Aided phytostabilisation reduces metal toxicity, improves soil fertility and enhances microbial activity in Cu-rich mine tailings.

(Aided) phytostabilisation has been proposed as a suitable technique to decrease the environmental risks associated with metal(loid)-enriched mine tailings. Field scale evaluations are needed for demonstrating their effectiveness in the medium- to long-term. A field trial was implemented in spring 2011 in Cu-rich mine tailings in the NW of Spain. The tailings were amended with composted municipal solid wastes and planted with Salix spp., Populus nigra L. or Agrostis capillaris L. cv. Highland. Plant growth, nutritive status and metal accumulation, and soil physico- and bio-chemical properties, were monitored over three years (four years for plant growth). The total bacterial community, α- and ß-Proteobacteria, Actinobacteria and Streptomycetaceae were studied by DGGE of 16s rDNA fragments. Compost amendment improved soil properties such as pH, CEC and fertility, and decreased soil Cu availability, leading to the establishment of a healthy vegetation cover. Both compost-amendment and plant root activity stimulated soil enzyme activities and induced important shifts in the bacterial community structure over time. The woody plant, S. viminalis, and the grassy species, A. capillaris, showed the best results in terms of plant growth and biomass production. The beneficial effects of the phytostabilisation process were maintained at least three years after treatment.

Reductive dechlorination of α-, ß-, γ-, and δ-hexachlorocyclohexane isomers with hydroxocobalamin, in soil slurry systems.

The present study was carried out to test the viability of a method of reductive dehalogenation of α-, ß-, γ-, and δ-hexachlorocyclohexane (HCH) in soil slurry systems. The soil slurries were maintained under anaerobic conditions, with titanium(III) citrate as a reducing agent and hydroxocobalamin (vitamin B(12a)) as a catalyzing agent. Experiments were carried out with two soil samples with markedly different characteristics (particularly regarding organic matter content), at a small scale and larger reactor scale. HCH concentration was monitored throughout the 24 h duration of the tests. In the low organic matter soil HCH isomers degraded rapidly, in both the small scale and reactor systems, and undetectable levels (<0.5%) were reached within 5 h. However, complete degradation of HCH isomers was not achieved in soil with high organic matter content, and there were differences between the results obtained in the small scale and reactor systems. In the small scale system, the levels of degradation reached 93, 88, 94, and 91%, for α-, ß-, γ-, and δ-HCH, respectively, and the nondegraded HCH was sorbed in the soil. In the reactor system, the reaction stopped after two hours (no more than 65% of any of the isomers was degraded).

Behaviour of alpha-, beta-, gamma-, and delta-hexachlorocyclohexane in the soil-plant system of a contaminated site.

The behaviour of the organochlorine pesticide hexachlorocyclohexane (HCH) is investigated. The concentrations of alpha-, beta-, gamma-, and delta-HCH isomers were measured in soils, rhizosphere and vegetation in a contaminated area in Galicia (NW Spain). The total concentration of HCH in soils reached values close to 20,000 mgkg(-1). The plants analysed (Avena sativa L., Chenopodium spp., Solanum nigrum L., Cytisus striatus (Hill) Roth, and Vicia sativa L.) accumulated HCH, especially the beta-HCH isomer, in their tissues. The most likely mechanisms of HCH accumulation in plants were sorption of soil HCH on roots and sorption of volatilized HCH on aerial plant tissues. The concentrations of HCH obtained from the bulk and rhizosphere soils of selected plant species suggest that roots tend to reduce levels of the HCH isomers in the rhizosphere. The results reflect the importance of vegetation in the distribution of organochlorine compounds in the soil-plant system.

Reductive dechlorination of alpha-, beta-, delta-, and gamma-hexachlorocyclohexane isomers by hydroxocobalamin in the presence of either dithiothreitol or titanium(III) citrate as reducing agents.

The effect of the reducing potential on the reductive dehalogenation of the different HCH (hexachlorocyclohexane) isomers has not yet been studied. In the present study, the potential for dehalogenation of (alpha-, beta-, delta-, and gamma-HCH isomers by the dithiothreitol (DTT) and titanium(III) citrate (reducing potential at pH 7, -0.33 and -0.48 V, respectively), with and without the addition of hydroxocobalamin was investigated. In the presence of DTT without catalyst, there was no disappearance of any of the HCH isomers studied after 1 h of treatment. However, disappearance of the gamma- and alpha-HCH isomers was observed during the same time period when titanium(III) citrate was used as the reductant in the absence of catalyst (62.9 and 16.6% disappearance, respectively). Addition of the hydroxocobalamin to the DTT system favored mainly the disappearance of gamma- and alpha-HCH (92.9 and 30.8% disappearance after 1 h, respectively); disappearance of delta-HCH and beta-HCH was small (11.9%) or negligible, respectively. Addition of the hydroxocobalamin to the titanium(III) citrate system favored the degradation of all HCH isomers under study: beta- and alpha-HCH completely disappeared to undetectable levels (<0.1%) after 1 and 2 min, respectively; degradation of delta-HCH and beta-HCH was slower than that of the other two isomers, although they had almost completely disappeared (99.9 and 99.6% disappearance, respectively) after 10 and 60 min, respectively. The order of disappearance, gamma-HCH > alpha-HCH > delta-HCH > beta-HCH, coincided with a decreasing order of the axially positioned Cl atoms of these isomers (considering their thermodynamically most stable configuration). This study is the first description of the rapid degradation of delta- and beta-HCH under abiotic conditions, and the results demonstrate the effect of the reducing potential on the reductive dehalogenation of HCH isomers.