International audience | In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces. © 2005 Elsevier Ltd. All rights reserved.

peer reviewed | Contamination of land and aquatic ecosystems with heavy metals (HMs) is a global issue having the persistent potential to damage the quality of food and water. In the present study, Tagetes erecta L. plants were used to assess their potential to uptake HMs from wastewater. Plants were grown in soil for 20 days and then transplanted in hydroponic system containing Hoagland nutrient solution. After more than 15 days of growth, plants were then subjected to wastewater from tannery and surgical industries in different concentrations ranging from 25 to 100% in combination of citric acid (5 and 10 mM). After 6 weeks of treatment, plants were collected and segmented into roots, stem, and leaves for characterizing the morphological properties including plant height, roots length, fresh and dry mass of roots, stem, and leaves. For evaluation of the effect of wastewater on the plants, photosynthetic pigments; soluble proteins; reactive oxygen species (ROS); antioxidant enzymes SOD, POD, CAT, and APX; and metal accumulation were analyzed. Application of industrial wastewater revealed a significant effect on plant morphology under wastewater treatments. Overall growth and physiological attributes of plant decreased, and metal accumulation enhanced with increasing concentration of wastewater. Similarly, the production of ROS and antioxidant enzymes were also increased. Chlorophyll, protein content, and enzyme production enhanced with CA (5 and 10 mM) mediation; however, ROS production and EL were reduced. Metals analysis showed that the maximum accumulation of Pb was in roots, while Cr and Ni in the stem which further increased under CA mediation. Overall, the metal accumulation ability was in the order of Pb > Ni > Cr under CA.

We correlated mineralogical and particle characteristics of Zn-containing particles with Zn geoavailability, bioaccessibility, and bioavailability following gavage and intranasal (IN) administration in rats. We compared samples of Zn/Pb mine waste and five pulverized pure-phase Zn minerals (<38 μm). Particles were neutron-activated to produce radioactive 65Zn. We assessed geoavailability using sequential extractions and bioaccessibility using in vitro extraction tests simulating various pH and biological conditions. Zn in vivo bioavailability and in vitro bioaccessibility decreased as follows: mine waste > hydrozincite > hemimorphite > zincite ≈ smithsonite >> sphalerite. We found significant correlations among geoavailability, bioaccessibility and bioavailability. In particular, Zn bioavailability post-gavage and post-IN was significantly correlated with bioaccessibility in simulated phagolysosomal fluid and gastric fluid. These data indicate that solid phase speciation influences biological uptake of Zn and that in vitro tests can be used to predict Zn bioavailability in exposure assessment and effective remediation design.

The performance of Cytisus striatus in association with different microbial inoculant treatments on the dissipation of the insecticide hexachlorocyclohexane (HCH) was studied. Two soils with different organic matter (A and B soil) content were spiked with 0 or 65 mg HCH kg−1. Plants were either not inoculated (NI), or inoculated with the endophyte Rhodococcus erythropolis ET54b and the HCH-degrader Sphingomonas sp. D4 separately or in combination (ET, D4 and ETD4). Unplanted pots were also established. HCH phytotoxicity was more pronounced in the B soil. Soil HCH concentrations in unplanted pots were similar to initial concentrations, whereas concentrations were reduced after plant growth: by 20% and 8% in A and B soil, respectively. Microbial inoculants also modified HCH dissipation, although effects were soil-dependent. Inoculation with the combination of strains (ETD4) led to a significant enhancement in HCH dissipation: up to 53% in the A soil and 43% in the B soil.

Polychlorinated biphenyl (PCB) congeners (PCB 52, 77, and 153) singly and in mixture were spiked and aged in soil microcosms and subsequently planted with switchgrass (Panicum virgatum) or poplar (Populus deltoids x nigra DN34). The planted reactors showed significantly greater reductions in PCB parent compounds when compared to unplanted systems after 32 weeks. There was evidence of reductive dechlorination in both planted and unplanted systems, but the planted microcosms with fully developed roots and rhizospheres showed greater biotransformation than the unplanted reactors. These dechlorination products accounted for approximately all of the molar mass of parent compound lost. Based on the transformation products, reductive dechlorination pathways are proposed for rhizospheric biotransformation of PCB 52, 77, and 153. This is the first report of rhizosphere biotransformation pathways for reductive dechlorination in marginally aerobic, intermittently flooded soil as evidenced by a mass balance on transformation products.

The concentrations of six priority phthalic acid esters (PAEs) in intensively managed suburban vegetable soils in Nanjing, east China, were analyzed using gas chromatography–mass spectrometry (GC–MS). The total PAE concentrations in the soils ranged widely from 0.15 to 9.68 mg kg−1 with a median value of 1.70 mg kg−1, and di-n-butyl phthalate (DnBP), bis-(2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DnOP) were the most abundant phthalate esters. Soil PAE concentrations depended on the mode of use of plastic film in which PAEs were incorporated as plasticizing agents and both the plastic film and poultry manure appeared to be important sources of soil PAEs. Vegetables in rotation with flooded rice led to lower concentrations of PAEs in soil. The results indicate that agricultural plastic film can be an important source of soil PAE contamination and further research is required to fully elucidate the mechanisms of PAE contamination of intensive agricultural soils with different use modes of use of plastic film.

Efficient bioremediation of PAH-contaminated sites is limited by the hydrophobic character and poor bioavailability of pollutants. In this study, stable isotope probing (SIP) was implemented to track bacteria that can degrade PAHs adsorbed on hydrophobic sorbents. Temperate and tropical soils were incubated with 13C-labeled phenanthrene, supplied by spiking or coated onto membranes. Phenanthrene mineralization was faster in microcosms with PAH-coated membranes than in microcosms containing spiked soil. Upon incubation with temperate soil, phenanthrene degraders found in the biofilms that formed on coated membranes were mainly identified as Sphingomonadaceae and Actinobacteria. In the tropical soil, uncultured Rhodocyclaceae dominated degraders bound to membranes. Accordingly, ring-hydroxylating dioxygenase sequences recovered from this soil matched PAH-specific dioxygenase genes recently found in Rhodocyclaceae. Hence, our SIP approach allowed the detection of novel degraders, mostly uncultured, which differ from those detected after soil spiking, but might play a key role in the bioremediation of PAH-polluted soils.

One-dimensional (1-D) and two-dimensional (2-D) nuclear magnetic resonance (NMR)-based metabolomics was used to investigate the toxic mode of action (MOA) of endosulfan, an organochlorine pesticide, and its degradation product, endosulfan sulfate, to Eisenia fetida earthworms in soil. Three soil concentrations (0.1, 1.0 and 10.0 mg/kg) were used for both endosulfan and endosulfan sulfate. Both earthworm coelomic fluid (CF) and tissues were extracted and then analyzed using 1H and 1H–13C NMR techniques. A similar separation trajectory was observed for endosulfan and endosulfan sulfate-exposed earthworms in the mean principal component analysis (PCA) scores plot for both the earthworm CF and tissue extracts.A neurotoxic and apoptotic MOA was postulated for both endosulfan and endosulfan sulfate exposed earthworms as significant fluctuations in glutamine/GABA–glutamate cycle metabolites and spermidine were detected respectively. This study highlights the application of NMR-based metabolomics to understand molecular-level toxicity of persistent organochlorine pesticides and their degradation products directly in soil.