Koen Oorts

Toxicity of Trace Metals in Soil as Affected by Soil Type and Aging After Contamination: Using Calibrated Bioavailability Models to Set Ecological Soil Standards

Total concentrations of metals in soil are poor predictors of toxicity. In the last decade, considerable effort has been made to demonstrate how metal toxicity is affected by the abiotic properties of soil. Here this information is collated and shows how these data have been used in the European Union for defining predicted-no-effect concentrations (PNECs) of Cd, Cu, Co, Ni, Pb, and Zn in soil. Bioavailability models have been calibrated using data from more than 500 new chronic toxicity tests in soils amended with soluble metal salts, in experimentally aged soils, and in field-contaminated soils. In general, soil pH was a good predictor of metal solubility but a poor predictor of metal toxicity across soils. Toxicity thresholds based on the free metal ion activity were generally more variable than those expressed on total soil metal, which can be explained, but not predicted, using the concept of the biotic ligand model. The toxicity thresholds based on total soil metal concentrations rise almost proportionally to the effective cation exchange capacity of soil. Total soil metal concentrations yielding 10% inhibition in freshly amended soils were up to 100-fold smaller (median 3.4-fold, n = 110 comparative tests) than those in corresponding aged soils or field-contaminated soils. The change in isotopically exchangeable metal in soil proved to be a conservative estimate of the change in toxicity upon aging. The PNEC values for specific soil types were calculated using this information. The corrections for aging and for modifying effects of soil properties in metal-salt-amended soils are shown to be the main factors by which PNEC values rise above the natural background range.

Soil properties affecting the toxicity of CuCl2 and NiCl2 for soil microbial processes in freshly spiked soils

It generally is unknown to what extent the toxicity of Cu and Ni for soil microbial processes varies among different soils. A comparative study was made using three different microbial assays (nitrification potential, glucose-induced respiration, and C-mineralization of a plant residue) in 19 (for Cu) or 16 (for Ni) soils with contrasting soil properties. Each soil was spiked with CuCl2 or NiCl2 at seven different concentrations, and the bioassays were started after a 7-d equilibration period. The Cu and Ni toxicity thresholds varied 19- to 90-fold among soils. The differences in both Cu and Ni toxicity among soils were neither explained by soil solution metal concentrations nor by free ion activities calculated from soil solution composition. Copper toxicity thresholds (total concentrations) increased with increasing organic matter content or cation exchange capacity (CEC) and, surprisingly, decreased with increasing pH depending on the assay. Nickel toxicity thresholds consistently increased with increasing CEC, background Ni, and clay content for all three assays. Thresholds expressed as soil solution free ion activities all significantly decreased with increasing soil solution pH (r2 = 0.57-0.93), consistent with a decreased H+:M2+ competition at the biological membrane. That competition largely counteracts the H+:M2+ competition for sorption, effectively explaining the insignificant or weak effect of pH on total Ni or Cu toxicity thresholds. It is concluded that free metal-ion activity alone does not explain variation in metal toxicity among soils.

Leaching and aging decrease nickel toxicity to soil microbial processes in soils freshly spiked with nickel chloride

Nickel is a trace metal that exhibits pronounced long-term immobilization reactions in soil. It is unknown if the slowly decreasing solubility of Ni in soil on aging correlates with decreased toxicity to soil biota. Three uncontaminated soils (pH 4.5-7.6) were contaminated with NiCl2 and experimentally leached or incubated outdoors with free drainage for up to 15 months. Nickel toxicity was measured for three microbial processes (potential nitrification rate, glucose-induced respiration, and C mineralization of maize residue). Results for leached and aged samples were compared with results for these soils tested immediately after spiking. Experimental leaching increased Ni ED50s (Ni dose to inhibit process by 50%) with a median factor of 2.0, whereas Ni ED50s in soils aged 15 months were a factor 1 to 23 (median, 4.6) larger compared to freshly spiked soils. Changes in soil Ni toxicity on aging generally were largest in the soil with the highest pH, consistent with the largest relative decreases of soil solution Ni concentration or predicted Ni2+ activity. Soil solution Ni concentrations explained part, but not all, of the reduction in Ni toxicity. The predicted soil solution Ni2+ activity also did not fully explain the reduced toxicity, which was ascribed to the variable concentrations of ions competing with Ni2+ at biological membranes (e.g., H+, Mg2+, or Ca2+) among treatments. It is concluded that testing Ni toxicity to soil microbial processes immediately after spiking soils in the laboratory overestimates Ni toxicity compared to aged soils. Soil solution composition in freshly spiked soils clearly is different from that in leached or aged soils; therefore, soil spiked with metal salts should be leached before toxicity tests begin.

Discrepancy of the microbial response to elevated copper between freshly spiked and long‐term contaminated soils

A systematic comparison of Cu toxicity thresholds was made between freshly spiked soils and soils in which elevated Cu concentrations have been present for various times. Three uncontaminated soils were spiked and experimentally leached or incubated outdoors for up to 18 months. Additionally, five field-contaminated soils with a 6- to 80-year-old Cu contamination were sampled, and corresponding uncontaminated soils were spiked to identical total concentrations. All soil samples were subjected to three microbial assays (nitrification potential, glucose-induced respiration, and maize residue C-mineralization). Experimental leaching or soil incubation after spiking reduced Cu toxicity (1.3- or 2.3-fold increase of dose, respectively, to inhibit process by 50% [ED50]). No significant effects of soil type, aging time (6, 12, or 18 months), or bioassay on the factor change of ED50 were found. Significant reductions of microbial activity in field-contaminated soils were only identified in 2 of the 15 series (three assays in five soils), whereas freshly spiking the corresponding control soils significantly affected these processes in 12 series. Soil solution Cu concentrations significantly decreased on leaching at corresponding total soil Cu, and smaller decreases were found during additional aging. Soil solution Cu concentrations largely explain changes in Cu toxicity on leaching and aging, although additional variation may be related to changes in the sensitivity of microbial populations. It is concluded that total Cu toxicity thresholds are lower in freshly spiked soils compared to soils in which Cu salts have equilibrated and leaching has removed excess soluble salts. The large variability of soil microbial processes creates a large uncertainty about the magnitude of the factor by which aging mitigates Cu toxicity.

Cation exchange capacities of soil organic matter fractions in a Ferric Lixisol with different organic matter inputs

Abstract Soil organic matter (SOM) has an important effect on the physicochemical status of highly weathered soils in the tropics. This work was conducted to determine the contribution of different SOM fractions to the cation exchange capacity (CEC) of a tropical soil and to study the effect of organic matter inputs of different biochemical composition on the CEC of SOM. Soil samples were collected from a 20-year-old arboretum established on a Ferric Lixisol, under seven multipurpose tree species: Afzelia africana, Dactyladenia barteri, Gliricidia sepium, Gmelina arborea, Leucaena leucocephala, Pterocarpus santalinoides, and Treculia africana. Fractions were obtained by wet sieving and sedimentation after ultrasonic dispersion. Relationships between CEC and pH were determined using the silver thiourea-method and were described by linear regression. The CEC of the fractions smaller than 0.053xa0mm was inversely related to their particle size: clay ( 0.002 mm )> fine silt (0.002–0.02 mm )> coarse silt (0.02–0.053xa0mm), except for the soils under T. africana, D. barteri, and L. leucocephala, where the CEC of the fine silt fraction was highest or comparable to the CEC of the clay fraction. The clay and fine silt fractions were responsible for 76–90% of the soil CEC at pH 5.8. The contribution of the fine silt fraction to the CEC at pH 5.8 ranged from 35 to 50%, which stressed the importance of the fine silt fraction for the physicochemical properties of the soil. Differences in CEC between treatments for the whole soil and the fractions could be explained by the differences in carbon content. Except for the intercept for the clay fraction, SOM had a significant (P

Copper toxicity in soils under established vineyards in Europe: a survey.

Copper (Cu) containing fungicides have been used for more than one century in Europe on agricultural soils, such as vineyard soils. Total Cu concentrations in such soils can exceed toxicological limits that are commonly derived using artificially spiked soils. This study surveyed Cu toxicity in vineyard soils with reference to soils spiked with CuCl(2). Soil was collected in six established European vineyards. At each site, samples representing a Cu concentration gradient were collected. A control (uncontaminated) soil sampled nearby the vineyard was spiked with CuCl(2). Toxicity was tested using standard ecotoxicity tests: two plant assays (Lycopersicon esculentum Miller (tomato) and Hordeum vulgare L. (barley) growth), one microbial assay (nitrification) and one invertebrate assay (Enchytraeus albidus reproduction). Maximal total Cu concentrations in the vineyard sites ranged 435-690 mg Cu kg(-1), well above the local background (23-105 mg Cu kg(-1)). Toxicity in spiked soils (50% inhibition) was observed at added soil Cu concentrations from 190 to 1039 mg Cu kg(-1) (mean 540 mg Cu kg(-1)) depending on the assay and the site. In contrast, significant adverse effects were only found for three bioassays in vineyard samples of one site and for two bioassays in another site. Biological responses in these cases were more importantly explained by other soil properties than soil Cu. Overall, no Cu toxicity to plants, microbial processes and invertebrates was observed in vineyard soil samples at Cu concentrations well above European Union limits protecting the soil ecosystem.

Influence of soil properties on copper toxicity for two soil invertebrates

Although a large body of evidence indicates that metal toxicity to soil organisms is affected by physicochemical soil properties, use of this knowledge in ecological risk assessments is limited because of the lack of a model applicable to a wide range of soils. To study the effect of soil characteristics on the toxicity of copper to terrestrial invertebrates, chronic toxicity tests with Eisenia fetida and Folsomia candida were performed in 19 European field soils. These soils were carefully selected to cover the range of toxicity-influencing parameters encountered in the European Union. Toxicity values varied greatly among soils, with 28-d median effect concentrations ranging from 72.0 to 781 mg Cu/kg dry weight for E. fetida and from 45.4 to 2,270 mg Cu/kg dry weight for F. candida. For both species, variation in copper toxicity values was best explained by differences in the actual cation-exchange capacity (CEC) at soil pH. Using the obtained regression algorithms, the observed toxicity could, in most cases, be predicted within a factor of two for E. fetida and within a factor of three for F. candida. The developed models were validated in three additional European field soils, a standard artificial soil and a standard field soil. The presented regression equations, based on the actual CEC, offer an easy-to-apply method for taking the influence of soil properties on metal toxicity into account.

Aging of nickel added to soils as predicted by soil pH and time

Although aging processes are important in risk assessment for metals in soils, the aging of Ni added to soils has not been studied in detail. In this study, after addition of water soluble Ni to soils, the changes over time in isotopic exchangeability, total concentrations and free Ni(2+) activity in soil pore water, were investigated in 16 European soils incubated outdoors for 18 months. The results showed that after Ni addition, concentrations of Ni in soil pore water and isotopic exchangeability of Ni in soils initially decreased rapidly. This phase was followed by further decreases in the parameters measured but these occurred at slower rates. Increasing soil pH increased the rate and extent of aging reactions. Semi-mechanistic models, based on Ni precipitation/nucleation on soil surfaces and micropore diffusion, were developed and calibrated. The initial fast processes, which were attributed to precipitation/nucleation, occurred over a short time (e.g. 1h), afterwards the slow processes were most likely controlled by micropore diffusion processes. The models were validated by comparing predicted and measured Ni aging in three additional, widely differing soils aged outdoors for periods up to 15 months in different conditions. These models could be used to scale ecotoxicological data generated in short-term studies to longer aging times.

Effect of long-term equilibration on the toxicity of molybdenum to soil organisms

To determine if long-term equilibration may alleviate molybdenum toxicity, earthworms, enchytraeids, collembolans and four plant species were exposed to three soils freshly spiked with Na(2)MoO(4).2H(2)O and equilibrated for 6 or 11 months in the field with free drainage. Total Mo concentrations in soil decreased by leaching, most (up to 98%) in sandy soil and less (54-62%) in silty and clayey soils. Changes in residual Mo toxicity with time were inconclusive in sandy soil. In the other two soils, toxicity of residual total Mo was significantly reduced after 11 months equilibration with a median 5.5-fold increase in ED50s. Mo fixation in soil, i.e. the decrease of soil solution Mo concentrations at equivalent residual total soil Mo, was maximally a factor of 2.1 only. This experiment shows natural attenuation of molybdate ecotoxicity under field conditions is related to leaching of excess Mo and other ions as well as to slow ageing reactions.

Modelling the effects of copper on soil organisms and processes using the free ion approach: Towards a multi-species toxicity model

The free ion approach has been previously used to calculate critical limit concentrations for soil metals based on point estimates of toxicity. Here, the approach was applied to dose-response data for copper effects on seven biological endpoints in each of 19 European soils. The approach was applied using the concept of an effective dose, comprising a function of the concentrations of free copper and protective major cations, including H(+). A significant influence of H(+) on the toxicity of Cu(2+) was found, while the effects of other cations were inconsistent. The model could be generalised by forcing the effect of H(+) and the slope of the dose-response relationship to be equal for all endpoints. This suggests the possibility of a general bioavailability model for copper effects on organisms. Furthermore, the possibility of such a model could be explored for other cationic metals such as nickel, zinc, cadmium and lead.