The transformation of ferrihydrite in the presence of trace Fe(II): The effect of the anionic media

The transformation from ferrihydrite to various iron oxides and iron oxyhydroxides has been given much attention not only in environmental science and geochemistry but also in biology and material science. This laboratory study attempted to investigate Fe(II)-induced transformation of ferrihydrite in sulfate-rich medium. The results indicate that the transformation in sulfate-rich medium differs from that in Cl⁻ medium in the species, the amount and the morphology of products and transformation rate. Lepidocrocite is a main ingredient in the product in Cl⁻ medium at room temperature (RT), while goethite is the only product in SO₄²⁻ medium at RT. Goethite particles obtained in Cl⁻ medium are star-like but rod-like in SO₄²⁻ medium. The transformation rate in the latter medium is obviously slower than that in the former medium. The formation of lepidocrocite depends on both the ionic strength of the system and the dissolution rate of ferrihydrite.     

Environmental Mobility of Pu(IV) in the Presence of Ethylenediaminetetraacetic Acid: Myth or Reality?

Ethylenediaminetetracetic acid (EDTA), which was co-disposed with Pu at several US Department of Energy sites, has been reported to enhance the solubility and transport of Pu. It is generally assumed that this enhanced transport of Pu in geologic environments is a result of complexation of Pu(IV) with EDTA. However, the fundamental basis for this assumption has never been fully explored. Whether EDTA can mobilize Pu(IV) in geologic environments is dependent on many factors, chief among them are not only the complexation constants of Pu with EDTA and dominant oxidation state and the nature of Pu solids, but also (1) the complexation constants of environmentally important metal ions (e.g., Fe, Al, Ca, Mg) that compete with Pu for EDTA and (2) EDTA interactions with the geomedia (e.g., adsorption, biodegradation) that reduce effective EDTA concentrations available for complexation. Extensive studies over a large range of pH values (1 to 14) and EDTA concentrations (0.0001 to 0.01 mol⋅L⁻¹) as a function of time were conducted on the solubility of 2-line ferrihydrite (Fe(OH)₃(s)), PuO₂(am) in the presence of different concentrations of Ca ions, and mixtures of PuO₂(am) and Fe(OH)₃(s). The solubility data were interpreted using Pitzer’s ion-interaction approach to determine/validate the solubility product of Fe(OH)₃(s), the complexation constants of Pu(IV)-EDTA and Fe(III)-EDTA, and to determine the effect of EDTA in solubilizing Pu(IV) from PuO₂(am) in the presence of Fe(III) compounds and aqueous Ca concentrations. Predictions based on these extensive fundamental data show that environmental mobility of Pu as a result of Pu(IV)-EDTA complexation as reported/implied in the literature is a myth rather than the reality. The data also show that in geologic environments where Pu(III) and Pu(V) are stable, the EDTA complexes of these oxidation states may play an important role in Pu mobility.     

不同因素影响下Fe(Ⅲ)水解中和法制备FeOOH矿相的光谱分析

羟基氧化铁(FeOOH)作为重金属等污染物的吸附材料倍受关注,但不同因素作用下形成的FeOOH产物矿相、结构性质的差异及其对环境功能的影响,却少有报道。采用X射线衍射仪,红外光谱仪,扫描电子显微镜和激光粒度分析仪,系统考察了Fe(Ⅲ)溶液水解中和形成FeOOH时,不同作用因素如铁盐种类、pH和温度等对产物矿相的影响。结果表明,pH 8条件下,Fe(Ⅲ)溶液水解产物均为二线水铁矿(Fe₅HO₈·4H₂O);随着pH升高,Fe₅HO₈·4H₂O会向α-FeOOH相转化。Cl-和NO-₃离子的存在分别有利于β-FeOOH和α-FeOOH的形成;SO2-₄会阻碍Fe₅HO₈·4H₂O向α-FeOOH相转化;Fe2+存在时,会促进Fe₅HO₈·4H₂O向α-FeOOH相转化。加热陈化,可促进Fe₅HO₈·4H₂O转化为α-FeOOH,且利于良好结晶α-FeOOH的形成。但pH≤5,富含Cl-的Fe(Ⅲ)溶液加热水解利于β-FeOOH的生成。不同因素影响下形成的FeOOH,在矿相、表面基团、颗粒形貌和粒径大小上存在一定的差异。     

Fe(II)-induced transformation from ferrihydrite to lepidocrocite and goethite

The transformation of Fe(II)-adsorbed ferrihydrite was studied. Data tracking the formation of products as a function of pH, temperature and time is presented. The results indicate that trace of Fe(II) adsorbed on ferrihydrite can accelerate its transformation obviously. The products are lepidocrocite and/or goethite and/or hematite, which is different from those without Fe(II). That is, Fe(II) not only accelerates the transformation of ferrihydrite but also leads to the formation of lepidocrocite by a new path. The behavior of Fe(II) is shown in two aspects—catalytic dissolution-reprecipitation and catalytic solid-state transformation. The results indicate that a high temperature and a high pH(in the range from 5 to 9) are favorable to solid-state transformation and the formation of hematite, while a low temperature and a low pH are favorable to dissolution-reprecipitation mechanism and the formation of lepidocrocite. Special attentions were given to the formation mechanism of lepidocrocite and goethite.     

Use of a photocatalytic membrane reactor for the removal of natural organic matter in water: Effect of photoinduced desorption and ferrihydrite adsorption

The photocatalytic degradation of natural organic matter (NOM) would be an attractive option in the treatment of drinking water. The performance of a submerged photocatalytic membrane reactor (PMR) was investigated with regard to the removal of NOM and the control of membrane fouling. In particular, this work focused on the adsorption and desorption of humic acids (HA) and lake water NOM at the surface of TiO₂ photocatalyts and ferrihydrite (FH) adsorbents in the PMR for water treatment. The addition of FH particles with a large sorption capacity helped remove the NOM released from TiO₂ particles, but FH suspended in water affected the photocatalysis of lake water NOM with a low specific UV absorbance (SUVA) value. To prevent the UV light being scattered by FH without any photocatalytic activity, FH particles were attached to a submerged microfiltration (MF) membrane, which contributed to a greater removal of NOM during long-term PMR operation. The further removal of NOM from aqueous solution was achieved due to the synergistic effect of TiO₂ photocatalysis and FH adsorption in PMR while minimizing the influence of photoinduced desorption of NOM. No significant membrane fouling occurred when the submerged PMR was operated even at high flux levels (>25 L/m² h), as long as photocatalytic decomposition took place.     

Adsorption of As (V) on iron oxide nanoparticle films studied by in situ ATR-FTIR spectroscopy

Stabilization of arsenic contaminated soils by iron oxides has been proposed as a remediation technique to prevent leaching of arsenate into the environment. Fundamental studies are needed to establish under which conditions the complexes formed are stable. In the present work, a powerful technique, viz. ATR-FTIR spectroscopy, is adapted to the studies of adsorption of arsenate species on iron oxides. This technique facilitates acquisition of both quantitative and qualitative in situ adsorption data.In the present work, about 800 nm thick films of 6-lineferrihydrite were deposited on ZnSe ATR crystals. Arsenate adsorption on the ferrihydrite film was studied at pD values ranging from 4 to 12 and at an arsenate concentration of 0.03 mM in D₂O solution. The amount of adsorbed arsenate decreased with increasing pD as a result of the more negatively charged iron oxide surface at higher pD values. The adsorption and desorption kinetics were also studied. Arsenate showed a higher adsorption rate within the first 70 min and a much lower adsorption rate from 70 to 300 min. The low adsorption rate at longer reaction times was partly due to a low desorption rate of already adsorbed carbonate species adsorbed at the surface. The desorption of carbonate species was evidenced by the appearance of negative absorption bands. The desorption of adsorbed arsenate complexes was examined by flushing with D₂O at pD 4 and 8.5 and it was found that the complexes were very stable at pD 4 suggesting formation of mostly inner-sphere complexes whereas a fraction of the complexes at pD 8.5 were less stable than at pD 4, possibly due to the formation of outer-sphere complexes.In summary, the ATR technique was shown to provide in situ information about the adsorption rate, desorption rate and the speciation of the complexes formed within a single experiment, which is very difficult to obtain using other techniques.     

The transformation of ferrihydrite in the presence of trace Fe(II): The effect of the ammonia, amine and the coordination ions of Fe(III)

This work examined Fe(II)-induced transformation of ferrihydrite in the presence of ammonia, amine and the coordination ions of Fe(III). Our earlier results showed that ferrihydrite transformed into the mixture of lepidocrocite, goethite and/or hematite in the presence of trace Fe(II) and absence of ammonia and similar species. However, the formation of lepidocrocite was restrained when using ammonia as precipitants. When introducing some amines (e.g. ethanolamine and diethanolamine) and some coordination ions (e.g. F⁻ and ions) into the reaction system, a similar effect on the transformation of ferrihydrite was found. Probably, the complexes formed between Fe(III) and those additives favor the formation of goethite. At the same time, the introduction of these additives hinders Fe(II) from interacting with ferrihydrite, which makes the catalytic dissolution of ferrihydrite be limited, thus, the formation of lepidocrocite be restrained.     

Partially hydrated iron–chromium oxide catalyst for the Fischer-Tropsch synthesis

Due to their well-developed surface, partially hydrated iron–chromium oxides with the ferrihydrite structure exhibit much higher activity in the Fischer-Tropsch synthesis than those that have the hematite structure.     

Synthesis, morphological-structural characterization and magnetic properties of amorphous iron (III)-oxyhydroxy-phosphate nanoparticles

The synthesis, the chemical, morphological, structural characterization and the magnetic properties of amorphous iron oxyhydroxy phosphate nanoparticles are reported. Aggregated spherical particles (diameter: 5-12 nm) are obtained showing a ferrihydrite-like behavior similar to that of the bacterial ferritin iron oxyhydroxy-phosphate core. A superparamagnetic behavior is observed with blocking temperatures ranging from ∼20 to ∼50 K depending on the iron and phosphate content.     

Studies on the controllable transformation of ferrihydrite

Ferrihydrite was prepared by two different procedures. Ferrihydrite-1 was prepared by dropping NaOH solution into Fe(III) solution. Ferrihydrite-2 was prepared by adding Fe(III) and NaOH solutions into a certain volume of water simultaneously. Our earlier results obtained at ∼100 °C have shown that the structure of ferrihydrite-2 favors its solid state transformation mechanism. Further research reveals that the structure of ferrihydrite-2 favors its dissolution re-crystallization mechanism at a temperature of ≤60 °C. Based on the transformation mechanism of ferrihydrite at different temperatures, the controllable transformation from ferrihydrite to various iron (hydr)oxides such as lepidocrocite, goethite, hematite and magnetite can be achieved by adjusting the pH, transformation temperature, transformation time, the amount of Fe(II) as well as the preparation procedures of ferrihydrite. The results in the present paper give a nice example that the transformation of a precursor can be controlled with the help of mechanism.