Parameterization and regionalization of Cd sorption characteristics of sandy soils. I. Freundlich type parameters

Cd sorption isotherms (n = 24) were established for arable, sandy soils of the ‘Fuhrberger Feld’ catchment area northeast of Hannover (Germany) using 0.01 M_c Ca(NO₃)₂ solution with Cd additions ranging from 0 to 44 μM_c Cd. Alternative fractions of initially (prior to analysis) sorbed Cd (S₀) were added to the amount sorbed during the experiments. The Freundlich equation was fitted to the resulting isotherms. The obtained retention parameters k and M varied with respect to the different S₀ fractions. Isotherms corrected with Cd_EDTA as S₀ fraction were nonlinear in their log-form. The highest degree of log-linearity is obtained if S₀ is characterized by 40% of the agua regia extractable Cd. The corresponding k values ranged from 36 to 1275 g^1-M L^M kg^?1 (mean 338 g^1-M L^M kg^?1, cv = 92%). The Freundlich exponent M showed less variation (0.7 to 1.1, cv = 12%) with a mean of 0.88. Functions based on these parameters predicted Cd concentrations in Ca(NO₃)₂?soil suspensions well (r² = 0.96) but were hardly related to Cd concentrations of ‘fresh’ soil solutions (r² = 0.20).     

Specific sorption of trace amounts of cadmium by soils

Abstract

Sorption of trace quantities of Cd in four soils of different chemical and mineralogical properties, was studied. Initial Cd concentrations were between 15 to 150 μg. 1^?1. The sorption isotherms were linear and had a positive intercept in three of the soils, indicating a constant partition‐high affinity sorption isotherm (Giles et. al⁶). The data also followed the Freundlich sorption isotherm, and the Freundlich K parameter was taken as a measure of the relative affinity of the different soils for the Cd metal sorbed. Cadmium sorbed was extracted by IN‐NH₄C1 followed by 0.1N HC1, and the fraction remaining in the soils was considered specifically sorbed Cd. This fraction also followed a linear sorption isotherm, and was around 30% for the four soils studied. The sorption order for the amount of specifically sorbed Cd showed that the Boomer soil (kaolinite‐iron oxides) had the lowest affinity for specific sorption of this metal. This was taken as evidence that kaolinite and iron oxides have a lower capacity for retaining cadmium through specific sorption mechanism(s) than the materials present on the other soils (2:1 layer silicates and humic substances). The existence of specific mecha‐nism(s) responsible by the sorption of trace quantities of Cd in soil solutions has important implications on soil‐plant relationships, Cd mobility in soil profiles and control of Cd activity in soil solutions.     

Characterization of clay and fine silt fractions of forest soils by standardized K/Ca sorption isotherms

For better comparison of selectivity characteristics of clay and fine silt fractions sorption isotherms standardized on the cation exchange capacity (CEC) are useful. Due to the effect of the CEC on the sorption isotherms, it is necessary to characterize the exchanging substance with regard to different ion selectivities with standardized potassium/calcium‐(K/Ca) sorption isotherms. This procedure helps to complete the knowledge about the mineralogical composition, which is obtained by X‐ray powder diffractometry. A Haplic Luvisol from boulder marl shows distinct differences in its K selectivity both between different particle size fractions and different horizons. This is partly due to the presence of smectites and vermiculites which are differently distributed within the particle size fractions. The increase of K selectivity with increasing particle diameter in the calcareous C horizon can be attributed to the marginal expansion of mica/illite by Ca²⁺ ions. The K selectivity of individual particle size fractions in different horizons of a Gleyic Cambisol from glacial sand shows major similarities. If pedogenic chlorite is formed, no changes in selectivity characteristics can be observed.     

Parameterization and regionalization of Cd sorption characteristics of sandy soils. II. Regionalization: Freundlich k estimates by pedotransfer functions

The aim was to describe Cd sorption in spatially variable sandy soils of the ‘Fuhrberger Feld’ catchment area as a prerequisite for prognosis of Cd transport in soil and of the threat of groundwater pollution. Thus, the possibility is evaluated to derive a generalized Freundlich equation based on multiple regressions relating the retention parameters k and M (from isotherm data of part 1 of this study) to basic soil properties (pedotransfer functions). For the parameter M (exponent), the correlation ‘measured vs estimated’ was weak (r² < 0.5) whereas k was well predictable by pedotransfer functions. The best regression was obtained if organic carbon (OC). clay content and H⁺ activity were combined as independent variables (r² up to 0.96). The obtained k values were much higher than those from comparable literature models, probably due to lower ionic strength and different composition of our background solutions used for the isotherms. As a critical evaluation, the estimates for k were used to derive solute Cd concentrations (C_est) which then were compared to measured data (range 0.1–3 μg L^?1). The best but still unsatisfactory r² was 0.77, obtained if G_est was compared to Cd in 0.01 M_c Ca(NO₃)₂ equilibria (Cd₀). Cd in fresh soil solution (Cd_z) showed no significant correlation with C_est, except for one relationship where OC had been excluded from the preceding multiple regression of k. Generally, the role of the variable OC remained unclear. Direct multiple regressions of measured solute Cd vs soil properties (bypassing k, no sorbed fraction) yielded much closer correlations, with r² = 0.9 for Cd₀ vs OC, H⁺ activity, clay (log data, OC decreases C) and r² = 0.7 for Cd₂ vs OC, H⁺ activity, clay (log data, OC enhances C).     

Ground water preservation by soil protection: Determination of tolerable total Cd contents and Cd breakthrough times

Taking Cd as an example we introduce a procedure to estimate tolerable total content of heavy metals in soils with regard to a specific ground water quality criterion. Furthermore, we present a piston‐flow approach to estimate breakthrough times of a sorptive solute to the ground water. Both procedures are applied to the sandy soils in the 4300 ha wastewater irrigation area Braunschweig, Germany. Applicability of these procedures is tested by numerical simulations. The calculated breakthrough times of Cd for an input concentration of 3 μg L⁻¹ and a mean water flux density of 570 mm yr⁻¹ varies, as a function of depth of water table and sorption characteristics, between 10 and 805 years (mean = 141 years). The deviation between the piston‐flow approach and the numerical simulation is on the average 1.6%. We determined a mean tolerable total Cd content of 0.61 mg kg⁻¹ with regard to a ground water quality criterion of 3 μg L⁻¹. The limit of the German sewage sludge regulation (AbfKlärV, 1992) of 1 mg Cd kg⁻¹ exceeds the calculated tolerable total content in 90% of the investigated Ap horizons. Moreover, the results of the numerical simulations show that the limit of 1 mg Cd kg⁻¹ would lead to a concentration in seepage water significantly above 8 μg Cd L⁻¹. We conclude that in the sandy soils of the wastewater irrigation area the current limit of 1 mg Cd kg⁻¹ is not sufficient to keep the Cd concentration in seepage water below 3 μg L⁻¹ and, thus, to ensure ground water protection in the long run.     

改性油菜秸秆生物质炭吸附/解吸Cd2+特征

该研究选用蒸汽爆破油菜秸秆,对其进行羟基磷灰石和KMnO4浸渍处理,再用壳聚糖和NaOH溶液改性所获得的生物质炭改性,以比较表面特性变化和吸附/解吸Cd~(2+)的特征。结果表明,改性处理可有效地在生物质炭表面负载相应官能团,如羟基磷灰石处理使生物质炭表面磷酸盐增多,比表面积提高至225.68 m2/g;而壳聚糖、KMnO4和NaOH处理,则引入了-NH2和-OH、-COOH等酸性含氧官能团。尽管改性生物质炭表面电荷减少,但Cd~(2+)吸附容量却提高了13%～315%,其吸附行为可用Langmuir等温吸附式拟合,并符合Pseudosecondorder吸附动力学方程。改性后,生物质炭对Cd~(2+)的吸附主要为专性吸附,其初始吸附速率提高了65%～379%,而解吸率降低了17%～91%,表明对Cd~(2+)的吸附更快且更加稳定,具有良好的应用潜力。     

海泡石对典型水稻土镉吸附能力的影响

通过吸附解吸实验研究了添加海泡石后典型水稻土对Cd的吸附解吸特性及其对吸附溶液pH值变化的响应。结果表明,Freundlich方程可以较好地拟合红黄泥、黄泥田和红沙泥3种典型水稻土对Cd的等温吸附过程（R2〉0.962）。在溶液初始Cd浓度相同的情况下,添加海泡石可使3种水稻土对Cd的吸附量增加20%以上,增强土壤对Cd的吸附强度,有效降低吸附Cd的解吸率,其效果随海泡石添加量的增大而增强。3种水稻土吸附Cd的解吸率均高于70%,而且都随吸附量的增加而上升。溶液的pH值是影响土壤吸附Cd的一个重要因素,在低pH值的条件下（pH〈4）,随着溶液pH值的降低,土壤对Cd的吸附量迅速降低,当溶液pH值高于5时,pH值的变化对吸附量的影响较小。在溶液初始pH值2-8范围内,添加海泡石均能有效提高3种水稻土对Cd的吸附能力。     

通过微量量热法研究Cd2+在针铁矿上的吸附机制

A study on energy changes and mechanisms of Cd sorbed on goethite was performed using the technique of microcalorimetry.The data of the amount of Cd sorpion(Aq) and concentration of Cd in equilibrium solution(Ce),and the data of Aq and the heat effect(AH) caused by Cd^2 sorption on goethite all fitted Langmuir isotherm.The amount of heat released from Cd sorption on goethite increased with the amount of Ce or Aq.The reaction process of Cd sorption on goethite may be divided into five stages and three plateaus,depending on the variation of enthalpy change(ΔaHm) of Cd sorption with Aq,which implied three mechanisms of interaction between Cd and goethite.The experimental results showed that the microcalorimetry may be useful for determination of microcalorie variation in soil.     

Equations to describe the amount and rate of sorption

The partition of materials that react with soil between the solid and the solution phase, and how this changes with time, can often be described by a simple equation: S = a c^b1t^b2 where S is the amount sorbed, c is the solution concentration, t the time of contact, and a, b₁ and b₂ are parameters. However, when the range of values for sorption is large, it is apparent that both b₁ and b₂ increase with decreasing sorption. At low values for sorption, b₁ approaches 1, and sorption plots are nearly linear. These observations are consistent with a mechanistic model in which it is postulated that the materials react with heterogenous sites. As the amount of sorption decreases, the heterogeneity of the occupied sites decreases. This is why b₁ increases. Because there is heterogeneity of occupied sites, there is a range of rates for the subsequent reaction. This is why the rates are proportional to a fractional index of time. It is better to describe the effects of time this way than by using several first-order equations.     

熟污泥改性黄土对镉的吸附解吸特征

使用序批实验方法,研究熟污泥改性黄土对镉(Cd)的吸附解吸特征。结果表明:Cd初始添加浓度大于20 mg/L,供试改性黄土对Cd的吸附等温线发生显著变化;Freundlich型吸附等温式是描述供试改性黄土对Cd吸附过程的最佳模型。各土样对Cd的解吸量与吸附量的关系可以用幂函数很好地描述。随着土样中熟污泥含量的增加,Cd的吸附固定作用增强。有机质成分是影响供试土样Cd固定能力最大的因素。     

不同发酵饼粕对土壤镉形态及烤烟镉含量的影响

为揭示发酵饼粕对植烟土壤镉形态及烤烟镉含量的影响,以烤烟品种云烟87为材料并采用欧共体标准局(BCR)方法,研究了4种发酵饼粕分别作基肥或追施,对改变土壤镉形态和消减烤烟镉含量的作用效果。结果表明,基肥中加入或追施发酵茶粕可使土壤中易被烟株吸收的弱酸提取态镉含量分别降低33.49%和42.08%,使土壤中不能被烟株吸收的残渣态及可还原态镉含量分别增加32.87%和38.19%;加入基肥或追施发酵菜粕使土壤弱酸提取态镉含量下降24.77%,可还原态与残渣态镉增加25.60%;发酵棉粕和芝麻粕固定土壤镉的效果较差。追施发酵菜粕可使初烤烟叶镉含量减少50.44%;在基肥中加入发酵菜粕和茶粕可分别减少初烤烟叶镉含量40.88%和38.36%,其降低初烤烟叶镉含量的效果明显好于发酵棉粕和芝麻粕。     

Immobilization of heavy metals in soils amended by nanoparticulate zeolitic tuff: Sorption‐desorption of cadmium

Immobilization of Cd in contaminated soil is a technique to improve soil quality. Zeolites are potentially useful additives to bind heavy metals. This study examines the influence of decreasing the grain size of raw zeolitic tuff to the nano‐range on Cd sorption‐desorption isotherms in a sandy soil. The aim was to evaluate the feasibility of using nanoparticulate zeolitic tuff as a sequestering agent for Cd in soil. Sorption and desorption of Cd on zeolitic nanotuff was investigated in batch experiments. The sandy soil was amended with zeolitic nanotuff, synthetic Al oxide nanoparticles, or raw zeolitic tuff. After a 48 h sorption step, three desorption steps were induced using the sequential dilution method. The measured sorption‐desorption data were adequately described by the Freundlich equation. A nonlinear two‐stage one‐rate model matched well with measured Cd sorption‐desorption isotherms of zeolitic nanotuff, raw zeolitic tuff, Al oxide nanoparticle, and control soil. The batch experiments demonstrated the strong influence of pH on Cd sorption. Zeta‐potential measurements of zeolitic nanotuff indicated that electrostatic interaction was important for sorption. Soil amended with zeolitic nanotuff showed the lowest hysteresis index based on the differences obtained from sorption‐desorption isotherms regarding the amount of Cd sorbed. The index decreased with increasing metal concentration. For soil amended with nanoparticulate zeolitic tuff, the estimated Freundlich coefficient was 4 orders of magnitude higher than in the control soil and 2 orders of magnitude higher than the soil amended with raw zeolitic tuff. In addition, this sorbent decreased the amount of Cd released after three desorption steps by up to 12 and 7 times compared to the control soil and the soil amended with raw zeolitic tuff, respectively. The effect on Cd sorption of grinding the raw zeolitic tuff to the nanorange was considerably more pronounced than the effect of raw zeolitic tuff.     

镉胁迫下生物炭与锌/钾叶面肥促进烟草生长降低镉富集的协同效应

[目的]生物炭和叶面肥在单独调控重金属胁迫条件下植物生长及重金属离子吸收方面的应用价值已被一些研究证实,然而它们在土壤重金属镉污染修复中的耦合效应及其机制尚不十分清楚。烟草为镉易富集植物,研究生物炭和锌/钾叶面肥单施或联合施用对烟草生长和镉富集特性的影响,为镉污染土壤的修复及烟草安全生产提供理论依据。[方法]采用盆栽模拟轻度土壤镉污染胁迫试验,供试烟草品种为‘中烟100’。设置6个试验处理:对照(CK)、土施生物炭20 g/kg(B)、喷施0.5%ZnSO4叶面肥(Zn)、喷施0.5%KH2PO4叶面肥(K)、生物炭+喷施ZnSO4叶面肥(B+Zn)、生物炭+喷施KH2PO4叶面肥(B+K),每个处理重复8次。将烟草分割为根、茎、下部叶(从下到上1~5片)、中部叶(6~10片)、上部叶(11~15片)5部分。测定株高、生物量、丙二醛含量(MAD)、超氧化物歧化酶(SOD)、过氧化物酶(POD)、过氧化氢酶(CAT)活性、烟株各部位的镉含量,计算了镉富集和转运系数,分析了土壤中镉形态的变化。[结果]1)单独施用叶面肥较单独施用生物炭更有利于增强镉胁迫下叶片的抗氧化性能,促进烟株生长。与B处理相比,Zn和K处理的MDA含量分别降低12.8%和15.1%,POD活性分别增加32.2%和29.9%,CAT活性分别增加25.5%和18.2%(P<0.05),Zn和K两处理之间的抗氧化酶活性无显著差异(P>0.05)。单独施用生物炭较单独施用叶面肥更有利于降低土壤中镉的生物有效性。与Zn和K处理相比,B处理的土壤弱酸提取态镉含量分别降低19.0%和19.3%,可还原态镉含量分别降低22.3%和23.9%(P<0.05)。单独喷施叶面肥对土壤镉形态无显著影响(P>0.05)。2)生物炭和叶面肥配施具有叠加效应,且B+Zn处理对促进镉胁迫下烟株生长和减少烟株镉吸收方面效果大于B+K处理。与CK、B、Zn处理相比,B+Zn处理的株高分别增加52.8%、25.9%和11.8%,地上干重分别增加146%、89.1%和45.3%,SOD活性分别增加29.8%、19.7%和11.0%,POD活性分别增加94.0%、64.1%和24.1%,CAT活性分别增加183.8%、90.9%和52.2%,烟株根镉含量分别减少53.9%、25.2%和31.6%,茎镉含量分别减少74.5%、53.9%和63.7%,上部叶镉含量分别减少63.1%、18.8%和40.1%,中部叶镉含量分别减少63.6%、27.7%和35.3%,下部叶镉含量分别减少63.8%、34.1%和46.9%,烟株镉生物富集系数分别降低64.4%、31.0%和48.4%,镉生物转运系数分别降低33.3%、20.2%和28.5%,土壤中弱酸提取态镉含量分别降低19.5%、7.5%和19.0%,土壤中还原态镉含量分别降低22.9%、2.0%和20.8%,土壤中可氧化态镉含量分别增加62.5%、5.6%和54.6%,土壤中残渣态镉含量分别增加206.9%、10.7%和174.7%。与B+K处理相比,B+Zn处理的烟株地上干重增加18.3%,上部叶、中部叶、下部叶镉含量分别减少8.4%、13.9%和16.9%,镉生物富集系数和转运系数分别降低20.8%和8.5%。[结论]在镉污染胁迫下,土施生物炭可以降低土壤中镉的生物有效性,减少烟草的吸收。叶面喷施锌、钾肥可以提高烟草植株的抗氧化性能,促进烟株生长。生物炭配合叶面肥具有明显的协同作用,降低烟草中镉的运转系数和富集系数的效果显著高于锌/钾叶面肥单独施用。在本试验条件下,生物炭配合喷施硫酸锌的效果好于生物炭配合喷施磷酸二氢钾,可作为提高烟草生产安全及土壤镉污染修复的一项有效措施。     

Response of the sorption behavior of Cu,Cd, and Zn to different soil management

This study investigated the effect of different farming practices over long time periods on the sorption‐desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long‐term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K_F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO₃)₂ < animal manure ≤ grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K_F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water‐soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.     

Soil affects on the cadmium and zinc contents of Chinese cabbage in Yunnan Province,China

Chinese cabbage and surface soil samples (0–20 cm) from a periurban market garden in Yunnan Province (P.R. China) were collected to determine variations of cadmium (Cd) and zinc (Zn) contents in Chinese cabbage and the influence of soil factors. Mean Cd content was 0.49 mg kg^?1 dry materials (DM) in Chinese cabbage, ranging between 0.23 and 1.34 mg kg^?1 DM (n = 21 samples). Mean Zn content was 51.2 mg kg^?1 DM, ranging from 34.9 to 157.5 mg kg^?1 DM (n = 21 samples). The soil factors best predicting Chinese cabbage Cd and Zn contents were total and available Cd and Zn contents and cation exchange capacity (CEC). Soil samples and corresponding Chinese cabbage samples were divided into two groups: soils with low pH (<6.5, n = 10) and soils with high pH (>6.5, n = 11). Positive correlation between CEC with pH > 6.5 and Cd and Zn contents in Chinese cabbage were observed. Available trace element contents and CEC explained 77% and 69% of variation of Cd and Zn contents in Chinese cabbage, respectively. AEC (enrichment coefficient related to trace element availability) and BCF (bioaccumulation factors) could be used to understand Cd and Zn accumulation in Chinese cabbage.     

Sources of error in the determination of Cd and Pb in plant material by atomic absorption

Abstract

Some difficulties were met when low levels of Cd and Pb were estimated in plant samples in this laboratory by atomic absorption spectrophotometry (AAS).

A modified procedure, based on methyl isobutyl ketone (MIBK) extraction of the metal complexes with ammonium pyrollidine dithio carbamate (APDC), has been developed for use on samples digested with HNO₃/HCIO₄. The procedure was compared with X‐ray fluorescence and with other AAS methods including those based on dry ashing. Dry ashing gave generally lower values for Cd and Pb. Improvement in conditions of digestion and analysis are described. Of these, the presence of small amounts of Fe in standards and unknown samples increases the stability and reproducibility of absorbance values, especially for cadmium.     

美国不同轻质集料的磷吸附特性比较

In this study, phosphorus(P) sorption of thirteen light-weight aggregates(LWAs) from USA was compared during batch equilibrium experiments in order to identify those materials which had the highest P sorption capacity for further study. Seven different levels of sorption activity were observed, which were broadly grouped into three categories—high performing, middle performing, and low performing aggregates. Chemical analysis of Ca, Al, Fe, and Mg was used to describe the differences between LWAs. There was a significant correlation between cation(especially Al, Ca, Fe, and Mg) content and P sorbed. Langmuir isotherms were used to describe P sorption maximum and binding affinity for four of the top five performing LWAs, Universal, Stalite "D", Stalite "Mix", and TXI.The fifth aggregate, Lehigh, exhibited more complex sorption, and was better described by the Freundlich isotherm. Universal had a mean P sorption at the highest concentration of 824 mg kg-1, well above its calculated sorption maximum(702 mg kg-1), and also had the highest binding affinity(1.1 L mg-1). This experiment suggests that the top performing LWA(Universal) may perform poorly in column and field studies due to observed precipitates, which could degrade constructed wetland performance. Other LWAs may exhibit superior field performance due to their high calculated sorption maxima. In general, these results highlight the importance of batch experiments as a first step in identifying materials suitable for column and field experiments.     

Effect of soil microorganisms on the sorption of zinc and lead compounds by goethite

The objectives of this study were (1) to determine the effect of microorganisms during in‐vitro incubation on the amount of Zn and Pb from solution retained on goethite precipitated as coatings on a sand matrix and (2) to evaluate accumulation of heavy metals in the biomass of soil microorganisms in the fresh soil samples using an extractive approach. A mixture of colonies of cultivated microorganisms extracted from a Haplic Luvisol (Russia) and an Antropi‐urbic Regosol (Germany) were used to prepare the cell and the microbial‐debris suspensions. The concentrations of Zn and Pb in the studied solutions supplied with microbial suspensions and/or goethite coated sand were 0.1 mM (130.8 and 414 mg kg^–1 of sand, respectively). Exchangeable forms of metals were determined by extraction with 10 mL of 1.0 M KNO₃. Nonexchangeable forms of Zn and Pb were recovered using 40 mL of 0.3 M NH₂OH‐HCl in 1 M HNO₃. Concentrations of Pb increased in the solutions and decreased on the surface of the Fe‐mineral due to living microorganisms. In comparison to incubation of heavy‐metal solutions with goethite only, the absolute concentrations of nonexchangeable forms of metal were reduced by microbial suspension to a greater extent than those of the exchangeable forms, whereas the relative content of both fractions decreased by a factor of almost two. Sorption of Pb by goethite was inversely correlated with the concentration of organic C in the solution. Microorganisms clearly influenced the Zn sorption by goethite at concentrations of C_org > 400 mg L^–1. The amount of Zn retained was decreased primarily due to decreasing Zn portions in the exchangeable fraction. Microbial debris prepared by autoclaving reduced the Pb sorption by goethite similar to the results for living cells. Living microorganisms accumulated more Zn than did microbial debris. The data of this paper show that a direct determination of heavy‐metal accumulation in soil microorganisms by extraction with 2.0 M KCl as well as by extraction with 1 M CH₃COONH₄ at the natural pH of the soils after chloroform fumigation of fresh soils samples with different concentrations of organic C was not possible.     

Influence of soil factors on the soil enzyme inhibition by Cd

A comparative study was conducted on the toxicity of Cd to alkaline phosphatase activity (ALP) and dehydrogenase activity (DHA) in 18 top soils with contrasting soil properties representative of 14 major soil types in China. Soil pH and carbonate content, soil organic matter, and cation exchange capacity (CEC) largely affected the Cd toxicity on two enzyme activities; with the soil pH having only minor effect on the median ecological dose values based on total Cd concentrations (ED_{50 T}). The values of ED_{50 T}/ED_{50 W} (based on water-soluble Cd content) of alkaline phosphatase and dehydrogenase were strongly influenced by pH and CEC contents, which explained up to 71% of the variation for alkaline phosphatase, 82% of the variation for dehydrogenase, and also were significantly correlated with the parameter K_F derived from Freundlich adsorption isotherms. This study suggests that the values of ED_{50 T}/ED_{50 W} could be useful to evaluate the buffer capacity of soils which protects soil enzymes from harmful effects of heavy metal.     

Short‐term transport of cadmium during a heavy‐rain event simulated by a dual‐continuum approach

The transport of solutes in soils, and its intensification due to preferential flow, plays crucial role when problems related to the groundwater pollution are dealt with. The objective of this study was to examine transport of cadmium (Cd) in response to an extreme rainfall event for three different soils using numerical modeling. The ^115mCd²⁺ concentration profile had been measured in the Bodiky reference site (Danubian Lowland, Slovakia) by the radioactive‐tracer technique and used for the calibration of the dual‐continuum model S1D. The Cd transport during a single rain event was predicted with the S1D model for light, medium‐heavy, and heavy soil in the same region. The Cd transport through the soil profile was simulated by the one‐dimensional dual‐permeability model, which assumes the existence of two pore domains: the soil‐matrix domain and the preferential‐flow domain. The model is based on Richards' equation for water flow and advection‐dispersion equation for solute transport. A modified batch technique enables to distinguish process of adsorption in the matrix domain and the preferential pathways. Modeling with classical single‐permeability approach and dual‐continuum approach without considering the particle‐facilitated transport led to negligible Cd penetration. The rainfall event with extremely high rainfall intensity induced deep penetration of Cd in the medium‐heavy and heavy soil, which may indicate increased vulnerability to shallow groundwater pollution for the respective sites in Danubian Lowland region. The highest Cd leaching was predicted for heavy clay soil, where the preferential particle‐facilitated transport of Cd through the soil profile was significant due to the contrasting properties of the soil‐matrix domain and the preferential‐flow domain. The results of the sensitivity analysis suggested only slight effect of the transfer rate coefficients on simulated Cd leaching.