Manganese and trace-metal mobility under reducing conditions following in situ oxidation of TCE by KMnO4: a laboratory column experiment

The stability of Mn oxides, and the potential for mobilization of associated trace metals, were assessed by simulating the onset of microbially-mediated reducing conditions in a continuous-flow column experiment. The column had previously been used for an in situ chemical oxidation (ISCO) experiment in which trichloroethylene was reacted with permanganate in the presence of aqueous trace metals, which produced Mn oxyhydroxides (MnO(x)) that sequestered the trace metals and coated the column sand. The column influent solution represented the incursion of ambient groundwater containing dissolved organic carbon (DOC) into an ISCO treatment zone. The influx of DOC-containing groundwater initiated a series of cation-exchange, surface-complexation and reductive-dissolution reactions that controlled the release of aqueous metals from the system. Peak concentrations in the effluent occurred in the order Na, Mo, Cr, Zn, K, Mn, Fe, Pb, Mg, Ni, Cu and Ca. Manganese release from the column was controlled by a combination of cation exchange, reductive dissolution and precipitation of rhodochrosite. The trend in Fe concentrations was similar to that of Mn, and also resulted from a combination of reductive dissolution and cation exchange. Cation exchange and/or surface-complexation were the primary mechanisms controlling Cu, Ni, Mo and Pb release to solution, while Zn and Cr concentrations did not display coherent trends. Although metal release from the treatment zone was evident in the data, concentrations of trace metals remained below 0.05 mg L(-1) with the exception of Mo which reached concentrations on the order of 1 mg L(-1). The establishment of anaerobic conditions in ISCO-treated aquifers may result in a prolonged flux of aqueous Mn(II), but with the exception of MoO(4)(2-), it is unlikely that trace metals sequestered with MnO(x) during ISCO will be released to the groundwater in elevated concentrations.     

Effect of biosolid incorporation on arsenic distribution in Mollisol soils in central Chile

The effect of biosolid incorporation on arsenic distribution in Mollisol soils in central Chile was studied. Two soils were sequentially extracted for arsenic with a five-step method that accounts for the following arsenic forms: non-specifically adsorbed (F1), specifically adsorbed (F2), amorphous and poorly crystallized Fe and Al oxides (F3), well-crystallized Fe and Al oxides (F4) and residual (F5). The arsenic residual fraction was predominant in Pintué soil, whereas in Graneros soil, arsenic was mostly associated to amorphous Fe and Al oxides. Graneros soil exhibited a higher As(V) adsorbing capacity than Pintué soil, which relates to the higher clay and iron and aluminum oxides contents, confirming that these components participation is essential for the adsorption of this metalloid. Biosolid application at a rate of 100Mg ha(-1) caused an increase in arsenic bound to amorphous Fe and Al oxides and in the residual fraction, in Pintué soil. When Pintué soil was spiked with arsenic, aged for two months, and treated with biosolid (100Mg ha(-1)), the content of arsenic in the most labile fractions decreased, thus showing a favorable effect in its application to soils with few specific sites for arsenic adsorption. Arsenic speciation was carried out in the first two fractions of the sequential extraction procedure. As(V) was the main form in both fractions. Biosolid incorporation at a rate of 100Mg ha(-1) caused a significant increase in organic arsenic forms.     

Arsenic in groundwater and sediment in the Mekong River delta, Vietnam

A study of groundwater and sediment during 2007-2008 in the Mekong River delta in Vietnam (MDVN) revealed that 26%, 74%, and 50% of groundwater samples were above the US EPA drinking water guidelines for As (10 μg/L), Mn (0.05 mg/L), and Fe (0.3 mg/L). The range of As, Fe, and Mn concentrations in the MDVN were <0.1-1351 μg/L, <0.01-38 mg/L, and <0.01−14 mg/L, respectively. Elevated levels of As were found in groundwater at sampling sites close to the Mekong River and in wells less than 60−70 m deep. An inverse relationship was found between As and Mn concentrations in groundwater. Sediment samples from An Giang and Dong Thap had the highest As concentrations (18 mg/kg and 38 mg/kg, respectively). Arsenic sediment occurred mainly in the poorly crystalline Fe oxide phases. Reductive dissolution of the Fe oxide phase is not necessarily the dominant mechanism of As release to groundwater.     

Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.     

Source and release mechanism of arsenic in aquifers of the Mekong Delta, Vietnam

In order to elucidate the arsenic source and its release mechanism into groundwater in the Mekong Delta, Vietnam, groundwater samples were collected from wells at different depths (20 to 440 m) and core samples (from 20 to 265 m depth) were analyzed. Based on the analytical results for groundwater and core samples, the As source in groundwater is considered to be pyrite (FeS(2)) in acid sulfate soil (ASS) under oxidizing conditions and hydrous ferric oxide (Fe(OH)(3)) under reducing conditions. Geochemical modeling demonstrated that As(III) is the dominant species and the presence of As-bearing sulfides, Fe-bearing sulfides and oxides phases may locally act as potential sinks for As. From variation between Fe and As concentrations in groundwater samples, the release mechanism of As is: dissolution of Fe(OH)(3) containing As under reducing conditions and oxidative decomposition of FeS(2) containing As under oxidizing conditions.     

Arsenic in the soils of Zimapán, Mexico

Arsenic concentrations of 73 soil samples collected in the semi-arid Zimapán Valley range from 4 to 14 700 mg As kg(-1). Soil arsenic concentrations decrease with distance from mines and tailings and slag heaps and exceed 400 mg kg(-1) only within 500 m of these arsenic sources. Soil arsenic concentrations correlate positively with Cu, Pb, and Zn concentrations, suggesting a strong association with ore minerals known to exist in the region. Some As was associated with Fe and Mn oxyhydroxides, this association is less for contaminated than for uncontaminated samples. Very little As was found in the mobile water-soluble or exchangeable fractions. The soils are not arsenic contaminated at depths greater than 100 cm below the surface. Although much of the arsenic in the soils is associated with relatively immobile solid phases, this represents a long-term source of arsenic to the environment.     

As(III) removal from groundwaters using fixed-bed upflow bioreactors

The application of biological oxidation of iron and manganese, as a potential treatment method for the removal of arsenic from contaminated groundwaters, was examined in this paper. This method was based on the growth of certain species of indigenous bacteria, which are capable of oxidizing the soluble iron and manganese ions; the oxidized forms can be subsequently removed from the aqueous stream by over 97%, through their transformation to insoluble oxides and separation by a suitable filter medium. Arsenic was removed by around 80%, under certain conditions, which were found to be sufficient for Fe(II) removal (dissolved oxygen 2.7 mg/l, redox 280-290 mV, pH 7.2, U 8.25 m/h). The specific treatment technique presents several advantages towards conventional physicochemical treatment methods, such as enhanced coagulation or direct adsorption since: (a) it does not require the addition of other chemicals for oxidizing and removing As(III), (b) it does not require close monitoring of a breakthrough point, as in conventional column adsorption processes and (c) it could find application for the removal of, at least, three groundwater contaminants (Fe, Mn, As).     

Effects of development time, biomass and ferromanganese oxides on nickel sorption by stream periphyton

Procedurally defined periphyton frequently includes substantial quantities of hydrous iron (Fe) and manganese (Mn) oxides. As these oxides are strong sorbers of heavy metals, their presence may complicate estimation of metal bioaccumulation by periphyton. We examined the relationship between nickel (Ni) sorption and the development time, biomass, and Fe and Mn oxide content of stream periphyton. Development time, the time during which periphyton accrued on submerged tile substrata, was used to provide variation in biomass, Fe and Mn levels. Stream periphyton from four development times was exposed to Ni for 2 h in the laboratory, and then ashed. Development time was significantly associated with ash-free dry mass (AFDM), Fe and Mn levels (ANOVA, P < or = 0.003). Ni extracted by a mild reductant (hydroxylamine hydrochloride) was significantly associated with development time, and with AFDM, Fe and Mn levels (linear models, P < or = 0.0002). A subsequent acid digestion yielded similar associations with the same variables (linear models, P < or = 0.0001). For both extractions, AFDM was significantly and positively correlated with Fe (r = 0.68 and 0.89) and with Mn (r = 0.77 and 0.93) (Spearman rank, P < or = 0.005). These data demonstrate the importance of periphyton development time in influencing both metal sorption and levels of biomass and ferromanganese oxides. The data also suggest that metal contaminant levels in periphyton should not be attributed automatically to biotic sorption. Periphyton metal-accumulation studies conducted where ferromanganese oxide concentrations are elevated should address the potential metal-sorbing roles of Fe and Mn oxides within the periphyton matrix.     

Lead adsorption to metal oxides and organic material of freshwater surface coatings determined using a novel selective extraction method

Surface coatings were collected in three lakes and a river in China to study the role of the components of natural surface coatings in controlling Pb adsorption. Chemical reagents, 0.02 mol/l NH2OH HCl+0.01 mol/l HNO3, 0.4 mol/l Na2S2O4 and 10% oxalic acid, were employed to extract one or more components from surface coatings, and then Pb adsorption to extracted and unextracted surface coatings was carried out. The observed Pb adsorption to extracted and Unextracted surface coatings were analyzed using the nonlinear least squares fitting (NLSF) to estimate the relative contribution of components to the total Pb adsorption. The amounts of Pb absorption to components described by estimated gamma(max) ranged from 0.1126 to 0.7291 (mol Pb/mol Mn) for Mn, 0.0528 to 0.1927 (mol Pb/mol Fe) for Fe and 0.0196 to 0.1020 (mol Pb/kg COD) for organic material, respectively. In all waters studied, metal oxides contributed most to Pb adsorption with a lesser role indicated for organic material.     

Effects of Mn(II) and Fe(II) on microbial removal of arsenic (III)

Goal, scope, and background  Arsenic contamination in groundwater creates severe health problems in the world. There are many physiochemical and biological methods available for remediation of arsenic from groundwater. Among them, microbial remediation could be taken as one of the least expensive methods, though it takes longer treatment time. The main objective of this research was to study the improvement on remediation by addition of some essential ion salts such as Mn and Fe. Materials and methods   Staphylococcus aureus, Bacillus subtilis, Klebsiella oxytoca, and Escherichia coli were taken as model microbes from Dhulikhel, 30 km east from Kathmandu, Nepal. Results and discussion  Microbes used in this study showed different abilities in their removal of As(III) with and without addition of Mn and Fe salts. The trend of remediation increased with time. S. aureus was found to be the best among the microbes used. It showed almost 100% removal after 48-h culture, both with and without Fe and Mn salts. Rate of removal of As increased with addition of Fe and Mn for all microbes. Removal efficiency was found to increase by about 32% on average after addition of salts in 24-h cultures of S. aureus.     

The impact of sequestration on the bioaccessibility of arsenic in long-term contaminated soils

Arsenic (As) contamination of soil poses a potential threat to human health, particularly for small children, through the incidental ingestion of soil from hand-to-mouth activity. In this study, we examined the relationship between As bioaccessibility using the simplified bioaccessibility extraction test (SBET) and the soil fractions that contribute to bioaccessible As in 12 long-term contaminated soils. Sequential fractionation of soils prior to As bioaccessibility assessment found that As was primarily associated with the specifically sorbed (3-26%), amorphous and poorly crystalline (12-82%), and the well crystalline (3-25%) oxyhydroxide Fe/Al phases with proportions varying depending on the mode of As input. Arsenic bioaccessibility in these soils ranged from less than 1% in the gossan soil to 48% in railway corridor soils. Soil fractions contributing to As bioaccessibility were found to be from the non-specifically (<1-11%), the specifically (<1-29%) sorbed and the amorphous and poorly-crystalline (30-93%) oxyhydroxide Fe/Al fractions. Significant correlations (p<0.05) were found between the As bioaccessible fraction and the amorphous and poorly-crystalline oxyhydroxide Fe/Al fractions indicating that this fraction is a key factor influencing As bioaccessibility in many anthropogenically contaminated soils.     

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.     

Geochemical modeling of arsenic release from a deep natural solid matrix under alternated redox conditions

Dissolved arsenic (As) concentrations detected in groundwater bodies of the Emilia-Romagna Region (Italy) exhibit values which are above the regulation limit and could be related to the natural composition of the host porous matrix. To support this hypothesis, we present the results of a geochemical modeling study reproducing the main trends of the dynamics of As, Fe, and Mn concentrations as well as redox potential and pH observed during batch tests performed under alternating redox conditions. The tests were performed on a natural matrix extracted from a deep aquifer located in the Emilia-Romagna Region (Italy). The solid phases implemented in the model were selected from the results of selective sequential extractions performed on the tested matrix. The calibrated model showed that large As concentrations have to be expected in the solution for low crystallinity phases subject to dissolution. The role of Mn oxides on As concentration dynamics appears significant in strongly reducing environments, particularly for large water–solid matrix interaction times. Modeled data evidenced that As is released firstly from the outer surface of Fe oxihydroxides minerals exhibiting large concentrations in water when persistent reducing conditions trigger the dissolution of the crystalline structure of the binding minerals. The presence of organic matter was found to strongly affect pH and redox conditions, thus influencing As mobility.

Spatial variability of arsenic concentration in soils and plants, and its relationship with iron, manganese and phosphorus

Spatial distribution of arsenic (As) concentrations of irrigation water, soil and plant (rice) in a shallow tube-well (STW) command area (8 ha), and their relationship with Fe, Mn and P were studied. Arsenic concentrations of water in the 110 m long irrigation channel clearly decreased with distance from the STW point, the range being 68-136 μg L⁻¹. Such decreasing trend was also noticed with Fe and P concentrations, but the trend for Mn concentrations was not remarkable. Concerning soil As, the concentration showed a decreasing tendency with distance from the pump. The NH₄-oxalate extractable As contributed 36% of total As and this amount of As was associated with poorly crystalline Fe-oxides. Furthermore only 22% of total As was phosphate extractable so that most of the As was tightly retained by soil constituents and was not readily exchangeable by phosphate. Soil As (both total and extractable As) was significantly and positively correlated with rice grain As (0.296 ± 0.063 μg g⁻¹, n = 56). Next to drinking water, rice could be a potential source of As exposure of the people living in the As affected areas of Bangladesh.     

Physical versus chemical effects on bacterial and bromide transport as determined from on site sediment column pulse experiments

Twenty-eight bacterial and Br transport experiments were performed in the field to determine the effects of physical and chemical heterogeneity of the aquifer sediment. The experiments were performed using groundwater from two field locations to examine the effects of groundwater chemistry on transport. Groundwater was extracted from multilevel samplers and pumped through 7-cm-long columns of intact sediment or repacked sieved and coated or uncoated sediment from the underlying aquifer. Two bacterial strains, Comamonas sp. DA001 and Paenibacillus polymyxa FER-02, were injected along with Br into the influent end of columns to examine the effect of cell morphology and cell surface properties on bacterial transport. The effects of column sediment grain size and mineral coatings coupled with groundwater geochemistry were also investigated. Significant irreversible attachment of DA001 was observed in the Fe oxyhydroxide-coated columns, but only in the suboxic groundwater where the concentrations of dissolved organic carbon (DOC) were ca. 1 ppm. In the oxic groundwater where DOC was ca. 8 ppm, little attachment of DA001 to the Fe oxyhydroxide-coated columns was observed. This indicates that DOC can significantly reduce bacterial attachment due electrostatic interactions. The larger and more negatively charged FER-02 displayed increasing attachment with decreasing grain size regardless of DOC concentration, and modeling of FER-02 attachment revealed that the presence of Fe and Al coatings on the sediment also promoted attachment. Finally, the presence of Al coatings and Al containing minerals appeared to significantly retard the Br tracer regardless of the concentration of DOC. These findings suggest that DOC in shallow oxic groundwater aquifers can significantly enhance the transport of bacteria by reducing attachment to Fe, Mn and Al oxyhydroxides. This effect appears to be profound for weakly and strongly charged hydrophilic bacteria and may contribute to differences in observations between laboratory experiments versus field-scale investigations particularly if the groundwater pH remains subneutral and Fe oxyhydroxide phases exist. These observation validate the novel approach taken in the experiments outlined here of performing laboratory-scale experiments on site to facilitate the use of fresh groundwater and thus be more representative of in situ groundwater conditions.     

Evaluation of various chemical extraction methods to estimate plant-available arsenic in mine soils

Elevated levels of bioavailable As in mining soils, agricultural areas and human habitats may cause potential toxicity to human health, plants and microbe. Therefore, it is essential to determine proper soil chemical extraction method in order to estimate plant-available As in mining soils and protect agricultural and environmental ecosystems by evaluation of environmental risk and implementation of remediation measures. In this study, six single soil chemical extraction processes and four-step sequential chemical extraction protocol were used to determine the relative distribution of As in different chemical forms of soils and their correlations with total As in plants grown in mining areas and greenhouse experiments. The strongest relationship between As determined by single soil chemical extraction and As in plant biomass was found for sodium acetate and mixed acid extractant. The mean percent of total As extracted was: ammonium oxalate (41%)>hydroxylamine hydrochloride (32%)>mixed acid (16%)>phosphate (6%)>sodium acetate (1.2%)>water (0.13%). This trend suggests that most of the As in these soils is inside the soil mineral matrix and can only be released when iron oxides and other minerals are dissolved by the stronger chemical extractant. Single soil chemical extraction methods using sodium acetate and mixed acids, that extract As fractions complexed to soil particles or on the surface of mineral matrix of hydrous oxides of Fe, Mn and Al (exchangeable+sorbed forms) can be employed to estimate and predict the bioavailable As fraction for plant uptake in mining affected soils. In sequential chemical extraction methods, ammonium nitrate and hydroxylamine hydrochloride may be used to provide closer estimates of plant-available As in mining soils.     

Arsenic and chromium speciation in an urban contaminated soil

The distribution and speciation of As and Cr in a contaminated soil were studied by synchrotron-based X-ray microfluorescence (μ-XRF), microfocused X-ray absorption spectroscopy (μ-XAS), and bulk extended X-ray absorption fine structure spectroscopy (EXAFS). The soil was taken from a park in Wilmington, DE, which had been an important center for the leather tanning industry along the Atlantic seaboard of the United States, until the early 20th century. Soil concentrations of As, Cr, and Pb measured at certain locations in the park greatly exceeded the background levels of these heavy metals in the State of Delaware. Results show that Cr(III) and As(V) species are mainly present in the soil, with insignificant amounts of Cr(VI) and As(III). Micro-XRF maps show that Cr and Fe are distributed together in regions where their concentrations are diffuse, and at local spots where their concentrations are high. Iron oxides, which can reduce Cr(VI) to Cr(III), are present at some of these hot spots where Cr and Fe are highly concentrated. Arsenic is mainly associated with Al in the soil, and to a minor extent with Fe. Arsenate may be sorbed to aluminum oxides, which might have transformed after a long period of time into an As-Al precipitate phase, having a structure and chemical composition similar to mansfieldite (AlAsO(4)?2H(2)O). The latter hypothesis is supported by the fact that only a small amount of As present in the soil was desorbed using the characteristic toxicity leaching procedure tests. This suggests that As is immobilized in the soil.     

The dynamics of arsenic in four paddy fields in the Bengal delta

Irrigation with arsenic contaminated groundwater in the Bengal Delta may lead to As accumulation in the soil and rice grain. The dynamics of As concentration and speciation in paddy fields during dry season (boro) rice cultivation were investigated at 4 sites in Bangladesh and West Bengal, India. Three sites which were irrigated with high As groundwater had elevated As concentrations in the soils, showing a significant gradient from the irrigation inlet across the field. Arsenic concentration and speciation in soil pore water varied temporally and spatially; higher As concentrations were associated with an increasing percentage of arsenite, indicating a reductive mobilization. Concentrations of As in rice grain varied by 2-7 fold within individual fields and were poorly related with the soil As concentration. A field site employing alternating flooded-dry irrigation produced the lowest range of grain As concentration, suggesting a lower soil As availability caused by periodic aerobic conditions.     

An interdisciplinary physical-chemical approach for characterization of arsenic in a calciner residue dump in Cornwall (UK)

During the later stages of hard-rock mining in Cornwall, UK, widespread processing and refining of arsenic in purpose-built calciners resulted in severe, localized contamination of soils with arsenic. Several physical-chemical techniques were applied to characterize arsenic in a calciner residue dump: X-ray powder diffraction (XRD), sequential extraction combined with hyphenated speciation methods, and X-ray absorption spectroscopic (XAS) methods such as XANES (X-ray absorption near-edge structure) and EXAFS (extended X-ray absorption fine structure). Arsenic was predominantly present in pentavalent form, bound to amorphous or poorly-crystalline hydrous oxides of Fe (probably alpha-hematite). A small amount of a non-classified crystalline iron arsenate phase was found, viz. Fe2(As(AsO4)3). There was also evidence for the presence of some arsenate bound to quartz (alpha-SiO2). The overall results make us believe that the normally assumed relative safety, from a mobility point of view, is questionable since only a small fraction of arsenic is found in a crystalline iron arsenate form.