Fe2+ catalyzed iron atom exchange and re-crystallization in a tropical soil

Tishchenko, Viktor; Meile, Christof; Scherer, Michelle M.; Pasakarnis, Timothy; Thompson, Aaron

doi:10.1016/j.gca.2014.09.018

Cited by 54 publications

(55 citation statements)

References 41 publications

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“…To our knowledge, the influence of Fe redox cycling on the availability of major nutrient cations (K, Ca, Mg) has not been previously addressed in terrestrial soils. This mechanism may be particularly important in humid tropical systems, which are often rich in SRO Fe (Thompson et al 2011;Tishchenko et al 2015), and where cations may limit or co-limit biological processes (Vitousek and Sanford 1986;Cuevas and Medina 1988;Kaspari et al 2008;Cleveland et al 2011;Wright et al 2011;Baribault et al 2011;Lloyd et al 2015). Our present data expand upon previous investigations of redox-mediated cation dynamics in wetland soils.…”

Section: Discussionsupporting

confidence: 72%

“…Soils at our study site are dominated by kaolinite, quartz, Fe oxyhydroxides, and gibbsite, with small amounts of chlorite (Tishchenko et al 2015;Porder et al 2015). Carbonates are negligible in these acidic soils (pH < 6; pH data from samples in this experiment are reported below).…”

Section: Soil Characterizationmentioning

confidence: 86%

“…Carbonates are negligible in these acidic soils (pH < 6; pH data from samples in this experiment are reported below). A valley soil at our site was characterized in detail by 57 Fe Mössbauer spectroscopy, showing that nano-goethite and ferrihydrite were the dominant Fe phases (Tishchenko et al 2015;Ginn et al 2017). Plagioclase feldspar was the dominant primary mineral source of cations in this ecosystem, and accounts for < 2 % of soil mass according to quantitative x-ray diffraction (Porder et al 2015).…”

Section: Soil Characterizationmentioning

confidence: 98%

“…This extraction is a classic method used to characterize labile Fe(II) in soils and sediments (Lovley and Phillips 1987), and its low pH effectively inhibits Fe(II) oxidation following extraction. It yields soluble and adsorbed Fe(II), in addition to a portion of the Fe (hydr)oxide surface layers (Tishchenko et al 2015). However, the Fe pool solubilized by 0.5M HCl accounts for only 10 -20% of the SRO Fe pool quantified by citrate-ascorbate (Hall and Silver 2015).…”

Section: Soil Analysesmentioning

confidence: 99%

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Iron reduction: a mechanism for dynamic cycling of occluded cations in tropical forest soils?

Hall

Huang

2017

Biogeochemistry

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Nutrient cations can limit plant productivity in highly weathered soils, but have received much less attention than phosphorus and nitrogen. The reduction of iron (Fe) in anaerobic microsites of surface soils can solubilize organic matter and P sorbed or occluded with short-range-ordered (SRO) Fe phases. This mechanism might also release occluded cations. In the Luquillo Experimental Forest, Puerto Rico, we measured cation release during anaerobic laboratory incubations, and assessed patterns of cation availability in surface soils spanning ridge-slope-valley catenas. During anaerobic incubations, potassium (K), calcium (Ca) and magnesium (Mg) significantly increased with reduced Fe (Fe(II)) in both water and 0.5M HCl extractions, but did not change during aerobic incubations. In the field, 0.5M HCl-extractable Fe(II) and Fe(III) were the strongest predictors of K, Mg, and Ca on ridges (R2: 0.57 -0.75). Here, both Ca and Mg decreased with Fe(III), while K, Ca, and Mg increased with Fe(II), consistent with release of Fe-occluded cations following Fe reduction. Manganese in ridge soils was extremely low, consistent with leaching following reductive dissolution of Mn(IV). On slopes, soil C was the strongest cation predictor, consistent with the importance of organic matter for cation exchange in these highly weathered Oxisols. In riparian valleys, cation concentrations were up to 16-fold greater than in other topographic positions but were weakly or unrelated to measured predictors, potentially reflecting cation-rich groundwater. Predictors of cation availability varied with topography, but were consistent with the potential importance of microsite Fe reduction in liberating occluded cations, particularly in the highly productive ridges. This mechanism may explain discrepancies among indices of "available" soil cations and plant cation uptake observed in other tropical forests. CommentsThis is a post-peer-review, pre-copyedit version of an article published in Biogeochemistry. The final authenticated version is available online at: http://dx. AbstractNutrient cations can limit plant productivity in highly weathered soils, but have received much less attention than phosphorus and nitrogen. The reduction of iron (Fe) in anaerobic microsites of surface soils can solubilize organic matter and P sorbed or occluded with short-range-ordered (SRO) Fe phases. This mechanism might also release occluded cations. In the Luquillo Experimental Forest, Puerto Rico, we measured cation release during anaerobic laboratory incubations, and assessed patterns of cation availability in surface soils spanning ridge-slopevalley catenas. During anaerobic incubations, potassium (K), calcium (Ca) and magnesium (Mg) significantly increased with reduced Fe (Fe(II)) in both water and 0.5M HCl extractions, but did not change during aerobic incubations. In the field, 0.5M HCl-extractable Fe(II) and Fe(III) were the strongest predictors of K, Mg, and Ca on ridges (R 2 : 0.57 -0.75). Here, both Ca and Mg decreased with Fe(III), while K, Ca, and Mg i...

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Section: Discussionsupporting

confidence: 72%

Section: Soil Characterizationmentioning

confidence: 86%

Section: Soil Characterizationmentioning

confidence: 98%

Section: Soil Analysesmentioning

confidence: 99%

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Iron reduction: a mechanism for dynamic cycling of occluded cations in tropical forest soils?

Hall

Huang

2017

Biogeochemistry

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“…Specifically, the Fe atom exchange and electron transfer between Fe 2+ aq and structural Fe(III) of iron (hydr)oxides were revealed through newly developed research methods including the stable Fe isotopic tracer and Mössbauer spectroscopy (Williams and Scherer, 2004; Pedersen et al, 2005; Hansel et al, 2005; Yanina and Rosso, 2008; Frierdich et al, 2015; Tishchenko et al, 2015; Jones et al, 2017; Joshi et al, 2017; Notini et al, 2018). The Fe 2+ aq –induced recrystallization of iron (hydr)oxides is also an important reaction in the Fe cycle in soils and exerts crucial effects on the environmental behavior and fates of heavy metal pollutants (Latta et al, 2012b; Frierdich and Catalano, 2012; Frierdich et al 2011, 2012; Liu et al, 2016).…”

mentioning

confidence: 99%

Stabilization of Cd²⁺/Cr³⁺ During Aqueous Fe(II)‐Induced Recrystallization of Al‐Substituted Goethite

Liu

Chen²,

Li³

et al. 2019

Soil Science Soc of Amer J

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Recrystallization of Al‐goethites affected mobility of heavy metals in soils. Co‐existing Cd2+/Cr3+ decreased the Fe atom exchange rates between Fe2+aq and Al‐goethites. Fe2+aq‐induced recrystallization of Al‐goethites stabilized Cd2+ and Cr3+. More Cr3+ are stabilized due to its similar ionic radius with Fe3+ and Al3+. Cd2+ ions more active than Cr3+ considering iron mineral activity in soils. The aqueous Fe2+ (Fe2+aq)–induced recrystallization of iron minerals is an important geochemical process with critical effects on the environmental behavior of metal pollutants in soils. However, the effects of different heavy metals with distinctive physicochemical properties on the Fe2+aq–induced recrystallization of iron minerals and the different stabilization behaviors of these heavy metals remain unclear. This study examined the effects of Cd2+ and Cr3+ on the Fe2+aq–induced recrystallization of Al‐substituted goethites and the simultaneous stabilization of Cd2+/Cr3+ ions by the recrystallized Al‐substituted goethites. Results from stable Fe isotopic tracer experiments and Mössbauer characterization show that Fe atoms were exchanged between Fe2+aq and structural Fe(III) in Al‐substituted goethites with coexisting Cd2+/Cr3+, although both Cd2+ and Cr3+ decreased the exchange rates. During the Fe atom exchange, Al‐substituted goethites were recrystallized and a portion of Cd2+/Cr3+ ions were stabilized by the resulting goethite products. Compared with Cd2+, more Cr3+ ions were immobilized by the recrystallized Al‐substituted goethites due to the lower hydrolysis constant of Cr3+ than Cd2+, as well as the closer ionic radius of Cr3+ with Fe3+ and Al3+. Al‐goethites with higher Al contents further decreased the Fe atom exchange rates while increasing the amounts of immobilized metal ions when in the presence of Cd2+ or Cr3+. The findings of the present study suggest that the physicochemical properties of metal ions play critical roles in affecting their environmental behavior and fates during Fe2+aq–induced recrystallization of iron minerals in soils.

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Mineral characteristics of volcanic ash‐derived soils affecting boron adsorption

Pira

Sumner

Plante

et al. 2023

Soil Science Soc of Amer J

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Volcanic ash-derived soils are naturally deficient in the essential micronutrient B, but they also have maximum adsorption capacities (b B ) that are as much as 40 times greater than in nonvolcanic soils, further exacerbating B availability. Because short-range-order (SRO) aluminosilicates (allophane and imogolite) and iron (Fe) oxyhydroxides are the main clay-sized minerals in these soils, we hypothesized that their relative abundances would explain variations in boron sorption capacity (b B ). We characterized 23 volcanic ash-derived soils (Andisols and non-Andisols) from the Pacific coastal plain of Guatemala by X-ray diffraction, oxalate and pyrophosphate extractions, and thermal analysis, with four selected soils further examined by Mössbauer spectroscopy (MBS). Only soils with andic character (high SRO Si-Al content) contained considerable amounts of imogolite, with allophane in the clay fraction. Overall, soil SRO Al-Si phases were strongly correlated with clay B adsorption capacity (R = 0.65, p < 0.001) and clay specific surface area (R = 0.88, p < 0.001) suggesting that SRO Al-Si phases are the dominate influence on B behavior in these soils. Fe mineral composition was dominated (39%-71% of total Fe) by SRO Fe(III) oxyhydroxides (nanogoethite and ferrihydrite) of various crystallinities. In low allophane soils, SRO Fe phase abundance correlated with b B as did the abundance of low crystallinity kaolinite phases, suggesting these phases are important when SRO Si-Al content is low. Any efforts to predict B behavior or plan soil fertility treatments in volcanic-influenced soils needs to consider the impact of SRO phases.

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Fe2+ catalyzed iron atom exchange and re-crystallization in a tropical soil

Cited by 54 publications

References 41 publications

Iron reduction: a mechanism for dynamic cycling of occluded cations in tropical forest soils?

Iron reduction: a mechanism for dynamic cycling of occluded cations in tropical forest soils?

Stabilization of Cd²⁺/Cr³⁺ During Aqueous Fe(II)‐Induced Recrystallization of Al‐Substituted Goethite

Mineral characteristics of volcanic ash‐derived soils affecting boron adsorption

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Fe2+ catalyzed iron atom exchange and re-crystallization in a tropical soil

Cited by 54 publications

References 41 publications

Iron reduction: a mechanism for dynamic cycling of occluded cations in tropical forest soils?

Iron reduction: a mechanism for dynamic cycling of occluded cations in tropical forest soils?

Stabilization of Cd2+/Cr3+ During Aqueous Fe(II)‐Induced Recrystallization of Al‐Substituted Goethite

Mineral characteristics of volcanic ash‐derived soils affecting boron adsorption

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Stabilization of Cd²⁺/Cr³⁺ During Aqueous Fe(II)‐Induced Recrystallization of Al‐Substituted Goethite