° or Hg(CI)⁴ _2? complexes.     

Modelling the Fate of Chromated Copper Arsenate in a sandy Soil

Afforestation of former agricultural land changes soil characteristics such as pH and organic matter content, which may affect heavy metal solubility in the soil. In this study the effects of different tree species on heavy metal solubility were investigated at four 34 years old adjacent stands of beech (Fagus sylvatica L.), grand fir (Abies grandis Lindl.), Norway spruce (Picea abies (L.) Karst.) and oak (Quercus robur L.) planted on former agricultural land at four different sites in Denmark. The sites differ in soil characteristics and represent two texture classes (loamy sand and sandy loam). Soil pH and soil organic matter content was measured in the 16 stands and soil solution was isolated by centrifugation from three depths at four different occasions. Dissolved organic carbon (DOC), pH in the soil solution and the soil solution concentrations (availability) of Cd, Cu, Ni, Pb and Zn were determined. Analysis of variance showed that the tree species affects soil pH and organic matter content in the topsoil, but not in the lower horizons. Norway spruce and grand fir acidify more than beech and oak, and the highest amount of accumulated soil organic matter is in the topsoil under Norway spruce. The effects of tree species on soil solution pH and DOC resemble the effect on soil pH and organic matter content. Grand fir enhances the solubility of Cd and Zn in the topsoil with the lower solubility found under beech and oak and Norway spruce enhances the solubility of Cu, Ni and Pb in the top horizons. The lowest solubility of Ni and Pb is found under beech and oak, whereas the lowest Cu concentrations in the soil solution are found under grand fir. After 34 years of afforestation no effects of tree species on the concentrations of heavy metals in the soil solution from the C-horizons were found. The tree species effect on the concentration of Cd, Cu and Ni in the soil solution depends on the soil characteristics with the higher concentrations found in sandy loam soils, whereas no effect of site on the solution concentration was found for Pb and Zn. It was not possible to find a clear correlation between the soil solution concentrations of heavy metals, pH and DOC concentration.     

Effect of Organic Matter and Salinity on Ethylenediaminetetraacetic Acid–Extractable and Solution Species of Cadmium and Lead in Three Agricultural Soils

Abstract

A study was conducted to investigate the chemical speciation of added cadmium (Cd) and lead (Pb) and their availability as influenced by fresh organic matter (OM) and sodium chloride (NaCl) in three agricultural soils. The soils were treated with 20 mg Cd/kg as cadmium nitrate [Cd(NO₃)₂ · 4H₂O], 150 mg Pb/kg as lead nitrate [Pb(NO₃)₂], 20 g/kg alfalfa powder, and 50 mmol/kg of NaCl and then incubated for 3 months at 60% water‐holding capacity (WHC) and constant temperature (25 °C). Subsamples were taken after 1, 3, 6, and 12 weeks of incubation, and electrical conductivity (EC), pH, dissolved organic carbon (DOC), and concentrations of cations and anions were determined in the 1:2.5 soil/water extract. Available Cd and Pb were determined in 0.05 M ethylenediaminetetraacetic acid (EDTA) extract. Concentrations of organic and inorganic species of Cd and Pb in soil solution were also predicted using Visual Minteq speciation program. The most prevalent species of dissolved Pb and Cd in the soils were Pb‐DOC and Cd²⁺ species, respectively. Salinity application increased the available and soluble Cd significantly in the acid and calcareous soils. It, however, had little effect on soluble Pb and no effect on available Pb. Organic‐matter application decreased availability of added Pb significantly in all soils. In contrast, it raised soluble Pb in all soils except for the acid one and approximated gradually to the added Pb with time. Impact of OM on available Cd was somewhat similar to that of Pb. Soluble Cd increased by OM application in the calcareous soil, whereas it decreased initially and then increased with time in the other soils.     

Differences between soil solutions obtained from rhizosphere and non-rhizosphere soils by water displacement and soil centrifugation

Soil solution was obtained from potted rhizosphere or non-rhizosphere soils by water displacement or soil centrifugation. The pH of the displaced solutions was lower than that of bulk soils when solutions were obtained from non-rhizosphere soil, although it increased as plants grew. This increase probably reflected true changes in rhizosphere pH, generated by the uptake by plants of N0₃-N. In contrast, the pH of soil centrifugates was usually close to that of the bulk soils, implying that buffering by colloids had occurred during sampling. Concentrations of elements in solutions from non-rhizosphere soil were similar for both methods when soils were incubated at ambient pCO₂. However, when non-rhizosphere soils were incubated at elevated pCO₂, displacement solutions had lower pH values, and much larger concentrations of elements, compared to soil centrifugates. Comparison of mass flow of elements versus actual plant uptake showed that Ca and Mg accumulated, while K, Zn and Cd were depleted from the rhizosphere. Displacement solutions showed this accumulation or depletion of the elements more clearly than soil centrifugates. These differences were attributed to the fact that, at constant soil moisture, the rhizosphere developed mainly in larger pores, which were sampled by displacement. With centrifugation, a mixture of pore sizes was sampled, so that rhizosphere solution was only obtained when all of the soil had become rhizosphere. Soil centrifugates obtained after 22 days of growth also contained higher concentrations of organic carbon than displacement solutions, indicating contamination due to the disruption of roots and/or micro-organisms. We conclude that water displacement is suitable for sampling solution from light to medium textured rhizosphere or non-rhizosphere soils and that soil centrifugation is only of limited suitability.     

Predicting the solubility of Cd,Cu, Pb and Zn in uncontaminated Croatian soils under different land uses by applying established regression models

Soil pH, soil organic matter (SOM), dissolved organic carbon (DOC) and total trace metal concentration (M_(tot)) control the solubility of metals in the soil. Several regression models have included these soil chemical variables for the prediction of metal solubility and free metal ion (FMI) concentrations in contaminated soils. We hypothesize that models developed on contaminated soils (after optimization of the coefficients) can be used on samples from uncontaminated sites. Soil samples were collected from unpolluted agricultural and forest soils located in Eastern Croatia and extracted with water to determine the concentrations of Cd, Cu, Pb and Zn. We used these data to test the applicability of three regression models on existing conditions under different land uses. The same predictors issued in the three models and the same regression coefficients were utilized in the present study. The results showed a good correlation between the observed and predicted values of metal solubility. However, the models overestimate the total solution concentration (M_(sol)) and the concentrations of free metal ions (FMI) in solution, and therefore the same regression coefficients were optimized to fit our own observations. This was found to be very successful. The results showed that pH and DOC played a very important role in controlling metal solubility, while SOM and CEC were somewhat less significant. The impact of total soil concentration of metals (M_(tot)) was rather minor. However, we feel that to carry out good predictions of M_(sol) and FMI, the M_(tot) is needed in such regression models.     

不同浸提剂处理森林土壤溶解性有机碳含量比较

为了解亚热带森林土壤溶解性有机碳(DOC)的特征规律,采用培养离心的方法获取土壤溶液测得DOC含量,对比传统水溶性有机碳(WSOC)提取法间的差异。选取湖南大山冲森林公园保存完好的3种亚热带典型次生林地,按10cm一层采集剖面土壤,采用不同方法提取测定土壤DOC和WSOC含量,分析与土壤理化指标的相关性及方法间的显著性关系。结果表明:①典型森林土壤DOC或WSOC含量随土壤剖面深度的增加,呈显著下降趋势。培养离心提取测得的土壤DOC含量明显较低,仅0.82～9.52 mg/kg,超纯水浸提的风干土WSOC含量达10.56～249.19 mg/kg,而0.5 mol/L K₂SO₄提取的鲜土WSOC含量达155.70～576.94 mg/kg,0.5mol/L K₂SO₄浸提的干土WSOC含量最高,达158.94～797.56 mg/kg,含量表现为:DOC<干土超纯水浸提WSOC<鲜土K₂SO₄浸提WSOC<干土K₂...     

土壤对镉的吸附与解吸——Ⅱ.吸附势与解吸势

本文提出了吸附势(logK_a)和解吸势(logK_d或相对解吸势logK_dr)两个有关吸附和解吸的强度概念,并进行了理论推导和实验验证。logK_a和logK_d或logK_dr是影响土壤或胶体吸附和解吸因素的综合反应。实验证实logK_a可用于表征土壤胶体对Cd的相对选择性,并且对胶体吸附Cd有着良好的预测性;logK_dr可用于表征土壤胶体对Cd的相对固定能力,并可用于估测Cd的污染程度。盆栽试验表明,随着土壤胶体logK_a的增加,或logK_dr的降低,稻草或糙米中Cd的含量下降。可以预期,吸附势和解吸势不但在土壤物理化学,土壤环境化学研究中,而且在植物营养化学、水化学、以及界面化学等方面有可能获得实际应用。     

General purpose Freundlich isotherms for cadmium,copper and zinc in soils

Assessing the accumulation and transport of trace metals in soils and the associated toxicological risks on a national scale requires generally applicable sorption equations. Therefore Freundlich equations were derived for Cd, Zn and Cu using multiple linear regression on batch sorption data from the literature with a wide variety of soil and experimental characteristics, and metal concentrations ranging over five orders of magnitude. Equations were derived based on both total dissolved metal concentrations and free metal activities in solution. Free metal activities were calculated from total metal concentrations taking into account ionic activity, and inorganic (all metals) and organic complexation (Cu only). Cadmium and Zn were present in solution predominantly as free ions, while Cu was present as organic complexes. Since actual dissolved organic carbon (DOC) concentrations were not available they were estimated using an empirical field relation between DOC and organic matter content. The logarithmic transformation of the Freundlich constant for Cd was regressed on the logarithmic transformations of cation exchange capacity (CEC) (H⁺) and dissolved Ca, and for Zn with CEC and (H⁺). For Cu the log–log regression model of the Freundlich constant included the solid:solution ratio of the batch to account for dilution of DOC in the batch as compared with the field. The explained variance for the fitted Freundlich equations was 79% for Cd, 65% for Cu and 83% for Zn, using log-transformed adsorbed concentrations and soil solution activities. The Freundlich adsorption models underestimated metal contents determined from 1 m HNO₃ digestion on field samples, up to a factor of 6 (Cd and Cu) or 10 (Zn).     

Affinity constants and behavior of Cd sorption in some acid soils

Cadmium sorption was studied in several acidic soils in a pH range from 4.5 to 6.5. The soils had two classes of surfaces with acidity constants (pKa₁ = 4.09 and pKa₂ = 6.39) similar to those for weakly and very weakly cidic carboxyls, and N-containing groups in fulvic acid. Titratable H and acidity constants were used to estimate the number of exchange sites at each pH level. Sorption of Cd was closely related to Cd concentration, pH, and soil type. Although the inclusion of pH and organic C contents in a regression accounted for some variations in the Cd distribution coefficient defined as the ratio of the quantity of Cd sorbed to the solution Cd concentration, the number of sorption sites was a more appropriate factor to explain the variability. Because of a negligible contribution to the number of exchange sites from Fe oxides, the sorption of Cd at pH = 4.5 was considered to be of a one-surface Langmuir type. A two-surface Langmuir equation was considered to model sorption at higher pH values. The average affinity constants (log K) were 3.61 and 4.89 for Cd sorption by the two classes of surfaces.     

Effect of Field Aging on Nickel Concentration in Soil Solutions

Abstract

The effect of field aging on nickel (Ni) concentration in soil solutions was studied on three soils, with pH 4.5, 6.1, and 7.6, that were spiked with Ni and aged outdoors for 5, 10, and 15 months. Field aging resulted in a minor decrease in total Ni content and a dramatic decrease in Ni concentration in soil solution. Nickel release isotherms in field‐aged soils differ from those in freshly spiked ones. The decrease in soluble Ni in noncalcareous soils at Ni loadings from 25 to 4800 mg kg^?1 followed a first‐order kinetic equation. In calcareous soil the observed relationships imply that soluble Ni may be controlled by dissolution of a surface precipitate either on the surface of soil carbonates [NiCO₃ or NiCO₃ · 2Ni(OH)₂] or on the surface of clay minerals (Ni‐aluminum double‐layer hydroxide).     

The solid solution equilibria of lead and cadmium in polluted soils

A method for the measurement of Pb and Cd in equilibrium soil solutions involving soil equilibration with a dilute Ca electrolyte, centrifugation and filtration to <0.2 μm was evaluated. The procedure was subsequently used for the analysis of 100 Pb- and 30 Cd-contaminated soils. Solutions were analysed for Pb- and Cd using graphite-furnace AAS and the concentrations of Pb²⁺ and Cd²⁺ were estimated using standard speciation calculations. The concentrations of Pb and Cd found in the soil solutions were in the range 3.5–3600 μg dmp ^?3 and 2.7–1278 μg dm ^?3 respectively; both ranges represented less than 0.1% of the total metal concentration in the soils. Depending on solution pH, Pb ⁺² accounted for between 42–78% of Pb in solution while about 65% of Cd in solution was present as Cd⁺². The concentrations of Pb²⁺ and Cd²⁺ in solution suggested that the soil solutions were undersaturated with respect to the solid phases PbC0₃ and CdC0₃ but supersaturated with respect to Pb₅(P0₄)₃Cl and, for some samples, Cd₃(P0₄)₂ respectively. However, for both metals, a good empirical relationship was obtained between the total metal concentration in soil (mol kg^?1), free metal concentration in solution (mol dm^?3) and solution pH. The relationships took the general form of a pH-dependent Freundlich adsorption equation: For both lead and cadmium relationships, the values ofn and K₁ were close to unity, so that the distribution coefficient could be estimated from pH and a single metal-dependent constant, K₂. The algorithms appeared to be valid over a metal concentration range of four logarithmic units and pH range of 3.5–7.5.