oxalates and goethite

Topics: Ferric Compounds; Hydrogen Peroxide; Hydroxyl Radical; Iron; Oxalates; Oxidation-Reduction; Oxides; Reactive Oxygen Species

Contaminated mining sites require ecological restoration work, of which phytoremediation using appropriate plant species is an attractive option. Our present study is focused on one typical contaminated mine site with indigenous plant cover. The X-ray absorption near edge structure (XANES) analysis indicated that Cu (the major contaminant) was primarily associated with goethite (adsorbed fraction), with a small amount of Cu oxalate-like species (organic fraction) in mine affected soil. With growth of plant species like Miscanthus floridulus and Stenoloma chusanum, the Cu-oxalate like organic species in rhizosphere soil significantly increased, with corresponding decrease in Cu-goethite. In the root cross-section of Miscanthus floridulus, synchrotron-based micro-X-ray fluorescence (μ-XRF) microscopy and micro-XANES results indicated that most Cu was sequestered around the root surface/epidermis, primarily forming Cu alginate-like species as a Cu-tolerance mechanism. From the root epidermis to the cortex and vascular bundle, more Cu(I)-glutathione was observed, suggesting reductive detoxification ability of Cu(II) to Cu(I) during the transport of Cu in the root. The observation of Cu-histidine in root internal cell layers showed another Cu detoxification pathway based on coordinating amino ligands. Miscanthus floridulus showed ability to accumulate phosphorous and nitrogen nutrients in rhizosphere and may be an option for in situ phytostabilization of metals in contaminated mining area.

Topics: Biodegradation, Environmental; Hazardous Waste Sites; Industrial Waste; Iron Compounds; Metals; Minerals; Mining; Oxalates; Plant Roots; Poaceae; Rhizosphere; Soil Pollutants

During biogeochemical iron cycling at redox interfaces, dissolved Fe(II) induces the recrystallization of Fe(III) oxides. Oxalate and other organic acids promote dissolution of these minerals and may also induce recrystallization. These processes may redistribute trace metals among the mineral bulk, mineral surface, and aqueous solution. However, the impact of interactions among organic acids, dissolved Fe(II), and iron oxide minerals on trace metal fate in such systems is unclear. The present study thus explores the effect of oxalate on Ni release from and incorporation into hematite and goethite in the absence and presence of Fe(II). When Ni is initially structurally incorporated into the iron oxides, both oxalate and dissolved Fe(II) promote the release of Ni to aqueous solution. When both species are present, their effects on Ni release are synergistic at pH 7 but inhibitory at pH 4, indicating that cooperative and competitive interactions vary with pH. In contrast, oxalate suppresses Ni incorporation into goethite and hematite during Fe(II)-induced recrystallization, decreasing the proportion of Ni substituting in a mineral structure by up to 36%. These observations suggest that at redox interfaces oxalate largely enhances trace metal mobility. In such settings, oxalate, and likely other organic acids, may thus enhance micronutrient availability and inhibit contaminant sequestration.

Topics: Catalysis; Ferric Compounds; Ferrous Compounds; Iron Compounds; Minerals; Oxalates; Oxidation-Reduction

Heterogeneous photodegradation of pentachlorophenol (PCP) in the goethite (alpha-FeOOH) and hematite (alpha-Fe(2)O(3)) systems with oxalate under UVA illumination was investigated. The PCP degradation, dechlorination and detoxification, in terms of Microtox acute toxicity, were all achieved to the higher efficiency in the hematite suspension than in the goethite suspension. The optimal initial concentration of oxalic acid (C(ox)(0)) for the PCP degradation with goethite and hematite under the experimental conditions was found to be 1.2mM, since sufficient Fe(III) as Fe(C(2)O(4))(3)(3-) and Fe(II) as Fe(C(2)O(4))(2)(2-) can be formed at C(ox)(0)>or=1.2mM. The main intermediates of PCP degradation were identified by GC-MS, HPLC and IC analyses. It was found that the cycling process between Fe(III) and Fe(II) in both the goethite and hematite systems occurred more vigorously at the initial stage and gradually became gentle, while the rate of PCP photodegradation varied from fast to slow during the reaction time. Furthermore, the formation of H(2)O(2) during photoreaction was studied to explore its relationship with the photodegradation efficiency and the iron cycling process.

Topics: Ferric Compounds; Hydrogen Peroxide; Iron; Iron Compounds; Minerals; Oxalates; Pentachlorophenol; Photochemistry; Ultraviolet Rays

Iron isotope fractionation during dissolution of goethite (alpha-FeOOH) was studied in laboratory batch experiments. Proton-promoted (HCl), ligand-controlled (oxalate dark), and reductive (oxalate light) dissolution mechanisms were compared in order to understand the behavior of iron isotopes during natural weathering reactions. Multicollector ICP-MS was used to measure iron isotope ratios of dissolved iron in solution. The influence of kinetic and equilibrium isotope fractionation during different time scales of dissolution was investigated. Proton-promoted dissolution did not cause iron isotope fractionation, concurrently demonstrating the isotopic homogeneity of the goethite substrate. In contrast, both ligand-controlled and reductive dissolution of goethite resulted in significant iron isotope fractionation. The kinetic isotope effect, which caused an enrichment of light isotopes in the early dissolved fractions, was modeled with an enrichment factor for the 57Fe/ 54Fe ratio of -2.6 per thousandth between reactive surface sites and solution. Later dissolved fractions of the ligand-controlled experiments exhibit a reverse trend with a depletion of light isotopes of approximately 0.5 per thousandth in solution. We interpret this as an equilibrium isotope effect between Fe(III)-oxalate complexes in solution and the goethite surface. In conclusion, different dissolution mechanisms cause diverse iron isotope fractionation effects and likely influence the iron isotope signature of natural soil and weathering environments.

Topics: Chemical Fractionation; Hydrochloric Acid; Iron Compounds; Iron Isotopes; Kinetics; Ligands; Minerals; Models, Theoretical; Oxalates; Oxidation-Reduction; Protons

It is well known that the dissolution of goethite plays an important role in catalyzing the oxidation of organic chemicals. Therefore, this study investigates how surface dissolution of goethite affects 2-chlorophenol oxidation in the goethite/H2O2 process. Experimental results indicate that ligand and reductant can enhance the dissolution rate of goethite, which is surface-controlled. Our results further indicate 2-chlorophenol degradation depends on goethite concentration. In addition, the oxidation rate of 2-CP is correlated with reductive dissolution rate at various dosages of goethite. Moreover, the oxidation mechanism of 2-CP is also a surface-controlled reaction. A mechanism proposed herein indicates that, in addition to the contaminant, its intermediate species affect the oxidation rate as well.

Topics: Ascorbic Acid; Chlorophenols; Dose-Response Relationship, Drug; Ferric Compounds; Hydrogen Peroxide; Industrial Waste; Iron; Iron Compounds; Ligands; Minerals; Models, Chemical; Oxalates; Oxidation-Reduction; Solubility; Surface Properties; Water

This paper reports steady-state dissolution rates of synthetic low-substitution Al-goethites (mol % Al < 10) at pH 5 in the presence of the trihydroxamate siderophore, desferrioxamine B (DFO-B), and the common biological ligand, oxalate. The siderophore-promoted Fe release rate increased both with the level of Al substitution and with DFO-B concentration up to about 100 microM, after which a plateau occurred, suggesting a saturation effect from DFO-B adsorption as a precursor to dissolution. At concentrations above 200 microM, oxalate also enhanced the Fe release rate, which however was not influenced by Al substitution. For Al-goethites with mol % Al < 4, the Fe release rate in the presence of 40 microM DFO-B together with varying concentrations of oxalate was typically greater than the corresponding sum of dissolution rates in the presence of the two ligands alone. This synergism may be the combined result of the ability of oxalate to adsorb strongly at the goethite surface, thus promoting Fe release, and of the high selectivity of DFO for Fe(III). Ferric oxalate complexes formed during dissolution will likely lose Fe3+ by ligand substitution with DFO-B, leading to the production of Fe(HDFO-B)+ and uncomplexed oxalate, the latter of which, in turn, could adsorb to the goethite surface again. For Al-goethites with mol % Al > 4, synergism was not apparent, which may signal the effect of a decreased surface density of Fe-OH sites associated with Al for Fe substitution. The oxalate-promoted release rates of Al did not scale with those of Fe, indicating incongruent dissolution. However, Al release rates in the presence of DFO-B did scale approximately with those of Fe but were not affected by the concentration of siderophore. These results are consistent with the presence of Al(OH)3 inclusions in Al-goethite.

Topics: Aluminum; Deferoxamine; Hydrogen-Ion Concentration; Iron Chelating Agents; Iron Compounds; Kinetics; Ligands; Minerals; Oxalates; Solubility