Freezing Enhances Leaching of Ferrous Ions but Hinders Reductive Dissolution of Ferric Ions from Iron Oxides

Doi, Minori; Harada, Makoto; Okada, Tetsuo

doi:10.1021/acsearthspacechem.1c00071

Cited by 10 publications

(5 citation statements)

References 36 publications

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“…This is especially important given the recent (Lepre and Olsen, 2021); thus, surface reddening could have a strong paleoclimate significance. Alternatively, freezethawing in proglacial systems could influence redox dynamics and lead to the preferential release of ferrous iron (Doi et al, 2021). Importantly, hematite persists and was detected by XRD in most green samples from across the study area (Figure 7), indicating they would have initially been red or otherwise experienced oxidation prior to green/bleaching alteration.…”

Section: Iron and Titanium Oxides Suggest Post-depositional Oxidationmentioning

confidence: 99%

Red-green-bleached redox interfaces in the proximal Permian Cutler red beds: implications for regional fluid alteration

Hullaster,

Soreghan,

Kukkadapu

et al. 2023

Front. Earth Sci.

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Siliciclastic strata of the Colorado Plateau attract attention for their striking red, green, bleached, and variegated colors that potentially record both early depositional and later diagenetic events. We investigated the proximal-most strata of the Paradox Basin, from their onlap contact with the Precambrian basement of the Uncompahgre Plateau to the younger Cutler strata exposed within 10 km of the Uncompahgre Plateau to attempt to understand the significance of the striking colors that occur here. These strata preserve a complex geology associated with buried paleorelief and sediment-related permeability variations at a major basin-uplift interface. Strata exposed within ∼1.5 km of the onlap contact exhibit a pervasive drab color in contrast to the generally red colors that predominate farther from this front. In-between, strata commonly host variegated red/green/bleached intercalations. Thin-section petrography, SEM, XRD, Raman spectroscopy, Mössbauer spectroscopy, and whole-rock geochemistry of samples representing different color variations from demonstrate that water–rock interactions charged the rocks with Fe(II) that persists primarily in the phyllosilicate fraction. Color variations reflect grain-size differences that allowed the reduction of fluids from regional fault and basement/fill contacts to permeate coarser-grained Cutler sediments. Hematite and chlorite occur in both red and green sediments but are absent in the bleached sediments. Pervasive hematite in both red and green layers suggests that sediments were hematite-rich before later alteration. Chlorite and smectite are elevated in green samples and inversely correlated with biotite content. Green coloration is generally associated with 1) coarser grain sizes, 2) spatial association with basement contacts, 3) elevated smectite and/or chlorite, 4) less total Fe but greater Fe(II)/Fe(III) primarily in the phyllosilicate fraction, and 5) uranium enrichment. The bleached coloration reflects the removal of pigmentary Fe(III) oxide, while the green coloration is due to the removal of pigmentary hematite and the abundance of Fe(II)-bearing phyllosilicates. Abundant mixed-layer and swelling clays such as smectite, illite/smectite, and chlorite/smectite (including tosudite) dominate the mineralogy of the clay fraction. These results are consistent with other studies demonstrating fault-associated fluid alteration in the Paradox Basin region. However, the pervasive greening was not observed in many of these studies and appears to reflect the unique aspects of the paleovalley system and the importance of biotite alteration to Fe(II)-bearing phyllosilicates.

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Section: Iron and Titanium Oxides Suggest Post-depositional Oxidationmentioning

confidence: 99%

Red-green-bleached redox interfaces in the proximal Permian Cutler red beds: implications for regional fluid alteration

Hullaster,

Soreghan,

Kukkadapu

et al. 2023

Front. Earth Sci.

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“…We recently showed that freezing enhances the leaching of ferrous ions but hinders the reduction of ferric ions in iron oxides. 17 It was also reported that, in the natural process, iron or manganese contained in the particles is reduced to a soluble form by the entrainment of particles in the grain boundary space. 18 Thus, the dissolution of metal ions from the particulate matter by freezing is an important process that may provide bioavailable trace metal elements.…”

Section: ■ Introductionmentioning

confidence: 99%

“…According to their study, coexistent chloride affects the redox reaction of Ag + during the freeze–thaw process. We recently showed that freezing enhances the leaching of ferrous ions but hinders the reduction of ferric ions in iron oxides . It was also reported that, in the natural process, iron or manganese contained in the particles is reduced to a soluble form by the entrainment of particles in the grain boundary space .…”

Section: Introductionmentioning

confidence: 99%

In Situ X-ray Fluorescence Evaluation of Metal Ion Adsorption on Ferric Oxyhydroxide in Frozen Solutions

Doi

Harada

Okada

2022

ACS Earth Space Chem.

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Cryosphere plays an important role in the global circulation of various chemical substances through the chemical processes that occur therein. Metal ions are adsorbed on adsorbents, such as ferric (oxy)hydroxides (FeOxH) and iron manganese oxides, and can be accumulated in the frozen phases. The metal ions can be supplied from the cryosphere to the hydrosphere in the bioavailable form by the desorption of metal ions during ice melting. Therefore, quantitative evaluation of the adsorption of metal ions in the frozen state is important to understand their exchange between the frozen and solution phases. Here, we propose in situ synchrotron X-ray fluorescence (XRF) as an appropriate method to quantitatively measure the adsorption of metal ions on FeOxH in a frozen solution. When NaCl solution freezes, a freeze-concentrated solution (FCS) is separated from ice. XRF imaging confirms that the first-row transition metal ions, that is, Mn2+, Co2+, Cu2+, and Zn2+, are enriched with FeOxH in the FCS. While in the presence of tris(hydroxymethyl)aminomethane (tris), Cu2+ forms a stable tris-complex and does not adsorb on FeOxH, other metal ions are partially adsorbed on FeOxH. Therefore, Cu2+ is always dissolved in the FCS, but other metal ions are distributed in both FCS and FeOxH. The linear correlations between the normalized XRF intensity of Cu2+ and those of other metal ions dissolved in the FCS are confirmed. Also, the normalized XRF intensity of Fe in FeOxH is proportional to those of the adsorbed metal ions. Thus, the XRF signals of Cu and Fe are considered to represent the other metal ions contained in the FCS and those adsorbed on FeOxH, respectively. The multivariate regression analysis provides the relative contributions of these two different states of the metal ion in frozen samples. From the regression coefficients, the adsorption ratio of the metal ion in the frozen phase can be estimated. The time change in the adsorption ratio is also successfully evaluated using this method.

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“…Electrochemical approaches including voltammetry are also attractive strategies for monitoring the chemical reactions in FCSs. Okada and coworkers reported the dissolution of ferrous ions from iron oxide (20) and viologens, (21) elucidated by cyclic voltammetry. Although electrochemical approaches can elucidate kinetic and thermodynamic parameters, it is still challenging to control the area of the surface in contact with an FCS and to obtain distribution maps of the chemical species therein when working electrodes are used.…”

Section: Introductionmentioning

confidence: 99%

In situ Visualization of Ferrous Ions Dissolved from Pure Iron Wire into Thin Frozen Aqueous Solution Films by Combination of Microscopy and Image Processing

Inagawa¹,

Maeda²,

Uehara³

2022

Sensors and Materials

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The dissolution of ferrous ions from pure iron into freeze-concentrated solutions (FCSs) formed in thin films of aqueous salt solutions was visualized by a combination of in situ diffusive-reflection microscopy and image processing. An iron surface in contact with an FCS was observed with a diffusive-reflection microscope. Ferrous ions dissolved from the iron surface were complexed with 1,10-phenanthroline doped in the ice film to develop reddish complexes. In situ observation enabled us to monitor the dissolution and migration behavior of ferrous ions in the FCS. Processing of the acquired microscopic images enabled quantitative mapping of the dissolved ferrous ions. The present approach has the potential for fast screening to assess the corrosion behavior of steel materials in contact with frozen aqueous electrolytes.

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Freezing Enhances Leaching of Ferrous Ions but Hinders Reductive Dissolution of Ferric Ions from Iron Oxides

Cited by 10 publications

References 36 publications

Red-green-bleached redox interfaces in the proximal Permian Cutler red beds: implications for regional fluid alteration

Red-green-bleached redox interfaces in the proximal Permian Cutler red beds: implications for regional fluid alteration

In Situ X-ray Fluorescence Evaluation of Metal Ion Adsorption on Ferric Oxyhydroxide in Frozen Solutions

In situ Visualization of Ferrous Ions Dissolved from Pure Iron Wire into Thin Frozen Aqueous Solution Films by Combination of Microscopy and Image Processing

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