针铁矿及其热活化产物除Sb(Ⅲ)效果对比

以合成针铁矿为原料,通过煅烧法获得比表面积分别为85.74和22.65 m2/g的多孔纳米赤铁矿和磁赤铁矿,通过静态实验探究了针铁矿和煅烧产物的Sb(Ⅲ)吸附性能.结果 表明,Sb(Ⅲ)吸附效率为赤铁矿＞磁赤铁矿＞针铁矿,其前二者效率显著高于针铁矿.Sb(Ⅲ)在3种矿物表面的吸附均为快速的化学吸附,吸附在2h内即可接近平衡,符合准二级动力学反应和Freundlich等温吸附模型,为自发进行的吸热反应,升高温度有利于反应的进行.在45 ℃、pH=7的条件下,针铁矿、赤铁矿和磁赤铁矿的最大吸附量分别可达16.04、50.44和33.53 mg/g.pH对赤铁矿和磁赤铁矿的Sb(Ⅲ)吸附效率影响不大,但pH升高会导致针铁矿的吸附能力降低.CO32-、SiO44-、PO43-和胡敏酸会与Sb(Ⅲ)竞争吸附位,抑制3种矿物对Sb(Ⅲ)的吸附,但这种抑制作用只在阴离子浓度较高的条件下有效.研究认为磁赤铁矿具有更多的表面活性位和较强的磁回收能力,是优于针铁矿和赤铁矿的含Sb(Ⅲ)废水处理材料.     

长江三角洲东部岛屿风尘堆积赤铁矿和针铁矿含量及古气候意义

长江三角洲东延海域嵊山岛屿风尘堆积地层是记录晚更新世晚期东亚季风演变的重要载体。采用漫反射光谱（DRS）法、柠檬酸钠-重碳酸钠-连二亚硫酸钠（CBD）浸提法结合标准赤铁矿、针铁矿建立标准铁氧化物含量与反射率之间的校准方程,定量重建了东部岛屿风尘堆积的赤铁矿、针铁矿含量的变化特征。结果显示,东海嵊山岛风尘堆积中赤铁矿的含量为0.18%~0.40%,平均值为0.31%,针铁矿的含量为0.7%~1.19%,平均值为1.11%。根据赤铁矿、针铁矿含量特征结合地球化学和环境磁学参数,分析其记录的古环境信息:54~46 ka B.P.时期内气候相对干燥,季风降水减弱,46~39 ka B.P.时期内气候相对潮湿,季风降水增强;46±4 ka B.P.时期的高值可能指示了一个冷事件。     

针铁矿和蒙脱石对菲的吸附解吸行为与热力学研究

采用批量振荡吸附平衡法设计针铁矿和蒙脱石对菲的吸附解吸试验,对比研究了针铁矿和蒙脱石对菲的吸附解吸行为,并考察了不同K＋浓度的溶液对蒙脱石吸附菲的影响,比较分析了线性吸附模型和Freundlich吸附模型描述矿物吸附等温线的准确性,并从吸附热力学角度探讨了矿物的吸附机理。结果表明：针铁矿和蒙脱石对菲的吸附解吸均表现出明显的非线性和解吸滞后现象;相对于线性吸附模型来说,针铁矿和蒙脱石对菲的吸附解吸更符合Freundiich吸附模型;与蒙脱石相比,针铁矿对菲的吸附更为显著,且具有更好的稳定性;溶液中软阳离子K＋的存在使蒙脱石对菲的吸附能力得到显著提高;菲在蒙脱石和针铁矿上的吸附过程是一个自发放热,同时伴随着熵值减小的过程;随着温度的升高,蒙脱石和针铁矿对菲的吸附能力均减弱。     

磷灰石对湖泊沉积物中水铁矿稳定性的制约

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。     

氧化铁矿物催化分解苯酚的动力学速率及其产物特征

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。     

针铁矿/水界面反应性的实验研究

选择针铁矿对Pb2+、Cu2+、Cd2+等3种重金属离子的吸附实验,开展矿物/水界面反应性研究.金属离子(M2+)在矿物-水溶液间分配有多种表面反应机制,这些表面反应发生作用的条件主要取决于吸附质水化学性质和矿物表面荷电性,因此,溶液pH值是影响矿物/水界面反应性的关键因素.在不同pH值条件下, 表面羟基可通过发生质子化或去质子化反应而使得矿物表面产生荷电性并发生改变,而金属离子的水解则可显著加快金属羟基配合物的形成,从而进一步增强了矿物/水界面反应.本实验条件下针铁矿表面对重金属离子的吸着量随pH值升高而升高,在一个较窄的pH值范围内吸附率急剧升高,呈S形分布.针铁矿对3种不同的重金属离子的吸附能力的强弱顺序是Cu2+＞Pb2+＞Cd2+.无论是Langmuir方程还是Freundlich方程,都能较好拟合针铁矿对重金属离子的等温吸附过程.Freundlich方程的n值均在0.1～0.5之间,说明重金属离子在针铁矿表面的吸附并不能简单地归结为单配位或双配位模式,可能存在着多种吸附结合形态.表观吸附常数KM值的变化规律,说明重金属离子与针铁矿表面反应模式及其表面吸附形态发生了变化,具体的吸附形态还有待谱学研究进一步证实.     

铁锰氧化物对苯酚氧化降解的实验研究

为了考察铁锰氧化物对酚类污染物的氧化降解能力,采用天然以及合成的铁锰氧化物对苯酚的氧化降解进行对比实验研究。土壤中铁锰氧化物样品分别为天然针铁矿及氧化锰,合成铁锰氧化物样品分别为合成针铁矿及软锰矿。结果表明：苯酚与铁锰氧化物发生氧化还原作用时,还可能与土壤中杂质发生吸附等作用;铁锰氧化物还原反应强度随着反应介质pH值的升高而迅速下降;可用零级反应动力学方程拟合铁氧化物还原溶解反应,针铁矿溶解反应的强度与介质的pH值呈负相关关系;天然针铁矿对酚类污染物的氧化降解能力明显高于合成针铁矿,pH值对天然针铁矿溶解反应影响较大;可用一级指数衰减方程拟合锰氧化物还原溶解反应,锰氧化物溶解反应的强度与介质的pH值呈指数衰减关系;pH值对软锰矿还原溶解反应的影响大于对土壤中氧化锰的影响,pH值越小,影响越显著;对比pH值对铁和锰还原作用的影响发现,在pH=6.5时,锰氧化物仍有较强的氧化性能。     

几种铁（氢）氧化物对溶液中磷的吸附作用对比研究

铁(氢)氧化物不仅是土壤中广泛存在的矿物,也是重要的矿物资源。表生地质作用形成的针铁矿、赤铁矿和无定形氢氧化铁都具有纳米尺度,具有很高的表面积,表现出对磷的专性吸附,是低浓度磷的潜在吸附材料。本文通过铁(氢)氧化物对水溶液中磷酸根的等温吸附实验,初步对比研究了针铁矿、合成氧化铁黄、赤铁矿和无定形氢氧化铁对水中低浓度磷的吸附作用。结果表明,无定形氢氧化铁对水溶液中磷酸根的吸附能力最强(对低浓度磷的吸附达到5.5mg/g),其次是氧化铁黄和针铁矿,赤铁矿的吸附能力最差。几种铁(氢)氧化物对磷吸附容量的差别主要受比表面积控制。无定形氢氧化铁、合成氧化铁黄、针铁矿、赤铁矿对磷的吸附符合Freundlich等温方程。针铁矿和赤铁矿对磷的吸附动力学符合双常数速率方程。     

铁锰氧化物在碱性条件下对镉的吸附特征研究

实验研究了不同的pH值、初始离子浓度、矿物用量、温度以及时间等因素对针铁矿和软锰矿吸附镉的影响。结果表明:在pH值从酸性到近中性的范围内,两种氧化矿物对镉的吸附量增加较快,然后在碱性条件下吸附量保持着最大值;反应前后两种氧化矿物溶液的pH值均有不同程度的变化,其中针铁矿和软锰矿的临界pH值分别为8和6.5;两种矿物对镉的吸附在6 h左右达到了吸附平衡,吸附等温线都较好地符合Freundlich等温方程式;随着两种氧化物用量的增加,其吸附量也有增加;室温下,针铁矿和软锰矿对镉的吸附效果较好。     

应用同步辐射技术解析黄色-红色石英质玉石中的致色矿物

质地细腻、颜色多彩的隐晶质-微粒脉石英在我国珠宝行业称为石英质玉石,颜色是石英质玉石价值判断的主要因素之一,揭示其致色矿物及致色机理对于研究石英质玉石的颜色评价指标和矿床成因具有重要意义,但前人并未直接获得致色矿物的准确信息。本文运用上海光源(SSRF)BL15U1线站的同步辐射硬X射线,使用μ-XRF和μ-XRD技术对黄色和红色隐晶质-微粒脉石英中的致色矿物进行了研究。结果表明,黄色石英质玉石由赋存于石英颗粒间或微裂纹中的针铁矿(特征衍射峰0.49574、0.41594、0.26887、0.25705、0.25189、0.24510、0.21806、0.17133 nm)或其集合体致色,红色石英质玉石由赋存于石英颗粒间或微裂纹中的赤铁矿(特征衍射峰0.36774、0.27091、0.25200 nm)或其集合体致色,黄色-红色石英质玉的颜色由针铁矿和赤铁矿共同致色,赤铁矿的显色能力要高于针铁矿。本文获得了石英质玉石中致色矿物的直接数据,为玉石结晶温度与致色机理的探讨、石英质玉石的品质评价提供了依据。     

Structural constraints of ferric (hydr)oxides on dissimilatory iron reduction and the fate of Fe(II)

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.     

Sorption and desorption of dissolved organic phosphorus onto iron (oxyhydr)oxides in seawater

Sorption of phosphorus (P) onto particulate surfaces significantly influences dissolved P concentrations in aquatic environments. We present results of a study contrasting the sorption behavior of several dissolved organic phosphorus (DOP) compounds and phosphate onto three commonly occurring iron (oxyhydr)oxides (Fe_ox): ferrihydrite, goethite, and hematite. The DOP compounds were chosen to represent a range of molecular weights and structures, and include: adenosine triphosphate (ATP), adenosine monophosphate (AMP), glucose-6-phosphate (G6P), and aminoethylphosphonic acid (AEP).All P compounds displayed decreasing sorption as a function of crystallinity of the Fe_ox substrate, with ferrihydrite adsorbing the most, hematite the least. In general, maximum sorption density decreased with increasing molecular weight of P compound; sorption of G6P onto goethite and hematite excepted. P compound size and structure, and the nature of the Fe_ox substrate all appear to play a role dictating relative sorption capacity. Failure of a simple, 1-step sorption-desorption model to describe the data suggests that P sorption cannot be explained by a simple balance between sorption and desorption. Instead, the data are consistent with a 2-step sorption model consisting of an initial rapid surface sorption, followed by a slow, solid-state diffusion of P from surface sites into particle interiors. Desorption experiments provide additional support for the 2-step sorption model.Without exception, DOP compounds showed less efficient sorption than did orthophosphate. This suggests that in aquatic systems enriched in reactive Fe_ox, whether as suspended particulates in the water column or in benthic sediments, DOP bioavailability may exceed that of orthophosphate. Since biological uptake of P from DOP requires enzymatic cleavage of orthophosphate, a system enriched in DOP relative to orthophosphate may impact ecosystem community structure.     

Fast transformation of iron oxyhydroxides by the catalytic action of aqueous Fe(II)

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.     

主要铁氧化物催化H2O2 氧化地下水中硝基苯实验

实验研究了含水层介质中主要铁氧化物催化H2O2 氧化地下水中硝基苯的机理和主要影响因素,为硝基苯污染地下水的原位化学修复技术提供了一定的理论依据。实验模拟在地下环境温度8 ℃ ～ 10 ℃条件下,利用动力学方程对硝基苯的衰减进行拟合,结果表明,其衰减系数K = 0. 044 3 min － 1 ; 硝基苯与H2O2 的最佳摩尔比为1∶200; 主要铁氧化物催化H2O2 氧化硝基苯能力依次为: 磁铁矿＞ 针铁矿＞ 氢氧化铁＞ 赤铁矿。     

Comparative data on the volatile component composition of magma

Ferrihydrite (2.5 Fe₂O₂-4.5 H₂O) is an unstable colloidal mineral. It dissolves in highly alkaline solutions and is precipitated from them in the form of goethite. Jarosite is stable at very low pH but is decomposed at higher values of pH with separation of iron oxides. Experiments show that in rapid decomposition of jarosite a protohematite substance, ferrihydrite, is formed. This transformation occurs at moderate pH values when solutions percolate through the aggregates of jarosite. Ferrihydrite, an unstable colloidal hydrated oxide of ferric iron, changes spontaneously to stable hematite with time. Very slow decomposition of jarosite results in its replacement by iron hydroxide, goethite. Under laboratory conditions in alkaline solutions lepidocrocite may be obtained from jarosite. The synthesis of this iron hydroxide passes through a stage of intermediate products: ferrihydrite and hydrated ferric oxide - ferriprotolepidocrocite, formed by solution of ferrihydrite in strongly alkaline solutions. The transformation of ferriprotolepidocrocite into lepidocrocite may be regarded as a topotactic reaction. —Authors.     

Molecular-scale mechanisms of distribution and isotopic fractionation of molybdenum between seawater and ferromanganese oxides

The distribution of Mo between seawater and marine ferromanganese oxides has great impacts on concentration and isotopic composition of Mo in modern oxic seawater. To reveal the adsorption chemistry of Mo to ferromanganese oxides, we performed (i) detailed structural analyses of Mo surface complexes on δ-MnO₂, ferrihydrite, and hydrogenetic ferromanganese oxides by L₃- and K-edge XAFS, and (ii) adsorption experiments of Mo to δ-MnO₂ and ferrihydrite over a wide range of pHs, ionic strengths, and Mo concentrations. XAFS analyses revealed that Mo forms distorted octahedral (Oh) inner-sphere complexes on δ-MnO₂ whereas it forms a tetrahedral (Td) outer-sphere complex on ferrihydrite. In the hydrogenetic ferromanganese oxides, the dominant host phase of Mo was revealed to be δ-MnO₂. These structural information are consistent with the macroscopic behaviors of Mo in adsorption experiments, and Mo concentration in modern oxic seawater can be explained by the equilibrium adsorption reaction on δ-MnO₂. In addition, the large isotopic fractionation of Mo between seawater and ferromanganese oxides detected in previous studies can be explained by the structural difference between and adsorbed species on the δ-MnO₂ phase in ferromanganese oxides. In contrast, smaller fractionation of Mo isotopes on ferrihydrite is due to little change in the Mo local structures during its adsorption to ferrihydrite.The structures of Mo species adsorbed on crystalline Fe (oxyhydr)oxides, goethite, and hematite were also investigated at pH 8 and I = 0.70 M (NaNO₃). Our XAFS analyses revealed that Mo forms inner-sphere complexes on both minerals: Td edge-sharing (46%) and Oh double corner-sharing (54%) for goethite, and Td double corner-sharing (14%) and Oh edge-sharing (86%) for hematite. These structural information, combined with those for amorphous ferrihydrite and δ-MnO₂, show the excellent correlation with the magnitude of adsorptive isotopic fractionation of Mo reported in previous studies: the proportion of Oh species or their magnitude of distortion in Mo surface complexes become larger in the order of ferrihydrite < goethite < hematite < δ-MnO₂, a trend identical to the magnitude of isotopic fractionation.Based on the comparison with previous reports for Mo surface species on various oxides, the chemical factors that affect Mo surface complex structures were also discussed. The hydrolysis constant of cation in oxides, log K_OH (or the acidity of the oxide surfaces, PZC) is well correlated with the mode of attachment (inner- or outer-sphere) of Mo surface complexes. Furthermore, the symmetric change in Mo species from Td to Oh is suggested to be driven by the formation of inner-sphere complexes on specific sites of the oxide surfaces.     

泥炭沼泽源酚酸对铁有机复合体的溶解作用及其环境意义

泥炭沼泽是具有全球意义的湿地类型,研究泥炭沼泽源酚酸对铁有机复合体的溶解作用有助于深入了解铁碳耦合地球化学循环过程.以中国东北金川泥炭沼泽为研究对象,提取了泥炭腐殖质,并实验合成了铁有机复合体及一系列的铁氧化物.选择原儿茶酸、咖啡酸和没食子酸等代表性泥炭沼泽源酚酸对铁有机复合体以及铁氧化物等系统开展了不同条件下的溶解试验.结果表明酚酸对无定型的水铁矿和新合成的铁有机复合溶解能力相对较弱,而对结晶态的赤铁矿、针铁矿和老化后的铁有机复合体的溶解能力较强.pH值、酚酸浓度和铁氧化物自身的结构和组成都对铁矿物的溶解作用产生影响.反映了铁有机复合体在酚酸溶液体系中比无机铁氧化物更稳定,这与泥炭沼泽中有机结合态铁比例较高、而普通矿质土壤中结晶态铁氧化物占比更大的事实相吻合.证明了铁有机复合体是泥炭沼泽中影响铁碳循环耦合的关键载体.泥炭沼泽中铁碳作用十分复杂,既能以铁有机络合物形式向海洋等水生生态系统输出大量的溶解性铁,也能通过铁有机复合体的形成促进泥炭沼泽有机碳的保存,进而影响全球铁碳循环耦合,具有重要的生态环境意义.      

Adsorption of Pentachlorophenol onto Oxide and Clay Minerals： Surface Reaction Model and Environmental Implications

The adsorption of pentachlorophenol （PCP） onto quartz, kaolinite, illite, montmorillonite and iron oxides has been investigated by batch equilibrium techniques. The pH-dependent isotherms are curves with peak values, the position of which is at about pH = 5-6 depending on the mineral species. Based on distribution of both speciation of surface hydroxyls on minerals and PCP in solution a surface reaction model involving surface complexation and surface electrostatic attraction is presented to fit the pH-dependent isotherms, and both reaction constants are calculated. The results show that on quartz and phyllosilicate minerals the predominant adsorption reaction is surface complexation, meanwhile both of surface electrostatic attraction and surface complexation are involved on the iron oxide minerals. The reaction constants of surface electrostatic adsorption are usually one to three orders in magnitude, larger than that of surface complexation. The concentration-dependent isotherms can be well fitted by Langmnir equation with the correlation coefficient R〉0.93 for kaolinite and iron oxides. The maximum adsorption is found in the order： hematite 〉 lepidocrocite 〉 goethite 〉 kaolinite 〉 quartz 〉 montmorillonite ≈ illite, which can be interpreted by consideration of both reaction mechanism and surface hydroxyl density. The significant adsorption of PCP onto mineral surfaces suggests that clay and iron oxide minerals will play an important role as HIOCs are adsorbed in laterite or latertoid soil, which is widespread in South China.     

Aggregate-scale spatial heterogeneity in reductive transformation of ferrihydrite resulting from coupled biogeochemical and physical processes

Iron (hydr)oxides are ubiquitous in soils and sediments and play a dominant role in the geochemistry of surface and subsurface environments. Their fate depends on local environmental conditions, which in structured soils may vary significantly over short distances due to mass-transfer limitations on solute delivery and metabolite removal. In the present study, artificial soil aggregates were used to investigate the coupling of physical and biogeochemical processes affecting the spatial distribution of iron (Fe) phases resulting from reductive transformation of ferrihydrite. Spherical aggregates made of ferrihydrite-coated sand were inoculated with the dissimilatory Fe-reducing bacterium Shewanella putrefaciens strain CN-32, and placed into a flow reactor, the reaction cell simulates a diffusion-dominated soil aggregate surrounded by an advective flow domain. The spatial and temporal evolution of secondary mineralization products resulting from dissimilatory Fe reduction of ferrihydrite were followed within the aggregates in response to a range of flow rates and lactate concentrations. Strong radial variations in the distribution of secondary phases were observed owing to diffusively controlled delivery of lactate and efflux of Fe(II) and bicarbonate. In the aggregate cortex, only limited formation of secondary Fe phases were observed over 30 d of reaction, despite high rates of ferrihydrite reduction. Under all flow conditions tested, ferrihydrite transformation was limited in the cortex (70-85 mol.% Fe remained as ferrihydrite) because metabolites such as Fe(II) and bicarbonate were efficiently removed in outflow solutes. In contrast, within the inner fractions of the aggregate, limited mass-transfer results in metabolite (Fe(II) and bicarbonate) build-up and the consummate transformation of ferrihydrite - only 15-40 mol.% Fe remained as ferrihydrite after 30 d of reaction. Goethite/lepidocrocite, and minor amounts of magnetite, formed in the aggregate mid-section and interior at low lactate concentration (0.3 mM) after 30 d of reaction. Under high lactate (3 mM) concentration, magnetite was observed only as a transitory phase, and rather goethite/lepidocrocite and siderite were the dominant secondary mineralization products. Our results illustrate the importance of slow diffusive transport of both electron donor and metabolites concentrations and concomitant biogeochemical reactions within soils and sediments, giving rise to heterogeneous products over small spatial (μm) scale.