This study estimates the effect of environmental parameters on the mobility of four inorganic contaminants (As, Zn, Pb and Cd) in soils from three areas in the Ebro and Meuse River basins, within the context of global change. An experimental method, applicable to various soil systems, is used to measure the effect of four global-change-sensitive parameters (temperature, gas phase composition, pH and microbial activity). The aqueous phase of batch incubations was sampled regularly to monitor toxic element concentrations in water. Statistical processing enabled discrimination of the most relevant variations in dissolved concentrations measured at different incubation times and under different experimental conditions. Gas phase composition was identified as the most sensitive parameter for toxic element solubilization. This study confirms that total soil concentrations of inorganic pollutants are irrelevant when assessing the hazard for ecosystems or water resource quality. An experimental method applicable for different soil systems enables the determination of the effect of environmental parameters, potentially affected by global change, on the mobilization of inorganic pollutants.

We conducted a field drought manipulation experiment in an evergreen oak Mediterranean forest from 1999 to 2005 to investigate the effects of the increased drought predicted for the next decades on the accumulation of trace elements that can be toxic for animals, in stand biomass, litter and soil. Drought increased concentrations of As, Cd, Ni, Pb and Cr in roots of the dominant tree species, Quercus ilex, and leaf Cd concentrations in Arbutus unedo and of Phillyrea latifolia codominant shrubs. The increased concentration of As and Cd can aggravate the toxic capacity of those two elements, which are already next or within the levels that have been shown to be toxic for herbivores. The study also showed a great reduction in Pb biomass content (100-135 g ha-1) during the studied period (1999-2005) showing the effectiveness of the law that prohibited leaded fuel after 2001. The results also indicate that drought increases the exportation of some trace elements to continental waters. Drought increased biomass concentrations of As and Cd and favors exportation of some trace elements to continental waters in a Mediterranean forest.

Vertical profiles of C, N, δ15N and Pb were measured in the Mondego and Mira estuaries as markers that conveyed notions as to the relative influence of anthropogenic influence over the past decades. Recent carbon changes in both estuaries may reflect changes in estuarine productivity, probably as a consequence of sediment reworking and erosion, and also of losses in salt marsh area and dwarf eelgrass beds. δ15N values began to diverge considerably before the %C and %N and were higher in Mondego. δ15N signatures detected N enrichment at relatively low rates, and indicated that Mondego received more enriched N than Mira. Lead concentrations differed between estuaries, with higher concentrations in Mondego. The secular increase in %N, Pb, and δ15N signatures was significantly related to human density in the watersheds of the estuaries and were sensitive indicators of anthropogenic activity. The variables C, %N, δ15N, and Pb were reliable sediment sentinels that reflected the level of anthropogenic influence in the past decades in estuarine ecosystems.

This study examined the effects of heavy metals and plant arsenic uptake on soil arsenic distribution. Chemical fractionation of an arsenic-contaminated soil spiked with 50 or 200 mg kg-1 Ni, Zn, Cd or Pb was performed before and after growing the arsenic hyperaccumulator Pteris vittata L for 8 weeks using NH4Cl (water-soluble plus exchangeable, WE-As), NH4F (Al-As), NaOH (Fe-As), and H2SO4 (Ca-As). Arsenic in the soil was present primarily as the recalcitrant forms with Ca-As being the dominant fraction (45%). Arsenic taken up by P. vittata was from all fractions though Ca-As contributed the most (51-71% reduction). After 8 weeks of plant growth, the Al-As and Fe-As fractions were significantly (p < 0.01) greater in the metal-spiked soils than the control, with changes in the WE-As fraction being significantly (p = 0.007) correlated with plant arsenic removal. The plant's ability to solubilize soil arsenic from recalcitrant fractions may have enhanced its ability to hyperaccumulate arsenic. Arsenic taken up by P. vittata was from all fractions with most from the Ca-fraction.

The use of a vegetation cover for the management of heavy metal contaminated soils needs prior investigations on the plant species the best sustainable. In this work, behaviors of Trifolium repens and Lolium perenne, growing in a metal-polluted field located near a closed lead smelter, were investigated through Cd, Pb and Zn-plant metal concentrations and their phytotoxicity. In these plant species, metals were preferentially accumulated in roots than in shoots, as follow: Cd > Zn > Pb. Plant exposure to such metals induced oxidative stress in the considered organs as revealed by the variations in malondialdehyde levels and superoxide dismutase activities. These oxidative changes were closely related to metal levels, plant species and organs. Accordingly, L. perenne seemed to be more affected by metal-induced oxidative stress than T. repens. Taken together, these findings allow us to conclude that both the plant species could be suitable for the phytomanagement of metal-polluted soils. Usefulness of Trifolium repens and Lolium perenne for the phytomanagement of heavy metal-contaminated soils.

Tobacco plants transformed with TaLCT1 were cultured on Knop's medium with modified calcium concentrations (0.01-3 mM) in the presence of Pb2+, and in soil contaminated by lead. A 4-5 μM Pb2+ administered in the presence of 1 mM Ca2+ inhibited the root growth of transgenic plants to much lesser degree than of control plants, whereas in the presence of 3 mM Ca2+ no differences were found between the studied lines. The reduction of Pb2+ toxicity in the presence of 1 mM Ca2+ was not accompanied by a change in the lead tissue concentration. However, when Ca2+ level in the medium was lowered to 0.01 mM, several fold higher root/shoot Pb ratio in transgenic plants was observed, twofold increase in the total amount of metal accumulated, and lower concentration of Pb in the xylem sap. Results suggest the involvement of TaLCT1 in the regulation of Ca-dependent Pb-detoxification, and under conditions of low calcium in lead uptake and distribution. Ca2+-dependent Pb2+ detoxification and uptake was regulated by TaLCT1.

Metals released by the extraction with aqua regia, EDTA, dilute HCl and sequential extraction (SE) by the BCR protocol were studied in urban soils of Sevilla, Torino, and Glasgow. By multivariate analysis, the amounts of Cu, Pb and Zn liberated by any method were statistically associated with one another, whereas other metals were not. The mean amounts of all metals extracted by HCl and by SE were well correlated, but SE was clearly underestimated by HCl. Individual data for Cu, Pb and Zn by both methods were correlated only if each city was considered separately. Other metals gave poorer relationships. Similar conclusions were reached comparing EDTA and HCl, with much lower values for EDTA. Dilute HCl extraction cannot thus be recommended for general use as alternative to BCR SE in urban soils. Dilute HCl extraction is tested as an alternative to the BCR sequential extraction in urban soils.

Previously recommended rhizosphere-based method (RHIZO) applied to moist rhizosphere soils was integrated with moist bulk soils, and termed adjusted-RHIZO method (A-RHIZO). The A-RHIZO and RHIZO methods were systematically compared with EDTA, DTPA, CaCl2 and the first step of the Community Bureau of Reference (BCR1) methods for assessing metal phytoavailability under field conditions. Results suggested that moist bulk soils are equally suited or even better than rhizosphere soils to estimate metal phytoavailability. The A-RHIZO method was preferred to other methods for predicting the phytoavailability of Ni, Cu, Zn, Cd, Pb and Mn to wheat roots with correlation coefficients of 0.730 (P < 0.001), 0.854 (P < 0.001), 0.887 (P < 0.001), 0.739 (P < 0.001), 0.725 (P < 0.001) and 0.469 (P < 0.05), respectively. When including soil properties, other extraction methods were also able to predict phytoavailability reasonably well for some metals. Soil pH, organic matter and Fe-Mn oxide contents, and cation-exchange capacity mostly influenced the extraction and phytoavailability of metals. An adjusted-RHIZO method was the most promising approach for predicting metal phytoavailability to wheat under field conditions.

Three experiments were conducted to optimize the use of ethylenediaminetetraacetic acid (EDTA) for reclaiming urban soils contaminated with trace metals. As compared to Na2EDTA, (NH4)2EDTA extracted 60% more Zn and equivalent amounts of Cd, Cu and Pb from a sandy loam. When successively saturating and draining loamy sand columns during a washing cycle, which submerged it once with a (NH4)2EDTA wash and four times with deionised water, the post-wash rinses largely contributed to the total cumulative extraction of Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn. Both the washing solution and the deionised water rinses were added in a 2:5 liquid to soil (L:S) weight ratio. For equal amounts of EDTA, concentrating the washing solution and applying it and the ensuing rinses in a smaller 1:5 L:S weight ratio, instead of a 2:5 L:S weight ratio, increased the extraction of targeted Cr, Cu, Ni, Pb and Zn. A single EDTA addition is best utilised in a highly concentrated washing solution given in a small liquid to soil weight ratio.

Options for wetland creation or restoration might be limited because of the presence of contaminants in the soil. The influence of hydrological management on the pore water concentrations of Cd, Cr, Cu, Fe, Mn, Ni and Zn in the upper soil layer of a contaminated overbank sedimentation zone was investigated in a greenhouse experiment. Flooding conditions led to increased Fe, Mn, Ni and Cr concentrations and decreased Cd, Cu and Zn concentrations in the pore water of the upper soil layer. Keeping the soil at field capacity resulted in a low pore water concentration of Fe, Mn and Ni while the Cd, Cu, Cr and Zn concentrations increased. Alternating hydrological conditions caused metal concentrations in the pore water to fluctuate. Formation and re-oxidation of small amounts of sulphides appeared dominant in determining the mobility of Cd, Cu, and to a lesser extent Zn, while Ni behaviour was consistent with Fe/Mn oxidation and reduction. These effects were strongly dependent on the duration of the flooded periods. The shorter the flooded periods, the better the metal concentrations could be linked to the mobility of Ca in the pore water, which is attributed to a fluctuating CO2 pressure. The hydrological regime is a key factor in determining the metal concentration in the pore water of a contaminated sediment-derived soil.