Distribution patterns of arsenic species in a lichen biomonitor

As stand-alone approaches, chromatographic separations of arsenic in lichen using HPLC-ICP-MS or the use of sequential extractions have historically been shown to have low analyte recoveries and poor analyte selectivity respectively. This study modifies the first step of a sequential extraction with a chromatographic separation of five arsenic species using HPLC-ICP-MS, followed by a three-step sequential extraction and analysis with ICP-MS. The method was applied to lichens from a rural and urban site to demonstrate the applicability thereof, and the sum of arsenic concentrations from the extraction steps were compared to the total arsenic concentrations. Short term species stability of the As species in the lichen matrix was also evaluated over 1 month in the water-extractable fraction, where As species concentrations changed week by week, providing insight into biotransformation mechanisms. In the modified extraction step, dimethylarsinic acid (DMA) and arsenobetaine and an unknown As species (AsB + U1) were statistically (p < 0.05) higher in the urban site than the rural site. Analyte recoveries using the combined method were higher than other studies reported in literature, with percentage recoveries of 104% and 111% of As in the urban and rural sites respectively. Arsenic concentrations were found in the following order of abundance at both sites: oxidizable > reducible > water-extractable > residual. Concentrations of total As in the oxidizable and non-bioavailable fraction were statistically lower (p < 0.05) in the rural site than in the urban site. Based upon the information gained from this study, we could draw concise conclusions regarding the source apportionment, timing and the magnitude of the pollution event.