Impact of temperature on the dynamics of organic matter and on the soil-to-plant transfer of Cd, Zn and Pb in a contaminated agricultural soil.

Predicting the soil-to-plant transfer of metals in the context of global warming has become a major issue for food safety. It requires a better understanding of how the temperature alters the bioavailability of metals in cultivated soils. This study focuses on one agricultural soil contaminated by Cd, Zn and Pb. DGT measurements were performed at 10, 20 and 30 °C to assess how the bioavailability of metals was affected by a rise in soil temperature. A lettuce crop was cultivated in the same conditions to determine if the soil-to-plant transfer of metals increased with a rise in soil temperature. A gradual decline in Cd and Zn bioavailability was observed from 10 to 30 °C, which was attributed to more intense complexation of metals in the pore water at higher temperatures. Together with its aromaticity, the affinity of dissolved organic matter (DOM) for metals was indeed suspected to increase with soil temperature. One main output of the present work is a model which satisfactorily explains the thermal-induced changes in the characteristics of DOM reported in Cornu et al. (Geoderma 162:65-70, 2011) by assuming that the mineralization of initial aliphatic compounds followed a first-order reaction, increased with soil temperature according to the Arrhenius law, and due to a priming effect, led to the appearance of aromatic molecules. The soil-to-plant transfer of Cd and Zn was promoted at higher soil temperatures despite a parallel decrease in Cd and Zn bioavailability. This suggests that plant processes affect the soil-to-plant transfer of Cd and Zn the most when the soil temperature rises.

Comparison of two experimental speciation methods with a theoretical approach to monitor free and labile Cd fractions in soil solutions.

This work focused on the suitability of two techniques to monitor cadmium speciation in soil solutions collected during a 7-day incubation of a contaminated soil. Anodic stripping voltammetry (ASV) and ion exchange were performed on soil solutions collected daily and results were compared with calculations obtained with the speciation software Visual MINTEQ. The electrochemically labile Cd fraction was greater than the exchange-estimated free Cd fraction during the first 6 days, after which it decreased sharply during the last 2 days to reach values close to the exchange-estimated free Cd fraction. Further investigations showed that the increase in pH was mainly responsible for the reduction. However, calculations performed with Visual MINTEQ software clearly demonstrated that a change in the nature of organic matter and/or its complexing capacity also needed to be taken into consideration.

Cadmium speciation assessed by voltammetry, ion exchange and geochemical calculation in soil solutions collected after soil rewetting.

Analytical techniques and speciation models have been developed to characterize the speciation of Cd in soil solution. They provide an estimate of operationally defined species of Cd that need to be compared, especially for soil solutions highly concentrated in organic matter as are the solutions collected after soil rewetting. This work deals with the comparison between the speciation of Cd measured by anodic stripping voltammetry (ASV) and ion exchange and the speciation of Cd calculated using Visual MINTEQ. The aim of this study was to quantify and explain the differences in Cd speciation observed between the three approaches. Cd speciation was assessed in soil solutions collected 4, 8, 24, 48, 96 and 144h after the rewetting of an air-dried contaminated soil. To optimize the computed speciation of Cd, other physico-chemical parameters were followed (e.g. pH, ionic strength and the concentrations of major anions, major cations and dissolved organic carbon) and a brief characterisation of dissolved organic matter (DOM) was performed. The discrepancy between model predictions and analytical measurements highlighted the need for caution in the interpretation of geochemical speciated data for Cd. The major result of this study was that a characterization of DOM based on its specific UV-absorbance at 254 nm improved the accuracy of model predictions. Another finding is that labile Cd complexes, even organic, may have been included in the electrochemically labile fraction of Cd measured by ASV.

Temporal evolution of redox processes and free Cd dynamics in a metal-contaminated soil after rewetting.

Soil testing procedures to address metals bioavailability currently use air-dried soil rewetted almost until saturation. Such practices may influence the redox state of soil and the related dynamics of metals. To assess this potential impact, a metal-contaminated soil was air-dried and rewetted to 90% water holding capacity. We monitored over a 21-day incubation period the temporal changes of soil redox potential and solution Cd concentration (either total or free). Other physico-chemical parameters were followed notably pH, ionic strength (I) and the concentrations of NO(3)(-), Mn, Fe and SO(4)(2-) in solution. Soil redox potential showed the progressive establishment of strong reducing conditions in soil, in agreement with the temporal changes of NO(3)(-), Mn, Fe and SO(4)(2-) concentrations. It decreased by 13 pe units over the culture period leading to sulphate-reducing conditions (pe<-3) within only 21days. Solution Cd concentration increased transitorily over the first 100-150h of incubation (2-fold increase) in relation with the parallel increase in the concentration of competing cations for adsorption (Ca, Mg). It steeply decreased over the last 300h of incubation (30-fold decrease) as a result of Cd precipitation as Cd sulphides. This biphasic evolution of Cd dynamics was related to the temporal changes of Cd resupply from the solid phase. Using the technique of DGT we described the kinetics of Cd resupply over time and needed to invoke the existence of two pools of Cd.

The organic carbon derived from sewage sludge as a key parameter determining the fate of trace metals.

In a sandy agricultural soil of south-west of France, continuously cultivated with maize and amended with sewage-sludge over 20 years, the behavior of three trace metals (Cu, Pb, and Zn) was studied during the sludge applications (1974-1993) and after its cessation (1993-1998). Using the delta13C analysis, the dynamics of different sources of organic matter were followed in order to elucidate the influence of the sludge-derived organic matter on the fate of trace metals in the soil and its particle size fractions. This study revealed that sludge-derived organic matter contributed to the formation of macroaggregates through the binding of preexisting microaggregates. These macroagreggates were thus responsible for the accumulation of trace metals in the coarsest fraction as well as for the protection of maize-derived organic matter against biodegradation. After sludge application ceased, the disaggregation of macroaggregates occurred simultaneously with high losses in Cu and Pb. On the contrary, Zn appeared less affected by the cessation of sludge application, with only a location change from coarse to fine fractions.

Modeling lead input and output in soils using lead isotopic geochemistry.

The aim of this study is to model downward migration of lead from the plow layer of an experimental site located in Versailles (about 15 km southwest of Paris, France). Since 1928, samples have been collected annually from the topsoil of three control plots maintained in bare fallow. Thirty samples from 10 different years were analyzed for their lead and scandium contents and lead isotopic compositions. The fluxes are simple because of the well-controlled experimental conditions in Versailles: only one output flux, described as a first-order differential function of the anthropogenic lead pool, was taken into account; the inputs were exclusively ascribed to atmospheric deposition. The combination of concentration and isotopic data allows the rate of migration from the plowed topsoil to the underlying horizon and, to a lesser extent, the atmospheric fluxes to be assessed. Both results are in good agreement with the sparse data available. Indeed, the post-depositional migration of lead appears negligible at the human time scale: less than 0.1% of the potentially mobile lead pool migrates downward, out of the first 25 cm of the soil, each year. Assuming future lead inputs equal to 0, at least 700 yr would be required to halve the amount of accumulated lead pollution. Such a low migration rate is compatible with the persistence of a major anthropogenic lead pool deposited before 1928. Knowledge of pollution history seems therefore to be of primary importance.

Is metal extraction by Arabidopsis halleri related to exchangeable metal rates in soils amended with different metal-bearing solids?

Metals are associated to various constituents in polluted soils, and their availability is closely related to their chemical speciation. Studies on relations between metal extraction efficiency by hyperaccumulators and location of metals with respect to soil constituents are scarce. In this study. we investigate the relationship between metal extraction by Arabidopsis halleri and the exchangeable metals from substrates amended with various metal-bearing solids collected in the vicinity of a Zn smelter complex. These consisted of fresh and decomposing organic matter, the soil clay fraction, and two types of waste slags. ZnSO4 was also used as metal-bearing solid. Each was mixed with an unpolluted soil to produce two types of substrate, one moderately polluted and the other highly polluted. Total Zinc, Cd, Cu, and Pb were measured in substrates and in roots and shoots of A. halleri. Analysis of 0.01 M CaCl2 exchangeable metals in each substrate was performed before and after plant growth. The results showed different concentrations of exchangeable metals after plant growth, depending on the nature of the metal-bearing solids. In the ZnSO4 soil substrate, the proportion of exchangeable Zn decreased after plant growth, whilst it increased significantly on substrates amended with the two waste slags. For the other substrates, exchangeable Zn was not significantly different before and after plant growth. The same trend was observed for Cd. In the case of Cu, exchangeable rates increased in all substrates. The results were discussed according to the characteristics of the metal-bearing solids and to the metal-uptake strategy of A. halleri.

Estimating distributions of endogenous and exogenous Pb in soils by using Pb isotopic ratios.

Metal contamination of soils by diffuse atmospheric deposition is a worldwide phenomenon. The assessment of incorporation of exogenous metal contaminants in soils is of major environmental importance. Once entering in the soil's biogeochemical cycling, specific pedogenetic soil processes govern metal distribution patterns with depth. In this paper, we attempt to estimate the distribution of endogenous and exogenous Pb in two soils with contrasting pedogenesis, both representative of undisturbed ecosystems. Pb isotope analyses were performed using high-precision thermal ionization mass spectrometry. Endogenous and exogenous Pb concentrations and exogenous 206Pb/207Pb ratios of the samples were calculated using bulk Pb and Sc concentrations and bulk 206Pb/207Pb ratios. Endogenous Pb distribution was in agreementwith dominant soil characteristics, almost constant in the young Andosol and with a clear minimum and maximum in the eluvial and illuvial horizons of the Podzol. The distribution of exogenous Pb was closely related to that of organic C in both soils. Exogenous Pb was evidenced in significant amounts at depth. Using moderate dispersive particle-size fractionation allowed us to evidence the presence of exogenous Pb in functional soil compartments and to highlight preferential distributions of Pb, according to pedology.

Dissolved and colloidal transport of Cd, Pb, and Zn in a silt loam soil affected by atmospheric industrial deposition.

As a result of processing of metal ores, trace metals have contaminated large areas of northern France. Metal migration from the soil to groundwater presents an environmental risk that depends on the physico-chemical properties of each contaminated soil. Soil water samples were obtained over the course of 1 year with zero-tension lysimeters from an acidic, loamy, metal contaminated soil. The average trace metal concentrations in the soil water were high (e.g. for Zn 11 mg l-1 under the surface horizon), but they varied during the sampling period. Zn concentrations were not correlated with pH or total organic carbon in the solutions but were correlated with Cd concentrations. On average, 95% of the Zn and Cd but only 50% of Pb was present in a dissolved form. Analytical transmission electron microscopy was used to identify the Zn or Pb carriers. Colloids containing Pb and Zn were biocolloids, whereas colloids containing only Zn were smectites.