Thermal transformations of akaganéite and lepidocrocite to hematite: assessment of possible precursors to Martian crystalline hematite     

Timothy D. Glotch  Michael D. Kraft 《Physics and Chemistry of Minerals》2008,35(10):569-581

We examine the possibility that crystalline hematite (α-Fe₂O₃) deposits on Mars were derived from the precursor iron oxyhydroxide minerals akaganéite (β-FeOOH) or lepidocrocite (γ-FeOOH) and compare them to an earlier study of goethite (α-FeOOH) and magnetite (Fe₃O₄) precursors. Both the mid-infrared and visible/near infrared spectra of hematite are dependent upon the hematite precursor mineral and the temperature of transformation. Laboratory spectra are compared to spectra from the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) and the Mars Exploration Rover (MER) Opportunity Mini-TES and Pancam experiments, allowing us to infer the formation environment of Martian crystalline hematite deposits. Akaganéite and lepidocrocite readily transform to hematite at temperatures of 300 and 500°C, respectively. The visible/near-infrared and mid-infrared spectra of akaganéite-derived hematite are poor matches to data returned from TES, Mini-TES, and Pancam. The spectra of lepidocrocite-derived hematite are slightly better fits, but previously published spectra of goethite-derived hematite still represent the best match to MGS and MER spectral data. The experiments demonstrate that hematite precursor mineralogy, temperature of formation, and crystal shape exert a strong control on the hematite spectra.  相似文献   

Lepidocrocite-catalyzed Mn(II) oxygenation by air and its effect on the oxidation and mobilization of As(III)     

《Applied Geochemistry》2016

Manganese (oxy)hydroxides (MnO_X) play important roles in the oxidation and mobilization of toxic As(III) in natural environments. Abiotic oxidation of Mn(II) to MnO_X in the presence of Fe minerals has been proved to be an important pathway in the formation of Mn(III, IV) (oxy)hydroxides. However, interactions between Mn(II) and As(III) in the presence of Fe minerals are still poorly understood. In this study, abiotic oxidation of Mn(II) on lepidocrocite, and its effect on the oxidation and mobilization of As(III) were investigated. The results show that MnO_X species are detected on lepidocrocite and their contents increase with increasing pH values ranging from 7.5 to 8.4. After 10 days, an MnOx component, groutite (α-MnOOH) was found on lepidocrocite. During the simultaneous oxidation of Mn(II) and As(III), and the As(III) pre-adsorbed processes, the presence and oxidation of Mn(II) significantly promotes the removal of soluble As(III). In addition, MnOx formed on lepidocrocite also contributes to the oxidation of soluble and adsorbed As(III) to As(V), the latter being subsequently released into solution. In the process where Mn(II) is pre-adsorbed on lepidocrocite, less As(III) is removed, given that the active sites occupied by MnOx inhibit the adsorption of As(III). In all experiments, the removal percentages of As(III) and the release of As(V) are correlated positively with pH values and initial concentrations of Mn(II), although they are not apparent in the Mn(II) pre-adsorbed system.  相似文献   

Behaviour of Fe-oxides relevant to contaminant uptake in the environment   总被引：6，自引：0，他引：6  

S. L. S. Stipp  M. Hansen  R. Kristensen  M. F. Hochella  Jr.  L. Bennedsen  K. Dideriksen  T. Balic-Zunic  D. Lonard  H. -J. Mathieu 《Chemical Geology》2002,190(1-4):321-337

The behaviour of Fe-oxides was investigated during precipitation and co-precipitation, phase transformation and dissolution, while their ability to adsorb and incorporate trace components was examined. Some samples were synthesised and studied under controlled laboratory conditions and other samples were taken from experiments designed to test the effectiveness of waste treatment strategies using iron. Surface-sensitive and high-resolution techniques were used to complement information gathered from classical, macroscopic methods.

Adsorption isotherms for Ni²⁺ uptake on synthetic ferrihydrite (Fe₅HO₈·4H₂O, often written simply Fe(OH)₃), goethite (-FeOOH), hematite (-Fe₂O₃) and magnetite (Fe₃O₄) were all similar, increasing as expected at higher pH. Desorption behaviour was also similar, but one third or more of the Ni²⁺ failed to return to solution. In the past, “irreversible sorption” has been blamed on uptake into micro-fractures or pores, but during examination (using Atomic force microscopy, AFM) of hundreds of Fe-oxide particles, no evidence for such features could be found, leading to the conclusion that Ni²⁺ must become incorporated onto or into the solids. When solutions of Fe(II) are oxidised in controlled laboratory conditions or during treatment of ash from municipal waste incinerators, two-line ferrihydrite forms rapidly and on never-dried samples, AFM shows abundant individual particles with diameter ranging from 0.5 to several tens of nanometers. Aging in solution at 70°C promotes growth of the particles into hematite and goethite and their identification (by X-ray powder diffraction, XRPD, with Rietveld refinement) becomes possible at the same aging stage as mineral morphology becomes recognisable by AFM. In other experiments that were designed to mimic natural attack by organic acids, colloidal lepidocrocite (γ-FeOOH) was observed in situ by AFM, while reductive dissolution removed material on specific crystal faces. Lath ends are eroded fastest while basal planes are more stable.

In order to help elucidate mechanisms of contaminant immobilisation by Fe-oxides, we examined samples from a reactive barrier made with 90% quartz sand, 5% bentonite and 5% zero-valent iron filings that had reacted with a solution typical of leachate from coal-burning fly ash using time-of-flight secondary ion mass spectroscopy (TOF-SIMS). Fe(0) oxidised to Fe(III), while soluble and toxic Cr(VI) was reduced to insoluble Cr(III). Chemical maps show Fe-oxide coatings on bentonite; Cr is associated with Fe-oxides to some extent but its association with Ca in a previously undescribed phase is much stronger. Other samples taken from municipal waste incinerator ash that had been treated by aeration in Fe(II) solutions were examined with transmission electron microscopy (TEM), selected area electron diffraction (SAED) and energy dispersive X-ray spectroscopy (EDS). Pb and some Zn are seen to be dispersed throughout two-line ferrihydrite aggregates, whereas Sn and some Zn are incorporated simply as a result of entrainment of individual ZnSn-oxide crystallites.

Geochemical speciation models that fail to account for contaminant uptake in solid solutions within major phases or as thin coatings or entrained crystals of uncommon phases such as those described here risk to underestimate contaminant retardation or immobilisation.  相似文献