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1.
骆少勇  周跃飞  刘星 《地学前缘》2020,27(5):218-226
通过在滇池开展原位实验,研究探讨了湖泊沉积物中磷灰石制约水铁矿分解和转化的机制,以及二者共存时的环境效应。结果表明:将水铁矿放置到沉积物中1个月,矿物保持稳定;放置时间达到3个月时,添加磷灰石实验中水铁矿发生了显著物相转变。冬天(12—2月)实验中,转化产物随深度的变化趋势为针铁矿+磁(赤)铁矿→针铁矿+纤铁矿→针铁矿;夏天(6—9月)实验中,转化产物随深度的变化趋势为针铁矿+纤铁矿+磁(赤)铁矿→针铁矿+纤铁矿→未转化。透射电镜分析结果显示冬天实验中生成的磁性铁氧化物为纳米磁铁矿和磁赤铁矿,夏天实验中产生的则主要为纳米磁铁矿。X射线光电子能谱分析结果显示冬天表层实验样品具有较高P含量。分析表明的湖泊沉积物中磷灰石促进水铁矿转化的过程为:(1)微生物促进磷灰石溶解;(2)磷灰石溶解释放的P促进铁还原菌生长;(3)铁还原菌促进水铁矿还原;(4)水铁矿还原产生的溶解态Fe2+催化水铁矿向针铁矿、纤铁矿和磁铁矿转化。冬天及沉积氧化-还原界面最适宜磷灰石分解菌和铁还原菌生长,水铁矿的转化和P释放能力也更强,相应地内源磷释放的风险也更大。  相似文献   

2.
The behaviour of trace amounts of arsenate coprecipitated with ferrihydrite, lepidocrocite and goethite was studied during reductive dissolution and phase transformation of the iron oxides using [55Fe]- and [73As]-labelled iron oxides. The As/Fe molar ratio ranged from 0 to 0.005 for ferrihydrite and lepidocrocite and from 0 to 0.001 for goethite. For ferrihydrite and lepidocrocite, all the arsenate remained associated with the surface, whereas for goethite only 30% of the arsenate was desorbable. The rate of reductive dissolution in 10 mM ascorbic acid was unaffected by the presence of arsenate for any of the iron oxides and the arsenate was not reduced to arsenite by ascorbic acid. During reductive dissolution of the iron oxides, arsenate was released incongruently with Fe2+ for all the iron oxides. For ferrihydrite and goethite, the arsenate remained adsorbed to the surface and was not released until the surface area became too small to adsorb all the arsenate. In contrast, arsenate preferentially desorbs from the surface of lepidocrocite. During Fe2+ catalysed transformation of ferrihydrite and lepidocrocite, arsenate became bound more strongly to the product phases. X-ray diffractograms showed that ferrihydrite was transformed into lepidocrocite, goethite and magnetite whereas lepidocrocite either remained untransformed or was transformed into magnetite. The rate of recrystallization of ferrihydrite was not affected by the presence of arsenate. The results presented here imply that during reductive dissolution of iron oxides in natural sediments there will be no simple correlation between the release of arsenate and Fe2+. Recrystallization of the more reactive iron oxides into more crystalline phases, induced by the appearance of Fe2+ in anoxic aquifers, may be an important trapping mechanism for arsenic.  相似文献   

3.
Iron oxides may undergo structural transformations when entering an anoxic environment. These transformations were investigated using the isotopic exchange between aqueous Fe(II) and iron oxides in experiments with 55Fe-labelled iron oxides. 55Fe was incorporated congruently into a ferrihydrite, two lepidocrocites (#1 and #2), synthesised at 10°C and 25°C, respectively, a goethite and a hematite. The iron oxides were then submerged in Fe2+ solutions (0-1.0 mM) with a pH of 6.5. In the presence of aqueous Fe2+, an immediate and very rapid release of 55Fe was observed from ferrihydrite, the two lepidocrocites and goethite, whereas in the absence of Fe2+ no release was observed. 55Fe was not released from hematite, even at the higher Fe2+ concentration. The release rate is mainly controlled by characteristics of the iron oxides, whereas the concentration of Fe2+ only has minor influence. Ferrihydrite and 5-nm-sized lepidocrocite crystals attained complete isotopic equilibration with aqueous Fe(II) within days. Within this timeframe ferrihydrite transformed completely into new and more stable phases such as lepidocrocite and goethite. Lepidocrocite #2 and goethite, having larger particles, did not reach isotopic equilibrium within the timeframe of the experiment; however, the continuous slow release of 55Fe suggests that isotopic equilibrium will ultimately be attained.Our results imply a recrystallization of solid Fe(III) phases induced by the catalytic action of aqueous Fe(II). Accordingly, iron oxides should properly be considered as dynamic phases that change composition when exposed to variable redox conditions. These results necessitate a reevaluation of current models for the release of trace metals under reducing conditions, the sequestration of heavy metals by iron oxides, and the significance of stable iron isotope signatures.  相似文献   

4.
Amorphous ferric iron species (ferrihydrite or akaganeite of <5 nm in size) is the only known solid ferric iron oxide that can be reductively transformed by dissimilatory iron-reducing bacteria to magnetite completely. The lepidocrocite crystallite can be transformed into magnetite in the presence of abiotic Fe(II) at elevated pH or biogenic Fe(II) with particular growth conditions. The reduction of lepidocrocite by dissimilatory iron-reducing bacteria has been widely investigated showing varying results. Vali et al. (Proc Natl Acad Sci USA 101:16121–16126, 2004) captured a unique biologically mediated mineralization pathway where the amorphous hydrous ferric oxide transformed to lepidocrocite was followed by the complete reduction of lepidocrocite to single-domain magnetite. Here, we report the 57Fe Mössbauer hyperfine parameters of the time-course samples reported in Vali et al. (Proc Natl Acad Sci USA 101:16121–16126, 2004). Both the quadrupole splittings and linewidths of Fe(III) ions decrease consistently with the change of aqueous Fe(II) and transformations of mineral phases, showing the Fe(II)-mediated gradual regulation of the distorted coordination polyhedrons of Fe3+ during the biomineralization process. The aqueous Fe(II) catalyzes the transformations of Fe(III) minerals but does not enter the mineral structures until the mineralization of magnetite. The simulated abiotic reaction between Fe(II) and lepidocrocite in pH-buffered, anaerobic media shows the simultaneous formation of green rust and its gradual transformation to magnetite plus a small fraction of goethite. We suggested that the dynamics of Fe(II) supply is a critical factor for the mineral transformation in the dissimilatory iron-reducing cultures.  相似文献   

5.
氧化铁矿物催化分解苯酚的动力学速率及其产物特征   总被引：3，自引：0，他引：3  
本文研究了针铁矿、纤铁矿、赤铁矿和磁铁矿在过氧化氢参与下催化分解苯酚的动力学速率与溶液pH值的关系,并用紫外吸收谱测定了反应产物的谱学特征。结果表明,纤铁矿反应体系催化分解苯酚的速率常数(k)最大,其余依次为磁铁矿、针铁矿和赤铁矿。在纤铁矿反应体系中又以pH=3.8时反应速率常数最大。除赤铁矿反应体系外,当溶液pH=3~4时苯酚被完全分解,并有50%~65%的有机碳(TOC)被矿化。在pH=3.25的赤铁矿反应体系中,苯酚大多仅被转化为多酚,小部分苯环被打开形成己烯酸。当溶液pH=4~5时,苯酚一般仅被转化为多酚类化合物,但TOC基本不变。当溶液pH>5时,苯酚没有发生明显的转化和矿化现象。  相似文献   

6.
The oxidation of carbonate green rust, GR(CO32−), in NaHCO3 solutions at T = 25°C has been investigated through electrochemical techniques, FTIR, XRD, TEM and SEM. The used GR(CO32−) samples were made of either suspended solid in solution or a thin electrochemically formed layer on the surface of an iron disc. Depending on experimental conditions, oxidation occurs, with or without major modifications of the GR(CO32−) structure, suggesting the existence of two pathways: solid-state oxidation (SSO) leading to a ferric oxyhydroxycarbonate as the end product, and a dissolution-oxidation-precipitation (DOP) mechanism leading to ferric oxihydroxides such as lepidocrocite, goethite, or ferrihydrite. A formula was proposed for this ferric oxyhydroxycarbonate, Fe6IIIO(2+x)(OH)(12-2x)(H2O)x(CO3), assuming that the solid-state oxidation reaction is associated to a deprotonation of the water molecules within the interlayers, or of the hydroxyl groups in the Fe(O,H) octahedra layers. The DOP mechanism involves transformation via solution with the occurrence of soluble ferrous-ferric intermediate species. A discussion about factors influencing the oxidation of carbonate green rust is provided hereafter. The ferric oxyhydroxycarbonate can be reduced back to GR(CO32−) by a reverse solid-state reduction reaction. The potentiality for a solid-state redox cycling of iron to occur may be considered. The stability of the ferric oxyhydroxycarbonate towards thermodynamically stable ferric phases, such as goethite and hematite, was also studied.  相似文献   

7.
The Fe(II)-catalysed transformation of synthetic schwertmannite, ferrihydrite, jarosite and lepidocrocite to more stable, crystalline Fe(III) oxyhydroxides is prevented by high, natural concentrations of Si and natural organic matter (NOM). Adsorption isotherms demonstrate that Si adsorbs to the iron minerals investigated and that increasing amounts of adsorbed Si results in a decrease in isotope exchange between aqueous Fe(II) and the Fe(III) mineral. This suggests that the adsorption of Si inhibits the direct adsorption of Fe(II) onto the mineral surface, providing an explanation for the inhibitory effect of Si on the Fe(II)-catalysed transformation of Fe(III) minerals. During the synthesis of lepidocrocite and ferrihydrite, the presence of equimolar concentrations of Si and Fe resulted in the formation of 2-line ferrihydrite containing co-precipitated Si in both cases. Isotope exchange experiments conducted with this freeze-dried Si co-precipitated ferrihydrite species (Si-ferrihydrite) demonstrated that the rate and extent of isotope exchange between aqueous Fe(II) and solid 55Fe(III) was very similar to that of 2-line ferrihydrite formed in the absence of Si and which had not been allowed to dry. In contrast to un-dried ferrihydrite formed in the absence of Si, Si-ferrihydrite did not transform into a more crystalline Fe(III) mineral phase over the 7-day period of investigation. Reductive dissolution studies using ascorbic acid demonstrated that both dried Si-ferrihydrite and un-dried 2-line ferrihydrite were very reactive, suggesting these species may be major contributors to the rapid release of dissolved iron following flooding and the onset of conditions conducive to reductive dissolution in acid sulphate soil environments.  相似文献   

8.
The Mars Global Surveyor, Mars Exploration Rover, and Mars Express missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major recent mission findings are the presence of jarosite (a ferric sulfate salt), which requires formation from an acid-sulfate brine, and the occurrence of hematite and goethite on Mars. Recent ferric iron models have largely focused on 25 °C, which is a major limitation for models exploring the geochemical history of cold bodies such as Mars. Until recently, our work on low-temperature iron-bearing brines involved ferrous but not ferric iron, also obviously a limitation. The objectives of this work were to (1) add ferric iron chemistry to an existing ferrous iron model (FREZCHEM), (2) extend this ferrous/ferric iron geochemical model to lower temperatures (<0 °C), and (3) use the reformulated model to explore ferrous/ferric iron chemistries on Mars.The FREZCHEM model is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <−70 to 25 °C and the pressure range from 1 to 1000 bars. Ferric chloride and sulfate mineral parameterizations were based, in part, on experimental data. Ferric oxide/hydroxide mineral parameterizations were based exclusively on Gibbs free energy and enthalpy data. New iron parameterizations added 23 new ferrous/ferric minerals to the model for this Na-K-Mg-Ca-Fe(II)-Fe(III)-H-Cl-SO4-NO3-OH-HCO3-CO3-CO2-O2-CH4-H2O system.The model was used to develop paragenetic sequences for Rio Tinto waters on Earth and a hypothetical Martian brine derived from acid weathering of basaltic minerals. In general, model simulations were in agreement with field evidence on Earth and Mars in predicting precipitation of stable iron minerals such as jarosites, goethite, and hematite. In addition, paragenetic simulations for Mars suggest that other iron minerals such as lepidocrocite, schwertmannite, ferricopiapite, copiapite, and bilinite may also be present on the surface of Mars. Evaporation or freezing of the Martian brine led to similar mineral precipitates. However, in freezing, compared to evaporation, the following key differences were found: (1) magnesium sulfates had higher hydration states; (2) there was greater total aqueous sulfate (SO4T = SO4 + HSO4) removal; and (3) there was a significantly higher aqueous Cl/SO4T ratio in the residual Na-Mg-Cl brine. Given the similarities of model results to observations, alternating dry/wet and freeze/thaw cycles and brine migration could have played major roles in vug formation, Cl stratification, and hematite concretion formation on Mars.  相似文献   

9.
Scorodite, ferric arsenate and arsenical ferrihydrite are important arsenic carriers occurring in a wide range of environments and are also common precipitates used by metallurgical industries to control arsenic in effluents. Solubility and stability of these compounds are controversial because of the complexities in their identification and characterization in heterogeneous media. To provide insights into the formation of scorodite, ferric arsenate and ferrihydrite, series of synthesis experiments were carried out at 70 °C and pH 1, 2, 3 and 4.5 from 0.2 M Fe(SO4)1.5 solutions also containing 0.02-0.2 M Na2HAsO4. The precipitates were characterized by transmission electron microscopy, X-ray diffraction and X-ray absorption fine structure techniques. Ferric arsenate, characterized by two broad diffuse peaks on the XRD pattern and having the structural formula of FeAsO4·4-7H2O, is a precursor to scorodite formation. As defined by As XAFS and Fe XAFS, the local structure of ferric arsenate is profoundly different than that of scorodite. It is postulated that the ferric arsenate structure is made of single chains of corner-sharing Fe(O,OH)6 octahedra with bridging arsenate tetrahedra alternating along the chains. Scorodite was precipitated from solutions with Fe/As molar ratios of 1 over the pH range of 1-4.5. The pH strongly controls the kinetics of scorodite formation and its transformation from ferric arsenate. The scorodite crystallite size increased from 7 to 33 nm by ripening and aggregation. Precipitates, resulting from continuous synthesis at pH 4.5 from solutions having Fe/As molar ratios ranging from 1 to 4 and resembling the compounds referred to as ferric arsenate, arsenical ferrihydrite and As-rich hydrous ferric oxide in the literature, represent variable mixtures of ferric arsenate and ferrihydrite. When the Fe/As ratio increases, the proportion of ferrihydrite increases at the expense of ferric arsenate. Arsenate adsorption appears to retard ferrihydrite growth in the precipitates with molar Fe/As ratios of 1-4, whereas increased reaction gradually transforms two-line ferrihydrite to six-line ferrihydrite at Fe/As ratios of 5 and greater.  相似文献   

10.
Aluminum, one of the most abundant elements in soils and sediments, is commonly found co-precipitated with Fe in natural Fe(III) (hydr)oxides; yet, little is known about how Al substitution impacts bacterial Fe(III) reduction. Accordingly, we investigated the reduction of Al substituted (0-13 mol% Al) goethite, lepidocrocite, and ferrihydrite by the model dissimilatory Fe(III)-reducing bacterium (DIRB), Shewanella putrefaciens CN32. Here we reveal that the impact of Al on microbial reduction varies with Fe(III) (hydr)oxide type. No significant difference in Fe(III) reduction was observed for either goethite or lepidocrocite as a function of Al substitution. In contrast, Fe(III) reduction rates significantly decreased with increasing Al substitution of ferrihydrite, with reduction rates of 13% Al-ferrihydrite more than 50% lower than pure ferrihydrite. Although Al substitution changed the minerals’ surface area, particle size, structural disorder, and abiotic dissolution rates, we did not observe a direct correlation between any of these physiochemical properties and the trends in bacterial Fe(III) reduction. Based on projected Al-dependent Fe(III) reduction rates, reduction rates of ferrihydrite fall below those of lepidocrocite and goethite at substitution levels equal to or greater than 18 mol% Al. Given the prevalence of Al substitution in natural Fe(III) (hydr)oxides, our results bring into question the conventional assumptions about Fe (hydr)oxide bioavailability and suggest a more prominent role of natural lepidocrocite and goethite phases in impacting DIRB activity in soils and sediments.  相似文献   

11.
Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10−11 mol Fe(II) m−2 g−1), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)aq and bacterially-generated Fe(II)aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area.  相似文献   

12.
尾矿酸浸液制备氢氧化铁过程中施威特曼石的形成与转变   总被引：4，自引：1，他引：3  
尾矿酸浸液在制备氢氧化铁的过程中,由于逐渐滴加碱液正好形成了pH值为2.8～3.8的高SO2-4、高Fe环境,因而生成了施威特曼石.施威特曼石是一种亚稳定矿物,随着时间的延长和体系状态改变,它可以转变为更稳定的针铁矿(氢氧化铁).考查了pH值、温度及时间对施威特曼石相转变的影响.结果表明,在60℃条件下,在pH值为12的碱溶液中转化36 h,施威特曼石可完全转变为Fe(OH)3.  相似文献   

13.
Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe2+ and Mn2+ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pHpzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe2+ (assuming surface detachment of Fe2+ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe2+ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe3+ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.  相似文献   

14.
硫酸盐还原菌是厌氧环境中参与砷形态转化的重要微生物种群,其介导的生物地球化学循环过程对铁氧化物表面吸附态砷迁移转化的影响亟待深入研究.选取江汉平原典型高砷含水层原位沉积物分离纯化出一株严格厌氧硫酸盐还原菌Desulfovibrio JH-S1,对其进行砷和铁还原能力鉴定,并通过模拟培养实验探究硫酸盐还原菌参与下的铁矿物相转化对吸附态砷迁移的影响.Desulfovibrio JH-S1具有Fe(III)还原能力,无硫和有硫体系中Fe(III)均能被还原,但在硫酸盐充足条件下铁还原量显著增加;该菌株不具备As(V)还原能力,但添加硫酸盐的培养体系中As(V)去除率可达96%以上.Desulfovibrio JH-S1能够还原硫酸盐从而促进载砷的水铁矿还原转化为纤铁矿,并导致吸附的砷释放.江汉平原高砷含水层土著硫酸盐还原菌兼具硫酸盐/铁还原功能,参与了高砷含水层系统中砷-铁-硫耦合循环,对高砷地下水的形成具有重要作用.   相似文献   

15.
Acid mine drainage (AMD) is one of the severe environmental problems that coal mines are facing. Generation of AMD in the northeastern part of India due to the coal mining activities has long been reported. However detailed geochemical characterization of AMD and its impact on water quality of various creeks, river and groundwater in the area has never been reported. Coal and coal measure rocks in the study area show finely disseminated pyrite crystals. Secondary solid phases, resulted due to oxidation of pyrite, occur on the surface of coal, and are mainly consisting of hydrated sulphate complexes of Fe and Mg (copiapite group of minerals). The direct mine discharges are highly acidic (up to pH 2.3) to alkaline (up to pH 7.6) in nature with high concentration of SO42−. Acidic discharges are highly enriched with Fe, Al, Mn, Ni, Pb and Cd, while Cr, Cu, Zn and Co are below their maximum permissible limit in most mine discharges. Creeks that carrying the direct mine discharges are highly contaminated; whereas major rivers are not much impacted by AMD. Ground water close to the collieries and AMD affected creeks are highly contaminated by Mn, Fe and Pb. Through geochemical modeling, it is inferred that jarosite is stable at pH less than 2.5, schwertmannite at pH less than 4.5, ferrihydrite above 5.8 and goethite is stable over wide range of pH, from highly acidic to alkaline condition.  相似文献   

16.
Evidence for a simple pathway to maghemite in Earth and Mars soils   总被引：1，自引：0，他引：1  
Soil magnetism is greatly influenced by maghemite (γ-Fe2O3), the presence of which is usually attributed to the following: (1) heating of goethite in the presence of organic matter; (2) oxidation of magnetite (Fe3O4); or (3) dehydroxylation of lepidocrocite (γ-FeOOH). Formation of the latter two minerals in turn requires the presence of Fe(II) in the system. No laboratory experiment or soil study to date has shown whether maghemite can form from ferrihydrite, a poorly crystalline Fe(III) oxide [∼Fe4.5(O,OH,H2O)13.5], below 250°C. However, ferrihydrite is the usual precursor of goethite (α-FeOOH) and hematite (α-Fe2O3), the most frequently occurring crystalline Fe(III) oxides in soils. Here is presented in vitro evidence that ferryhidrite can partly transform into maghemite at 150°C. This transformation occurs upon aging of ferrihydrite precipitated in the presence of phosphate or other ligands capable of ligand exchange with Fe-OH surface groups. This maghemite coexists with hematite and is a transient phase in the transformation of ferrihydrite to hematite, which is apparently stabilized by the adsorbed ligands. Its particle size is small (10 to 30 nm), and its X-ray diffraction pattern exhibits superstructure reflections. The possible formation of maghemite in Mars and in different Earth soils can partly be explained in the light of this pathway with minimal ad hoc assumptions.  相似文献   

17.
The poorly crystalline Fe(III) hydroxide ferrihydrite is considered one of the most important sinks for (in)organic contaminants and nutrients within soils, sediments, and waters. The ripening of ferrihydrite to more stable and hence less reactive phases such as goethite is catalyzed by surface reaction with aqueous Fe(II). While ferrihydrite within most natural environments contains high concentrations of adsorbed or co-precipitated cations (particularly Al), little is known regarding the impact of these cations on Fe(II)-induced transformation of ferrihydrite to secondary phases. Accordingly, we explored the extent, rates, and pathways of Fe(II)-induced secondary mineralization of Al-ferrihydrites by reacting aqueous Fe(II) (0.2 and 2.0 mM) with 2-line ferrihydrite containing a range of Al levels substituted within (6-24 mol% Al) or adsorbed on the surface (0.1-27% Γmax). Here, we show that regardless of the Fe(II) concentration, Al substituted within or adsorbed on ferrihydrite results in diminished secondary mineralization and preservation of ferrihydrite. In contrast to pure ferrihydrite, the concentration of Fe(II) may not in fact influence the mineralization products of Al-compromised ferrihydrites. Furthermore, the secondary mineral profiles upon Fe(II) reaction with ferrihydrite are not only a function of Al concentration but also the mode of Al incorporation. While Al substitution impedes lepidocrocite formation and magnetite nucleation, Al adsorption completely inhibits goethite formation and appears to have a lesser impact on magnetite nucleation. When normalized to total Al content associated with ferrihydrite, Al adsorption results in greater degree of ferrihydrite preservation relative to Al substitution. These findings provide insight into mechanisms that may be responsible for ferrihydrite preservation and low levels of secondary magnetite typically found in sedimentary environments. Considering the preponderance of cation substitution within and adsorption on ferrihydrite in soils and sediments, the reactivity of natural (compromised) ferrihydrites and the subsequent impact on mineral evolution needs to be more fully explored.  相似文献   

18.
Trichloroethylene (TCE) is one of the most common and persistent groundwater contaminants encountered at hazardous waste sites around the world. A growing body of evidence indicates that iron sulfides play an important role in degrading TCE in natural environments and in engineered systems designed for groundwater cleanup. In this study, we investigate transformation processes of iron sulfides and consequent impacts on TCE degradation using batch experimental techniques, transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). Our results show that mackinawite is highly reactive toward TCE and no detectable mineralogical changes were detected during the course of reaction. However, freeze-dried FeS transformed to a mixture of mackinawite and greigite during the freeze drying process, with further mineralogical changes during reaction with TCE to lepidocrocite, goethite and pyrite. Newly formed lepidocrocite is a transient phase, with conversion to goethite over time. TCE transformation kinetics show that freeze-dried FeS is 20-50 times less reactive in degrading TCE than non-freeze-dried FeS, and the TCE degradation rate increases with pH (from 5.4 to 8.3), possibly due to an increase of surface deprotonation or electron transfer at higher pH. Results suggest that freeze drying could cause FeS particle aggregation, decreased surface area and availability of reactive sites; it also could change FeS mineralogy and accelerate mineral transformation. These aspects could contribute to the lower reactivity of freeze-dried FeS toward TCE degradation. Modeling results show that FeS transformation in natural environments depends on specific biogeochemical conditions, and natural FeS transformation may affect mineral reactivity in a similar way as compared to the freeze drying process. Rapid transformation of FeS to FeS2 could significantly slow down TCE degradation in both natural and engineered systems.  相似文献   

19.
We studied biomimetic mineralization of self-assembling polymer matrices in order to develop a model for biomineralization of iron oxides in nature. High-resolution transmission electron microscopy (HRTEM), rheology, and fluorescence probe analyses show self-assembly of acidic polysaccharide alginic acid (Alg) to form fibrils in dilute solutions. The resulting Alg fibrils are subsequently mineralized by FeOOH in a biomimetically controlled process. Experiments were conducted in pH 9.2 solutions containing millimolar concentrations of iron at 38°C. The unperturbed state of the hybrid mineral-organic structures was studied by characterization of samples of interfacial films collected from an inorganic-organic interface. Progress of mineralization over a 4-week period was followed by HRTEM, energy-dispersive X-ray analysis, and selected area electron diffraction. Morphologies of hybrid structures determined by HRTEM, X-ray powder diffraction, Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, and selected area electron diffraction suggest formation of iron (III) oxyhydroxide phases and their assembly through a variety of mechanisms, possibly occurring simultaneously. An initial step involves precipitation of nanometer-scale amorphous particles and two-line ferrihydrite in bulk solution. Some nanoparticles assemble into chains that recrystallize to form akaganeite (β-FeOOH), presumably via a solid-state transformation pathway. Small organic molecules may mediate this process by stabilizing the akaganeite structure and controlling particle assembly. Ferrihydrite particles also bind to acidic polysaccharide fibrils and are transformed to ordered arrays of akaganeite. The parallel orientation of adjacent akaganeite nanocrystals may be inherited from the orientation of precursor ferrihydrite, possibly conferred during attachment of ferrihydrite to the polyacid fibrils. Alternatively, particle-particle interactions may induce orientation, leading to recrystallization. Subsequently, akaganeite is transformed to goethite that is characterized by nanoscale porosity and fine-scale twinning on {021}. Dislocation, twin, and nanopore microstructures are consistent with coarsening by nanoparticle assembly, possibly templated by the substrate. Nanoparticle assembly to generate biomimetic hybrid materials may be relevant to formation of complex natural biominerals in natural systems where mineral nanoparticles, small organic molecules, and more complex polymers coexist.  相似文献   

20.
The reaction between dissolved sulfide and synthetic iron (oxyhydr)oxide minerals was studied in artificial seawater and 0.1 M NaCl at pH 7.5 and 25°C. Electron transfer between surface-complexed sulfide and solid-phase Fe(III) results in the oxidation of dissolved sulfide to elemental sulfur, and the subsequent dissolution of the surface-reduced Fe. Sulfide oxidation and Fe(II) dissolution kinetics were evaluated for freshly precipitated hydrous ferric oxide (HFO), lepidocrocite, goethite, magnetite, hematite, and Al-substituted lepidocrocite. Reaction kinetics were expressed in terms of an empirical rate equation of the form:
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