Interactions between magnetite and humic substances: redox reactions and dissolution processes

Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe₃O₄) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.

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Cu and Zn ternary surface complex formation with SO4 on ferrihydrite and schwertmannite

The use of adsorption data from single sorbate systems to model metal adsorption in SO₄-rich waters, such as acid mine drainage, can lead to inaccurate predictions of metal speciation. The adsorption of Cu and Zn on ferrihydrite, for example, is enhanced at low pH values in the presence of SO₄. This effect can only be accurately modeled using the diffuse layer model and surface complexation theory if ternary surface complexes, ≡FeOHCuSO₄ or ≡FeOHZnSO₄, are taken into consideration. Intrinsic adsorption constants for the formation of these ternary complexes on ferrihydrite have been derived from experimental data. When included in the model, Cu and Zn adsorption in the presence of SO₄ is accurately predicted for a wide range of metal, ferrihydrite and SO₄ concentrations. Adsorption of Cu and Zn onto the SO₄-rich Fe oxyhydroxide, schwertmannite, could also be accurately predicted and is indistinguishable from adsorption onto ferrihydrite in the presence of high solution SO₄ concentrations (e.g. 0.01 mol kg⁻¹ SO₄).     

X-ray absorption spectroscopy study on the effect of hydroxybenzoic acids on the formation and structure of ferrihydrite

Organic ligands are known to interfere with the polymerization of Fe(III), but the extent of interference has not been systematically studied as a function of structural ligand properties. This study examines how the number and position of phenol groups in hydroxybenzoic acids affect both ferrihydrite formation and its local (<5 Å) Fe coordination. To this end, acid Fe(III) nitrate solutions were neutralized up to pH 6.0 in the presence of 4-hydroxybenzoic acid (4HB), 2,4-dihydroxybenzoic acid (2,4DHB), and the hydroquinone 3,4-dihydroxybenzoic acid (3,4DHB). The initial molar ligand/Fe ratios ranged from 0 to 0.6. The precipitates were dialyzed, lyophilized, and subsequently studied by X-ray absorption spectroscopy and synchrotron X-ray diffraction. The solids contained up to 32 wt.% organic C (4HB ∼ 2,4DHB < 3,4DHB). Only precipitates formed in 3,4DHB solutions comprised considerable amounts of Fe(II) (Fe(II)/Fe_tot ≤ 6 mol%), implying the abiotic mineralization of the catechol-group bearing ligand during Fe(III) hydrolysis under oxic conditions. Hydroxybenzoic acids decreased ferrihydrite formation in the order 4HB ∼ 2,4DHB ? 3,4DHB, which documents that phenol group position rather than the number of phenol groups controls the ligand’s interaction with Fe(III). The coordination numbers of edge- and double corner-sharing Fe in the precipitates decreased by up to 100%. Linear combination fitting (LCF) of Fe K-edge X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra revealed that this decrease was due to increasing amounts of organic Fe(III) complexes in the precipitates. Although EXAFS derived coordination numbers of Fe in ferrihydrite remained constant within error, all organic ligands decreased the coherently scattering domain (CSD) size of ferrihydrite as indicated by synchrotron X-ray diffraction analysis (4HB < 2,4DHB ? 3,4DHB). With decreasing particle size of ferrihydrite its Fe(O,OH)₆ octahedra became progressively distorted as evidenced by an increasing loss of centrosymmetry of the Fe sites. Pre-edge peak analysis of the Fe K-edge XANES spectra in conjunction with LCF results implied that ferrihydrite contains on an average 13 ± 3% tetrahedral Fe(III), which is in very good agreement with the revised single-phase structural model of ferrihydrite (Michel, F. M., Barron, V., Torrent, J., Morales, M. P. et al. (2010) Ordered ferrimagnetic form of ferrihydrite reveals links among structure, composition, and magnetism. Proc. Natl. Acad. Sci. USA107, 2787-2792). The results suggest that hydroxybenzoic acid moieties of natural organic matter (NOM) effectively suppress ferrihydrite precipitation as they kinetically control the availability of inorganic Fe(III) species for nucleation and/or polymerization reactions. As a consequence, NOM can trigger the formation of small ferrihydrite nanoparticles with increased structural strain. These factors may eventually enhance the biogeochemical reactivity of ferrihydrite formed in NOM-rich environments. This study highlights the role of hydroquinone structures of NOM for Fe complexation, polymerization, and redox speciation.     

Effect of citrate on the local Fe coordination in ferrihydrite, arsenate binding, and ternary arsenate complex formation

In oxic environments contaminated with arsenate (As(V)), small polyhydroxycarboxylates such as citrate may impact the structure of precipitating ferrihydrite (Fh) and thus the surface speciation of As(V). In this study, ‘2-line’ Fh was precipitated from ferric nitrate solutions that were neutralized to pH 6.5 in the presence of increasing citrate concentrations and in the absence or presence of As(V). The initial citrate/Fe and As/Fe ratios were 0-50 mol% and 5 mol%, respectively. The reaction products, enriched with up to 0.32 mol citrate per mole Fe, were characterized by X-ray diffraction, transmission electron microscopy, and Fe and As K-edge X-ray absorption spectroscopy. Citrate decreased the particle size of Fh by impairing the polymerization of Fe(O,OH)₆ octahedra via edge and corner linkages. In the presence of citrate and As(V), coordination numbers of Fe decreased by up to 28% relative to pure Fh. Citrate significantly reduced the static disorder of Fe-O bonds, implying a decreased octahedral distortion in Fh. Mean bond distances in Fh were not affected by citrate and remained constant within error at 1.98 Å for Fe-O, 3.03 Å for Fe-Fe1, and 3.45 Å for Fe-Fe2. Likewise, citrate had no effect on the As-Fe (3.31 Å) bond distance in As(V) coprecipitated with Fh. The As K-edge EXAFS data comply with the formation of (i) only monodentate binuclear (²C) As(V) surface complexes and (ii) combinations of ²C, monodentate mononuclear (¹V), and outersphere As(V) surface complexes. Our results suggest that increasing citrate concentrations led to a decreasing ¹V/²C ratio and/or that citrate increasingly impaired the formation of outersphere As(V) complexes. Moreover, citrate stabilized colloidal suspensions of Fh (pH 4.3-6.6, I ∼0.45 M) and reduced Fh formation at the expense of soluble Fe(III)-citrate complexes. At initial citrate/Fe ratios ?25 mol%, between 8% and 41% of total Fe was bound in Fe(III)-citrate complexes after Fh formation. Polynuclear Fe(III)-citrate species were found to bind As(V) via surface complexes indistinguishable by EXAFS from those of As(V) adsorbed to or coprecipitated with Fh. Our study implies that low molecular weight polyhydroxycarboxylates may enhance the mobility of As(V) in aqueous systems of high ionic strength (e.g., neutralizing acid mine drainage) by colloidal stabilization of suspended Fh particles and the formation of ternary As(V) complexes.     

Microscale oxygen isotopic exchange and magnetite formation in the Ningqiang anomalous carbonaceous chondrite

We report in situ measurements of O-isotopic compositions of magnetite, olivine and pyroxene in chondrules of the Ningqiang anomalous carbonaceous chondrite. The petrographic setting of Ningqiang magnetite is similar to those in oxidized-CV chondrites such as Allende, where magnetite is found together with Ni-rich metal and sulfide in opaque assemblages in chondrules. Both magnetite and silicate oxygen data fall close to the carbonaceous-chondrite-anhydrous-mineral line with relatively large ranges in δ¹⁸O in magnetite (−4.9 to +4.2‰) and in silicates (−15.2 to −4.5‰). Magnetite and silicates are not in O-isotopic equilibrium: the weighted average Δ¹⁷O (=δ¹⁷O − 0.52 × δ¹⁸O) values of magnetite are 1.7 to 3.6‰ higher than those of the silicates in the same chondrules. The petrological characteristics and O-isotopic disequilibrium between magnetite and silicates suggest the formation of Ningqiang magnetite by the oxidation of preexisting metal grains by an aqueous fluid during parent body alteration. The weighted average Δ¹⁷O of −3.3 ± 0.3‰ is the lowest magnetite value measured in unequilibrated chondrites and there is a positive correlation between Δ¹⁷O values of magnetite and silicates in each chondrule. These observations indicate that, during aqueous alteration in the Ningqiang parent asteroid, the water/rock ratio was relatively low and O-isotopic exchange between the fluid and chondrule silicates occurred on the scale of individual chondrules.     

Influences of microbial communities on groundwater component concentrations during managed artificial recharge

Managed aquifer recharge is one of the most popular methods for dealing with local water shortage issues, and the bacterial community could be a vital factor influencing groundwater quality during this process. In this study, analysis of variations in groundwater components during artificial recharge revealed three stages at a text site in China. During stage I, total iron and dissolved organic carbon levels are stable basically, dissolved oxygen and SO₄ ^2? levels have rising trends, NO₃ ^? curve varied not obviously. Variation curves show increases in dissolved oxygen, NO₃ ^?, SO₄ ^2? and stabilization in dissolved organic carbon and total iron at stage II. During stage III, dissolved oxygen and NO₃ ^? have rising trends, dissolved organic carbon, total iron, and SO₄ ^2? keep stable. At 25 and 70 days the Simpson and Shannon–Wiener indices show that microbial community richness and population diversity underwent a gradual dynamic change after recharge water arrived. Correlation analysis shows that the Simpson index was mainly affected by dissolved oxygen and NO₃ ^?. PCR-DGGE confirmed these findings. Overall, the results revealed that the main bacterial communities reduce total nitrogen, total phosphorous, and chemical oxygen demand, which corresponded to the calculated correlation index.     

Composition and structural aspects of naturally occurring ferrihydrite

A series of naturally occurring ferrihydrites sampled from an acid mine drainage environment were characterized and compared with synthetic 2-line ferrihydrite using high energy X-ray total scattering and pair distribution function analysis, Scanning Transmission X-ray Microscopy (STXM), Transmission Electron Microscopy (TEM), BET N₂ surface area measurements, and chemical extractions in order to place constraints on their structural and physical properties as a function of composition. Overall, the short- and intermediate-range ordering of the natural samples is comparable to synthetic ferrihydrite. However, with increasing Al, Si, and organic matter contents, a decrease in particle size and an increase in structural disorder were observed. Silica is suspected to have a pronounced effect on the crystallinity of ferrihydrite as a result of its inhibitory effect on Fe polymerization and particle growth, and it is likely complexed at the surfaces of ferrihydrite nanoparticles. Aluminum, on the other hand may substitute for Fe³⁺ in natural ferrihydrite. Organic matter is pervasive and intimately associated with ferrihydrite aggregates, and its presence during ferrihydrite precipitation may have contributed to additional structural disorder. The increase in impurity content affects not only the particle size and structural order of ferrihydrite but may also have a significant effect on its surface reactivity.     

斜长石和橄榄石成分对四川攀枝花钒钛磁铁矿床成因的指示意义

攀枝花岩体下部和中部岩相带各旋回中磁铁辉长岩和辉长岩的岩相结构特征表明,钛铁氧化物和斜长石、橄榄石的结晶发生在相近的温度区间内,这为我们利用斜长石和橄榄石的成分探讨磁铁矿形成时温度、氧逸度和岩浆成分的变化提供了可能.电子探针分析结果表明,下部和中部岩相带中斜长石An牌号自下向上有规律地逐渐降低,而在每一个旋回内部,橄榄石的F(o)值总是由磁铁辉长岩向辉长岩表现出强烈降低的趋势.这些特征说明攀枝花岩体经历了多次富铁钛的岩浆的补充.斜长石An牌号小幅度的规律性降低说明岩浆氧逸度和Fe3/Fe2+比值变化对斜长石成分影响很小,因此,我们可以根据斜长石成分估计钛铁氧化物结晶过程中温度变化.然而,同一旋回中橄榄石Fo值变化较大说明橄榄石成分在很大程度上取决于岩浆中的Fe3+/Fe2+和Fe2 +/Mg含量,因此,可以根据橄榄石成分分析磁铁辉长岩与辉长岩形成过程中氧逸度和Fe3+/Fe2比值的相对变化.计算得到下部和中部岩相带中斜长石的结晶温度介于1079～1121℃之间,认为钛铁氧化物的结晶也大致发生在此温度区间;根据同一旋回中磁铁辉长岩与邻近辉长岩中橄榄石Fo值的差异,发现每次新补充的岩浆分离结晶过程中氧逸度总是逐渐降低,这与前人对封闭体系岩浆结晶分异过程中氧逸度变化规律的认识一致.     

铁氧化物型铜金矿中磁铁矿微量元素含量对结构参数影响的初步研究

磁铁矿是一种重要的铁氧化物,广泛分布于自然界的三大类岩石和各种不同类型的矿床中.采用激光剥蚀电感耦合等离子质谱仪,分析了澳大利亚Ernest Henry铁氧化物型铜金矿床中磁铁矿的微量元素含量,并用X衍射测定微量元素含量最高和最低时磁铁矿相应的晶胞参数,从而评价微量元素变化对磁铁矿结构参数的影响.结果表明,磁铁矿中存在着阳离子替代关系;微量元素含量高的磁铁矿晶胞参数a0值小于标准磁铁矿的a0值,含微量元素低的磁铁矿晶胞参数a0值则大于标准磁铁矿的a0值;磁铁矿中所含微量元素不同,其对应的晶胞参数a0值亦有明显变化.     

On heavy metal concentrations and biogenic enrichment in microbial mat environments

Heavy metal concentrations of a recent salina on the shore of the Mediterranean Sea near Port Said (Egypt) were investigated. Samples for the heavy metal study were taken in different ponds of the salina. It was found that microbial mat dominated brine sediments concentrated and enriched heavy metal 2–3 times more than sediments lacking microbial mat developments, suggesting that cyanobacteria play a major role in this enrichment. Heavy metal enrichment by cyanobacteria was therefore also studied in the laboratory environment. This study is compared with a recent study of Solar Lake and Sabkha Gavish sediments (Sinai, Egypt). Our conclusion is that recent hypersaline environments with ambient microbial mat (potential stromatolite) developments are ideal examples of present-day environments of metal accumulations.     

铁（氢）氧化物悬液中磷酸盐的吸附-解吸特性研究

铁（氢）氧化物对P的吸持和释放在一定程度上决定着P的生物有效性和水体富营养化。以两种环境中常见晶质铁氧化物（针铁矿和赤铁矿）为对照,采用X射线衍射（XRD）、透射电镜（TEM）、热重分析（TGA）和孔径分析以及动力学和吸附-解吸热力学平衡等技术方法,研究了弱晶质水铁矿对P吸附-解吸特性,并探讨了相关机制。实验表明,三种矿物对P的吸附分为起始的快速反应和随后的慢速反应,它们均符合准一级动力学过程,反应中OH释放明显滞后于P吸附,P吸附经历了从外围到内囤配位、单齿到多齿配位过渡的过程,与晶质氧化铁比,水铁矿吸附容量和OH释放量更大、慢速吸附反应更快、存在缓慢扩散反应阶段,吸附容量依次是：水铁矿（436μmol／m^2）〉针铁矿（262μmol／m^2）〉赤铁矿（228μmol／m^2）,针铁矿和赤铁矿吸附P符合L（Langmuir）模型,而水铁矿更符合F（Fremldlictl）模型。中性盐介质（KCl）中在最大吸附量时P的解吸率依次为：水铁矿（85％）〈针铁矿（10％）〈赤铁矿（125％）,柠檬酸通过配体解吸和诱导溶解两种机制促进P的解吸,最大吸附量时解吸率依次是：针铁矿（25％）〈水铁矿（32％）〈赤铁矿（50％）。     

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)_(aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III)_(s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.     

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。     

胶西北金城金矿床物质组成及矿床成因研究

研究了金城金矿床蚀变岩石的常量元素和微量元素、蚀变矿物的金含量和化学组成,并首次对铁碳酸盐化及煌斑岩杏仁体的组成进行了研究。结果表明,形成不同类型金矿化的成矿流体组成有差异,但总体以富Fe、Si、K、Au、Ag、Bi、Co、Cu等为特征;黄铁矿为主要载金矿物,石英为金的洁净矿物;铁碳酸盐与黄铁矿、黄铜矿的沉淀关系密切;煌斑岩岩浆晚期残余气液与成矿流体组成相近、沉淀次序相同,表明它们可能有成因联系。     

A microbial pathway for the formation of gold-anomalous calcrete

The formation of pedogenic carbonate (calcrete) in terrestrial environments is commonly mediated by microorganisms. In Australia, Au-anomalous calcrete is an important sampling medium for geochemical exploration, but current models describing its formation do not include a confirmed microbial component. This study demonstrates that bacterial communities in calcareous sands from dunes overlying the Barns Gold Deposit in semi-arid South Australia, are capable of mediating the biomineralisation of Au-anomalous carbonates. Bacterial enrichment cultures obtained from calcareous sands at three depths (0.1, 0.64 and 2.1 m, plus abiotic control) were incubated in urea and Ca²⁺-containing growth media (pH 8), unamended and amended with Au (100 parts-per-billion, ppb) as Au–aspartic-acid complex. During the incubation of the enrichment cultures urea was turned over to NH₄⁺ within 96 h to 220 h. The solution pH increased concurrently by approximately 1.2 units, and Au-anomalous Ca-carbonate crystallites were precipitated on cells, which functioned as nucleation sites; no carbonate precipitation was observed in abiotic controls. Compared to the medium, Au was strongly enriched in these carbonates and appeared to be uniformly dispersed in the individual crystallites, as shown using LA-ICP-MS; a similar distribution is present in naturally occurring Au-anomalous calcrete. Phylogenetic 16S rRNA PCR DGGE analyses, shotgun cloning and functional microbial analyses (BioLog, ureC quantitative PCR) demonstrated that naturally occurring and culture-enriched bacterial communities were dominated by alkaliphylic, halotolerant Bacillus spp. The indigenous bacterial communities were capable of utilising amino acids (including l-aspartic acid) and urea, which appears to lead to the destabilisation of the Au–amino acid complexes and concomitant co-precipitation of Au in the Ca-carbonates. In conclusion, a model combining geomicrobial– with evapotranspiration– and plant-based components is likely to best describe the formation of (Au-anomalous) calcrete in semi-arid and arid zones.     

Experimental constraints on Fe isotope fractionation during magnetite and Fe carbonate formation coupled to dissimilatory hydrous ferric oxide reduction

Iron isotope fractionation between aqueous Fe(II) and biogenic magnetite and Fe carbonates produced during reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens, Shewanella algae, and Geobacter sulfurreducens in laboratory experiments is a function of Fe(III) reduction rates and pathways by which biogenic minerals are formed. High Fe(III) reduction rates produced ⁵⁶Fe/⁵⁴Fe ratios for Fe(II)_aq that are 2-3‰ lower than the HFO substrate, reflecting a kinetic isotope fractionation that was associated with rapid sorption of Fe(II) to HFO. In long-term experiments at low Fe(III) reduction rates, the Fe(II)_aq-magnetite fractionation is −1.3‰, and this is interpreted to be the equilibrium fractionation factor at 22°C in the biologic reduction systems studied here. In experiments where Fe carbonate was the major ferrous product of HFO reduction, the estimated equilibrium Fe(II)_aq-Fe carbonate fractionations were ca. 0.0‰ for siderite (FeCO₃) and ca. +0.9‰ for Ca-substituted siderite (Ca_0.15Fe_0.85CO₃) at 22°C. Formation of precursor phases such as amorphous nonmagnetic, noncarbonate Fe(II) solids are important in the pathways to formation of biogenic magnetite or siderite, particularly at high Fe(III) reduction rates, and these solids may have ⁵⁶Fe/⁵⁴Fe ratios that are up to 1‰ lower than Fe(II)_aq. Under low Fe(III) reduction rates, where equilibrium is likely to be attained, it appears that both sorbed Fe(II) and amorphous Fe(II)(s) components have isotopic compositions that are similar to those of Fe(II)_aq.The relative order of δ⁵⁶Fe values for these biogenic minerals and aqueous Fe(II) is: magnetite > siderite ≈ Fe(II)_aq > Ca-bearing Fe carbonate, and this is similar to that observed for minerals from natural samples such as Banded Iron Formations (BIFs). Where magnetite from BIFs has δ⁵⁶Fe >0‰, the calculated δ⁵⁶Fe value for aqueous Fe(II) suggests a source from midocean ridge (MOR) hydrothermal fluids. In contrast, magnetite from BIFs that has δ⁵⁶Fe ≤0‰ apparently requires formation from aqueous Fe(II) that had very low δ⁵⁶Fe values. Based on this experimental study, formation of low-δ⁵⁶Fe Fe(II)_aq in nonsulfidic systems seems most likely to have been produced by dissimilatory reduction of ferric oxides by Fe(III)-reducing bacteria.     

Zn isotopic fractionation caused by sorption on goethite and 2-Lines ferrihydrite

Zn isotopic fractionation caused by sorption on 2-Lines ferrihydrite (Fh2L) and goethite was investigated to assess the role of reactions at the Fe-oxyhydroxide/water interface in changes of the isotopic distribution of Zn. Since sorption reactions are ubiquitous in Earth’s surface environments, it is important to evaluate their influence on the isotopic distribution of Zn before it can be used to track and quantify contributions of various sources and/or biogeochemical processes involving this element. Our results show that Zn isotopes are fractionated upon sorption on Fe-oxyhydroxides with an enrichment of the heavy isotopes present on the solid’s surface. This fractionation appears to proceed through an equilibrium mechanism and yields different (Δ^66/64Zn)_{sorbed-aqueous} values for Zn sorption on goethite [(Δ^66/64Zn)_{sorbed-aqueous} around +0.29‰] and Fh2L [(Δ^66/64Zn)_{sorbed-aqueous} around +0.53‰]. These different magnitudes of Zn fractionation are related to structural differences between Zn complexes existing on the surface of goethite (octahedrally coordinated Zn by oxygen atoms) and Fh2L (tetrahedrally coordinated Zn by oxygen atoms), as evidenced by Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy and CD-MUSIC modeling. These results show the importance of accounting for reactions at the Fe-oxyhydroxide/water interface when dealing with the isotopic distribution of Zn at the Earth’s surface. Considering the large range of other possible sorbents (Mn or Al oxides, phyllosilicates, carbonates, biologic surfaces, etc.) and the importance of reactions at sorbent/water interfaces for other non-traditional stable isotopes (i.e. Cr, Fe, Ni and Cu) that are increasingly used in environmental studies, these results emphasize the need for further experimental studies that are needed to quantify the isotopic fractionation of these elements possibly accompanying their sorption.