A methodological approach to evaluate arsenic speciation and bioaccumulation in different plant species from two highly polluted mining areas.

Arsenic accumulation and speciation in different plant species growing in two polluted sites were examined, in addition to arsenic transfer from soils to plants. The studied areas were two abandoned mercury mines in Northern Spain, La Soterraña and Los Rueldos. Plants accumulated extremely high amounts of arsenic in their tissues. Accumulation rates depend on both the grade of pollution of the site and on the plant species itself. Total arsenic concentrations varied depending on the part of the plant, with roots accumulating the most arsenic in all the studied plants (up to 1400 mg · kg(-1)). A suitable extraction method for arsenic speciation in the studied samples was developed and optimized using 0.3M orthophosphoric acid as the extracting agent in a graphite block digestion system at 90 °C for 1h. Extraction efficiencies were above 80% and speciation was not altered, since recoveries of the spiked arsenic species (As(III), As(V), DMA (dimethylarsonic acid) and MMA (monomethylarsonic acid)) were between 94 and 102%. Speciation studies were performed on the parts of each plant species by means of HPLC-ICP-MS with the results indicating no significant differences in the speciation between parts of the plants. As(V) was always the predominant species, although a non-negligible amount of As(III) was found for all samples. Little amounts of MMA and DMA occurred in certain samples. Arsenic uptake by plants depends on the plant available arsenic fraction in soils, here considered as the sum of water-soluble and phosphate-extractable fractions. Although soils from La Soterraña were less polluted, arsenic bioavailability was much higher than in Los Rueldos. Soil-to-plant transfer factors, based on total and available arsenic in soils, were evaluated for the studied plants. Dryopteris filix-mas and Calluna vulgaris (L.) Hull, from La Soterraña and Los Rueldos respectively, were the plants with the highest abilities to extract arsenic from their corresponding soils.