Keisuke Fukushi

A natural attenuation of arsenic in drainage from an abandoned arsenic mine dump

Abstract At the abandoned As mine in Nishinomaki, Japan, discharged water from the mining and waste dump area is acidic and rich in As. However, the As concentration in the drainage has been decreased to below the maximum contaminant level (0.01 mg/l for drinking water, Japan) without any artificial treatments before mixing with a tributary to populated areas. This implies that the As concentration in water from the waste dump area has been naturally attenuated. To elucidate the reaction mechanisms of the natural attenuation, analysis of water quality and characterization of the precipitates from the stream floor were performed by measuring pH, ORP and electric conductivity on-site, as well as X-ray diffraction, ICP-mass spectrometry and ion-chromatography. Selective extractions and mineral alteration experiments were also conducted to estimate the distribution of As in constituent phases of the precipitates and to understand the stability of As-bearing phases, respectively. The water contamination resulted from oxidation of sulfide minerals in the waste rocks, i.e., the oxidation of pyrite and realgar and subsequent release of Fe, SO4, As(V) and proton. The released Fe(II) transformed to Fe(III) by bacterial oxidation; schwertmannite then formed immediately. While the As concentrations in the stream were lowered nearly to background level downstream, those in the ochreous precipitates were up to several tens of mg/g. The As(V) was effectively removed by the formed schwertmannite and had been naturally attenuated. Although schwertmannite is metastable with respect to goethite, the experiments show that the transformation of schwertmannite to goethite may be retarded by the presence of absorbed As(V) in the structure. Therefore, the attenuation of As in the drainage and the retention of As by schwertmannite are expected to be maintained for the long term.

Monohydrocalcite: a promising remediation material for hazardous anions

Abstract The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite.

Arsenate sorption on schwertmannite

Abstract The sorption mechanism of arsenate [As(V)] on schwertmannite was investigated by means of batch sorption experiments as a function of As(V) concentration in acidic solution at 25 °C. Structural simulation indicated that the surface sites of schwertmannite comprised various O atom (or hydroxyl) and SO4 groups. Sorption experiments showed that the reactive sites for As(V) sorption are surfacecoordinated SO4 groups rather than surface hydroxyl groups, as reported in earlier studies. The As(V) sorption mechanism involves ligand exchange with surface-adsorbed and structural SO4. The results of the sorption experiments also suggested monodentate As(V) coordination at the surface-adsorbed SO4 sites [(Fe1)2SO4] and bidentate As(V) coordination at the structural SO4 sites [(Fe3)2SO4]. The overall ligand-exchange reaction was 0.61 (Fe1)2SO4 + 0.39 (Fe3)2SO4 + 1.61 H2AsO4- → 1.22 Fe1H2AsO4 + 0.39 (Fe3)2HAsO4 + 0.39 H+ + SO42- where the 1 and 3 in Fe1 and Fe3 are coordination numbers. The equilibrium constant derived for the exchange reaction, log KEX = 4.96, describes the observed As(V) sorption behavior. Nanocrystalline materials like schwertmannite are widespread in nature and typically contain significant amounts of anionic impurities, such as sulfate and silicate. Our results indicate that the effects of impurities can be significant and should be considered in order to gain a realistic understanding of sorption processes in natural systems.

Extended Triple Layer Modeling of Arsenate and Phosphate Adsorption on a Goethite-based Granular Porous Adsorbent

The extended triple layer model (ETLM), which is consistent with spectroscopic and theoretical molecular evidence, is first systematically tested for its capability to model adsorption of arsenate and phosphate, a strong competitor, on a common goethite-based granular porous adsorptive media (Bayoxide E33 (E33)) in water treatment systems under a wide range of solution conditions. Deprotonated bidentate-binuclear, protonated bidentate-binuclear, and deprotonated monodentate complexes are chosen as surface species for both arsenate and phosphate. The estimated values of the ETLM parameters of arsenate for the adsorbent are close to those for pure goethite minerals previously determined by others. The ETLM predictions for arsenate and phosphate adsorption basically agree with experimental results over a wide range of pH, surface coverage, and solid concentrations. High background electrolyte concentration (i.e., I = 0.1 M), however, was found to strongly impact arsenate and phosphate adsorption on E33 probably because of the porous structure of the adsorbent, which cannot be observed for pure goethite minerals and could not be completely modeled by the ETLM. Prediction of phosphate adsorption isotherms at higher pH were relatively poor, and this may suggest searching for alternative surface species for phosphate. Since adsorption equilibrium constants of major coexisting ions encountered in water treatment systems for goethite minerals have been estimated by others, the application of ETLM theory to this common goethite-based adsorptive media will enable us to understand how those coexisting ions macroscopically and thermodynamically interact with arsenate and phosphate in the environment of adsorptive water treatment system in a way consistent with molecular and spectroscopic evidence.

Prediction of iodide adsorption on oxides by surface complexation modeling with spectroscopic confirmation.

A deficiency in environmental iodine can cause a number of health problems. Understanding how iodine is sequestered by materials is helpful for evaluating and developing methods for minimizing human health effects related to iodine. In addition, (129)I is considered to be strategically important for safety assessment of underground radioactive waste disposal. To assess the long-term stability of disposed radioactive waste, an understanding of (129)I adsorption on geologic materials is essential. Therefore, the adsorption of I(-) on naturally occurring oxides is of environmental concern. The surface charges of hydrous ferric oxide (HFO) in NaI electrolyte solutions were measured by potentiometric acid-base titration. The surface charge data were analyzed by means of an extended triple-layer model (ETLM) for surface complexation modeling to obtain the I(-) adsorption reaction and its equilibrium constant. The adsorption of I(-) was determined to be an outer-sphere process from ETLM analysis, which was consistent with independent X-ray absorption near-edge structure (XANES) observation of I(-) adsorbed on HFO. The adsorption equilibrium constants for I(-) on beta-TiO(2) and gamma-Al(2)O(3) were also evaluated by analyzing the surface charge data of these oxides in NaI solution as reported in the literature. Comparison of these adsorption equilibrium constants for HFO, beta-TiO(2), and gamma-Al(2)O(3) based on site-occupancy standard states permitted prediction of I(-) adsorption equilibrium constants for all oxides by means of the Born solvation theory. The batch adsorption data for I(-) on HFO and amorphous aluminum oxide were reasonably reproduced by ETLM with the predicted equilibrium constants, confirming the validity of the present approach. Using the predicted adsorption equilibrium constants, we calculated distribution coefficient (K(d)) values for I(-) adsorption on common soil minerals as a function of pH and ionic strength.

Removal of phosphate from solution by adsorption and precipitation of calcium phosphate onto monohydrocalcite.

The sorption behavior and mechanism of phosphate on monohydrocalcite (CaCO(3)·H(2)O: MHC) were examined using batch sorption experiments as a function of phosphate concentrations, ionic strengths, temperatures, and reaction times. The mode of PO(4) sorption is divisible into three processes depending on the phosphate loading. At low phosphate concentrations, phosphate is removed by coprecipitation of phosphate during the transformation of MHC to calcite. The sorption mode at the low-to-moderate phosphate concentrations is most likely an adsorption process because the sorption isotherm at the conditions can be fitted reasonably with the Langmuir equation. The rapid sorption kinetics at the conditions is also consistent with the adsorption reaction. The adsorption of phosphate on MHC depends strongly on ionic strength, but slightly on temperature. The maximum adsorption capacities of MHC obtained from the regression of the experimental data to the Langmuir equation are higher than those reported for stable calcium carbonate (calcite or aragonite) in any conditions. At high phosphate concentrations, the amount of sorption deviates from the Langmuir isotherm, which can fit the low-to-moderate phosphate concentrations. Speciation-saturation analyses of the reacted solutions at the conditions indicated that the solution compositions which deviate from the Langmuir equation are supersaturated with respect to a certain calcium phosphate. The obtained calcium phosphate is most likely amorphous calcium phosphate (Ca(3)(PO(4))(2)·xH(2)O). The formation of the calcium phosphate depends strongly on ionic strength, temperature, and reaction times. The solubility of MHC is higher than calcite and aragonite because of its metastability. Therefore, the higher solubility of MHC facilitates the formation of the calcium phosphates more than with calcite and aragonite.

Quantification of the Effects of Organic and Carbonate Buffers on Arsenate and Phosphate Adsorption on a Goethite-Based Granular Porous Adsorbent

Interest in the development of oxide-based materials for arsenate removal has led to a variety of experimental methods and conditions for determining arsenate adsorption isotherms, which hinders comparative evaluation of their adsorptive capacities. Here, we systematically investigate the effects of buffer (HEPES or carbonate), adsorbent dose, and solution pH on arsenate and phosphate adsorption isotherms for a previously well characterized goethite-based adsorbent (Bayoxide E33 (E33)). All adsorption isotherms obtained at different adsorbate/adsorbent concentrations were identical when 1 mM of HEPES (96 mg C/L) was used as a buffer. At low aqueous arsenate and phosphate concentration (∼1.3 μM), however, adsorption isotherms obtained using 10 mM of NaHCO(3) buffer, which is a reasonable carbonate concentration in groundwater, are significantly different from those obtained without buffer or with HEPES. The carbonate competitive effects were analyzed using the extended triple layer model (ETLM) with the adsorption equilibrium constant of carbonate calibrated using independent published carbonate adsorption data for pure goethite taking into consideration the different surface properties. The successful ETLM calculations of arsenate adsorption isotherms for E33 under various conditions allowed quantitative comparison of the arsenate adsorption capacity between E33 and other major adsorbents initially tested under varied experimental conditions in the literature.

Desorption of intrinsic cesium from smectite: inhibitive effects of clay particle organization on cesium desorption.

Fine clay particles have functioned as transport media for radiocesium in terrestrial environments after nuclear accidents. Because radiocesium is expected to be retained in clay minerals by a cation-exchange reaction, ascertaining trace cesium desorption behavior in response to changing solution conditions is crucially important. This study systematically investigated the desorption behavior of intrinsic Cs (13 nmol/g) in well-characterized Na-montmorillonite in electrolyte solutions (NaCl, KCl, CaCl2, and MgCl2) under widely differing cation concentrations (0.2 mM to 0.2 M). Batch desorption experiments demonstrated that Cs(+) desorption was inhibited significantly in the presence of the environmental relevant concentrations of Ca(2+) and Mg(2+) (>0.5 mM) and high concentrations of K(+). The order of ability for Cs desorption was Na(+) = K(+) > Ca(2+) = Mg(2+) at the highest cation concentration (0.2 M), which is opposite to the theoretical prediction based on the cation-exchange selectivity. Laser diffraction grain-size analyses revealed that the inhibition of Cs(+) desorption coincided with the increase of the clay tactoid size. Results suggest that radiocesium in the dispersed fine clay particles adheres on the solid phase when the organization of swelling clay particles occurs because of changes in solution conditions caused by both natural processes and artificial treatments.

Individual and combined effects of water quality and empty bed contact time on As(V) removal by a fixed-bed iron oxide adsorber: Implication for silicate precoating

The individual and combined effects of changes in water quality (i.e. pH, initial concentrations of arsenate (As(V)) and competing ions) and empty bed contact time (EBCT) on As(V) removal performance of a fixed-bed adsorber (FBA) packed with a nanostructured goethite-based granular porous adsorbent were systematically studied under environmentally relevant conditions. Rapid small scale column tests (RSSCTs) were extensively conducted at different EBCTs with synthetic waters in which pH and the concentrations of competing ions (phosphate, silicate, and vanadate) were controlled. In the absence of the competing ions, the effects of initial As(V) concentration, pH, and EBCT on As(V) breakthrough curves were successfully predicted by the homogeneous surface diffusion model (HSDM) with adsorption isotherms predicted by the extended triple layer model (ETLM). The interference effects of silicate and phosphate on As(V) removal were strongly influenced by pH, their concentrations, and EBCT. In the presence of silicate (≤21 mg/L as Si), a longer EBCT surprisingly resulted in worse As(V) removal performance. We suggest this is because silicate, which normally exists at much higher concentration and moves more quickly through the bed than As(V), occupies or blocks adsorption sites on the media and interferes with later As(V) adsorption. Here, an alternative operating scheme of a FBA for As(V) removal is proposed to mitigate the silicate preloading. Silicate showed a strong competing effect to As(V) under the tested conditions. However, as the phosphate concentration increased, its interference effect dominated that of silicate. High phosphate concentration (>100 μg/L as P), as experienced in some regions, resulted in immediate As(V) breakthrough. In contrast to the observation in the presence of silicate, longer EBCT resulted in improved As(V) removal performance in the presence of phosphate. Vanadate was found to compete with As(V) as strongly as phosphate. This study reveals the competitive interactions of As(V) with the competing ions in actual adsorptive treatment systems and the dependence of optimal operation scheme and EBCT on water quality in seeking improved As(V) removal in a FBA.

Sorption of Eu(III) on granite: EPMA, LA-ICP-MS, batch and modeling studies.

Eu(III) sorption on granite was assessed using combined microscopic and macroscopic approaches in neutral to acidic conditions where the mobility of Eu(III) is generally considered to be high. Polished thin sections of the granite were reacted with solutions containing 10 μM of Eu(III) and were analyzed using EPMA and LA-ICP-MS. On most of the biotite grains, Eu enrichment up to 6 wt % was observed. The Eu-enriched parts of biotite commonly lose K, which is the interlayer cation of biotite, indicating that the sorption mode of Eu(III) by the biotite is cation exchange in the interlayer. The distributions of Eu appeared along the original cracks of the biotite. Those occurrences indicate that the prior water-rock interaction along the cracks engendered modification of biotite to possess affinity to the Eu(III). Batch Eu(III) sorption experiments on granite and biotite powders were conducted as functions of pH, Eu(III) loading, and ionic strength. The macroscopic sorption behavior of biotite was consistent with that of granite. At pH > 4, there was little pH dependence but strong ionic strength dependence of Eu(III) sorption. At pH < 4, the sorption of Eu(III) abruptly decreased with decreased pH. The sorption behavior at pH > 4 was reproducible reasonably by the modeling considering single-site cation exchange reactions. The decrease of Eu(III) sorption at pH < 4 was explained by the occupation of exchangeable sites by dissolved cationic species such as Al and Fe from granite and biotite in low-pH conditions. Granites are complex mineral assemblages. However, the combined microscopic and macroscopic approaches revealed that elementary reactions by a single mineral phase can be representative of the bulk sorption reaction in complex mineral assemblages.