A Robust Model for Prediction of U(VI) Adsorption onto Ferrihydrite Consistent with Spectroscopic Observations.

A robust model that can predict the adsorption behavior of U(VI) on ferrihydrite under a wide range of environmental conditions was developed with the aid of an extended triple-layer model. X-ray absorption spectroscopic observations from previous studies showed that the predominant U(VI) surface species on ferrihydrite was commonly a bidentate inner-sphere species under ambient CO2 conditions. Previous surface complexation models, however, could not predict U(VI) surface speciation because of the lack of sufficient macroscopic adsorption datasets with which to estimate the surface complexation reaction. In this study, we obtained U(VI) adsorption data at U(VI) concentrations of 10nM under a wide range of pH, ionic strength, and solid concentrations in NaNO3 solutions with/without atmospheric CO2. We determined the stoichiometries of the U(VI) adsorption reactions and the equilibrium constants with the adsorption data and the U(VI) hydroxyl constants recently estimated from direct luminescence measurements. A single set of equilibrium constants for the reactions could reproduce reasonably well the reported adsorption datasets obtained under a wide range of pH values (2-12), U(VI) concentrations (10-8 to 10-4 M), ionic strengths (0.004-0.5), and CO2 partial pressures (<10-6 to 10-1.7 atm). The model could also predict all U(VI) surface speciation consistent with previous spectroscopic observations under a wide range of solution conditions.

Amorphous Silica-Promoted Lysine Dimerization: a Thermodynamic Prediction.

It has long been suggested that mineral surfaces played a crucial role in the abiotic polymerization of amino acids that preceded the origin of life. Nevertheless, it remains unclear where the prebiotic process took place on the primitive Earth, because the amino acid-mineral interaction and its dependence on environmental conditions have yet to be understood adequately. Here we examined experimentally the adsorption of L-lysine (Lys) and its dimer (LysLys) on amorphous silica over a wide range of pH, ionic strength, adsorbate concentration, and the solid/water ratio, and determined the reaction stoichiometries and the equilibrium constants based on the extended triple-layer model (ETLM). The retrieved ETLM parameters were then used, in combination with the equilibrium constant for the peptide bond formation in bulk water, to calculate the Lys-LysLys equilibrium in the presence of amorphous silica under various aqueous conditions. Results showed that the silica surface favors Lys dimerization, and the influence varies greatly with changing environmental parameters. At slightly alkaline pH (pH 9) in the presence of a dilute NaCl (1 mM), the thermodynamically attainable LysLys from 0.1 mM Lys reached a concentration around 50 times larger than that calculated without silica. Because of the versatility of the ETLM, which has been applied to describe a wide variety of biomolecule-mineral interactions, future experiments with the reported methodology are expected to provide a significant constraint on the plausible geological settings for the condensation of monomers to polymers, and the subsequent chemical evolution of life.

Glycine Polymerization on Oxide Minerals.

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH3+ group of adsorbed Gly to the nucleophilic NH2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

Prediction of Intrinsic Cesium Desorption from Na-Smectite in Mixed Cation Solutions.

Quantitative understanding of the stability of sorbed radionuclides in smectite is necessary to assess the performance of engineering barriers used for nuclear waste disposal. Our previous study demonstrated that the spatial organization of the smectite platelets triggered by the divalent cations led to the apparent fixation of intrinsic Cs in smectite, because some Cs is retained inside the formed tactoids. Natural water is usually a mixture of Na(+) and divalent cations (Ca(2+) and Mg(2+)). This study therefore investigated the desorption behavior of intrinsic Cs in Na-smecite in mixed Na(+)-divalent cation solutions under widely various cation concentrations using batch experiments, grain size measurements, and cation exchange modeling (CEM). Results show that increased Na(+) concentrations facilitate Cs desorption because Na(+) serves as the dispersion agent. A linear relation was obtained between the logarithm of the Na(+) fraction and the accessible Cs fraction in smectite. That relation enables the prediction of accessible Cs fraction as a function of solution cationic compositions. The corrected CEM considering the effects of the spatial organization suggests that the stability of intrinsic Cs in the smectite is governed by the Na(+) concentration, and suggests that it is almost independent of the concentrations of divalent cations in natural water.

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.

Solid-liquid partitioning and speciation of Pb(II) and Cd(II) on goethite under high pH conditions, as examined by subnanomolar heavy metal analysis, X-ray absorption spectroscopy, and surface complexation modeling.

The adsorption of heavy metals on iron oxides generally increases with pH and is almost complete at neutral to slightly alkaline pH. However, almost complete adsorption on a linear scale does not imply sufficient removal of the heavy metals in terms of their toxicity. Here, we elucidated the chemical reactions that determine the solid-liquid partitioning of Pb(II) and Cd(II) on goethite at high pH. While the removal of both heavy metals was almost complete on a linear scale above pH 7 for Pb(II) and pH 9 for Cd(II), the dissolved metal concentrations decreased on a logarithmic scale with pH, reaching minima at around pH 10 for Pb(II) and pH 10-11 for Cd(II), and then they increased with pH thereafter. The XAFS spectra of Pb(II)- or Cd(II)-adsorbed goethite prepared at pH > 11 were almost the same as those at neutral pH, suggesting that removal of the heavy metals from solution was achieved by a single adsorption reaction over the entire pH range. Based on the observed macroscopic and microscopic adsorption behaviors at high pH, a robust surface complexation model was developed to predict the solid-liquid partitioning of divalent heavy metals over the entire pH range.

Size-classified aerosol-bound heavy metals and their effects on human health risks in industrial and remote areas in Japan.

Airborne aerosols were collected in six size classes (PM<0.1, PM0.1-0.5, PM0.5-1, PM1-2.5, PM2.5-10 and PM>10) to investigate aerosol health risks in remote and industrial areas in Japan. We focused on heavy metals and their water-dispersed fractions. The average concentration of heavy metals was 18 ± 25-86 ± 48 ngm-3 for PM<0.1, 46 ± 19-154 ± 80 for PM0.5-1 ngm-3, 98 ± 49-422 ± 186 ngm-3 for PM1-2.5, 321 ± 305-1288 ± 727 ngm-3 for PM2.5-10 and 65 ± 52-914 ± 339 ngm-3 or PM>10, and these concentrations were higher in industrial areas. Heavy metals emitted from domestic anthropogenic sources were added to the long-range transport component of the aerosols. The water-dispersed fraction of heavy metals contained 3.3-40.1% of the total heavy metals in each size class. The relative contribution of Zn and other species (As, Cd, Cr, Ni, Pb, Mn, V and Cu) increased in the water-dispersed fraction. Smaller particles contained greater proportions of the water-dispersed heavy metal fraction. Carcinogenic risk (CR) and the hazard index (HI) were estimated for each size class. The CR of carcinogens was at acceptable levels (<1 ×10-6) for five particle size fractions. The HI values for carcinogens and noncarcinogens were also below acceptable levels (<1) for the same five size fractions. The estimated CR and HI values were dominated by contributions from the inhalation process.

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.

Kynurenine promotes Calcitonin secretion and reduces cortisol in the Japanese flounder Paralichthys olivaceus.

Deep ocean water (DOW) exerts positive effects on the growth of marine organisms, suggesting the presence of unknown component(s) that facilitate their aquaculture. We observed that DOW suppressed plasma cortisol (i.e., a stress marker) concentration in Japanese flounder (Paralichthys olivaceus) reared under high-density condition. RNA-sequencing analysis of flounder brains showed that when compared to surface seawater (SSW)-reared fish, DOW-reared fish had lower expression of hypothalamic (i.e., corticotropin-releasing hormone) and pituitary (i.e., proopiomelanocortin, including adrenocorticotropic hormone) hormone-encoding genes. Moreover, DOW-mediated regulation of gene expression was linked to decreased blood cortisol concentration in DOW-reared fish. Our results indicate that DOW activated osteoblasts in fish scales and facilitated the production of Calcitonin, a hypocalcemic hormone that acts as an analgesic. We then provide evidence that the Calcitonin produced is involved in the regulatory network of genes controlling cortisol secretion. In addition, the indole component kynurenine was identified as the component responsible for osteoblast activation in DOW. Furthermore, kynurenine increased plasma Calcitonin concentrations in flounders reared under high-density condition, while it decreased plasma cortisol concentration. Taken together, we propose that kynurenine in DOW exerts a cortisol-reducing effect in flounders by facilitating Calcitonin production by osteoblasts in the scales.

Dark microbiome and extremely low organics in Atacama fossil delta unveil Mars life detection limits.

Identifying unequivocal signs of life on Mars is one of the most important objectives for sending missions to the red planet. Here we report Red Stone, a 163-100 My alluvial fan-fan delta that formed under arid conditions in the Atacama Desert, rich in hematite and mudstones containing clays such as vermiculite and smectites, and therefore geologically analogous to Mars. We show that Red Stone samples display an important number of microorganisms with an unusual high rate of phylogenetic indeterminacy, what we refer to as "dark microbiome", and a mix of biosignatures from extant and ancient microorganisms that can be barely detected with state-of-the-art laboratory equipment. Our analyses by testbed instruments that are on or will be sent to Mars unveil that although the mineralogy of Red Stone matches that detected by ground-based instruments on the red planet, similarly low levels of organics will be hard, if not impossible to detect in Martian rocks depending on the instrument and technique used. Our results stress the importance in returning samples to Earth for conclusively addressing whether life ever existed on Mars.

Arsenic and uranium contamination of Orog Lake in the Valley of Gobi Lakes, Mongolia: Field evidence of conservative accumulation of U in an alkaline, closed-basin lake during evaporation.

The shrinkage of inland, alkaline, and saline lakes has caused the elevation of arsenic and uranium concentrations in lake water. However, the chemical reactions associated with these enrichments remain unclear. We conducted a five-year study of the water chemistry of Orog Lake (Mongolia) and the chemical and spectroscopic characteristics of the sediment to determine the geochemical behavior of arsenic and uranium during evaporation. The arsenic and uranium concentrations increased as evaporation caused the lake to shrink. The maximum concentrations of arsenic and uranium exceeded 200 µg/L and 600 µg/L, respectively, when the lake area was the smallest. Comparisons of the monitoring results with predictions of geochemical modeling suggested that some arsenic was removed from the lake water under highly desiccated conditions. Sequential extraction and X-ray absorption near-edge structure analyses showed that ferrihydrite can take up As(V). The accumulation of uranium could be reproduced by considering only evaporation. The conservative behavior of uranium can be explained by the low affinity of U(VI) for carbonate and ferrihydrite at pH > 9 and high dissolved inorganic carbon concentrations. The ubiquitous formation of extremely soluble U-bearing salts after the complete desiccation of inland lakes may thus become a serious threat to limnetic ecosystems.

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.

Monohydrocalcite: a promising remediation material for hazardous anions.

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.

Desorption Behavior of Fukushima-derived Radiocesium in Sand Collected from Yotsukura Beach in Fukushima Prefecture.

Beach sand samples were collected along a coastal area 32 km south of the Fukushima Daiichi Nuclear Power Plant (FDNPP) in Fukushima Prefecture, Japan, 5 years after the FDNPP accident. Desorption experiments were performed on the sand samples using seawater in a batch experimental system to understand the forms of existence of radiocesium in sand and their desorption behavior in a coastal environment. The percentage of radiocesium desorption decreased exponentially with an increase in the number of desorption experiments for the four sand samples, with 137Cs radioactivity from 16 to 1077 Bq kg-1 at surface and deeper layers from three sites. Total desorption percentage ranged from 19 to 58% in 12 desorption experiments. The results indicate that the weak adsorption varies with the sampling sites and their depth layer. To understand the desorption behavior of radiocesium in the sand samples, the desorption experiments were performed for a sand sample by using natural and artificial seawater, and NaCl solution in the presence and absence of KCl. The 137Cs desorption from the sand collected at a depth of 100 - 105 cm from the ground surface (137Cs radioactivity 1052 ± 25 Bq kg-1) was 0.1% by ultrapure water, 3.7% by 1/4 seawater and 7.1% by 1/2 seawater, 2.2% by 470 mM NaCl solution (corresponding to a similar concentration of seawater) and 10 - 12% by seawater, artificial seawater and 470 mM NaCl + 8 mM KCl solution. These results indicate that about 10% of radiocesium adsorbed on the sand is mainly desorbed by ion exchange of potassium ion in seawater, though the concentration of major cation, or sodium ion, in seawater makes a small contribution on 137Cs desorption from the sand samples.

Ecological and Human Health Risk Assessment of Heavy Metal Pollution in the Soil of the Ger District in Ulaanbaatar, Mongolia.

The aim of the present study was to evaluate human health and potential ecological risk assessment in the ger district of Ulaanbaatar city, Mongolia. To perform these risk assessments, soil samples were collected based on reference studies that investigated heavy element distribution in soil samples near the ger area in Ulaanbaatar city. In total, 42 soil samples were collected and 26 heavy metals were identified by inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) methods. The measurement results were compared with the reference data in order to validate the soil contamination level. Although there was a large difference between the measurement results of the present and reference data, the general tendency was similar. Soil contamination was assessed by pollution indexes such as geoaccumulation index and enrichment factor. Mo and As were the most enriched elements compared with the other elements. The carcinogenic and noncarcinogenic risks to children exceeded the permissible limits, and for adults, only 12 out of 42 sampling points exceeded the permissible limit of noncarcinogenic effects. According to the results of the ecological risk assessment, Zn and Pb showed from moderate to considerable contamination indexes and high toxicity values for ecological risk of a single element. The Cr and As ranged as very high ecological risk than that of the other measured heavy metals.

Superior removal of selenite by periclase during transformation to brucite under high-pH conditions.

The sorption of selenite (Se(IV)) at trace (sub-ppm) to high concentrations on periclase (MgO) under high-pH conditions (pH > 10) was examined by macroscopic sorption experiments and nanoscale solid phase analyses via transmission electron microscopy and X-ray absorption spectroscopy. The maximum distribution coefficient (Kd) of Se(IV) on MgO was 100 L/g, the highest among any reported mineral sorbents at pH > 10. Since MgO is a metastable phase under ambient conditions, it transforms instantaneously to brucite (Mg(OH)2) in solution. Se(IV) was preferentially and homogeneously distributed onto the newly formed Mg(OH)2. The Mg(OH)2 formed thin flake-like platelets, which appeared to be aggregates of nanoscale Mg(OH)2 particles, the primary alteration product of MgO. The chemical form of Se(VI) adsorbed on nanoscale particles was outer-sphere complexes. Therefore, the outer-spherically adsorbed Se(IV) was occluded into the large flake-like Mg(OH)2 particles, resulting in its effective isolation from the solution.

Semiarid climate and hyposaline lake on early Mars inferred from reconstructed water chemistry at Gale.

Salinity, pH, and redox states are fundamental properties that characterize natural waters. These properties of surface waters on early Mars reflect palaeoenvironments, and thus provide clues on the palaeoclimate and habitability. Here we constrain these properties of pore water within lacustrine sediments of Gale Crater, Mars, using smectite interlayer compositions. Regardless of formation conditions of smectite, the pore water that last interacted with the sediments was of Na-Cl type with mild salinity (~0.1-0.5 mol/kg) and circumneutral pH. To interpret this, multiple scenarios for post-depositional alterations are considered. The estimated Na-Cl concentrations would reflect hyposaline, early lakes developed in 104-106-year-long semiarid climates. Assuming that post-depositional sulfate-rich fluids interacted with the sediments, the redox disequilibria in secondary minerals suggest infiltration of oxidizing fluids into reducing sediments. Assuming no interactions, the redox disequilibria could have been generated by interactions of upwelling groundwater with oxidized sediments in early post-depositional stages.

Arsenate sorption on monohydrocalcite by coprecipitation during transformation to aragonite.

The metastability of monohydrocalcite (CaCO3·H2O: MHC) suggests high reactivity to dissolved trace elements. Using kinetic and isotherm sorption experiments with different reaction times (24h, 48h), As(V) sorption on MHC was examined to elucidate As(V) uptake by MHC. Although the MHC was transformed to aragonite with time, the MHC in higher As(V) loading conditions was able to persist longer than in lower loading conditions. Actually, As(V) uptake was negligible for samples in which the MHC remained. However, remarkable uptake of As(V) was observed for samples in which a complete transformation of MHC to aragonite occurred. Results of kinetic study confirmed that the timing of the MHC transformation coincided perfectly with that of As(V) removal from the solution. XAFS measurements showed that the local structure of As after the MHC transformation was almost identical to that of As in the As(V) coprecipitated aragonite. Sorption behavior of As(V) during the transformation is explainable theoretically by the substitution of As(V) into the aragonite structure. The distribution coefficient and (apparent) maximum sorption capacity of As(V) sorption on MHC after 48h at low-to-moderate As(V) concentrations are 500L/kg and 25µmol/g, respectively, which are much higher than those of simple adsorption of As(V) on calcite.

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.

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.