Biogeochemical cycling of ferric oxyhydroxide affecting As partition in groundwater aquitard.

High arsenic (As) concentration in groundwater potentially poses a serious threat to the health of local residents in southwestern Taiwan. Although the As release to groundwater is responsible for the reducing bacteria-mediated reductive dissolution of As-rich Fe hydroxides, the influences of FeRB and different organic substrates on As and Fe mobility and transformation were rarely discussed. An experiment that involved As-adsorbed synthetic amorphous Fe(III) hydroxide (HFO) and the inoculation of in situ Fe-reducing bacteria (FeRB) was performed to evaluate the contribution of FeRB to the As mobility and transformation. The batched experiment of As-free HFO showed that the reducing bacteria rapidly induced the reduction of amorphous Fe oxyhydroxide to Fe(II) by reductive dissolution of HFO and formation of Fe-citrate complexation. For aqueous As(V) reduction experiment, arsenate was effectively reduced to As(III) by the facultative anaerobic bacterium in the cultured FeRB. In the experiment of As-containing HFO reduction, the aqueous As(V) acts as an electron acceptor and reduced to As(III) after the reductive dissolution of Fe(III) on HFO. However, the increase in the As(III) concentrations with time for various organic substrates in the As-adsorbed HFO-reducing experiment differ from the rates of As(V) reduction with various organic substrates in the As(V)-reducing experiment. The decrease in sorption sites by coupled reductive dissolution of HFO and the competitive desorption of small molecular organic carbon is apparently the important factor of As mobility. For large molecular organic carbon (i.e., citrate), the significant contribution of citrate on As mobility is the complexation of iron citrate. A working hypothesis model of As biogeochemical cycling is proposed to illustrate the relevant processes in the groundwater aquitard of southwestern Taiwan.

Assessing the characteristics of groundwater quality of arsenic contaminated aquifers in the blackfoot disease endemic area.

Redox couples approach and multivariate statistical techniques, including factor analysis, cluster analysis and discriminant analysis, were applied to evaluate and to interpret the complex groundwater quality in the blackfoot disease endemic area, Taiwan. Most groundwater samples were characterized as Na-Ca-HCO(3) with HCO(3)(-) as the dominant anion. Total arsenic (As) concentration, predominantly as As(3+), ranged from <1.0 to 562.7 µg/L. The patterns of measured reducing potential were consistent with those values calculated from As couple, revealing the in situ environment enhanced the accumulation of As concentration in the groundwater. Factor analysis proposed a four-factor model, comprising salination, reductive dissolution of Fe/Mn oxyhydroxides, As reduction and chemical potential factor, and explained 89.94% of total variance in groundwater. Furthermore, two factors, reductive dissolution of Fe/Mn oxyhydroxides and As reduction, suggested that the decoupled reductive processes accounted for high As concentration in this area. Cluster analysis was adopted to spatially categorize the sampled wells into three main clusters and characterized by the factor scores of the four-factor model. Two-parameter (pH and Eh) model derived from discriminant analysis can be used for preliminary assessment to determine whether the As concentration exceeds 10 µg/L with simple field measurements in this area.

Delimitation of arsenic-contaminated groundwater using risk-based indicator approaches around blackfoot disease hyperendemic areas of southern Taiwan.

This work determined scopes of arsenic(As)-contaminated groundwater using risk-based indicator classification approaches in blackfoot disease hyperendemic areas of southern Taiwan. Indicator kriging was first used to establish a conditional cumulative distribution function at each cell. Three approaches--the p-quantile estimate, the E-type estimate and the minimization of the expected loss--were then adopted to delimit contaminated regions for a regulated standard of As concentrations in groundwater. According to a risk assessment model established in our previous research, the standard was set to 250 microg/l for aquacultural use, corresponding to the 77.1th percentile of observed concentrations. Misclassification risks and uncertainty were examined for the classification approaches. The analyzed results reveal that contaminated areas are the largest using the 0.771-quantile estimate, whereas they are the smallest using the minimization of the expected loss. Proportions of credible polluted areas with low risks to false positives maintain a constant, 12.9-13.2%, for the classification approaches. To reduce a great impact on human health, As-polluted groundwater should be strictly prohibited to cultivate fish in credible polluted zones and monitored persistently in polluted zones with high risks to false positives.