Dissolution Of Fe Minerals Research Articles

Iron Oxyhydroxide Transformation in a Flooded Rice Paddy Field and the Effect of Adsorbed Phosphate.

The mobility and bioavailability of phosphate in paddy soils are closely coupled to redox-driven Fe-mineral dynamics. However, the role of phosphate during Fe-mineral dissolution and transformations in soils remains unclear. Here, we investigated the transformations of ferrihydrite and lepidocrocite and the effects of phosphate pre-adsorbed to ferrihydrite during a 16-week field incubation in a flooded sandy rice paddy soil in Thailand. For the deployment of the synthetic Fe-minerals in the soil, the minerals were contained in mesh bags either in pure form or after mixing with soil material. In the latter case, the Fe-minerals were labeled with 57Fe to allow the tracing of minerals in the soil matrix with 57Fe Mössbauer spectroscopy. Porewater geochemical conditions were monitored, and changes in the Fe-mineral composition were analyzed using 57Fe Mössbauer spectroscopy and/or X-ray diffraction analysis. Reductive dissolution of ferrihydrite and lepidocrocite played a minor role in the pure mineral mesh bags, while in the 57Fe-mineral-soil mixes more than half of the minerals was dissolved. The pure ferrihydrite was transformed largely to goethite (82-85%), while ferrihydrite mixed with soil only resulted in 32% of all remaining 57Fe present as goethite after 16 weeks. In contrast, lepidocrocite was only transformed to 12% goethite when not mixed with soil, but 31% of all remaining 57Fe was found in goethite when it was mixed with soil. Adsorbed phosphate strongly hindered ferrihydrite transformation to other minerals, regardless of whether it was mixed with soil. Our results clearly demonstrate the influence of the complex soil matrix on Fe-mineral transformations in soils under field conditions and how phosphate can impact Fe oxyhydroxide dynamics under Fe reducing soil conditions.

Enhanced oil recovery efficiency of low-salinity water flooding in oil reservoirs including Fe2+ ions

The low-salinity waterflooding is an attractive eco-friendly producing method, recently, for carbonate reservoirs. When ferrous ion is present in the formation water, that is, acidic water, the injection of low-salinity water generally with neutral pH can yield precipitation or dissolution of Fe-minerals by pH mixing effect. FeSO4 and pyrite can be precipitated and re-dissolved, or vice versa, while siderite and Fe(OH)2 are insoluble which are precipitated, causing permeability reduction. Particularly, pyrite chemically reacts with low-salinity water and release sulfate ion, altering the wettability, favorably, to water-wet. In this aspect, we analyzed oil production focusing on dissolution of Fe-minerals and Fe-precipitation using a commercial compositional reservoir simulator. From the simulation results, the quantities of precipitation and dissolution were enormously large regardless of the type of Fe-minerals and there was almost no difference in terms of total volume in this system. However, among Fe-minerals, Fe(OH)2 precipitation and pyrite dissolution were noticeably large compared to troilite, FeSO4, and siderite. Therefore, it is essential to analyze precipitation or dissolution for each Fe-mineral, individually. Meanwhile, in dissolving process of pyrite, sulfate ions were released differently depending on the content of pyrite. Here, the magnitude of the generated sulfate ion was limited at certain level of pyrite content. Thus, it is necessary to pay attention for determining the concentration of sulfate ion in designing the composition of injection water. Ultimately, in the investigation of the efficiency of oil production, it was found that the oil production was enhanced due to an additional sulfate ion generated from FeS2 dissolution.

Emerging investigator series: As(v) in magnetite: incorporation and redistribution.

Exposure to As in groundwater negatively impacts millions of people around the globe, and As mobility in groundwater is often controlled by Fe mineral dissolution and precipitation. Additionally, trace elements can be released from and incorporated into the structure of Fe oxides in the presence of dissolved Fe(ii). The potential for As to redistribute between sorbed on the magnetite surface and incorporated in the magnetite structure, however, remains unclear. In this study, we use selective chemical extraction and X-ray absorption spectroscopy (XAS) to distinguish magnetite-sorbed and incorporated As(v) and to provide evidence for As(v) incorporation during magnetite precipitation. While As in the As-magnetite coprecipitates did not redistribute between sorbed and incorporated over a 4 month period, a small, but measurable increase in incorporated As(v) of up to 13% was observed for sorbed As(v). We suggest that Fe(ii)-catalyzed recrystallization of magnetite did not significantly influence the redistribution of sorbed As(v) because the extent of Fe atom exchange was small (∼10%). In addition, the extent of As redistribution was the same in the absence and presence of added aqueous Fe(ii), suggesting that aqueous Fe(ii) had, overall, a minor effect on As redistribution for both coprecipitated and sorbed As(v). Our results suggest that coprecipitation of As(v) with magnetite and redistribution of As(v) sorbed on magnetite are potential pathways for irreversible As(v) uptake and sequestration. These pathways are likely to play a significant role in controlling As mobility in natural systems, during human-induced redox cycling of groundwater such as aquifer storage and recovery, as well as in iron oxide-based As removal systems.

Arsenic release from flooded paddy soils is influenced by speciation, Eh, pH, and iron dissolution

Arsenic (As) is highly mobilized when paddy soil is flooded, causing increased uptake of As by rice. We investigated factors controlling soil-to-solution partitioning of As under anaerobic conditions. Changes in As and iron (Fe) speciation due to flooded incubation of two paddy soils (soils A and B) were investigated by HPLC/ICP-MS and XANES. The flooded incubation resulted in a decrease in Eh, a rise in pH, and an increase in the As(III) fraction in the soil solid phase up to 80% of the total As in the soils. The solution-to-soil ratio of As(III) and As(V) ( R L/S) increased with pH due to the flooded incubation. The R L/S for As(III) was higher than that for As(V), indicating that As(III) was more readily released from soil to solution than was As(V). Despite the small differences in As concentrations between the two soils, the amount of As dissolved by anaerobic incubation was lower in soil A. With the development of anaerobic conditions, Fe(II) remained in the soil solid phase as the secondary mineral siderite, and a smaller amount of Fe was dissolved from soil A than from soil B. The dissolution of Fe minerals rather than redox reaction of As(V) to As(III) explained the different dissolution amounts of As in the two paddy soils. Anaerobic incubation for 30 d after the incomplete suppression of microbial activity caused a drop in Eh. However, this decline in Eh did not induce the transformation of As(V) to As(III) in either the soil solid or solution phases, and the dissolution of As was limited. Microbial activity was necessary for the reductive reaction of As(V) to As(III) even when Eh reached the condition necessary for the dominance of As(III). Ratios of released As to Fe from the soils were decreased with incubation time during both anaerobic incubation and abiotic dissolution by sodium ascorbate, suggesting that a larger amount of As was associated with an easily soluble fraction of Fe (hydr) oxide in amorphous phase and/or smaller particles.

Colloid Mobilization During Soil Iron Redox Oscillations

In redox-dynamic soils, iron reduction-oxidation events may initiate wide shifts in the concentration of colloidal and dissolved material because of either Fe mineral dissolution or pH shifts associated with Fe oxidation state changes. This can have profound effects on the mobilization of organic and metal constituents. We conducted laboratory studies of colloid dynamics in a Hawaiian soil subjected to four consecutive 14-day reduction-oxidation cycles across the "soil-Fe" (Fe(OH)3)/(Fe2+(aq)) equilibrium. Size fractionated samples were isolated by differential centrifugation and characterized based on analysis of the framework and trace elements (Si, C, Fe, Ti, Al, Zr, Nb, La, and U). Intracycle oscillations in all colloidal (3 kDa to 160 nm) elements peaked during the reduction half-cycles, mobilizing 10% of total soil Ti and from 1-5% of total soil Zr, Nb, La, and U at peak dispersion. Colloid dynamics were dependent on pH shifts accompanying the redox oscillations rather than the fluctuating solubility of Fe oxides. TEM/EDS and mass-balance calculations suggest a carbon-based colloid matrix with zones of metal enrichment. The cumulative effects of four redox cycles included an apparent increase in colloid stability. Proton production/consumption associated with Fe-redox cycling has important implications for mobilization colloid-borne trace elements and sorbed contaminants.

Arsenic, iron and organic matter in sediments and groundwater in the Pannonian Basin, Hungary

In the central part of the Pannonian Basin, factors controlling the distribution of As in sediments and groundwater of the upper 500 m were studied. In core samples, the amounts of As, Fe and Mn extractable with hydroxylamine hydrochloride (NH 2OH · HCl) in 25% acetic acid, the proportion of the <0.063 mm size fraction, and the sediment organic C (C org) contents were measured. In the groundwaters concentrations of As, humic substances, and selected major chemical components were determined. In most core samples extractable Fe, as FeOOH, and C org are correlated, but some samples have excess Fe, or organic matter. In cases where either excess Fe or excess organic matter is found, the amount of As is also elevated. The spatial distribution of As in the groundwater and the lack of a consistent correlation of As with a single component indicate that there is no single factor controlling the concentration of dissolved As over the entire study area. The only consistent feature is enrichment of As relative to Fe in the groundwater, compared to the sediments. This suggests that the dissolution of Fe minerals, which primarily adsorb As, is not congruent. In reducing conditions Fe(III) oxyhydroxides together with adsorbed As dissolve, and siderite with little or no As precipitates. When sub-regions are separated and studied individually, it can be shown that hydrogeological features of the sediments, the proportions of Fe minerals and sedimentary organic matter, and the concentration of dissolved humic materials, all influence the accumulation and mobilization of As. The significance of the different mobilizing processes, however, and the mean concentration of As, is different in the recharge, through-flow and discharge areas.