Impact of historical mining assessed in soils by kinetic extraction and lead isotopic ratios.

The aim of this study is to estimate the long-term behaviour of trace metals, in two soils differently impacted by past mining. Topsoils from two 1 km(2) zones in the forested Morvan massif (France) were sampled to assess the spatial distribution of Cd, Cu, Pb and Zn. The first zone had been contaminated by historical mining. As expected, it exhibits higher trace-metal levels and greater spatial heterogeneity than the second non-contaminated zone, supposed to represent the local background. One soil profile from each zone was investigated in detail to estimate metal behaviour, and hence, bioavailability. Kinetic extractions were performed using EDTA on three samples: the A horizon from both soil profiles and the B horizon from the contaminated soil. For all three samples, kinetic extractions can be modelled by two first-order reactions. Similar kinetic behaviour was observed for all metals, but more metal was extracted from the contaminated A horizon than from the B horizon. More surprising is the general predominance of the residual fraction over the "labile" and "less labile" pools. Past anthropogenic inputs may have percolated over time through the soil profiles because of acidic pH conditions. Stable organo-metallic complexes may also have been formed over time, reducing metal availability. These processes are not mutually exclusive. After kinetic extraction, the lead isotopic compositions of the samples exhibited different signatures, related to contamination history and intrinsic soil parameters. However, no variation in lead signature was observed during the extraction experiment, demonstrating that the "labile" and "less labile" lead pools do not differ in terms of origin. Even if trace metals resulting from past mining and metallurgy persist in soils long after these activities have ceased, kinetic extractions suggest that metals, at least for these particular forest soils, do not represent a threat for biota.

Thermodynamic and kinetic study of the single extraction of mercury from soil using sodium-thiosulfate.

The use of sodium-thiosulfate (Na-thiosulfate) as a reagent for the extraction of mercury (Hg) from soil was investigated. High organic matter content in soil plays a major role in retaining metals. It has previously been reported that using the cold vapour atomic absorption method, powerful reagents such as EDTA, DTPA and cysteine could not release Hg from soil samples. The optimal conditions for using Na-thiosulfate to extract soil-Hg are presented here. Our results show that 50±5% of total Hg was extracted from soil samples using 0.01molL(-1) of the reagent without pH adjustment. Increasing the reagent concentration above this level showed no significant change in Hg extraction. From this extraction three fractions of Hg were obtained, the labile, slowly labile and un-extractable. We further applied the use of a kinetic extraction approach that has never been applied for Hg. We observed a correlation between the first two fractions and the quantity of organic matter content in soils. The labile fraction could be released by using any concentration of the reagent. However, the slowly labile fraction was dependent on time and increased concentrations of Na-thiosulfate. Furthermore, our results suggest that the labile and slowly labile fractions involve two different sites of reduced sulphur groups contained in soil organic matter and Hg levels present in the soil samples did not appear high enough to saturate all these high affinity sulphur sites. The capacity of Na-thiosulfate to reduce (Hg(II)) to (Hg(0)), was determined to be negligible. Our results further suggest the implication of iron (Fe(II)) for reducing Hg(II) to Hg(0). Here we have demonstrated that Na-thiosulfate is an effective reagent in the extraction of Hg from soil, with the particular characteristic of its ability to remove strongly bound Hg from sulphur groups contained in soil organic matter.

Fractionation studies of mercury in soils and sediments: a review of the chemical reagents used for mercury extraction.

Mercury in contaminated soils and sediments could be extracted by various chemical reagents in order to determine the different mercury species and partitions, providing useful information of toxicology, bioavailability and biogeochemical reactivity. Unfortunately, at present, neither specific extractants nor standard protocols exist for the isolation of particular mercury species. Although there has been considerable research focused on reagents for extracting mercury species, there is still little consensus. Thus, workers are advised to select the most appropriate reagent based on the nature of their sample, and to take all possible steps to validate the analyses performed. Therefore, the aim of this paper is to review the current reagents used for determining total mercury and its speciation as well as fractionation such as methylmercury, ethylmercury, elemental mercury, mercury sulphide and organically bound mercury by supposed selective (one reagent) and sequential (several reagents) extractions. The gathering information presented here bring to light the need for standard protocol for which the used chemical reagents should take into account the particular chemistry of mercury associated with specific properties of soil and sediment. Beside this required scheme, appropriate reference materials are also demanded.

Study of the trace metal ion influence on the turnover of soil organic matter in cultivated contaminated soils.

The role of metals in the behaviour of soil organic matter (SOM) is not well documented. Therefore, we investigated the influence of metals (Pb, Zn, Cu and Cd) on the dynamic of SOM in contaminated soils where maize (C4 plant) replaced C3 cultures. Three pseudogley brown leached soil profiles under maize with a decreasing gradient in metals concentrations were sampled. On size fractions, stable carbon isotopic ratio (delta13C), metals, organic carbon and nitrogen concentrations were measured in function of depth. The determined sequence for the amount of C4 organic matter in the bulk fractions: M3 (0.9)>M2 (0.4)>M1 (0.3) is in agreement with a significant influence of metals on the SOM turnover. New C4 SOM, mainly present in the labile coarser fractions and less contaminated by metals than the stabilised C3 SOM of the clay fraction, is more easily degraded by microorganisms.

Application of a kinetic fractionation of trace elements (Cd, Cu and Pb) in unpolluted soil samples.

The hazard due to the presence of large amounts of trace metals in some soils is strongly related to the speciation of these metals. The aim of this work was to apply an operationally defined fractionation based on kinetics which could distinguish "labile" (quickly extracted) and "non labile or slowly labile i.e. slowly extracted) cations, using the extraction kinetics of trace metals by EDTA. This kinetic fractionation has been applied to ten soil samples from Burgundy (France), which are known to be unpolluted. Copper, lead and cadmium were determined using this fractionation procedure. According to this fractionation, cadmium was found to be more mobile than copper or lead, both in terms of the labile concentration and the kinetic constants.

Electrochemical generation of the Fenton's reagent: application to atrazine degradation.

The degradation of refractory chemicals in water requires chemical oxidation by hydroxyl radicals. Among the systems that may be used to generate OH(o), the Fenton's reagent consists of the mixing of ferrous iron and hydrogen peroxide. Even though this system is very simple, the oxidation of an organic compound is difficult to control and the ferrous iron regeneration is limited. Very recently, electrochemical systems have merged that allow the electrochemical production of ferrous iron and/or hydrogen peroxide, thereby allowing the generation of OH(o). So a simple electro-Fenton system has been used and tested for its efficiency in producing hydroxyl radicals. Atrazine was chosen as a model organic compound as its reaction with OH(o) has been extensively studied. Comparison with the classical Fenton system gives advantage to the electrochemical system, due to a more thorough oxidation of atrazine.

Trace metal sorption ability of insolubilized humic acids.

The objective of this work was to study the trace metal sorption ability of Insolubilized Humic Acids (IHA) in comparison with regular Humic Acids (HA). IHA were prepared from HA by heating at 330 degrees C for one hour under a nitrogen atmosphere. A solubility study was carried out at different pH values in NaNO3 (0.1 M) as a background electrolyte. It showed that IHA were insoluble until pH 10 whereas the solubility of HA increased with pH in one main step in the pH range 4-5 over which the soluble fraction of humic acids increased from 10% to 90%. We observed that trace metal sorption was dramatically influenced by these solubility properties. Indeed this study showed that above pH 5-6, HA and IHA may have opposite effects in terms of trace metal sorption. Solubilization of HA made possible the formation of soluble metal-humic complexes, retaining metal in solution even for pH at which hydroxide can form. Under such pH conditions, which very numerous soils show, HA could be involved in the transport and uptake of trace metals in the plant-soil system. In terms of remediation, HA are not a suitable binding phase. On the contrary IHA were not solubilized at neutral and alkaline pH, avoiding then the solubilization of sorbed trace metals. They appeared to be a suitable binding additive phase for future remediation trials.

Determination of trihalomethanes in chlorinated sea water samples using a purge-and-trap system coupled to gas chromatography.

In power stations, the cooling effluents are chlorinated to avoid excessive biofouling. Yet, this disinfecting treatment leads to the formation of halogenated by-products, mainly trihalomethanes. So, there is a need for precise and accurate methods that allow trace levels determination of these compounds. A system that combines purge-and-trap and gas chromatography (with an electron capture detector) was used in this study. After careful choice of the experimental conditions, the performance of the system were evaluated. Precise and accurate determinations were obtained, allowing the determination of trihalomethanes in sea water samples chlorinated on site in three French coastal power stations. Bromoform was the predominant component formed, while traces of dibromochloromethane, chloroform and bromodichloromethane were also detected.

Determination of dihaloacetonitriles and halophenols in chlorinated sea water.

The cooling effluents in power stations are chlorinated to avoid excessive biofouling. However, this disinfecting treatment leads to the formation of halogenated by-products, mainly trihalomethanes, haloacetonitriles and halophenols. There is therefore a need for precise and accurate methods that allow trace level determinations of these compounds. Experimental procedures combining liquid-liquid extraction and gas chromatography coupled to mass spectrometry were developed in this study to determine dihaloacetonitriles and halophenols. The extraction step was improved and the performance of both methods evaluated. Precise and accurate determinations were obtained, allowing the measurement of the investigated compounds in chlorinated sea water samples from three French nuclear power stations.

Determination of traces of pesticides in water by solid-phase extraction and liquid chromatography-ionspray mass spectrometry.

A multi-residue analytical method for six pesticides (atrazine, hydroxyatrazine, carbofuran, promecarb, linuron and monolinuron) in drinking water has been developed. The method combines liquid chromatography and mass spectrometry using an ionspray interface. The linearity domain, as well as the limits of detection and quantification, were determined for each compound. Although satisfactory performance could be achieved, present drinking water regulations (0.1 microgram l-1 for single pesticide) requires a pre-concentration step. This was performed using solid-phase extraction with octadecyl-bonded silica cartridges. The analytical procedure was tested on water samples spiked at the 0.04 and 0.08 microgram l-1 levels, and allowed the determination of the investigated pesticides (except hydroxyatrazine) at these trace concentrations.

Influence of soluble organic matter on cadmium mobility in model compounds and in soils.

The role of soluble organic matter on the mobility of cadmium in model compounds and soils is discussed. For model compounds, a simple predictive model is proposed to describe the competition between metal adsorption and the formation of complexes in the solution, using conditional constants to predict the adsorption behaviour of metallic cations in the presence of an organic ligand. Experimental results are presented using a clay mineral and ethylenediaminetetraacetic acid as organic ligand to assess this model for cadmium. Soil experiments are also presented to illustrate the influence of soluble complexing organic matter on the mobility of cadmium. In this instance, mobility is shown to depend on three interactive parameters: pH, oxidation-reduction reactions and formation of complexes.