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We report, for the first time, a detailed study at river water and hyporheic zone systems through collection and analyses of shallow sediments and selected source rocks, pore water, and river water from forty-two locations at the Chianan Plain (CP), SW Taiwan. The study was focused to understand the possible changes in the river water and sediment chemistry as a consequence of high arsenic (mean±SD=71.28±16.24μg/L, n=46) groundwater discharge to three major rivers in the plain. The study shows, except few locations, As concentration in river sediments corresponds to average As concentration in soil and upper crustal abundance and of source rock. Sequential extraction indicates that As is mostly bound to FeOOH. No enrichment of arsenic in river sediments or depletion of aqueous As and iron in pore water was observed down to the maximum sampling depth of 1.7m although manganese is enriched in sediments. Dissolved As concentrations in the river sediments are much lower compared to the hotspots in the CP aquifers. This suggests that no As attenuation processes are active or they cannot be detected in this zone. Mn precipitates at higher redox level compared to Fe and As and thus attenuates in the studied zone.

Elevated concentration of arsenic (As) prevailed in deep aquifers of Chianan Plain, Taiwan. Arsenic release in relation to microbially induced transformations and shift in bacterial communities in deep aquifer sediments of Budai, southwestern Taiwan were investigated using microcosm experiments and substrate amendments over 90 days of anaerobic incubation. The results revealed that As reduction was independent of Fe reduction and a modest rate of sedimentary As release into aqueous phase occurred at the expense of the native organic carbon. Addition of lactate resulted in a parallel increase in As(III) (3.7-fold), Fe(II) (6.2-fold) and Mn (3.5 fold) in aqueous phase compared to un-amended slurries and the enrichment of sequences related to mostly Bacillus, Flavisolibacter, and Geobacter spp, suggesting the important role of these bacteria in As enrichment through reductive dissolution of As-bearing Fe and Mn minerals. The increase in phosphate-extractable As in solid phase with concomitant rise in As in aqueous phase over the course of incubation further attested to the importance of reductive dissolution in promoting As release. Furthermore, the increase in arrA gene abundance with addition of labile carbon suggests that dissimilatory As reduction also may contribute to As enrichment in the water of the deep aquifer of Budai.

Phytoremediation of arsenic (As)-contaminated soil by hyperaccumulator Pteris vittata is promising. A better understanding of the rhizosphere microbial dynamics that regulate As availability and plant growth is important to optimize the phytoremediation process. In this study, Illumina sequencing of 16S rRNA genes was applied to assess the rhizosphere microbial community structure of P. vittata. Microbial functionality was monitored by soil enzyme activities and MPN-PCR targeting genes of interest. Arsenic (100mgkg-1 AsV) addition to soil significantly increased DOC, root exudates, As and P uptake and the frond biomass of P. vittata. Moreover, As-enrichment significantly increased soil enzyme activities involved in N, P and S cycling and the gene abundance of As transforming bacteria, Fe- and S-reducing bacteria and N and C fixing bacteria in the rhizosphere of P. vittata. Together, the results revealed that the combined selective pressure of As and rhizosphere resulted in stimulation of microbial community, which most likely has a role in reductive dissolution of Fe and S, As and P mobilization, C degradation and fixation, and N fixation. These changes appeared to have a role in mitigation of As toxicity and to promote growth and the As uptake ability of P. vittata under As-enriched conditions.

The present study deals with geochemical characterization of mud fluids and sediments collected from Kunshuiping (KSP), Liyushan (LYS), Wushanting (WST), Sinyangnyuhu (SYNH), Hsiaokunshui (HKS) and Yenshuikeng (YSK) mud volcanoes in southwestern Taiwan. Chemical constituents (cations, anions, trace elements, organic carbon, humic acid, and stable isotopes) in both fluids and mud were analyzed to investigate the geochemical processes and spatial variability among the mud volcanoes under consideration. Analytical results suggested that the anoxic mud volcanic fluids are highly saline, implying connate water as the probable source. The isotopic signature indicated that δ(18)O-rich fluids may be associated with silicate and carbonate mineral released through water-rock interaction, along with dehydration of clay minerals. Considerable amounts of arsenic in mud irrespective of fluid composition suggested possible release through biogeochemical processes in the subsurface environment. Sequential extraction of As from the mud indicated that As was mostly present in organic and sulphidic phases, and adsorbed on amorphous Mn oxyhydroxides. Volcanic mud and fluids are rich in organic matter (in terms of organic carbon), and the presence of humic acid in mud has implications for the binding of arsenic. Functional groups of humic acid also showed variable sources of organic matter among the mud volcanoes being examined. Because arsenate concentration in the mud fluids was found to be independent from geochemical factors, it was considered that organic matter may induce arsenic mobilization through an adsorption/desorption mechanism with humic substances under reducing conditions. Organic matter therefore plays a significant role in the mobility of arsenic in mud volcanoes.