Difference in attenuation among Mn, As, and Fe in riverbed sediments.

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.

Arsenic-enrichment enhanced root exudates and altered rhizosphere microbial communities and activities in hyperaccumulator Pteris vittata.

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.

Distribution and hosts of arsenic in a sediment core from the Chianan Plain in SW Taiwan: Implications on arsenic primary source and release mechanisms.

High arsenic abundance of 50-700µg/L in the groundwater from the Chianan Plain in southwestern Taiwan is a well-known environmental hazard. The groundwater-associated sediments, however, have not been geochemically characterized, thus hindering a comprehensive understanding of arsenic cycling in this region. In this study, samples collected from a 250m sediment core at the centre of the Chianan Plain were analyzed for arsenic and TOC concentrations (N=158), constituent minerals (N=25), major element abundances (N=105), and sequential arsenic extraction (N=23). The arsenic data show a prevalence of >10mg/kg with higher concentrations of 20-50mg/kg concentrated at 60-80 and 195-210m. Arsenic was extracted mainly as an adsorbate on clay minerals, as a co-precipitate in amorphous iron oxyhydroxide, and as a structural component in clay minerals. Since the sediments consist mainly of quartz, chlorite, and illite, the correlations between arsenic concentration and abundances of K2O and MgO pinpoint illite and chlorite as the major arsenic hosts. The arsenic-total iron correlation reflects the role of chlorite along with the contribution from amorphous iron oxyhydroxide as indicated by arsenic extraction data. Organic matter is not the dominant arsenic host for low TOC content, low arsenic abundance extracted from it, and a relatively low R(2) of the arsenic-TOC correlation. The major constituent minerals in the sediments are the same as those of the upriver metapelites, establishing a sink-source relationship. Composition data from two deep groundwater samples near the sediment core show Eh values and As(V)/As(III) ratios of reducing environments and high arsenic, K, Mg, and Fe contents necessary for deriving arsenic from sediments by desorption from clay and dissolution of iron oxyhydroxide. Therefore, groundwater arsenic was mainly derived from groundwater-associated sediments with limited contributions from other sources, such as mud volcanoes.

CO2 sequestration utilizing basic-oxygen furnace slag: Controlling factors, reaction mechanisms and V-Cr concerns.

Basic-oxygen furnace slag (BOF-slag) contains >35% CaO, a potential component for CO2 sequestration. In this study, slag-water-CO2 reaction experiments were conducted with the longest reaction duration extending to 96hr under high CO2 pressures of 100-300kg/cm(2) to optimize BOF-slag carbonation conditions, to address carbonation mechanisms, and to evaluate the extents of V and Cr release from slag carbonation. The slag carbonation degree generally reached the maximum values after 24hr slag-water-CO2 reaction and was controlled by slag particle size and reaction temperature. The maximum carbonation degree of 71% was produced from the experiment using fine slag of ≤0.5mm under 100°C and a CO2 pressure of 250kg/cm(2) with a water/slag ratio of 5. Vanadium release from the slag to water was significantly enhanced (generally >2 orders) by slag carbonation. In contrast, slag carbonation did not promote chromium release until the reaction duration exceeded 24hr. However, the water chromium content was generally at least an order lower than the vanadium concentration, which decreased when the reaction duration exceeded 24hr. Therefore, long reaction durations of 48-96hr are proposed to reduce environmental impacts while keeping high carbonation degrees. Mineral textures and water compositions indicated that Mg-wüstite, in addition to CaO-containing minerals, can also be carbonated. Consequently, the conventional expression that only considered carbonation of the CaO-containing minerals undervalued the CO2 sequestration capability of the BOF-slag by ~20%. Therefore, the BOF-slag is a better CO2 storage medium than that previously recognized.

Effects of microbially induced transformations and shift in bacterial community on arsenic mobility in arsenic-rich deep aquifer sediments.

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.

Water management impacts on arsenic behavior and rhizosphere bacterial communities and activities in a rice agro-ecosystem.

Although rice cultivated under water-saturated conditions as opposed to submerged conditions has received considerable attention with regard to reducing As levels in rice grain, the rhizosphere microbiome potentially influencing As-biotransformation and bioavailability in a rice ecosystem has rarely been studied. In this study, the impacts of flooded, non-flooded and alternate wetting and drying (AWD) practices on rhizosphere bacterial composition and activities that could potentially impact As speciation and accumulation in rhizosphere soil and pore water, As fractions in rhizosphere soil and As speciation and distribution in plant parts were assessed. The results revealed that in addition to pore water As concentration, non-specifically sorbed As fraction, specifically sorbed As fraction and amorphous iron oxide bound As fraction in soil were bio-available to rice plants. In the flooded treatment, As(III) in the pore water was the predominant As species, accounting for 87.3-93.6% of the total As, whereas in the non-flooded and AWD treatments, As(V) was the dominant As species, accounting for 89.6-96.2% and 73.0-83.0%, respectively. The genera Ohtaekwangia, Geobacter, Anaeromyxobacter, Desulfuromonas, Desulfocapsa, Desulfobulbus, and Lacibacter were found in relatively high abundance in the flooded soil, whereas the genera Acinetobacter, Ignavibacterium, Thiobacillus, and Lysobacter were detected in relatively high abundance in the non-flooded soil. Admittedly, the decrease in As level in rice cultivated under the non-flooded and AWD conditions was mostly linked to a relatively high soil redox potential, low As(III) concentration in the soil pore water, a decrease in the relative abundance of As-, Fe- and sulfur-reducing bacteria and an increase in the relative abundance of As-, Fe- and sulfur-oxidizing bacteria in the rhizosphere soil of the rice. This study demonstrated that with substantial reduction in grain As levels and higher water productivity, AWD practice in rice cultivation should be favored over the non-flooded and continuously flooded rice cultivations in As-contaminated sites.

Naturally occurring arsenic in terrestrial geothermal systems of western Anatolia, Turkey: potential role in contamination of freshwater resources.

Arsenic (As) contamination in terrestrial geothermal systems has been identified in many countries worldwide. Concentrations higher than 0.01 mg/L are detrimental to human health. We examined potential consequences for As contamination of freshwater resources based on hydrogeochemical investigations of geothermal waters in deep wells and hot springs collected from western Anatolia, Turkey. We analyzed samples for major ions and trace element concentrations. Temperature of geothermal waters in deep wells showed extreme ranges (40 and 230 °C), while, temperature of hot spring fluids was up to 90 °C. The Piper plot illustrated two dominant water types: Na-HCO3(-) type for geothermal waters in deep wells and Ca-HCO3(-) type for hot spring fluids. Arsenic concentration ranged from 0.03 to 1.5mg/L. Dominance of reduced As species, i.e., As(III), was observed in our samples. The Eh value ranged between -250 and 119 mV, which suggests diverse geochemical conditions. Some of the measured trace elements were found above the World Health Organization guidelines and Turkish national safe drinking water limits. The variation in pH (range: 6.4-9.3) and As in geothermal waters suggest mixing with groundwater. Mixing of geothermal waters is primarily responsible for contamination of freshwater resources and making them unsuitable for drinking or irrigation.

Linking geochemical processes in mud volcanoes with arsenic mobilization driven by organic matter.

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.

A comparative study on arsenic and humic substances in alluvial aquifers of Bengal delta plain (NW Bangladesh), Chianan plain (SW Taiwan) and Lanyang plain (NE Taiwan): implication of arsenic mobilization mechanisms.

Humic substances in groundwater and aquifer sediments from the arsenicosis and Blackfoot disease (BFD) affected areas in Bangladesh (Bengal delta plain) and Taiwan (Lanyang plain and Chianan plain) were characterized using fluorescence spectrophotometry and Fourier transform infrared (FT-IR) spectroscopy. The results demonstrate that the mean concentration of As and relative intensity of fluorescent humic substances are higher in the Chianan plain groundwater than those in the Lanyang plain and Bengal delta plain groundwater. The mean As concentrations in Bengal delta plain, Chianan plain, and Lanyang plain are 50.65 µg/l (2.8-170.8 µg/l, n=20), 393 µg/l (9-704 µg/l, n=5), and 104.5 µg/l (2.51-543 µg/l, n = 6), respectively. Average concentrations and relative fluorescent intensity of humic substances in groundwater are 25.381 QSU (quinine standard unit) and 17.78 in the Bengal delta plain, 184.032 QSU and 128.41 in the Chianan plain, and 77.56 QSU and 53.43 in the Lanyang plain. Moreover, FT-IR analysis shows that the humic substances extracted from the Chianan plain groundwater contain phenolic, alkanes, aromatic ring and amine groups, which tend to form metal carbon bonds with As and other trace elements. By contrast, the spectra show that humic substances are largely absent from sediments and groundwater in the Bengal delta plain and Lanyang plain. The data suggest that the reductive dissolution of As-adsorbed Mn oxyhydroxides is the most probable mechanism for mobilization of As in the Bengal delta plain. However, in the Chianan plain and Lanyang plain, microbially mediated reductive dissolution of As-adsorbed amorphous/crystalline Fe oxyhydroxides in organic-rich sediments is the primary mechanism for releasing As to groundwater. High levels of As and humic substances possibly play a critical role in causing the unique BFD in the Chianan plain of SW Taiwan.

Implications of organic matter on arsenic mobilization into groundwater: evidence from northwestern (Chapai-Nawabganj), central (Manikganj) and southeastern (Chandpur) Bangladesh.

Boreholes (50 m depth) and piezometers (50 m depth) were drilled and installed for collecting As-rich sediments and groundwater in the Ganges, Brahmaputra, and Meghna flood plains for geochemical analyses. Forty-one groundwater samples were collected from the three areas for the analyses of cations (Ca(2+), Mg(2+), K(+), Na(+)), anions (Cl(-), NO(3)(-), SO(4)(2-)), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction (XRD) and X-ray fluorescence (XRF) were performed to characterize the major mineral and chemical contents of aquifer sediments. In all three study areas, results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescent intensity of humic substances in groundwater samples ranges from 30 to 102 (mean 58 ± 20, n = 20), 54-195 (mean 105 ± 48, n = 10), and 27-243 (mean 79 ± 71, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Arsenic concentration in groundwater (20-50 m of depth) ranges from 3 to 315 µg/L (mean 62.4 ± 93.1 µg/L, n = 20), 16.4-73.7 µg/L (mean 28.5 ± 22.4 µg/L, n = 10) and 4.6-215.4 µg/L (mean 30.7 ± 62.1 µg/L, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Specific ultra violet adsorption (SUVA) values (less than 3 m(-1) mg(-1) L) indicate that the groundwater in the Ganges flood plain has relatively low percentage of aromatic organic carbon compared to those in the Brahmaputra and Meghna flood plains. Arsenic content in sediments ranges from 1 to 11 mg/kg (mean 3.5 ± 2.7 mg/kg, n = 17) in the three flood plains. Total organic carbon content is 0.5-3.7 g/kg (mean 1.9 ± 1.1 g/kg) in the Ganges flood plain, 0.5-2.1 g/kg (mean: 1.1 ± 0.7 g/kg) in the Brahmaputra flood plain and 0.3-4.4 g/kg (mean 1.9 ± 1.9 g/kg) in the Meghna flood plain. Arsenic is positively correlated with TOC (R(2) = 0.50, 0.87, and 0.85) in sediments from the three areas. Fourier transform infrared (FT-IR) analysis of the sediments revealed that the functional groups of humic substances in three areas include amines, phenol, alkanes, and aromatic carbon. Arsenic and Fe speciation in sediments were determined using XANES and the results imply that As(V) and Fe(III) are the dominant species in most sediments. The results also imply that As (V) and Fe (III) in most of the sediment samples of the three areas are the dominant species. X-ray absorption fine structure (EXAFS) analysis shows that FeOOH is the main carrier of As in the sediments of three areas. In sediments, As is well correlated with Fe and Mn. However, there is no such correlation observed between As and Fe as well as As and Mn in groundwater, implying that mobilizations of Fe, Mn, and As are decoupled or their concentrations in groundwater have been affected by other geochemical processes following reductive dissolution of Fe or Mn-hydroxides. For example, dissolved Fe and Mn levels may be affected by precipitation of Fe- and Mn-carbonate minerals such as siderite, while liberated As remains in groundwater. The groundwaters of the Brahmaputra and Meghna flood plains contain higher humic substances in relative fluorescence intensity (or fluorescence index) and lower redox potential compared to the groundwater of Ganges flood plain. This leads to the release of arsenic and iron to groundwater of these three plains in considerable amounts, but their concentrations are distributed in spatial variations.

Occurrence of arsenic in core sediments and groundwater in the Chapai-Nawabganj District, northwestern Bangladesh.

Groundwater and core sediments of two boreholes (to a depth of 50m) from the Chapai-Nawabganj area in northwestern Bangladesh were collected for arsenic concentration and geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10-40m of depth) range from 2.8microgL(-1) to 462.3microgL(-1). Groundwater geochemical conditions change from oxidized to successively more reduced, higher As concentration with depth. Higher sediment arsenic levels (55mgkg(-1)) were found within the upper 40m of the drilled core samples. X-ray absorption near-edge structure spectroscopy was employed to elucidate the arsenic speciation of sediments collected from two boreholes. Environmental scanning electron microscopy and transmission X-ray microscopy were used to investigate the characteristics of FeOOH in sediments which adsorb arsenic. In addition, a pH-Eh diagram was drawn using the Geochemist's Workbench (GWB) software to elucidate the arsenic speciation in groundwater. The dominant groundwater type is Ca-HCO(3) with high concentrations of As, Fe and Mn but low levels of NO(3)(-) and SO(4)(2-). Sequential extraction analysis reveals that Mn and Fe hydroxides and organic matter are the major leachable solids carrying As. High levels of arsenic concentration in aquifers are associated with fine-grained sediments. Fluorescent intensities of humic substances indicate that both groundwater and sediments in this arsenic hotspot area contain less organic matter compared to other parts of Bengal basin. Statistical analysis clearly shows that As is closely associated with Fe and Mn in sediments while As is better correlated with Mn in groundwater. These correlations along with results of sequential leaching experiments suggest that reductive dissolution of MnOOH and FeOOH mediated by anaerobic bacteria represents an important mechanism for releasing arsenic into the groundwater.

Geochemistry of high arsenic groundwater in Chia-Nan plain, Southwestern Taiwan: possible sources and reactive transport of arsenic.

Major ion, trace element, and stable isotope analyses were performed on groundwater samples collected during November 2005 and 2006 in Chia-Nan plain of southwestern Taiwan to examine As mobilization in aquifers. The high concentrations of As, Fe and Mn in the groundwater is consistent with low Eh values (under moderately reduced state). Moreover, the observed Na/Cl and SO(4)/Cl molar ratios in groundwater demonstrate the influence of seawater intrusion. Seawater intrusion could provide required electron acceptors (i.e., SO(4)) for bacterial sulfate reduction and promote reducing conditions that are favorable for As mobilization. The concurrent increases in the concentrations of Fe and Mn from 2005 to 2006 may be caused by bacterial Fe(III) and Mn(IV) reduction. Geochemical modeling demonstrate that As(III) is the dominant As species and the presence of Fe-bearing carbonates, sulfides, and oxide phases may locally act as potential sinks for As. Mud volcano fluids were also collected and analyzed to assess the possible source of As in the Chia-Nan plain groundwater. The oxygen and hydrogen isotopic signatures indicate that the As-rich mud volcano fluids may have been modified by chemical exchange with (18)O-rich crustal rocks and possibly originated from mixing of deep brines with circulating meteoric water. Thus As in the Chia-Nan plain groundwater may have been evolved from deep crustal fluids or rock sources. The hydrogeochemistry and widespread As enrichment in groundwater of Chia-Nan plain result from multiple processes, e.g., de-watering of deep crustal fluids, seawater intrusion, and biogeochemical cycling of Fe, As, and S in alluvial sediments.