Adsorption of As(III), As(V) and dimethylarsinic acid onto synthesized lepidocrocite.

The trapping of arsenic by zero valent iron is strongly dependant on iron by-products. Among these, lepidocrite has been scarcely studied. In this work, we studied the adsorption of two inorganic (As(III), As(V)) and one organic (dimethylarsinic acid, DMA) arsenic species onto lepidocrocite. pH influence was considered in the range 5 to 9, which corresponds to natural water pH. Langmuir model was used to simulate As adsorption isotherms. Our results showed that lepidocrocite offers high adsorption capacities: up to 0,25, 0,41 and 1 mol for As(V), DMA and As(III) could be respectively trapped per kilogram of zero-valent iron. pH influence varied from one arsenic species to another: increasing pH improve As(III) and DMA sorption whereas it has a very low effect on As(V) sorption.

Acetochlor mineralization and fate of its two major metabolites in two soils under laboratory conditions.

The degradation of the herbicide acetochlor, in a neoluvisol and in a calcosol were studied as a function of depth (0-25cm and 25-50cm) and temperature (25 degrees C and 15 degrees C) under controlled laboratory conditions during 58 and 90 days, respectively. The surface and sub-surface soil samples were respectively spiked with 1 and 0.01mgkg(-1) of 14C-acetochlor, the concentrations observed in previous field monitoring. The half-lives (DT50) varied from 1.4 to 14.9 days depending on the soil, temperature and applied concentration. The maximal mineralization (24%) was observed for the surface calcosol at 25 degrees C. The comparison of results obtained for sterilized and non-sterilized soils, the decrease of DT50 with the increase of temperature, the shape of CO2 emissions and the increase of number of aerobic endogenous microflora through the experiment suggested that biological process are dominant in degradation. A particular attention was paid to the formation and dissipation of metabolites ESA (ethanesulphonic acid) and OA (oxanilic acid) during the whole experiment. At 25 degrees C, ESA and OA were observed after three days, but as ESA concentration decreased over time in surface calcosol, it remained constant in surface neoluvisol. A difference in ESA/OA ratio depends on the soil with a predominance of OA in surface neoluvisol and a disappearance of OA in surface calcosol.

Decoupling of arsenic and iron release from ferrihydrite suspension under reducing conditions: a biogeochemical model.

High levels of arsenic in groundwater and drinking water are a major health problem. Although the processes controlling the release of As are still not well known, the reductive dissolution of As-rich Fe oxyhydroxides has so far been a favorite hypothesis. Decoupling between arsenic and iron redox transformations has been experimentally demonstrated, but not quantitatively interpreted. Here, we report on incubation batch experiments run with As(V) sorbed on, or co-precipitated with, 2-line ferrihydrite. The biotic and abiotic processes of As release were investigated by using wet chemistry, X-ray diffraction, X-ray absorption and genomic techniques. The incubation experiments were carried out with a phosphate-rich growth medium and a community of Fe(III)-reducing bacteria under strict anoxic conditions for two months. During the first month, the release of Fe(II) in the aqueous phase amounted to only 3% to 10% of the total initial solid Fe concentration, whilst the total aqueous As remained almost constant after an initial exchange with phosphate ions. During the second month, the aqueous Fe(II) concentration remained constant, or even decreased, whereas the total quantity of As released to the solution accounted for 14% to 45% of the total initial solid As concentration. At the end of the incubation, the aqueous-phase arsenic was present predominately as As(III) whilst X-ray absorption spectroscopy indicated that more than 70% of the solid-phase arsenic was present as As(V). X-ray diffraction revealed vivianite Fe(II)3(PO4)2.8H2O in some of the experiments. A biogeochemical model was then developed to simulate these aqueous- and solid-phase results. The two main conclusions drawn from the model are that (1) As(V) is not reduced during the first incubation month with high Eh values, but rather re-adsorbed onto the ferrihydrite surface, and this state remains until arsenic reduction is energetically more favorable than iron reduction, and (2) the release of As during the second month is due to its reduction to the more weakly adsorbed As(III) which cannot compete against carbonate ions for sorption onto ferrihydrite. The model was also successfully applied to recent experimental results on the release of arsenic from Bengal delta sediments.

Remediation by chemical reduction in laboratory mesocosms of three chlordecone-contaminated tropical soils.

Chlordecone (CLD), a highly persistent organochlorine pesticide commonly encountered in French West Indies (FWI) agricultural soils, represents a major source of contamination of FWI ecosystems. The potential of chemical reduction for remediation of CLD-contaminated soil has been investigated in laboratory pilot-scale 80 kg mesocosms for andosol, ferralsol, and nitisol from FWI banana plantations. Six cycles consisting of a 3-week reducing phase followed by a 1-week oxidizing phase were applied, with 2 % (dw/dw) Daramend® (organic plant matter fortified with zero valent iron) added at the start of each cycle. Complementary amendments of zero valent iron and zinc (total of 3 % dw/dw) were added at the start of the first three cycles. After the 6-month treatment, the CLD soil concentration was lowered by 74 % in nitisol, 71 % in ferralsol, and 22 % in andosol. Eleven CLD-dechlorinated transformation products, from mono- to penta-dechlorinated, were identified. None of them accumulated over the duration of the experiment. Six of the seven ecotoxicological tests applied showed no difference between the control and treated soils. The treatment applied in this study may offer a means to remediate CLD-contaminated soils, especially nitisol and ferralsol.

Distinct bacterial community structure of 3 tropical volcanic soils from banana plantations contaminated with chlordecone in Guadeloupe (French West Indies).

In the French West Indies (FWI), the soil, andosols, ferralsols and nitisols, is highly polluted by chlordecone, although this organochlorine insecticide extensively applied to banana crops has been banned for 20years. This contamination has led to a major human health concern inducing the need for remediation of the contaminated soils. Work was conducted to help to evaluate the impact of remediation processes on the microbial communities from these soils. Microbial biomass was estimated after direct DNA extraction from three chlordecone-contaminated soils (an andosol, a ferralsol and a nitisol) and the bacterial community analyzed using t-RFLP. The FWI volcanic andosol was particularly recalcitrant to usual direct DNA extraction protocols hampering analysis of soil microbial communities until now, in contrast with the 2 other soils. For the first time, DNA was directly extracted from a FWI andosol based on yeast RNA addition at the lysis step. Differences in microbial biomass were thus observed between the 3 FWI soils. Moreover, the bacterial community structure was significantly distinct from each other's and related to soil physico-chemical characteristics. Interestingly, differences in bacterial diversity could not be exclusively attributed to the level of chlordecone contamination.

Role of exopolymeric substances (EPS) in the stability of the biofilm of Thiomonas arsenivorans grown on a porous mineral support.

Biochemical methods were selected to evaluate the role of exopolymeric substances in the stability of biofilms used in bioremediation processes. Biofilms of Thiomonas arsenivorans formed on pozzolana were thus treated with pronase (protein target), lectins (Con A or PNA), calcofluor or periodic acid (polysaccharides target), DNase (DNA target), and lipase (triglycerides target). Neither protease nor DNase treatments had any effect on bacterial adhesion. Lectins and calcofluor treatments mainly affected young biofilms. Lipase treatment had a noticeable effect on biofilm stability whatever the biofilm age. Results suggest that it would be an increased resistance of mature biofilms that protects them from external attacks.

AsIII oxidation by Thiomonas arsenivorans in up-flow fixed-bed reactors coupled to As sequestration onto zero-valent iron-coated sand.

The combined processes of biological As(III) oxidation and removal of As(III) and As(V) by zero-valent iron were investigated with synthetic water containing high As(III) concentration (10 mg L(-1)). Two up-flow fixed-bed reactors (R1 and R2) were filled with 2 L of sieved sand (d = 3 ± 1 mm) while zero-valent iron powder (d = 76 µm; 1% (w/w) of sand) was mixed evenly with sand in R2. Thiomonas arsenivorans was inoculated in the two reactors. The pilot unit was studied for 33 days, with HRT of 4 and 1 h. The maximal As(III) oxidation rate was 8.36 mg h(-1) L(-1) in R1 and about 45% of total As was removed in R2 for an HRT of 1 h. A first order model fitted well with the As(III) concentration evolution at the different levels in R1. At the end of the pilot monitoring, batch tests were conducted with support collected at different levels in R1. They showed that bacterial As(III) oxidation rate was correlated with the axial length of reactor, which could be explained by biomass distribution in reactor or by bacterial activity. In opposition, As(III) oxidation rate was not stable in R2 due to the simultaneous bacterial As(III) oxidation and chemical removal by zero-valent iron and its oxidant products. However, a durable removal of total As was realized and zero-valent iron was not saturated by As over 33 days in R2. Furthermore, the influence of zero-valent iron and its oxidant corrosion products on the evolution of As(III)-oxidizing bacteria diversity was highlighted by the molecular fingerprinting method of PCR-DGGE using aoxB gene as a functional marker of aerobic As(III) oxidizers.

Oxidation of arsenite by Thiomonas strains and characterization of Thiomonas arsenivorans sp. nov.

A novel bacterium, strain b6(T) (T=type strain), was isolated from a disused mine site by growth using arsenite [As(III)] as energy source in a simple mineral medium. Cells of strain b6(T) were rod-shaped, Gram-negative, non-sporulating and motile. Optimum growth occurred at temperatures between 20 and 30 degrees C, and at pH between 4.0 and 7.5. Strain b6(T) grew chemoautotrophically on As(III), sulphur and thiosulphate, and also heterotrophically on yeast extract and a variety of defined organic compounds. Several other Thiomonas strains, including the type species Thiomonas (Tm.) intermedia, were able to oxidize As(III), though only strain b6(T) and strain NO115 could grow using As(III) as sole energy source in the absence of any organic compound. The G+C content of the DNA of strain b6(T) was 65.1 mol %. Comparative small subunit (SSU) ribosomal RNA (rRNA) analysis indicated that strain b6(T) belongs to the genus Thiomonas in the beta-subdivision of the Proteobacteria. It was closely related to an unnamed Thiomonas strain (NO115) isolated from a Norwegian mining site, though sequence identities between strain b6(T) and characterized Thiomonas species were less than 95%. DNA-DNA hybridization between strain b6(T) and the type species of the genus Tm. intermedia showed less than 50% homology. On the basis of phylogenetic and phenotypic characteristics, strain b6(T) (DSM 16361(T), LMG 22795(T)) is proposed as the type strain of the new species Thiomonas arsenivorans, sp. nov.