Goethite and Hematite Nucleation and Growth from Ferrihydrite: Effects of Oxyanion Surface Complexes.

The presence of oxyanions, such as nitrate (NO3-) and phosphate (PO43-), regulates the nucleation and growth of goethite (Gt) and hematite (Hm) during the transformation of ferrihydrite (Fh). Our previous studies showed that oxyanion surface complexes control the rate and pathway of Fh transformation to Gt and Hm. However, how oxyanion surface complexes control the mechanism of Gt and Hm nucleation and growth during the Fh transformation is still unclear. We used synchrotron scattering methods and cryogenic transmission electron microscopy to investigate the effects of NO3- outer-sphere complexes and PO43- inner-sphere complexes on the mechanism of Gt and Hm formation from Fh. Our TEM results indicated that Gt particles form through a two-step model in which Fh particles first transform to Gt nanoparticles and then crystallographically align and grow to larger particles by oriented attachment (OA). In contrast, for the formation of Hm, imaging shows that Fh particles first aggregate and then transform to Hm through interface nucleation. This is consistent with our X-ray scattering results, which demonstrate that NO3- outer-sphere and PO43- inner-sphere complexes promote the formation of Gt and Hm, respectively. These results have implications for understanding the coupled interactions of oxyanions and iron oxy-hydroxides in Earth-surface environments.

Oxyanion Surface Complexes Control the Kinetics and Pathway of Ferrihydrite Transformation to Goethite and Hematite.

The rate and pathway of ferrihydrite (Fh) transformation at oxic conditions to more stable products is controlled largely by temperature, pH, and the presence of other ions in the system such as nitrate (NO3-), sulfate (SO42-), and arsenate (AsO43-). Although the mechanism of Fh transformation and oxyanion complexation have been separately studied, the effect of surface complex type and strength on the rate and pathway remains only partly understood. We have developed a kinetic model that describes the effects of surface complex type and strength on Fh transformation to goethite (Gt) and hematite (Hm). Two sets of oxyanion-adsorbed Fh samples were prepared, nonbuffered and buffered, aged at 70 ± 1.5 °C, and then characterized using synchrotron X-ray scattering methods and wet chemical analysis. Kinetic modeling showed a significant decrease in the rate of Fh transformation for oxyanion surface complexes dominated by strong inner-sphere (SO42- and AsO43-) versus weak outer-sphere (NO3-) bonding and the control. The results also showed that the Fh transformation pathway is influenced by the type of surface complex such that with increasing strength of bonding, a smaller fraction of Gt forms compared with Hm. These findings are important for understanding and predicting the role of Fh in controlling the transport and fate of metal and metalloid oxyanions in natural and applied systems.

A Critical Review for Real-Time Continuous Soil Monitoring: Advantages, Challenges, and Perspectives.

Most soil quality measurements have been limited to laboratory-based methods that suffer from time delay, high cost, intensive labor requirement, discrete data collection, and tedious sample pretreatment. Real-time continuous soil monitoring (RTCSM) possesses a great potential to revolutionize field measurements by providing first-hand information for continuously tracking variations of heterogeneous soil parameters and diverse pollutants in a timely manner and thus enable constant updates essential for system control and decision-making. Through a systematic literature search and comprehensive analysis of state-of-the-art RTCSM technologies, extensive discussion of their vital hurdles, and sharing of our future perspectives, this critical review bridges the knowledge gap of spatiotemporal uninterrupted soil monitoring and soil management execution. First, the barriers for reliable RTCSM data acquisition are elucidated by examining typical soil monitoring techniques (e.g., electrochemical and spectroscopic sensors). Next, the prevailing challenges of the RTCSM sensor network, data transmission, data processing, and personalized data management are comprehensively discussed. Furthermore, this review explores RTCSM data application for updating diverse strategies including high-fidelity soil process models, control methodologies, digital soil mapping, soil degradation, food security, and climate change mitigation. Finally, the significance of RTCSM implementation in agricultural and environmental fields is underscored through illuminating future directions and perspectives in this systematic review.

Recurrence and metastatic potential in Type 1 gastric neuroendocrine neoplasms.

BACKGROUND: The aim of our study was to assess clinico-pathological and biochemical parameters of Type 1 Gastric Neuroendocrine Neoplasms (GNEN1) with respect to tumours propensity for recurrence and metastasis. METHODS: Hospital charts of GNEN1 patients were reviewed at a single tertiary referral centre. RESULTS: We included 114 consecutive patients (74 women; age at baseline 54.5 ± 12.7 years [mean ± SD]) with GNEN1. All tumours (n = 114) were well differentiated; Grade 1 (G1) accounted for 56 patients (49%), whereas 46 (40%) were Grade 2 (G2) and 12 (11%) of unknown Grade. Overall follow-up encompassed 45.3 ± 46 (mean ± SD) months in 84 patients who were subjected to annual surveillance; 44 (52%) developed recurrence in the stomach during follow-up with 22 experiencing multiple recurrences; three (2.6%) presented with metastases in locoregional lymph nodes (n = 3) and/or the liver (n = 2); No metastasis or death was reported during follow-up. Median recurrence-free survival (RFS) was 31 months (95% CI: 7.6-54.4). Among clinico-pathological and biochemical parameters investigated, endoscopic intervention compared with surgery (P-value = .009) and higher serum-gastrin levels (s-gastrin) at baseline and first-year follow-up were associated with recurrence (P-value = .022 and .003 respectively) and also shorter RFS (log-rank P = .009 for type of intervention and .014 for s-gastrin, respectively). Receiver Operator Curve analysis of s-gastrin levels at first-year follow-up for recurrence demonstrated an area under the curve of 0.702. CONCLUSION: Despite the relatively high prevalence of G2 tumours, endoscopically and/or surgically treated GNEN1 remains an indolent disease with a low metastatic propensity and no disease-specific mortality reported in our series. Many patients though will experience local recurrence, warranting long-term endoscopic surveillance with s-gastrin biomarker being a complementary tool in recurrence prediction.

A Unified Surface Complexation Modeling Approach for Chromate Adsorption on Iron Oxides.

A multistart optimization algorithm for surface complexation equilibrium parameters (MUSE) was applied to a large and diverse data set for chromate adsorption on iron (oxy)hydroxides (ferrihydrite and goethite). Within the Basic Stern and the charge-distribution multisite complexation (CD-MUSIC) framework, chromate binding constants and the Stern Layer capacitance were optimized simultaneously to develop a consistent parameter set for surface complexation models. This analysis resulted in three main conclusions regarding the model parameters: (a) There is no single set of parameter values that describes such diverse data sets when modeled independently. (b) Parameter differences among the data sets are mainly due to different amounts of total sites, i.e., surface area and surface coverages, rather than structural differences between the iron (oxy)hydroxides. (c) Unified equilibrium constants can be extracted if total site dependencies are taken into account. The implementation of the MUSE algorithm automated the process of optimizing the parameters in an objective and consistent manner and facilitated the extraction of predictive relationships for unified equilibrium constants. The extracted unified parameters can be implemented in reactive transport modeling in the field by either adopting the appropriate values for each surface coverage or by estimating error bounds for different conditions. The evaluation of a forward model with unified parameters successfully predicted chromate adsorption for a range of capacitance values.

Density functional theory modeling of chromate adsorption onto ferrihydrite nanoparticles.

Density functional theory (DFT) calculations were performed on a model of a ferrihydrite nanoparticle interacting with chromate ([Formula: see text]) in water. Two configurations each of monodentate and bidentate adsorbed chromate as well as an outer-sphere and a dissolved bichromate ([Formula: see text]) were simulated. In addition to the 3-D periodic planewave DFT models, molecular clusters were extracted from the energy-minimized structures. Calculated interatomic distances from the periodic and cluster models compare favorably with Extended X-ray Absorption Fine Structure spectroscopy values, with larger discrepancies seen for the clusters due to over-relaxation of the model substrate. Relative potential energies were derived from the periodic models and Gibbs free energies from the cluster models. A key result is that the bidentate binuclear configuration is the lowest in potential energy in the periodic models followed by the outer-sphere complex. This result is consistent with observations of the predominance of bidentate chromate adsorption on ferrihydrite under conditions of high surface coverage (Johnston Environ Sci Technol 46:5851-5858, 2012). Cluster models were also used to perform frequency analyses for comparison with observed ATR FTIR spectra. Calculated frequencies on monodentate, bidentate binuclear, and outer-sphere complexes each have infrared (IR)-active modes consistent with experiment. Inconsistencies between the thermodynamic predictions and the IR-frequency analysis suggest that the 3-D periodic models are not capturing key components of the system that influence the adsorption equilibria under varying conditions of pH, ionic strength and electrolyte composition. Model equilibration via molecular dynamics (MD) simulations is necessary to escape metastable states created during DFT energy minimizations based on the initial classical force field MD-derived starting configurations.

Mechanisms of Chromate, Selenate, and Sulfate Adsorption on Al-Substituted Ferrihydrite: Implications for Ferrihydrite Surface Structure and Reactivity.

Ferrihydrite is a nanocrystalline Fe (hydr)oxide and important sink for environmental contaminants. Although Fe (hydr)oxides are rarely pure in natural systems, little is known about the effects of structural impurities such as Al on the surface properties and reactivity of ferrihydrite. In this study, we characterized the adsorption mechanisms of chromate, selenate, and sulfate on Al-substituted ferrihydrite (0, 6, 12, 18, and 24 mol % Al) using in situ attenuated total reflection Fourier transform infrared spectroscopy. Spectral data sets recorded as a function of pH were processed using a multivariate curve resolution technique to identify which types of surface species form and to generate their concentration profiles as a function of pH and Al content. Results show a significant increase in relative fraction of outer-sphere complexes for all three oxyanions with increasing Al substitution. In addition, the effect of Al substitution is found to be mechanism-specific in the case of chromate, with bidentate complexes disproportionately suppressed over monodentate complexes at higher Al contents. Overall, our findings have important implications for the fate of chromate, selenate, and sulfate in subsurface environments and offer new insight into the surface reactivity of Al-ferrihydrite.

Investigation of chromate coordination on ferrihydrite by in situ ATR-FTIR spectroscopy and theoretical frequency calculations.

Chromate mobility, reactivity, and bioavailability in soil environments are affected by adsorption reactions on iron oxide minerals, but the adsorption mechanisms remain controversial. In this study, we employed in situ attenuated total reflectance Fourier transform infrared spectroscopy and theoretical frequency calculations to characterize chromate adsorption on 2-line ferrihydrite. The effects of pH, aqueous chromate concentration, ionic strength, and deuterium exchange were investigated. Results suggest the formation of monodentate and bidentate surface complexes. It was determined that monodentate complexes are dominant at low surface coverage and pH ≥ 6.5 and that bidentate complexes form at high surface coverage and pH < 6. Deuterium exchange experiments indicated that the inner-sphere complexes are not protonated. Difference spectra revealed that monodentate complexes are particularly susceptible to ionic strength effects under acidic conditions.

Multiple heavy metal immobilization and strength improvement of contaminated soil using bio-mediated calcite precipitation technique.

Bio-mediated calcite precipitation potential for multiple heavy metal immobilization in contaminated soils at industrial, waste dump, abandoned mine, and landfill sites is not explored yet. This study includes investigation of bio-mediated calcite precipitation for strength improvement and immobilization of heavy metals, specifically lead (Pb), zinc (Zn), and hexavalent chromium (Cr(VI)), in contaminated soils. Firstly, the toxicity resistance of bacteria against different concentrations (1000, 2000, 3000, 4000, and 5000 mg/l) of each heavy metals was investigated and observed that Pb and Cr were less toxic to Sporosarcina pasteurii than Zn. The poorly graded sand was spiked with 333-2000 mg/kg concentrations of a selected individual or mixed metal solutions, i.e., 1000 mg/kg and 2000 mg/kg individual concentrations of Pb, Zn, and Cr(VI); 500 mg/kg and 1000 mg/kg concentration of each metal in "Pb and Zn," "Pb and Cr(VI)," and "Zn and Cr(VI)" mixture of heavy metals; and 333 mg/kg and 666 mg/kg concentration of each metal in "Pb, Zn, and Cr(VI)" mixed metal concentration. Contaminated soil was biotreated with Sporosarcina pasteurii and cementation (a solution of urea and calcium chloride dihydrate) solutions for 18 days. Biocemented sand specimens were subjected to testing of hydraulic conductivity, ultrasonic pulse velocity (UPV), unconfined compressive strength (UCS), calcite content, pH, toxicity characteristic leaching procedure (TCLP), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The heavy metal contaminated samples showed decrease in hydraulic conductivity and increase in UPV and UCS after biotreatment; however, the changes in engineering properties were found more moderate than clean biocemented sand. The conversion of Cr(VI) to Cr(III) followed by Cr2O3 precipitation in calcite lattice was observed. Zn was precipitated as smithsonite (ZnCO3), while no Pb precipitate was identified in XRD results. TCLP leaching showed Pb and Cr immobilized proportional to calcite precipitated amount, and higher calcite amounts yielded levels within regulatory limits. Pb and Cr(VI) immobilization up to 92 % and 94 % was achieved, respectively, in contaminated biocemented sand. Zn was found completely leachable as smithsonite is only stable down to pH~5, and strongly acidic TCLP solution reversed all immobilization at natural soil pH~8-9.

Microstructural analyses of Cr(VI) speciation in chromite ore processing residue from the soda ash process.

The microstructure of Chromite Ore Processing Residue (COPR) derived from the soda ash roasting process was investigated prior to and after removal of water exchangeable chromate using a host of microscopy and spectroscopy techniques. Soda ash COPR consists mostly of a magnesioferrite (MgFe2O4) matrix that has substantial substitution of trivalent chromium (Cr) for iron. The chromite particles are generally larger than the overall particle size distribution of COPR, containing most of the Cr mass in areas that are greater than 20 µm in diameter; chromite particles are also associated with most of the non-exchangeable hexavalent Cr (Cr(VI)), even though the binding mechanism is not well understood. The remaining non-exchangeable Cr(VI) was found in association with the surrounding Si- and Al-matrix, with spectroscopic evidence of the presence of Cr(VI)-hydrotalcite.

Phosphate treatment of firing range soils: lead fixation or phosphorus release?

Phosphate treatment of lead (Pb)-contaminated soils relies on the premise that Pb converts to the thermodynamically stable, insoluble mineral class of pyromorphites. Recent research showed that treatment performance is kinetically controlled and strongly dependent on soil pH; this study employed an acidic phosphate (P) form, monobasic calcium phosphate (MCP), to investigate treatment performance of Pb occurring in an alkaline-buffered and an acidic firing range soil. The results of leaching, X-ray powder diffraction (XRPD), and modeling analyses showed that P and Pb dissolution in the alkaline soil and transformation reactions were kinetically controlled, so that: (i) TCLP (toxicity characteristic leaching procedure) and SPLP (synthetic precipitation leaching procedure) results were poor to marginal even at high MCP dosages; (ii) brushite (Ca(HPO(4)).2H(2)O) and cerussite (PbCO(3)) persisted in XRPD patterns; and, (iii) geochemical modeling failed to predict leaching and phase assemblages. In the acidic soil, Pb-P reactions promoted further soil acidification, improved TCLP performance, and generated better agreement with the equilibrium-based model; however, SPLP and modeling results showed that Pb concentrations could not be reduced below 15 microg/L mainly due to the low soil pH. The marginal or inadequate Pb immobilization was observed in both soils despite the elevated MCP dosages, which were well in excess of the pyromorphite stoichiometric ratio (P/Pb = 0.6). Additionally, P leaching concentrations and rates were extremely high (>300 mg/L), under both SPLP and deionized (DI) water extraction conditions, and as predicted by thermodynamic equilibrium. The performance and sustainability of phosphate-based treatment therefore seem questionable.

Influence of x-ray diffraction sample preparation on quantitative mineralogy: implications for chromate waste treatment.

Powders of chromite ore processing residue (COPR) were mineralogically evaluated using quantitative X-ray powder diffraction (XRPD) to illustrate the impacts of sample preparation procedures. Chromite ore processing residue is strongly alkaline, reactive, contains minerals of varying hardness and absorption coefficients, and exhibits significant amorphicity. This poses a challenge to produce powders for XRPD analysis that are sufficiently fine and of uniform particle size while avoiding mineral reactions and overgrinding effects. Dry, hand pulverization to different grain sizes, and wet, mechanical pulverization (micromilling) using four milling liquids (cyclohexane, isopropanol, ethanol, and water), and variable milling durations (up to 15 min) were evaluated. Micromilling with a light, nonpolar, highly evaporative liquid such as cyclohexane with a milling time of 5 min mitigated systematic errors such as microabsorption and preferred orientation as it produced finer and more uniform particle size distributions than the hand-pulverized powders, while simultaneously affording the least time for sample preparation. Conversely, the use of water as milling liquid resulted in extensive hydration reactions during sample preparation, causing mischaracterization and significant underestimation of its reactive brownmillerite content, which can complicate the remediation design process for COPR. Hand pulverization emerged as a necessary complement to quantify Cr(VI)-containing, softer minerals destroyed during mechanical milling, the quantification of which has also important implications for COPR treatment design. The findings of this study may be applicable in a variety of geochemically complicated and reactive environmental media (metal-contaminated soils, stabilized/solidified media, inorganic waste), and points to the importance of the sample preparation method to obtain reliable quantitative XRPD results.

Application of the Rietveld method to assess chromium(VI) speciation in chromite ore processing residue.

The Rietveld method allows the quantification of crystalline phases and amorphous material identified by X-ray powder diffraction (XRPD) and other diffraction methods. The method assists in determining the speciation of contaminants in solid matrices both qualitatively and quantitatively in a statistically defensible approach, as it does not focus on a microscale. Rietveld was applied to chromite ore processing residue (COPR), a cementitious waste containing hexavalent chromium. Calcium aluminum chromium oxide hydrates (CACs) were the crystalline phases identified by XRPD that bind Cr(6+) in COPR according to their chemical formula. Rietveld quantification, combined with mass balances on Cr(6+), showed that CACs may bind Cr(6+) in variable percentages, ranging from 25% to 85%. Analysis of duplicate samples showed that material variability is the predominant factor of uncertainty in evaluating the role of CACs in Cr(6+) speciation, provided that a consistent quantification strategy is pursued. The choice of strategy was performed on the basis of the pertinent literature, preliminary analyses of the equipment and the software settings, and mass balances. The correlation between the average CAC-bound Cr(6+) concentration and the total Cr(6+) for five samples (R(2)=0.94), extracted from different zones and soil borings, suggests that CACs are a primary sink for Cr(6+) in COPR.

Phosphate application to firing range soils for Pb immobilization: the unclear role of phosphate.

Phosphate treatment has emerged as a widely accepted approach to immobilize Pb in contaminated soils and waste media, relying on the formation of the highly insoluble mineral pyromorphite as solubility-controlling phase for Pb. As such, phosphate treatment has been proposed as a Best Management Practice (BMP) for firing ranges where Pb occurs in its metallic forms and several other phases (carbonates, oxides). While pyromorphite thermodynamically has the potential to control Pb solubility at low levels, its formation is kinetically controlled by pH, the solubility of the phosphate source, and the solubility of Pb species. Treatability studies have shown that excess quantities of soluble and acidic phosphate sources, such as phosphoric acid, are necessary for successful in situ treatment. Even under these conditions, Extended X-ray Absorption Fine Structure (EXAFS), the only reliable method to identify and quantify Pb speciation, showed that Pb conversion to pyromorphite in in situ treated soils was less than 45% after 32 months. Furthermore, the use of lime (CaO) to restore soil pH in acidified soil treatments inhibited further conversion. Additionally, phosphate treatment is known to reduce bioavailability through pyromorphite formation in the intestinal tract, and the phytoaccumulation of Pb; both desirable effects for Pb-impacted areas. Given the costs of phosphate treatment, the use of biogenic phosphate sources, such as bone meal, may be a more environmentally sustainable approach toward this end. In the many studies focusing on phosphate treatment, the attendant P leaching and eutrophication have been largely overlooked, along with other issues such as the enhanced leaching of oxyanionic contaminants, such as Se, As and W. The success and sustainability of applying phosphate as a BMP in firing range soils therefore remain questionable.

Long-term treatment issues with chromite ore processing residue (COPR): Cr(6+) reduction and heave.

A pugmill treatability study was conducted to remediate chromite ore processing residue (COPR) using ferrous sulfate heptahydrate (FeSO(4) x 7H(2)O) as a reductant. Two different types of COPR, with respect to particle size and mineralogy, were tested in this study. Two different stoichiometric ratios of FeSO(4) x 7H(2)O to Cr(6+) (5x and 8x) were applied to reduce Cr(6+) to Cr(3+). The effectiveness of FeSO(4).7H(2)O treatment was assessed using the toxicity characteristic leaching procedure (TCLP) tests and X-ray absorption near edge structure (XANES) analyses. TCLP results obtained from the pugmill treatability study showed that TCLP Cr concentrations were less than the TCLP regulatory limit of 5mg/L upon 8x FeSO(4) x 7H(2)O treatment for up to 420 days but may fail to meet this regulatory limit in the long-term. XANES results obtained from samples cured for 300 days showed that all of the treated samples failed the New Jersey Department of Environmental Protection (NJDEP) clean up level for Cr(6+) of 240 mg/kg. However, the Cr(6+) concentration from the sample with the smaller particle size approached 240 mg/kg (338 mg/kg), suggesting that particle size reduction prior to the addition of reductant may improve the effectiveness of the treatment. COPR heaving was investigated with unconfined swell tests upon 5x and 8x FeSO(4) x 7H(2)O treatment. The formation of ettringite, an expansive material, was investigated following the swell tests using X-ray powder diffraction (XRPD). Significant heaving (>50 vol%) was observed at curing times of 138 days for the 5x treatment and the ettringite formation was identified by XRPD analyses.

Investigation of hexavalent chromium sorption in serpentine sediments.

In this study the removal of hexavalent chromium (Cr6+) by serpentine sediments was investigated in order to delineate Cr6+ sorption behavior in aquifers with ultramafic geologic background. Batch experiments were conducted in order to determine the influence of several parameters on Cr6+ removal, including the pH of the sediment solution, mineralogy, sediment's particle size and Cr6+ initial concentration. The results showed that Cr6+ removal was due to both adsorption and reduction phenomena. Reduction was attributed to the presence of a magnetic fraction in the sediment, mostly related to magnetite, which contributed almost 50% of the total removal in the pH range 3-7. Adsorption behavior was dominated by the finer sediment fraction (d<0.075mm). The amount of Cr6+ adsorbed was constant in the pH range 3-7, while it decreased sharply in the range 7-8.5. Cr6+ adsorption was found to increase and decrease proportionally with increasing initial Cr6+ concentration of and particle size, respectively. The linear Langmuir and Freundlich adsorption isotherms were used to describe the experimental data, with Freundlich providing a better fit to determine distribution factors for transport modeling.

Evaluation of ettringite and hydrocalumite formation for heavy metal immobilization: literature review and experimental study.

The immobilization of heavy metal oxyanions like chromate, arsenate and selenate, has proven to be a challenging task as they are highly mobile in alkaline environments involving S/S of contaminated media. Ettringite, a pozzolanic phase that forms in cementitious materials, has been proposed as a viable immobilization mechanism for oxyanions, wherein the oxyanion may substitute for sulfate in the ettringite structure. A literature review on the immobilization potential of ettringite showed that the substitution potential exists from the thermodynamic point of view where the formation of substituted ettringites occurs under strictly controlled conditions. The pH control over a narrow range is essential for ettringite stability; it becomes even narrower for substituted ettringites, as competing effects with sulfate ettringite and monophases are significantly affected by pH. The presence of sulfate has a catalytic effect on oxyanion incorporation in ettringite. Rapid leaching may occur when the treated media is exposed to sulfate influx. Conversely, monophases seem to be more suitable than ettringite for oxyanion immobilization, mainly as they control oxyanion solubility to lower levels than ettringite. A shift to the thermodynamic equilibrium caused by a shift in environmental conditions may result in monophase conversion to ettringite, which may lead to catastrophic expansion, as widely demonstrated in the cement and soils literature. Overall, the sensitivity of phase equilibria in cement-like systems involving oxyanions is significant with regard to multiple parameters and it is uncertain to what extent these can be predicted and/or controlled in the field.

Polysulfide speciation and reactivity in chromate-contaminated soil.

Calcium polysulfide (CPS) has been observed to maintain a reducing capacity for prolonged time periods when used to treat Cr(VI)-contaminated soils. This study utilized bulk and micro-X-ray absorption near edge structure (XANES) spectroscopy to investigate sulfur speciation in soil samples treated with CPS in batch and column studies and to determine the source of the reducing potential. Bulk XANES spectra indicated the presence of two dominant sulfur species: elemental sulfur, which is the product of the sulfide-chromate redox reaction, and thiosulfate (S2O3(2-)). Micro-XANES analyses confirmed these findings and showed that elemental sulfur precipitated as large particles, while thiosulfate was diffused within the soil grains and thus available to react with chromate that leached from slowly dissolving PbCrO4. Micro-X-ray fluorescence (µXRF) analyses indicated a close association of Pb and thiosulfate, so that PbS2O3 is a likely sink for thiosulfate, accounting for up to 20% of the total S added. Sorption of thiosulfate on iron oxides below pH 8 is a second retention mechanism for thiosulfate in the solid. Given that thiosulfate cannot reduce chromate but can reduce solid-bound Fe(III) under neutral pH conditions, it is hypothesized that ferrous iron production is an additional mechanism to maintain reductive conditions in CPS-treated soils.

Mechanisms of chromate adsorption on boehmite.

Adsorption reactions play an important role in the transport behavior of groundwater contaminants. Molecular-scale information is needed to elucidate the mechanisms by which ions coordinate to soil mineral surfaces. In this study, we characterized the mechanisms of chromate adsorption on boehmite (γ-AlOOH) using a combination of extended X-ray absorption fine structure (EXAFS) measurements, in situ attenuated total reflectance Fourier transform infrared spectroscopy, and quantum chemical calculations. The effects of pH, ionic strength, and aqueous chromate concentration were investigated. Our overall findings were that chromate primarily forms outer-sphere complexes on boehmite over a broad range of pH and aqueous concentrations. Additionally, a small fraction of monodentate and bidentate inner-sphere complexes are present under acidic conditions, as evidenced by two sets of chromate stretching vibrations at approximately 915, 870, and 780cm(-1), and 940, 890, 850, and 780cm(-1), respectively. The bidentate complex is supported by a best-fit CrAl distance in the EXAFS of 3.2Å. Results from DFT also support the formation of monodentate and bidentate complexes, which are predicted to results in Gibbs energy changes of -140.4 and -62.5kJmol(-1), respectively. These findings are consistent with the intermediate binding strength of chromate with respect to similar oxyanions such as sulfate and selenite. Overall, the surface species identified in this work can be used to develop a more accurate stoichiometric framework in mechanistic adsorption models.

Origin and concentration profile of chromium in a Greek aquifer.

In this paper the origin and concentration of chromium (Cr) in an ophiolitic aquifer in Vergina, northern Greece were investigated. The study area has only agricultural activity so that industrial Cr contamination was precluded. Soil sampling included topsoil and drillcore samples collected down to 98 m depth. Groundwater samples were collected from three existing wells and a spring at the area and from different depths of the soil boring using the discrete sampling method. Mineralogical analysis of soils confirmed the presence of ultramafic minerals, including chrysotile and chromite. Soil elemental analysis showed significant concentration of total chromium (Crtot; max 12,000 mg/kg) and hexavalent chromium (Cr(VI); max 7.5mg/kg). Significant Crtot (91 µg/L) and Cr(VI) (64 µg/L) concentrations exceeding the drinking water limit of 50 µg/L were also detected in groundwater. In both the discrete soil and groundwater samples a decreasing trend of Cr(VI) concentration was observed with increasing depth, while Crtot increased. The increasing trend in Crtot is attributed to the increasing contribution of unweathered ultramafic minerals with depth, while the decreasing Cr(VI) may be related to the increasing soil pH that does not favor Cr(III) oxidation by Mn-oxides.