Speciation In Soil Solution Research Articles

Solution chemistry mechanisms of exogenous silicon influencing the speciation and bioavailability of cadmium in alkaline paddy soil

The mechanism of silicon (Si) influencing cadmium (Cd) speciation and bioavailability in alkaline paddy soil solution remains unclear. Therefore, this study sought to elucidate the effect of Si on Cd by combining chemical analysis and rice pot experiments. In this work, the effects of Na2SiO3 alkalinity and the differences in Na+ were eliminated in all treatments, and the Cd speciation in soil solutions was determined in-situ using a Field-Donnan membrane technology (DMT) cell. Additionally, rice yields and the Cd content in various parts of the rice plant were studied. The results showed that Si application significantly increased rice biomass by 32% (P < 0.05) while significantly reduced the Cd content in brown rice by 52% (P < 0.01) and the free Cd2+ concentration in the soil solution. Further analysis of the interaction of Si and Cd using Fourier transform-infrared spectroscopy (FT-IR), Raman, and X-ray photoelectron spectroscopy (XPS) indicated that a Si-Cd complex was formed by Cd and Si-O groups. In summary, Si changed the chemical speciation of Cd in the alkaline soil solution and formed a water-soluble Si-Cd complex that the rice could not absorb, consequently reducing Cd bioavailability.

Soil acidity and aluminum speciation affected by liming in the conversion of a natural pasture from the Brazilian Campos Biome into no-tillage system for grain production

ABSTRACTThe conversion of Pampa Biome soils into no-till system for grain production requires acidity correction, at least to fully neutralize exchangeable aluminum (Al). The aim of the study is to evaluate changes in solid phase acidity and Al speciation in soil solution that was conducted to prepare the soil for the implementation of a no-tillage system in a natural pasture area in Southern Brazil. We collected soil samples from the 0–5, 5–10, 10–15 and 15–20 cm layers in soils subjected, or not, to acidity correction to pH 6.0, as well as in soils with, and without, limestone incorporation through plowing and harrowing. Changes in the solid and solution phase attributes, such as soil acidity, were limited to 5 and 10 cm, respectively, 44 months after surface and incorporated liming. Regardless of liming addition to, or lack of thereof in the soil, Al found in the soil solution was mainly associated with organic carbon. This was the main way to decrease plant toxicity under these conditions, which can be supported by plant behavior, especially that of soybean. Liming induced the soil solution Al to exchange its ligand from organic carbon to hydroxyl.

Towards an understanding of the Cd isotope fractionation during transfer from the soil to the cereal grain

Cd in soils might be taken up by plants, enter the food chain and endanger human health. This study investigates the isotopic fractionation of major processes during the Cd transfer from soils to cereal grains. Thereto, soil, soil solution, wheat and barley plants (roots, straw and grains) were sampled in the field at three study sites during two vegetation periods. Cd concentrations and δ114/110Cd values were determined in all samples. The composition of the soil solution was analyzed and the speciation of the dissolved Cd was modelled. Isotopic fractionation between soils and soil solutions (Δ114/110Cd20-50cm-soil solution = −0.61 to −0.68‰) was nearly constant among the three soils. Cd isotope compositions in plants were heavier than in soils (Δ114/110Cd0-20cm-plants = −0.55 to −0.31‰) but lighter than in soil solutions (Δ114/110Cdsoil solution-plants = 0.06–0.36‰) and these differences correlated with Cd plant-uptake rates. In a conceptual model, desorption from soil, soil solution speciation, adsorption on root surfaces, diffusion, and plant uptake were identified as the responsible processes for the Cd isotope fractionation between soil, soil solution and plants whereas the first two processes dominated over the last three processes. Within plants, compartments with lower Cd concentrations were enriched in light isotopes which might be a consequence of Cd retention mechanisms, following a Rayleigh fractionation, in which barley cultivars were more efficient than wheat cultivars.

Organic matter and salinity modify cadmium soil (phyto)availability

Although Cd availability depends on its total concentration in soil, it is ultimately defined by the processes which control its mobility, transformations and soil solution speciation. Cd mobility between different soil fractions can be significantly affected by certain pedovariables such as soil organic matter (SOM; over formation of metal-organic complexes) and/or soil salinity (over formation of metal-inorganic complexes). Phytoavailable Cd fraction may be described as the proportion of the available Cd in soil which is actually accessible by roots and available for plant uptake. Therefore, in a greenhouse pot experiment Cd availability was observed in the rhizosphere of faba bean exposed to different levels of SOM, NaCl salinity (50 and 100mM) and Cd contamination (5 and 10mgkg−1). Cd availability in soil does not linearly follow its total concentration. Still, increasing soil Cd concentration may lead to increased Cd phytoavailability if the proportion of Cd2+ pool in soil solution is enhanced. Reduced Cd (phyto)availability by raised SOM was found, along with increased proportion of Cd-DOC complexes in soil solution. Data suggest decreased Cd soil (phyto)availability with the application of salts. NaCl salinity affected Cd speciation in soil solution by promoting the formation of CdCln2−n complexes. Results possibly suggest that increased Cd mobility in soil does not result in its increased availability if soil adsorption capacity for Cd has not been exceeded. Accordingly, chloro-complex possibly operated just as a Cd carrier between different soil fractions and resulted only in transfer between solid phases and not in increased (phyto)availability.

Parameterizing the binding properties of dissolved organic matter with default values skews the prediction of copper solution speciation and ecotoxicity in soil.

Parameterizing speciation models by setting the percentage of dissolved organic matter (DOM) that is reactive (% r-DOM) toward metal cations at a single 65% default value is very common in predictive ecotoxicology. The authors tested this practice by comparing the free copper activity (pCu2+ = -log10 [Cu2+ ]) measured in 55 soil sample solutions with pCu2+ predicted with the Windermere humic aqueous model (WHAM) parameterized by default. Predictions of Cu toxicity to soil organisms based on measured or predicted pCu2+ were also compared. Default WHAM parameterization substantially skewed the prediction of measured pCu2+ by up to 2.7 pCu2+ units (root mean square residual = 0.75-1.3) and subsequently the prediction of Cu toxicity for microbial functions, invertebrates, and plants by up to 36%, 45%, and 59% (root mean square residuals ≤9 %, 11%, and 17%), respectively. Reparametrizing WHAM by optimizing the 2 DOM binding properties (i.e., % r-DOM and the Cu complexation constant) within a physically realistic value range much improved the prediction of measured pCu2+ (root mean square residual = 0.14-0.25). Accordingly, this WHAM parameterization successfully predicted Cu toxicity for microbial functions, invertebrates, and plants (root mean square residual ≤3.4%, 4.4%, and 5.8%, respectively). Thus, it is essential to account for the real heterogeneity in DOM binding properties for relatively accurate prediction of Cu speciation in soil solution and Cu toxic effects on soil organisms. Environ Toxicol Chem 2017;36:898-905. © 2016 SETAC.

Aluminum cycling in a tropical montane forest ecosystem in southern Ecuador

Growth limitation induced by Al toxicity is believed to commonly occur in tropical forests, although a direct proof is frequently lacking. To test for the general assumption of Al toxicity, Al, Ca, and Mg concentrations in precipitation, throughfall, stemflow, organic layer leachate, mineral soil solutions, stream water, and the leaves of 17 native tree species were analyzed. We calculated Al fluxes and modeled Al speciation in the litter leachate and mineral soil solutions. We assessed potential Al toxicity based on soil base saturation, Al concentrations, Ca:Al and Mg:Al molar ratios and Al speciation in soil solution as well as Al concentrations and Ca:Al and Mg:Al molar ratios in tree leaves. High Al fluxes in litterfall (8.77±1.3 to 14.2±1.9kgha−1yr−1, mean±SE) indicated a high Al circulation through the ecosystem. The fraction of exchangeable and potentially plant-available Al in mineral soils was high, being a likely reason for a low root length density in the mineral soil. However, Al concentrations in all solutions were consistently below critical values and Ca:Al molar and the Ca2+:Alinorganic molar ratios in the organic layer leachate and soil solutions were above 1, the suggested threshold for Al toxicity. Except for two Al-accumulating and one non-accumulating tree species, the Ca:Al molar ratios in tree leaves were above the Al toxicity threshold of 12.5. Our results demonstrate high Al cycling through the vegetation partly because of the presence of some Al accumulator plants. However, there was little indication of an Al toxicity risk in soil and of acute Al toxicity in plants likely reflecting that tree species are well adapted to the environmental conditions at our study site and thus hardly prone to Al toxicity.

Amendments affect lead mobility and modulated chemo-speciation under different moisture regimes in normal and salt-affected lead-contaminated soils

The total lead content in the soil itself is insufficient as a measure to indicate the actual environmental risks related to the presence of lead in the soil. Understanding the mobility of lead and its chemical speciation in soil solution is of great importance for accurately assessing environmental risks posed by lead. Therefore, a laboratory study was carried out to evaluate the effect of inorganic amendments (gypsum, rock phosphate and di-ammonium phosphate) on lead mobility and chemical speciation under different moisture regimes (flooding regime and 75 % field capacity) in normal and salt-affected lead-contaminated soils. After 2, 7, 15, 30, 100 and 110 days of incubation, pore water samples were collected by using Rhizon soil moisture samplers. In order to estimate the chemical speciation of lead in pore water, Visual MINTEQ 3.0 modeling approach was used. The results showed that presence of free Pb2+, PbCl+, Pb(SO4)22−, and PbH2PO4+ was significantly (P ≤ 0.05) affected by the soil moisture regime, incubation time and applied amendments in lead-contaminated soils. The Visual MINTEQ 3.0 predicted free Pb2+ species concentration was found higher in lead-contaminated soils, while PbCl+ was more pronounced in salt-affected soils. Gypsum increased the occurrence of Pb(SO4)22−, while di-ammonium phosphate and rock phosphate enhanced the PbH2PO4+ species formation and decreased free Pb2+ species in pore water. Thus, gypsum is the most effective in reducing lead and free Pb2+ species concentrations in the pore water under different soil moisture regimes and incubation times in normal and salt-affected lead-contaminated soils.

Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach

Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies.

Toxicity in lead salt spiked soils to plants, invertebrates and microbial processes: Unraveling effects of acidification, salt stress and ageing reactions

The fate and effects of toxic trace metals in soil freshly spiked soluble metal salts do not mimic those of metals in the field. This study was set up to test the magnitude of effects of salinity, acidification, and ageing on toxicity of lead (Pb) to plants, invertebrates and soil microbial processes. Three soils were spiked with Pb2+ salts up to a concentration of 8000mgPb/kg and were tested either after spiking, after soil leaching followed by pH correction, or after a 5-year outdoor ageing period with free drainage followed by pH correction. Soil solution ionic strength exceeded 150mmol/L in soils tested directly after spiking and this decreased partially after leaching and returned back to background values after 5-year outdoor equilibration. Chronic toxicity to two plants, two invertebrates, and three microbial endpoints was consistently found in all spiked soils that were not leached. This toxicity significantly decreased or became absent after 5years of ageing in 19 of the 20 toxicity tests by a factor 8 (median factor; range: 1.4–>50), measured by the factor increase of total soil Pb dose required to induce 10% inhibition. The toxicity of Pb in leached soils was intermediate between the other two treatments. The lowest detectable chronic thresholds (EC10) in aged soils ranged 350–5300mgPb/kg. Correlation analysis, including data of Pb2+ speciation in soil solution, suggests that reduced ionic strength rather than acidification or true ageing is the main factor explaining the soil treatment effects after spiking. It is suggested that future toxicity studies should test fine PbO powder as a relevant source for Pb in soils to exclude the confounding salt effects.

Zinc speciation in soil solution of selected Poland’s agricultural soils

The influence of soil properties (pH, organic carbon content, soil texture, content of available zinc (Zn)) on the percentage share of the various forms of Zn in the soil solution of 62 arable soils of Poland were investigated. The soil solution was obtained following the vacuum displacement method. Speciation of zinc ions (Zn 2+ ) was determined with MINTEQA2 for Windows software. The investigation showed that the concentration of active Zn 2+ in the soil solution and related Zn bioavailability for the most part relies upon soil reaction when compared with other investigated physical and chemical soil properties. The effects of soil texture, and above all those of organic matter contents in soil, are significantly lesser. The results of speciation analysis showed that apart from physical and chemical soil properties active Zn 2+ are the main forms of Zn occurring in the soil solution. Depending on soil properties these ions add up to from 60% to almost 80% of all Zn forms in the soil solution. Zinc forms can be arranged with regard to their percentage share in the soil solution as follows: Zn-DOC > ZnCO 3 > ZnCl + > ZnHCO 3 + > ZnOH + .

Effects of soil properties on copper speciation in soil solution

The numerical speciation analysis relies on quantitative assessment of concentrations of different forms of an element in soil solution (free ions, complex ions, neutral complexes), which have different abilities to react (ion activity). The reactivity affects the element’s mobility and bioavailability. This method can be employed to estimate potential bioavailability and toxicity of a given element. This study was undertaken to evaluaate effects of selected soil properties on changes in the total concentration of copper (Cu) and percentages of particular forms of this element in soil solution. The study was based on a microplot experiment. The investigated factors were the soil texture, pH, organic carbon content and degree of soil copper contamination. Soil solutions were obtained with the vacuum displacement method. The concentration of copper in soil solution was determined with the ICP method, and the percentages of particular copper forms in the total copper concentration were calculated with the MINTEQA 2 software. It was found that copper in the analysed soil solutions occurred mainly in the form of metalorganic complexes. The increasing soil acidity was correlated with an increased percentage of free copper ions and copper complexes with organic matter. Simultaneously, the share of bonds with carbonates, sulfates and hydroxyl groups decreased. A decrease in the percentage of Cu 2+ free ions in the soil solution was observed in response to an increasing organic carbon content, while the percentage of copper complexes with organic matter rose. The degree of soil copper contamination and soil texture had no influence on the percentages of different copper forms in the soil solution.

Soluble organic carbon and pH of organic amendments affect metal mobility and chemical speciation in mine soils

We evaluated the effects of pH and soluble organic carbon affected by organic amendments on metal mobility to find out the optimal conditions for their application in the stabilization of metals in mine soils. Soil samples (pH 5.5–6.2) were mixed with 0, 30 and 60tha−1 of sheep–horse manure (pH 9.4) and pine bark compost (pH 5.7). A single-step extraction procedure was performed using 0.005M CaCl2 adjusted to pH 4.0–7.0 and metal speciation in soil solution was simulated using NICA-Donnan model. Sheep–horse manure reduced exchangeable metal concentrations (up to 71% Cu, 75% Zn) due to its high pH and degree of maturity, whereas pine bark increased them (32% Cu, 33% Zn). However, at increasing dose and hence pH, sheep–horse manure increased soluble Cu because of higher soluble organic carbon, whereas soluble Cu and organic carbon increased at increasing dose and correspondingly decreasing pH in pine bark and non-amended treatments. Near the native pH of these soils (at pH 5.8–6.3), with small doses of amendments, there was minimum soluble Cu and organic carbon. Pine bark also increased Zn solubility, whereas sheep–horse manure reduced it as soluble Zn always decreased with increasing pH. Sheep–horse manure also reduced the proportion of free metals in soil solution (from 41% to 4% Cu, from 97% to 94% Zn), which are considered to be more bioavailable than organic species. Sheep–horse manure amendment could be efficiently used for the stabilization of metals with low risk of leaching to groundwater at low doses and at relatively low pH, such as the native pH of mine soils.

Release kinetics and distribution of boron in different fractions in some calcareous soils

The aim of this study was to evaluate the release kinetics, speciation, and fractionation of boron (B) in some calcareous soils of western Iran. Ten surface soil samples were incubated with 100 mg B kg−1 for a week at field capacity moisture. After air drying of samples, the trend of B release was experimented using sequential extraction with 10 mM CaCl2. B speciation in soil solution was calculated for the first and the last steps of extraction by the visual MINTEQ program. The distribution of B among five fractions including exchangeable (F1), specially adsorbed (F2), bound by Fe–Mn oxides (F3), organically bound (F4) and residual (F5), was determined in control and spiked soils. The results indicated that the release rates were initially rapid followed by a slower reaction and the main proportion of the added B was extracted by CaCl2. The release kinetics of B was described well with Elovich, parabolic diffusion, power function, and first-order equations. The speciation results revealed that the uncharged boric acid (H3BO30) was the dominant species in soil solutions. In control soils, B concentration in different fractions decreased in the following order: F5 > F1 > F2 > F3 > F4. In spiked soils, however, the largest and the smallest fractions were exchangeable and residual, respectively. This implies that B transformation from soluble to less mobile and non-labile forms is not a rapid process and requires more than a week. The significant relationship observed between kinetic parameters of power and parabolic equations and organically bound B fraction and OM content indicated that organic matter played an important role in B adsorption and release in calcareous soils.

Sequential extraction and speciation of Ba, Cu, Ni, Pb and Zn in soil contaminated with automotive industry waste

Sequential extraction or fractionation of heavy metals in the solid phase and their speciation in soil solution are important tools for assessing changes resulting from land use and/or pollution. The distribution of the various forms of Ba, Cu, Ni, Pb and Zn was evaluated in soil samples taken from a polluted area, and the speciation of cations and anions in a soil solution contaminated with automotive industry waste. We evaluated the sequential extraction and speciation of Ba, Cu, Ni, Pb and Zn in a Leptosol associated with a Cambisol and contaminated with automotive industry waste. Soil samples were collected at 0-0.2 m (a mix of soil and waste); 0.2-0.4 m (waste only), and 0.4-0.6 m (soil only) both in the polluted area and in two contiguous unpolluted areas: a sugarcane plantation and a forest fragment. Total concentrations of metals in the polluted area were above limits for intervention established by European Community regulations. Cu was mostly distributed in the residual and in the oxide-bonded fractions, except for the waste-only sample, in which the carbonate-bonded fraction was significant. Zn was concentrated in the residual and carbonate-bonded fractions, while Ba, Ni and Pb predominated in the residual fraction of the contaminated samples. Metals in the soil solution were predominantly in the hydroxyl forms, except for Ba, which was mostly in the ionic form (Ba2+).

Inorganic species of arsenic in soil solution determined by microcartridges and ferrihydrite-based diffusive gradient in thin films (DGT)

The bioavailability of soil arsenic (As) is determined by its speciation in soil solution, i.e., arsenite [As(III)] or arsenate [As(V)]. Soil bioavailability studies require suitable methods to cope with small volumes of soil solution that can be speciated directly after sampling, and thereby minimise any As speciation change during sample collection. In this study, we tested a self-made microcartridge to separate both As species and compared it to a commercially available cartridge. In addition, the diffusive gradient in thin films technique (DGT), in combination with the microcartridges, was applied to synthetic solutions and to a soil spiked with As. This combination was used to improve the assessment of available inorganic As species with ferrihydrite(FH)-DGT, in order to validate the technique for environmental analysis, mainly in soils. The self-made microcartridge was effective in separating As(III) from As(V) in solution with detection by inductively coupled plasma optical emission spectrometry (ICP-OES) in volumes of only 3ml. The DGT study also showed that the FH-based binding gels are effective for As(III) and As(V) assessment, in solutions with As and P concentrations and ionic strength commonly found in soils. The FH-DGT was tested on flooded and unflooded As spiked soils and recoveries of As(III) and As(V) were 85–104% of the total dissolved As. This study shows that the DGT with FH-based binding gel is robust for assessing inorganic species of As in soils.

Acidity and Aluminum Speciation as Affected by Surface Liming in Tropical No‐Till Soils

Aluminum toxicity is one of the major soil factors limiting root growth in acidic soils. Because of the increase in organic matter content in the upper few centimeters of soils under no‐till systems (NTS), most Al in soil solution may be complexed to dissolved organic C (DOC), thus decreasing its bioavailability. The aim of this study was to evaluate the effects of surface liming on Al speciation in soil solution in Brazilian sites under NTS. Field experiments were performed in two regions with contrasting climates and levels of soil acidity: Rondonopolis, Mato Grosso State, on a Rhodic Haplustox, and Ponta Grossa, Paraná State, on a Typic Hapludox. The treatments consisted of a control and three lime rates, surface applied to raise the base saturation to 50, 70, and 90%. Soil solution was obtained at soil water equilibrium (1:1 w/w soil/water ratio). The effects of surface liming on soil chemical attributes and on the composition of the soil solution were dependent on weather conditions, time under NTS, and soil weathering. Most Al in soil solution was complexed to DOC, representing about 70 to 80% of the total Al at pH &lt;5.0, and about 30 to 40% at pH &gt;5.0. Under pH 5.5, the results were closely correlated with the solubility line for amorphous Al. Organic complexes may control Al3+ release into soil solution at pH &lt;5.5. Results suggest that in areas under NTS for a long period of time, Al toxicity might decrease due to its complexation to high‐molecular‐weight organic compounds.

Uncertainty Analysis of the Nonideal Competitive Adsorption−Donnan Model: Effects of Dissolved Organic Matter Variability on Predicted Metal Speciation in Soil Solution

Ion binding models such as the nonideal competitive adsorption-Donnan model (NICA-Donnan) and model VI successfully describe laboratory data of proton and metal binding to purified humic substances (HS). In this study model performance was tested in more complex natural systems. The speciation predicted with the NICA-Donnan model and the associated uncertainty were compared with independent measurements in soil solution extracts, including the free metal ion activity and fulvic (FA) and humic acid (HA) fractions of dissolved organic matter (DOM). Potentially important sources of uncertainty are the DOM composition and the variation in binding properties of HS. HS fractions of DOM in soil solution extracts varied between 14 and 63% and consisted mainly of FA. Moreover, binding parameters optimized for individual FA samples show substantial variation. Monte Carlo simulations show that uncertainties in predicted metal speciation, for metals with a high affinity for FA (Cu, Pb), are largely due to the natural variation in binding properties (i.e., the affinity) of FA. Predictions for metals with a lower affinity (Cd) are more prone to uncertainties in the fraction FA in DOM and the maximum site density (i.e., the capacity) of the FA. Based on these findings, suggestions are provided to reduce uncertainties in model predictions.

Accumulation, Subcellular Distribution and Toxicity of Copper in Earthworm (Eisenia fetida) in the Presence of Ciprofloxacin

Land application of wastes from concentrated animal feeding operations results in accumulation of copper (Cu) and antimicrobials in terrestrial systems. Interaction between Cu and antimicrobials may change Cu speciation in soil solution, and affect Cu bioavailability and toxicity. In this study, earthworms were exposed to quartz sand percolated with different concentrations of Cu and ciprofloxacin (CIP). Copper uptake by earthworms, its subcellular partition, and toxicity were studied. An increase in the applied CIP decreased the free Cu ion concentration in external solution and mortalities of earthworm, while Cu contents in earthworms increased. Copper and CIP in earthworms were fractionated into five fractions: a granular fraction (D), a fraction consisting of tissue fragments, cell membranes, and intact cells (E), a microsomal fraction (F), a denatured proteins fraction (G), and a heat-stable proteins fraction (H). Most of the CIP in earthworms was in fraction H. Copper was redistributed from the metal-sensitive fraction E to fractions D, F, G, and H with increasing CIP concentration. These results challenge the free ion activity model and suggested that Cu may be partly taken up as Cu-CIP complexes in earthworms, changing the bioavailability, subcellular distribution, and toxicity of Cu to earthworms.

Chemodynamics of heavy metals in long-term contaminated soils: Metal speciation in soil solution

The concentration and speciation of heavy metals in soil solution isolated from long-term contaminated soils were investigated. The soil solution was extracted at 70% maximum water holding capacity (MWHC) after equilibration for 24 h. The free metal concentrations (Cd2+, CU2+, Pb2+, and Zn2+) in soil solution were determined using the Donnan membrane technique (DMT). Initially the DMT was validated using artificial solutions where the percentage of free metal ions were significantly correlated with the percentages predicted using MINTEQA2. However, there was a significant difference between the absolute free ion concentrations predicted by MINTEQA2 and the values determined by the DMT. This was due to the significant metal adsorption onto the cation exchange membrane used in the DMT with 20%, 28%, 44%, and 8% mass loss of the initial total concentration of Cd, Cu, Pb, and Zn in solution, respectively. This could result in a significant error in the determination of free metal ions when using DMT if no allowance for membrane cation adsorption was made. Relative to the total soluble metal concentrations the amounts of free Cd2+ (3%-52%) and Zn2+ (11%-72%) in soil solutions were generally higher than those of Cu2+ (0.2%-30%) and Pb2+ (0.6%-10%). Among the key soil solution properties, dissolved heavy metal concentrations were the most significant factor governing free metal ion concentrations. Soil solution pH showed only a weak relationship with free metal ion partitioning coefficients (K(p)) and dissolved organic carbon did not show any significant influence on K(p).

Relationship between Metal Speciation in Soil Solution and Metal Adsorption at the Root Surface of Ryegrass

The total metal content of the soil or total metal concentration in the soil solution is not always a good indicator for metal availability to plants. Therefore, several speciation techniques have been developed that measure a defined fraction of the total metal concentration in the soil solution. In this study the Donnan Membrane Technique (DMT) was used to measure free metal ion concentrations in CaCl(2) extractions (to mimic the soil solution, and to work under standardized conditions) of 10 different soils, whereas diffusive gradients in thin-films (DGT) and scanning chronopotentiometry (SCP) were used to measure the sum of free and labile metal concentrations in the CaCl(2) extracts. The DGT device was also exposed directly to the (wetted) soil (soil-DGT). The metal concentrations measured with the speciation techniques are related to the metal adsorption at the root surface of ryegrass (Lolium perenne L.), to be able to subsequently predict metal uptake. In most cases the metal adsorption related pH-dependently to the metal concentrations measured by DMT, SCP, and DGT in the CaCl(2) extract. However, the relationship between metal adsorption at the root surface and the metal concentrations measured by the soil-DGT was not-or only slightly-pH dependent. The correlations between metal adsorption at the root surface and metal speciation detected by different speciation techniques allow discussion about rate limiting steps in biouptake and the contribution of metal complexes to metal bioavailability.