Thibault Sterckeman

Vertical distribution of Cd, Pb and Zn in soils near smelters in the North of France

The analysis of the horizons of 12 soil profiles confirm occasionally significant levels of Cd, Pb and Zn contamination in the areas surrounding two lead and zinc smelters in the North of France. A pedological approach enabled the original Cd, Pb and Zn content of the horizons to be estimated, based on physico-chemical characteristics of soil unaffected by contamination. The main contamination was found in the upper 20-30 cm. Traces of Cd and Zn contamination were found at a depth of around 2 m. The mobility of the metals may be classified in the following order: Cd>>Pb> or =Zn. The concentration profile of a metal seems insufficient to evaluate its movement as the metal could have been leached beyond the contaminated horizons. The depth reached by the metals increases with their concentration in the surface horizon; a decrease in pH and an increase in sand content seem to facilitate their movement. The depth reached by Zn increases with the organic carbon content in the surface horizon. Earthworm galleries act as paths via which metals migrate downwards

Of the necessity of knowledge of the natural pedo-geochemical background content in the evaluation of the contamination of soils by trace elements

In order to evaluate the contamination of the Dornach (Switzerland) site within the framework of the CEEM-Soil project, each participating team was allowed to take a maximum of 15 samples. The French teams sampling was organized in such a way as to answer the following questions: (i) what is the natural concentration of the soils at this site (local pedo-geochemical background content)?; (ii) what are the levels of Cd, Cu, Pb and Zn contamination of the soil?; (iii) what is the depth reached by the surface contamination that is derived from atmospheric fallout?; (iv) how is the contamination spread along the longest axis of the area under study? The relationships between total Fe and the trace metals have allowed local variations in the natural pedo-geochemical background content to be detected and thus permitted the anthropogenic contamination to be estimated. There would appear to be a low level of Pb contamination over all the site investigated (an increase of the order of 5-10 mg kg(-1) on the background level), limited to the surface humus-bearing layers. There is also a significant contamination by Cu over all of the site (an increase of the order of 30-40 mg kg(-1)). This contamination has remained in the surface horizons (0-20 cm). Very high Zn and Cd concentrations have been found in the four surface (0-4 cm) and deep horizons (15-70 cm) taken under the forest and very much lower values in the samples taken from cultivated soils. The most likely explanation is an unequal inheritance between the upper part of the site (wooded with thinner very clayey soils) and the lower cultivated part of the site (with thicker less clayey soils developed in a loamy material). For various reasons, it seems unlikely that a contamination of the wooded part should be so much higher than the cultivated part due to the interception of atmospheric dust by the trees. The local pedo-geochemical background Cd and Zn content of the upper wooded part proved to be clearly higher than that which would be encountered in most soils of Switzerland and France. Given this evaluation of the background content, it seems that only the surface horizons have been affected by Zn contamination (an addition of approx. 60-100 mg kg(-1)). In the case of Cd, the increase in concentrations is only 0.5-1 mg kg(-1) for the ploughed horizons, as well as the for the A horizons.

Assessment of the Contamination of Cultivated Soils by Eighteen Trace Elements Around Smelters in the North of France

Ag, As, Bi, Cd, Co, Cr, Cu, Hg, In, Ni, Pb, Sb, Se, Sn,Tl, Th, U and Zn contamination of cultivated surfacehorizons has been assessed around two lead and zincsmelters in the North of France. The verticaldistribution of Ag, As, Bi, Cu, Hg, Se, Sb and Tl inthe soils has also been examined. The soils around thelead and zinc smelter at Noyelles-Godault arecontaminated by Ag, As, Bi, Cd, Cu, Hg, In, Ni, Pb, Sb,Se, Sn, Tl and Zn. The original concentration in themost contaminated soils may be multiplied by a factorof around 2 to 100, according to the element. Cadmium,Pb and Zn are the most abundant contaminants. The Pband Zn concentrations are correlated to those of theother contaminants, with the exception of Se. Aroundthe Auby zinc smelter, there is a contamination by thesame elements, but in different proportions, inaddition to Cr contamination. Contamination by Se canreach a depth of around 1 m, whereas contamination byAg, As, Bi, Cu, Hg, Sb and Tl is confined to the top 30cm. Although the contaminant content in most soilsdepends on the distance from the plant, Secontamination would appear to vary to a greater extentaccording to the physico-chemical soil conditions.

Thallium in French agrosystems—I. Thallium contents in arable soils

The thallium (Tl) content of the upper horizons of 244 French soils was determined as the first step towards the creation of a reference data bank for total Tl content of arable soils. Forty soil samples were collected in the vicinity of potential anthropogenic sources of Tl, but the remainder came from rural areas. The distribution of Tl concentrations in soils was characterized by a median value of 0.29 mg Tl kg(-1) and a 90th percentile value of 1.54 mg Tl kg(-1). Very high pedogeochemical contents were found (up to 55 mg Tl kg(-1)) but none could be attributed to obvious anthropogenic pollution. Areas of very high Tl concentration belong to an epihercynian transgression zone with a contact between a sedimentary basin and a crystalline massif. This contact is associated with stratified mineralizations (Zn, Pb, F, Sb, Ba, Tl and pyrites). High Tl concentrations were common in limestone, marl or granite derived soils, and the Tl in limestones or marls is probably concentrated in the sulfides contained in these rocks because Tl has a high affinity to S. In granites, Tl may be in the micas and feldspars because Tl+ can replace K+ in these minerals. Silty or clay-silty soils showed the highest concentrations. These granulometric fractions contain the majority of the minerals, which are supposed to be the major hosts of Tl in soils, i.e. clay minerals, oxides and micas. Tl in the soils was positively correlated with Ba, V, Pb, Fe, Ni, Cd, Zn, Co, As and especially Mn. A significant proportion of Tl may be in the Mn oxides: in oxidizing conditions, Tl(III) could enter the Mn oxides by sorption, or Tl(I) could replace K(I) in the oxide.

Assessment and control of the bioavailability of nickel in soils

Nickel, a potentially toxic metal, is present in all soils with an average concentration of 20 to 30 mg/kg, sometimes exceeding 10,000 mg/kg (e.g., ultramafic soils). The ecotoxicological risk of Ni in soils to organisms is controlled by its availability. It is therefore essential to identify an efficient and reliable method for the evaluation of this risk. This paper presents a complete study of the effect of Ni origin, localization, and soil properties on its availability as assessed with the isotopic exchange kinetics (IEK) method and compares plant response to isotopically exchangeable properties of Ni in soils. We performed IEK on 100 soil samples representing a worldwide range of Ni fate, and concentrations showed that pH was the main influencing parameter and that labile Ni (i.e., isotopically exchangeable Ni, Et) could be reasonably well assessed by a single diethylene triamine pentaacetic acid extraction. The identification of the soil mineral phases that bear Ni (bearing phases) in 16 Ni-rich samples selected among the 100 soils showed a strong effect of the mineralogy of the bearing phases on Ni availability (IEK). Plants with different Ni accumulation strategies all took up Ni from the same labile pool of Ni in four contrasting soils, and the amount taken up by hyperaccumulator plants could be anticipated with the IEK parameters, thus confirming the usefulness of isotopic dilution methods for risk assessment.

Designing Cropping Systems for Metal-Contaminated Sites: A Review

Considering that even contaminated soils are a potential resource for agricultural production, it is essential to develop a set of cropping systems to allow a safe and sustainable agriculture on contaminated lands while avoiding any transfer of toxic trace elements to the food chain. In this review, three main strategies, i.e., phytoexclusion, phytostabilization, and phytoextraction, are proposed to establish cropping systems for production of edible and non-edible plants, and for extraction of elements for industrial use. For safe production of food crops, the selection of low-accumulating plants/cultivars and the application of soil amendments are of vital importance. Phytostabilization using non-food energy and fiber plants can provide additional renewable energy sources and economic benefit with minimum cost of agricultural measures. Phytoextracting trace elements (e.g., As, Cd, Ni, and Zn) using hyperaccumulator species is more suitable for slightly and moderately polluted sites, and phytomining of Ni from serpentine soils has shown a great potential to extract Ni-containing bio-ores of economic interests. We conclude that appropriate combinations of soil types, plant species/cultivars, and agronomic practices can restrict trace metal transfer to the food chain and/or extract energy and metals of industrial use and allow safe agricultural activities.

Nickel and Zinc Isotope Fractionation in Hyperaccumulating and Nonaccumulating Plants

Until now, there has been little data on the isotope fractionation of nickel (Ni) in higher plants and how this can be affected by plant Ni and zinc (Zn) homeostasis. A hydroponic cultivation was conducted to investigate the isotope fractionation of Ni and Zn during plant uptake and translocation processes. The nonaccumulator Thlaspi arvense, the Ni hyperaccumulator Alyssum murale and the Ni and Zn hyperaccumulator Noccaea caerulescens were grown in low (2 μM) and high (50 μM) Ni and Zn solutions. Results showed that plants were inclined to absorb light Ni isotopes, presumably due to the functioning of low-affinity transport systems across root cell membrane. The Ni isotope fractionation between plant and solution was greater in the hyperaccumulators grown in low Zn treatments (Δ(60)Ni(plant-solution) = -0.90 to -0.63‰) than that in the nonaccumulator T. arvense (Δ(60)Ni(plant-solution) = -0.21‰), thus indicating a greater permeability of the low-affinity transport system in hyperaccumulators. Light isotope enrichment of Zn was observed in most of the plants (Δ(66)Zn(plant-solution) = -0.23 to -0.10‰), but to a lesser extent than for Ni. The rapid uptake of Zn on the root surfaces caused concentration gradients, which induced ion diffusion in the rhizosphere and could result in light Zn isotope enrichment in the hyperaccumulator N. caerulescens. In high Zn treatment, Zn could compete with Ni during the uptake process, which reduced Ni concentration in plants and decreased the extent of Ni isotope fractionation (Δ(60)Ni(plant-solution) = -0.11 to -0.07‰), indicating that plants might take up Ni through a low-affinity transport system of Zn. We propose that isotope composition analysis for transition elements could become an empirical tool to study plant physiological processes.

Factors affecting trace element concentrations in soils developed on recent marine deposits from northern France

Total concentrations of 18 trace and 2 major elements (Al, Fe) as well as physico-chemical characteristics (texture, organic C, pH, CaCO 3 , CEC) were measured in cultivated soil samples (fraction <2 mm) from 23 surface and 38 deeper horizons developed in recent marine deposits. Correlations between trace element contents and other soil parameters were compared in order to reveal those soil factors affecting the trace element distributions. Whatever the horizon type, Co, Cr, In, Ni and V are almost exclusively associated with the fine (<20 μm) mineral fraction and do not show a direct association with organic matter. Bismuth, Sn, Tl and Zn also show a close association with the fine mineral fraction of the deep horizons, but seem to be partly associated with organic matter in the ploughed horizons. In the deep horizons, the association of Cd, Cu and Pb with the fine mineral fraction is clearly less close, while these elements appear to be associated with organic matter in the ploughed horizons. The Mn content increases with that of the fine mineral fraction up to a certain point. Arsenic, Mo and Sb contents are poorly correlated with the fine solid phase of the deep horizons. The distribution of Hg does not appear to be associated with any specific soil component. The ploughed horizons are highly enriched with Pb, Cu, Cd, Hg and Se (+ 84% to + 225%) and moderately enriched with Tl, Mn, Sb, Bi, Sn and Zn (+ 7% to + 48%). There is no surface enrichment of As, Co, Cr, In, Mo, Ni and V. It is possible to model most of the trace element distributions with pedotransfer functions of the physico-chemical characteristics.

Estimation of Soil Trace Metal Bioavailability using Unbuffered Salt Solutions: Degree of Saturation of Polluted Soil Extracts

Soil trace metal extractability by 0.01 mol l−1 CaCl2, 0.1 mol l−1 NaNO3 and 1 mol l−1 NH4NO3 solutions is very low. The hypothesis, according to which the saturation of extracts limits the concentrations in solution, was tested by the study of polluted soils. Thus, according to our calculations, cadmium and copper did not precipitate as carbonates, hydroxides and phosphates. In contrast, zinc might precipitate as phosphate, lead as carbonate, hydroxide, sulfate and phosphates. The influence of such phenomena on the estimation of Pb bioavailability was tested by studying the lead uptake of radish plants cultivated in sandy soils artificially enriched with lead. It was then demonstrated that the saturation of the solutions did not in these conditions allow the evaluation of lead bioavailability using such chemical extractions.

Variation of trace metal accumulation, major nutrient uptake and growth parameters and their correlations in 22 populations of Noccaea caerulescens

Background and aimsNoccaea caerulescens is a model plant for the understanding of trace metal accumulation and a source of cultivars for phytoextraction. The aim of this study was to investigate natural variation for trace metal accumulation, major nutrient uptake and growth parameters in 22 populations. The correlations among these traits were particularly examined to better understand the eco-physiology and the phytoextraction potential of the species.MethodsPopulations from three edaphic groups, i.e. calamine (CAL), serpentine (SERP) and non metalliferous (NMET) sites were grown in hydroponics for seven weeks at moderate trace metal exposure. Growth indicators, element contents and correlations between these variables were compared.ResultsAll the phenotypic characteristics showed a wide variability among groups and populations. The SERP populations showed a smaller plant size, higher cation contents and strong correlations between all element concentrations. NMET populations did not differ in plant size from the CAL ones, but had higher Zn and Ni contents. The CAL populations showed higher Cd and Mn accumulations and lower Ca contents. The trade-off between biomass production and Cd, Ni and Zn accumulation was high in SERP populations and low in the CAL and NMET ones.ConclusionsN. caerulescens is a genetically diverse species, showing specific features depending on the group and the population. These features may reflect the wide adaptive capacities of the species, and also reveal promising potential for phytoextraction of Cd, Ni and Zn.