Risk assessment of heavy metals in pipe scales and loose deposits formed in drinking water distribution systems.

Much uncertainty exists in mechanisms and kinetics controlling the adsorption and desorption of molybdenum (Mo) in the soil environment. To investigate the characteristics of Mo adsorption and desorption and predict Mo behavior in the vadose zone, kinetic batch experiments were performed using three soils: Webster loam, Windsor sand and Mahan sand. Adsorption isotherms for Mo were strongly nonlinear for all three soils. Strong kinetic adsorption of Mo by all soils was also observed, where the rate of retention was rapid initially and was followed by slow retention behavior with time. The time-dependent Mo sorption rate was not influenced when constant pH was maintained. Desorption or release results indicated that there were significant fractions of Mo that appeared to be irreversible or slowly reversibly sorbed by Windsor and Mahan. X-ray absorption near edge structure (XANES) analysis for Windsor and Mahan soils indicated that most of Mo had been bound to kaolinite, whereas Webster had similar XANES features to those of Mo sorbed to montmorillonite. A sequential extraction procedure provided evidence that a significant amount of Mo was irreversibly sorbed. A multireaction model (MRM) with nonlinear equilibrium and kinetic sorption parameters was used to describe the adsorption-desorption kinetics of Mo on soils. Our results demonstrated that a formulation of MRM with two sorption sites (equilibrium and reversible) successfully described Mo adsorption-desorption data for Webster loam, and an additional irreversible reaction phase was recommended to describe Mo desorption or release with time for Windsor and Mahan soils.

Kinetics of Molybdenum Adsorption and Desorption in Soils

A Reliable and Sensitive Voltammetric Determination of Mo(VI) at the In Situ Renovated Bismuth Bulk Annular Band Electrode

Among all iron oxides, hematite (α-Fe2O3), goethite (α-FeOOH), and ferrihydrite (FeOOH⋅nH2O) are the most common mineral species. While immobilization of Mo6+ by surface adsorption on ferric oxides has been studied extensively, the mechanisms of incorporation in their structure have been researched little. The objective of this study was to investigate the relation between Mo content and its structural incorporation in hematite, goethite, and six-line ferrihydrite by a combination of X-ray absorption spectroscopy (XAS), powder X-ray diffraction (pXRD), and inductively-coupled plasma optical emission spectrometry (ICP-OES). Synthesized in the presence of Mo, the hematite, goethite, and six-line ferrihydrite phases incorporated up to 8.52, 0.03, and 17.49 wt. % Mo, respectively. For hematite and goethite, pXRD analyses did not indicate the presence of separate Mo phases. Refined unit-cell parameters correlated with increasing Mo concentration in hematite and goethite. The unit-cell parameters indicated an increase in structural disorder within both phases and, therefore, supported the structural incorporation of Mo in hematite and goethite. Analysis of pXRD measurements of Mo-bearing six-line ferrihydrites revealed small amounts of coprecipitated akaganeite. X-ray absorption near edge structure (XANES) measurements at the Mo L3-edge indicated a strong distortion of the MoO6 octahedra in all three phases. Fitting of extended X-ray absorption fine structure (EXAFS) spectra of the Mo K-edge supported the presence of such distorted octahedra in a coordination environment similar to the Fe position in the investigated specimen. Incorporation of Mo6+ at the Fe3+-position for both hematite and goethite resulted in the formation of one Fe vacancy in close proximity to the newly incorporated Mo6+ and, therefore, charge balance within the hematite and goethite structures.

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INCORPORATION OF Mo6+ IN FERRIHYDRITE, GOETHITE, AND HEMATITE

Among all highly-crystalline iron oxides present in the environment, akaganeite (β-FeO(OH, Cl)) possesses one of the most unconventional structural setups and is a known scavenger for large quantitates of molybdenum (Mo6+). The factors controlling the exact mechanism for Mo6+ incorporation into the akaganeite crystal structure are poorly understood and the ability of dissimilatory Fe(III)-reducing microorganisms to reduce pure akaganeite or Mo-carrying iron oxides is not well characterized. In the current study, we investigated the short-range order around Mo6+ in akaganeite and the fate of Mo6+ under microbially-mediated Fe(III)-reducing conditions. We found that akaganeite can incorporate up to 14.11 ± 0.22 wt% Mo, while the Fe content decreases from 59.70 ± 0.31 to 40.40 ± 0.24 wt%, which indicates a loss of 2–3 Fe atoms for each Mo incorporated. Simultaneously, the crystal structure unit cell parameters a, b and c decrease, while β increases with increasing Mo content. Surprisingly, dissolution of akaganeite by Shewanella loihica PV-4 showed higher dissolution rates of Mo-bearing akaganeite compared to Mo-free akaganeite. Moreover, these results suggest the reduction of Mo6+ is most likely microbially-induced (Fe3+ → Fe2+, Mo6+ + 2Fe2+ → Mo4+ + 2Fe3+). Furthermore, X-ray absorption spectra collected at the Mo L3-edge show a peak-splitting of the white line with a splitting gap of 2.7 eV and an increased amplitude for the first peak. This observation indicates Mo6+ is octahedrally coordinated by oxygen, assuming a strongly distorted MoO6-octhaedron. Fitting of the short-range order around Mo6+ in akaganeite supports the presence of a strongly distorted MoO6-octahedron in a coordination environment similar to the Fe position in akaganeite and the formation of Fe-vacancies close to the newly incorporated Mo6+.

Incorporation of molybdenum(VI) in akaganéite (β-FeOOH) and the microbial reduction of Mo–akaganéite by Shewanella loihica PV-4

By comparing three sequential extraction procedures, a new optimized extraction scheme for the molybdenum association in environmental samples was proposed. Five operational steps were described as exchangeable (KH2PO4 + K2HPO4: including water-soluble), associated with organic matter (NaOH), Fe–Mn oxides and/or carbonates (HCl), sulfides (H2O2) and residue (HNO3 + HF + H2O2). An optimized extraction scheme was compared with Tessier’s procedure and the Commission of European Communities Bureau of Reference (BCR) was applied to black shales. Results showed Tessier’s procedure gave the lowest concentration values for exchangeable molybdenum and the highest values for the residual molybdenum, which could not present the efficiency of the extraction reagents. BCR’s procedure showed the highest values in oxidizable molybdenum and presented four fractions of molybdenum, which did not demonstrate the fractions of molybdenum in the black shales in detail. The optimized extraction scheme demonstrated a certain improvement on extraction efficiency over Tessier’s procedure for the lowest residual molybdenum, and revealed more featured fraction information of molybdenum in black shales than BCR’s. Therefore, after a comparison with other two extraction procedures, the optimized extraction scheme proved suitable for the molybdenum in black shales and it also showed an accurate determination of the molybdenum in the fractions and source of bioavailable Mo.

Jian-Ming Zhu

Papers

An optimized sequential extraction scheme for molybdenum association in environmental samples