利用碳酸盐岩的Fe/Mn比值恢复海洋的氧化还原状态

碳酸盐岩的Fe/Mn元素比值,作为一项新的地球化学指标,可以用于恢复海洋的氧化还原状态.在氧化条件下,Fe³⁺和Mn⁴⁺均不可溶,因此氧化海水中的溶解Fe和Mn的含量均很低.Fe³⁺和Mn⁴⁺在还原条件下可以被细菌还原为可溶的Fe²⁺和Mn²⁺,而氧化还原电位的计算表明,Mn⁴⁺的还原要早于Fe³⁺的还原,因此细菌的Mn还原过程发生在沉积物的更浅层.可溶的Fe²⁺和Mn²⁺向上扩散到海水中,替代碳酸盐岩晶格里的Ca²⁺,因此碳酸盐岩晶格中的Fe²⁺和Mn²⁺的含量受控于来自沉积物孔隙水的扩散,而后者又与水岩界面的氧化还原状态相关.因此可以预测,随着海水变得逐渐缺氧,碳酸盐岩中的Fe/Mn比值会逐渐增高.为了验证这一假说,我们分析了中元古代高于庄组白云岩的Fe/Mn比值.研究发现,几乎所有的样品的Fe/Mn比值介于20～30之间,显著高于泥盆纪末期深水碳酸盐岩和浅水台地碳酸盐岩的Fe/Mn比值.高于庄组碳酸盐岩高的Fe/Mn比值一方面可能指示了中元古代低的大气氧气浓度和海洋的广泛缺氧,也可能反映了白云岩形成于缺氧的沉积物空隙水里.     

The effect of Fe-oxidizing bacteria on Fe-silicate mineral dissolution

Acidithiobacillus ferrooxidans are commonly present in acid mine drainage (AMD). A. ferrooxidans derive metabolic energy from oxidation of Fe²⁺ present in natural acid solutions and also may be able to utilize Fe²⁺ released by dissolution of silicate minerals during acid neutralization reactions. Natural and synthetic fayalites were reacted in solutions with initial pH values of 2.0, 3.0 and 4.0 in the presence of A. ferrooxidans and in abiotic solutions in order to determine whether these chemolithotrophic bacteria can be sustained by acid-promoted fayalite dissolution and to measure the impact of their metabolism on acid neutralization rates. The production of almost the maximum Fe³⁺ from the available Fe in solution in microbial experiments (compared to no production of Fe³⁺ in abiotic controls) confirms A. ferrooxidans metabolism. Furthermore, cell division was detected and the total cell numbers increased over the duration of experiments. Thus, over the pH range 2–4, fayalite dissolution can sustain growth of A. ferrooxidans. However, ferric iron released by A. ferrooxidans metabolism dramatically inhibited dissolution rates by 50–98% compared to the abiotic controls.

Two sets of abiotic experiments were conducted to determine why microbial iron oxidation suppressed fayalite dissolution. Firstly, fayalite was dissolved at pH 2 in fully oxygenated and anoxic solutions. No significant difference was observed between rates in these experiments, as expected, due to extremely slow inorganic ferrous iron oxidation rates at pH 2. Experiments were also carried out to determine the effects of the concentrations of Fe²⁺, Mg²⁺ and Fe³⁺ on fayalite dissolution. Neither Fe²⁺ nor Mg²⁺ had an effect on the dissolution reaction. However, Fe³⁺, in the solution, inhibited both silica and iron release in the control, very similar to the biologically mediated fayalite dissolution reaction. Because ferric iron produced in microbial experiments was partitioned into nanocrystalline goethite (with very low Si) that was loosely associated with fayalite surfaces or coated the A. ferrooxidans cells, the decreased rates of accumulation of Fe and Si in solution cannot be attributed to diffusion inhibition by goethite or to precipitation of Fe–Si-rich minerals. The magnitude of the effect of Fe³⁺ addition (or enzymatic iron oxidation) on fayalite dissolution rates, especially at low extents of fayalite reaction, is most consistent with suppression of dissolution by interaction between Fe³⁺ and surface sites. These results suggest that microorganisms can significantly reduce the rate at which silicate hydrolysis reactions can neutralize acidic solutions in the environment.     

地下水系统中砷活化的钼同位素地球化学指示

砷在天然环境中的迁移富集与氧化还原状态密切相关.盆地环境地下水中砷的活化迁移机制主要为沉积物中铁/锰氢氧化物由氧化还原条件变化导致发生还原性溶解进而释放吸附在其表面的砷.钼及钼同位素为氧化还原环境的重要指示参数, 且铁/锰氢氧化物对钼同位素分馏有着重要的控制作用.将地下水的钼同位素应用于砷的活化迁移规律研究.大同盆地地下水中钼同位素比值(δ98Mo)范围为-0.12‰~+2.17‰, 相比于淡水中钼同位素组成偏重.桑干河河水的δ98Mo为+0.72‰, 与文献报道的河水平均钼同位素比值+0.7‰相当.大同盆地地下水中δ98Mo与硫化物之间存在正相关关系, 表明Mo-Fe-S复合物可能形成于特定条件下, 并优先利用水溶液中轻的钼使地下水中δ98Mo比值升高.砷浓度与钼浓度之间的微弱负相关以及砷浓度与钼同位素之间的正相关说明, Mo-Fe-S的形成过程可能与同环境中As-Fe-S的复合物的形成存在竞争关系, 进而使得地下水中砷富集.地下水中相对偏高的δ98Mo可能来源于铁的氢氧化物对溶液中轻的钼的吸附速率高于先前吸附在铁的氢氧化物的钼的释放, 且铁的氢氧化物对水溶液中钼的再吸附这一循环过程会导致地下水中钼浓度降低及钼同位素比值的升高.钼同位素指示的循环性的铁的氢氧化物的还原溶解及再氧化过程对砷的富集也有重要影响.      

Comprehensive chemical analyses of natural cordierites: implications for exchange mechanisms

Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H₂O and CO₂ (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg₋₁ and MnMg₋₁ on the octahedral site, some minor KNa₋₁ on the Ch0 channel site, and Fe³⁺Al₋₁ on the T₁1 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□₋₁Mg₋₁), and of Be and other divalent cations on the tetrahedral T₁1 site (NaBe□₋₁Al₋₁ and Na(Mg,Fe²⁺)□₋₁Al₋₁). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: ^Ch(Na,K)_0–1 ^VI(Mg,Fe²⁺,Mn,Li)₂ ^IVSi₅ ^IVAl₃ ^IV(Al, Be, Mg, Fe²⁺, Fe³⁺)O₁₈ *x^Ch(H₂O, CO₂…). Our results show that the population of (Mg, Fe²⁺) on the T₁1-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under P–T conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M²⁺–Na.     

Phase relations of pumpellyite-actinolite facies metabasites in the Sanbagawa metamorphic belt in central Shikoku, Japan

Sanbagawa metabasites metamorphosed at conditions near the upper limit of the pumpellytic-actinolite facies were examined in terms of phase equilibria in the five component system Al₂O₃---Fe₂O₃---CaO---MgO---FeO. The Fe³⁺ content of epidote measured as X^Ep_Fe (=Fe/(Fe + Al) of epidote) in the assemblage epidote-chlorite-actinolite-pumpellyite decreases gradually towards the higher-grade, pumpellyite-free areas. The progressive change in X_Fe^Ep can be detected within one metabasite bed 200 meters thick near the upper limit of the pumpellyite-actinolite facies. The Mg---Fe²⁺ substitution, as expressed by variation of Fe/(Fe + Mg) in chlorite (0.40–0.55) has little effect on the Fe³⁺ + Al) ratios of epidote and pumpellyite in the above-mentioned assemblage. The lowet X_Fe^Ep in the pumpellite-bearing assemblage is 0.15 and hence the upper limit of the pumpellyite-actinolite facies is defined by the appearance of an epidote-chlorite-actinolite assemblage with X^Ep_Fc = C.15     

Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments

Subterranean estuaries are characterized by the mixing of terrestrially derived groundwater and seawater in a coastal aquifer. Subterranean estuaries, like their river water-seawater counterparts on the surface of the earth, represent a major, but less visible, hydrological and geochemical interface between the continents and the ocean. This article is the first in a two-part series on the biogeochemistry of the subterranean estuary at the head of Waquoit Bay (Cape Cod, MA, USA). The pore-water distributions of salinity, Fe and Mn establish the salt and redox framework of this subterranean estuary. The biogeochemistry of Fe, Mn, P, Ba, U and Th will be addressed from the perspective of the sediment composition. A second article will focus on the groundwater and pore-water chemistries of Fe, Mn, U and Ba.Three sediment cores were collected from the head of Waquoit Bay where the coastal aquifer consists of permeable sandy sediment. A selective dissolution method was used to measure the concentrations of P, Ba, U and Th that are associated with “amorphous (hydr)oxides of iron and manganese” and “crystalline Fe and Mn (hydr)oxides.” The deeper sections of the cores are characterized by large amounts of iron (hydr)oxides that are precipitated onto organic C-poor quartz sand from high-salinity pore waters rich in dissolved ferrous iron. Unlike Fe (hydr)oxides, which increase with depth, the Mn (hydr)oxides display midcore maxima. This type of vertical stratification is consistent with redox-controlled diagenesis in which Mn (hydr)oxides are formed at shallower depths than iron (hydr)oxides. P and Th are enriched in the deep sections of the cores, consistent with their well-documented affinity for Fe (hydr)oxides. In contrast, the downcore distribution of Ba, especially in core 3, more closely tracks the concentration of Mn (hydr)oxides. Even though Mn (hydr)oxides are 200-300 times less abundant than Fe (hydr)oxides in the cores, Mn (hydr)oxides are known to have an affinity for Ba which is many orders of magnitude greater than iron (hydr)oxides. Hence, the downcore distribution of Ba in Fe (hydr)oxide rich sediments is most probably controlled by the presence of Mn (hydr)oxides. U is enriched in the upper zones of the cores, consistent with the formation of highly reducing near-surface sediments in the intertidal zone at the head of the Bay. Hence, the recirculation of seawater through this type of subterranean estuary, coupled with the abiotic and/or biotic reduction of soluble U(VI) to insoluble U(IV), leads to the sediments acting as a oceanic net sink of U. These results highlight the importance of permeable sediments as hosts to a wide range of biogeochemical reactions, which may be impacting geochemical budgets on scales ranging from coastal aquifers to the continental shelf.     

青海东昆仑洪水河铁矿床新元古代含铁建造铁同位素特征及其成因意义

青海省东昆仑造山带洪水河铁矿床为一中型铁矿床,其含铁建造产于狼牙山组千枚岩中,矿石类型主要为块状磁铁石英岩型,少量为条带状磁铁石英岩型,前人一般认为其属于沉积变质型铁矿床。本文在前人研究基础上,对洪水河铁矿区含铁建造中块状铁矿石进行了铁同位素、主量元素、稀土元素和微量元素分析。结果显示：除1件样品外,其余含铁建造样品的铁同位素δ56FeIRMM014均介于0.97‰~1.97‰之间,和全球典型新元古代含铁建造的Fe同位素特征基本一致;铁矿石的SiO₂+Fe₂O₃质量分数高达78.56%~98.06%,具有极低的Al/(Al+Fe+Mn)值（0.00~0.06）,为典型的化学沉积岩;总稀土元素（w (∑REE)）变化范围为(16.49~80.89)×10^-6,没有明显的Ce异常(Ce/Ce*为0.93~1.05),轻稀土元素轻微亏损,显示出类似新元古代含铁建造型的特点。综合对比洪水河铁矿区含铁建造的Fe同位素组成、沉积时代和地球化学特征,推断洪水河铁矿区含铁建造的沉积环境为新元古代柴达木—东昆北陆块的被动大陆边缘构造环境,铁等成矿物质主要来源于海相热液流体;富含Fe²+的海相热液流体上涌并逐渐演变为低温热液后在亚氧化水体环境中与含氧海水混合,最后导致Fe²+被部分氧化并形成氢氧化铁,氢氧化铁逐渐沉积在大陆斜坡上最终形成含铁建造。洪水河铁矿的成因类型可划归为拉皮坦型新元古代含铁建造。     

长江口沉积物-水界面砷的迁移转化机制与微生物调控分析

为探析长江口沉积物-水界面砷的迁移转化机制,本文分析了2019年夏季长江口4个站位上覆水和间隙水中总As浓度及形态的剖面变化特征,耦合氧化还原敏感元素(Fe、Mn和S)的剖面变化剖析了沉积物-水界面砷循环的Fe-Mn-S控制机制,同时结合砷相关功能基因探讨了沉积物-水界面砷迁移转化的微生物调控过程,估算了沉积物-水界面总As的扩散通量。结果表明,除A7-4站位外,长江口其他3个站位间隙水总As以As³⁺为主要存在形态,且总As浓度均在上覆水中为最低值(0.748~1.57 μg·L^-1),而在间隙水中随着深度增加而逐渐增加并在6~9 cm深度达到峰值(7.14~26.9 μg·L^-1)。间隙水总As及As³⁺浓度的剖面变化趋势与溶解态Fe²⁺、Mn²⁺相似,其均在中间层出现高值,说明沉积物Fe/Mn还原带砷的释放可能是随固相Fe(Ⅲ)或Mn(Ⅳ)的还原而转移到间隙水中的。氧化层和Fe/Mn还原带过渡区间隙水砷浓度与砷异化还原菌功能基因arrA和arsC丰度存在对应关系(除A1-3站外),说明砷异化还原菌将溶解As⁵⁺或固相As⁵⁺还原为溶解As³⁺可能是该过渡层砷迁移转化的另一重要过程。硫酸盐还原带的间隙水总As和As³⁺浓度降低,但由于间隙水的低S^2-浓度不利于砷硫化物生成,因此深层间隙水砷可能与铁硫矿物结合而被移除。底层环境氧化还原条件是影响沉积物-水界面砷迁移转化的重要因素,随底层水DO浓度的降低,砷迁移转化更倾向于微生物还原控制。长江口沉积物-水界面总As的扩散通量为1.18×10^-7~2.07×10^-7 μmol·cm^-2·s^-1,均表现为沉积物间隙水中总As向上覆水释放,即沉积物是研究区域水体总As的来源之一。     

湖南栗山铅锌铜多金属矿床闪锌矿微量元素特征及成矿指示意义

位于江南造山带中段的湘东北地区是我国华南重要的金铅锌铜钴多金属矿产地之一,栗山铅锌铜多金属矿床是该区近年来找矿勘查新发现的一大型矿床。该矿床位于晚侏罗世—早白垩世幕阜山岩体南缘,矿体主要赋存于岩体及其与地层接触带的构造破碎带内,空间上与岩体关系密切,然而目前关于该矿床的研究十分薄弱。本文采用电子探针和激光剥蚀电感耦合等离子质谱仪开展了闪锌矿的原位微区微量元素分析。微量元素组成分析结果表明,闪锌矿以富集Co、Ga而贫Fe、Cd、Ge为特征,其中Fe、Mn、Cd、Co、Ga等元素以类质同象形式产出,而Cu、Pb、Ag和Sn等元素则还以包裹体形式赋存于闪锌矿中。根据不同微量元素间的相关关系,认为闪锌矿中可能存在Zn²⁺↔Fe²⁺、4 Zn²⁺↔2 Fe²⁺+Ge⁴⁺+□(其中□表示空位)、3 Zn²⁺↔2 Cu⁺+Ge⁴⁺、2 Zn²⁺↔Ag⁺+Sb³⁺等简单和复杂替代关系。闪锌矿的Zn/Fe、Ga/Ge、Ge/In、Ga/In比值和Fe温度计等指示闪锌矿形成于中低温(240~250 ℃)、低硫逸度(lgf(S₂)=-13.3~-9.6)环境。栗山矿区闪锌矿的微量元素组成特征有别于金顶砂岩型、SEDEX型、VMS型、MVT型和夕卡岩型铅锌矿,结合低的Cd/Fe(0.03~0.14,平均0.06)、Cd/Mn(1.54~6.30,平均2.91)比值和Ge含量,暗示该矿床成矿作用与岩浆活动有关。综合矿区地质特征和区域构造-岩浆演化,认为该矿床是在太平洋板块俯冲后撤引起的伸展构造背景下形成的与燕山期幕阜山岩体有关的中低温岩浆热液充填交代型矿床。该类型矿床闪锌矿具有鲜明的微量元素组成特征,可为判别具相似地质特征的矿床成因提供借鉴。     

Some Key Problems on the Petrogenesis of Seafloor Basalts,Abyssal Peridotites and Geodynamics—A Non-traditional Isotope Approach

This paper discusses some major research to be carried out in the next five years in the newly established Laboratory of Ocean Lithosphere and Mantle Geodynamics. By using our existing sample collections of global mid-ocean ridge basalts, gabbros and abyssal peridotites from the Pacific, Atlantic and Indian oceans, the research includes: ①Using Ti-Zr-Hf stable isotope methods to test the hypothesis that the observed huge Nb-Ta and Zr-Hf fractionations result from mass-dependent fractionation under mantle magmatic conditions; ②Using a MORB sample suite of uniform ratios of incompatible elements and Sr-Nd-Pb isotopes with large major element compositional variation to test the common hypothesis of iron isotope fractionation, i.e, the affinity of heavy Fe with ferric Fe (Fe³⁺), and both heavy Fe and ferric Fe (Fe³⁺) being more incompatible than light Fe and ferrous Fe (Fe²⁺) during magma evolution; while using an incompatible trace element and Sr-Nd-Pb isotope highly variable MORB suite to test the same hypothesis during low-degree mantle melting (i.e, the effect of mantle metasomatism); ③Proposing and testing the hypothesis that the high oxygen fugacity of the Earth’s mantle is a consequence of plate tectonics by subducting partially serpentinized oceanic mantle lithosphere with abundant ferric Fe (e.g. Fe³⁺/SFe>2); ④The recent work by Andersen et al. (Nature, 2015) is a milestone contribution by using U isotope variation in oceanic basalts to hypothesize that the O₂-rich atmosphere since the late Archean (abont 2.4 Ga) mobilized the water soluble U (6+ vs. 4+) from continents, transported to the ocean and subducted with sediments to the upper mantle, which explains the low Th/U in MORB (<2.5) and the high Th/U (>3.5) ocean island basalts (OIB) do not see such U addition effect probably because OIB source materials are all ancient (> abont 2.4 Ga) if there were subducted component. The Cenozoic alkali basalts from eastern China are ideal materials for evaluating the significance of the subducted seafloor materials for the petrogenesis of OIB and enriched MORB by using the U isotope approach, which is expected to revise and improve the Andersen et al hypothesis.     

Micro-XANES determination of ferric iron and its application in thermobarometry

Micro-X-ray absorption near-edge structure (XANES) analysis was employed to determine the content of ferric iron in minerals formed in ultrahigh-pressure (UHP) eclogites. It is observed that omphacite and phengite contain significant amounts of Fe³⁺/Fe_tot (0.2–0.6), whereas only very low contents are present in garnet (Fe³⁺/Fe_tot=0.0–0.03), the latter being consistent with results from stoichiometric charge-balance calculations. Furthermore, considerable variations in the Fe³⁺/Fe_tot ratios of omphacite and phengite are observed depending on the textural sites and local bulk chemistry (eclogite and calc-silicate matrix) within one thin section. The oxidation state of isofacial minerals is thus likely to depend on the local fluid composition, which, in the studied case, is controlled by calcareous and meta-basic mineral compositions. These first in-situ measurements of ferric iron in an eclogite sample from the Dabie Shan, E China, are used to recalculate geothermobarometric data. Calculations demonstrate that the temperature during UHP metamorphism was as high as 780 °C, about 80–100 °C higher than previously estimated. Temperatures based on charge balance calculations often give erroneous results. Pressure estimates are in good agreement with former results and confirm metamorphism in the stability field of diamond (43.7 kbar at 750 °C). These P–T data result in a geothermal gradient of ca. 6 °C/km during UHP metamorphism in the Dabie Shan. However, accounting for ferric iron contents in geothermobarometry creates new difficulties inasmuch as calibrations of geothermometers may not be correctable for Fe³⁺ and the actual effect on Mg–Fe²⁺ partitioning is unknown. The present study further shows that micro-XANES is a promising technique for the in situ determination of ferric iron contents without destroying the textural context of the sample: a clear advantage compared to bulk methods.     

Early diagenetic influences on iron transformations in a freshwater lake sediment

Iron transformations in a calcium carbonate rich fresh-water sediment were studied by analyzing the relevant constituents of both interstitial water and solid matter. Analysis of interstitial water shows that the observed redox sequence NO⁻₃/NH⁺₄, MnO₂/Mn(II), FeOOH/Fe(II), SO²⁻₄/S(−II) is roughly in agreement with that predicted by the Gibbs Free Energy for the corresponding reactions. In contrast to marine sediments, these redox transitions occur in the uppermost sediments, i.e., at depths of 0–4 cm.

Deeper in the sedimentary sequence, the depth profile for dissolved iron exhibits a steady non-linear increase up to 400 μmol dm⁻³. In this anoxic zone, according to thermodynamic predictions, iron (II)-minerals such as iron sulfide, siderite, and vivianite should precipitate while Fe(III) oxides should be completely dissolved. However, microscopic analysis showed that Fe(III) oxides were present throughout the studied sediment. Furthermore, scanning electron microscope/energy dispersive spectroscopy analysis suggests the presence of iron sulfide could be verified but not that of siderite or vivianite. These observations indicate kinetic control of iron transformations.

We have investigated the importance of kinetic control of iron distribution in anoxic sediments using a diagenetic model for dissolved iron(II). A rough estimate of time scales for dissolution and precipitation rates was made by imposing limiting boundary conditions. Using the calculated rate constant, we established that more than 1000 years would be required for the complete dissolution of Fe(III) oxides, which is agreement with our observations and experimental data from the literature. Calculated precipitation rates of Fe(II) for a given mineral phase such as siderite yield a maximum value of 3 μg_(FeCO3) g⁻¹_{(dry sediment)} yr⁻¹. Such low rates would explain the absence of siderite and vivianite.

Finally, it can be inferred from the Mn_T/Fe_T ratio in the sediments that this ratio depends on the redox conditions of the sediment-water interface at the time of deposition. Thus, this ratio can be used as “paleo-redox indicator” in lacustrine sediments.     

Deciphering the weathering processes using environmental mineralogy and geochemistry: Towards an integrated model of laterite and podzol genesis in the Upper Amazon Basin

This article reports major results from collaborative research between France and Brazil on soil and water systems, carried out in the Upper Amazon Basin. It reveals the weathering processes acting in the partly inundated, low elevation plateaus of the Basin, mostly covered by evergreen forest. Our findings are based on geochemical data and mineral spectroscopy that probe the crystal chemistry of Fe and Al in mineral phases (mainly kaolinite, Al- and Fe-(hydr)oxides) of tropical soils (laterites). These techniques reveal crystal alterations in mineral populations of different ages and changes of metal speciation associated with mineral or organic phases. These results provide an integrated model of soil formation and changes (from laterites to podzols) in distinct hydrological compartments of the Amazon landscapes and under altered water regimes.     

Fe---Mg partitioning between coexisting garnet and phengite at high pressure, and comments on a garnet-phengite geothermometer

The Fe---Mg exchange reaction between coexisting garnet and phengite has been studied by reacting a natural phengite (mg = 67) in the presence of quartz and water at pressures of 20–35 kb and temperatures of 800–1000°C. Compositions of coexisting garnet and mica indicate a linear relation between both the InK_D((Fe/Mg) garnet/(Fe/Mg) phengite) and temperature, and InK_D and pressure in the above P.T range. This Fe---Mg exchange reaction between garnet and phengite is shown to be dependent on the Ca-content of the garnet, and on the mg number of the bulk composition. These two composition effects have been studied by usin phengitic mica mixes with mg numbers of 23 and 46, and by using a synthetic basaltic composition. The overall results allow broad empirical calibration of separate geothermometers for pelitic and basaltic systems, respectively. However, because of non-ideality in the exchange reaction, this geothermometer should not be used in any practical application outside the composition ranges studied. Also, careful consideration of the presence of Fe³⁺ in phengite must be made. If the Fe³⁺ content of the natural phengite is unknown, then the temperatures obtained will be maximum temperatures only.     

Aluminum coprecipitates with Fe (hydr)oxides: Does isomorphous substitution of Al for Fe in goethite occur?

Iron (hydr)oxides are common in natural environments and typically contain large amounts of impurities, presumably the result of coprecipitation processes. Coprecipitation of Al with Fe (hydr)oxides occurs, for example, during alternating reduction-oxidation cycles that promote dissolution of Fe from Fe-containing phases and its re-precipitation as Fe-Al (hydr)oxides. We used chemical and spectroscopic analyses to study the formation and transformation of Al coprecipitates with Fe (hydr)oxides. In addition, periodic density functional theory (DFT) computations were performed to assess the structural and energetic effects of isolated or clustered Al atoms at 8 and 25 mol% Al substitution in the goethite structure. Coprecipitates were synthesized by raising the pH of dilute homogeneous solutions containing a range of Fe and Al concentrations (100% Fe to 100% Al) to 5. The formation of ferrihydrite in initial suspensions with ?20 mol% Al, and of ferrihydrite and gibbsite in initial suspensions with ?25 mol% Al was confirmed by infrared spectroscopic and synchrotron-based X-ray diffraction analyses. While base titrations showed a buffer region that corresponded to the hydrolysis of Fe in initial solutions with ?25 mol% Al, all of the Al present in these solutions was retained by the solid phases at pH 5, thus indicating Al coprecipitation with the primary Fe hydroxide precipitate. In contrast, two buffer regions were observed in solutions with ?30 mol% Al (at pH ∼2.25 for Fe³⁺ and at pH ∼4 for Al³⁺), suggesting the formation of Fe and Al (hydr)oxides as two separate phases. The Al content of initial coprecipitates influenced the extent of ferrihydrite transformation and of its transformation products as indicated by the presence of goethite, hematite and/or ferrihydrite in aged suspensions. DFT experiments showed that: (i) optimized unit cell parameters for Al-substituted goethites (8 and 25 mol% Al) in clustered arrangement (i.e., the formation of diaspore-like clusters) were in good agreement with available experimental data whereas optimized unit cell parameters for isolated Al atoms were not, and (ii) Al-substituted goethites with Al in diaspore-like clusters resulted in more energetically favored structures. Combined experimental and DFT results are consistent with the coprecipitation of Al with Fe (hydr)oxides and with the formation of diaspore-like clusters, whereas DFT results suggest isomorphous Al for Fe substitution within goethite is unlikely at ?8 mol% Al substitution.     

辽宁北部秀水盆地白垩系义县组泥岩地球化学特征及地质意义

沉积岩的地球化学特征蕴含了大量的地质信息,对于沉积环境的重塑及物源研究具有重要意义。通过对辽宁北部秀水盆地秀D1井义县组泥岩样品常量、微量及稀土元素等地球化学特征的研究表明:泥岩样品轻稀土元素富集,重稀土元素亏损严重,配分曲线"右倾",可见中等Eu负异常和微弱的Ce负异常,指示稳定的上地壳物源注入。盆地北东—东部的侏罗系、二叠系酸性侵入岩与义县组沉积岩具有较好的亲缘性,可能为其主要物源,源区构造背景主要为活动大陆边缘。B、Sr/Ba、La_N/Sm_N、V/(V+Ni)、Fe²⁺/Fe³⁺、Cu/Zn及Ce_anom等地球化学指标表明义县组沉积时期为淡水环境,古沉积环境为深水还原环境。     

Adsorption as a cause for iron isotope fractionation in reduced groundwater

Iron isotopes were used to investigate iron transformation processes during an in situ field experiment for removal of dissolved Fe from reduced groundwater. This experiment provided a unique setting for exploring Fe isotope fractionation in a natural system. Oxygen-containing water was injected at a test well into an aquifer containing Fe(II)-rich reduced water, leading to oxidation of Fe(II) and precipitation of Fe(III)(hydr)oxides. Subsequently, groundwater was extracted from the same well over a time period much longer than the injection time. Since the surrounding water is rich in Fe(II), the Fe(II) concentration in the extracted water increased over time. The increase was strongly retarded in comparison to a conservative tracer added to the injected solution, indicating that adsorption of Fe(II) onto the newly formed Fe(III)(hydr)oxides occurred. A series of injection-extraction (push-pull) cycles were performed at the same well. The δ⁵⁷Fe/⁵⁴Fe of pre-experiment background groundwater (−0.57 ± 0.17 ‰) was lighter than the sediment leach of Fe(III) (−0.24 ± 0.08 ‰), probably due to slight fractionation (only ∼0.3 ‰) during microbial mediated reductive dissolution of Fe(III)(hydr)oxides present in the aquifer. During the experiment, Fe(II) was adsorbed from native groundwater drawn into the oxidized zone and onto Fe(III)(hydr)oxides producing a very light groundwater component with δ⁵⁷Fe/⁵⁴Fe as low as −4 ‰, indicating that heavier Fe(II) is preferentially adsorbed to the newly formed Fe(III)(hydr)oxides surfaces. Iron concentrations increased with time of extraction, and δ⁵⁷Fe/⁵⁴Fe linearly correlated with Fe concentrations (R² = 0.95). This pattern was reproducible over five individual cycles, indicating that the same process occurs during repeated injection/extraction cycles. We present a reactive transport model to explain the observed abiotic fractionation due to adsorption of Fe(II) on Fe(III)(hydr)oxides. The fractionation is probably caused by isotopic differences in the equilibrium sorption constants of the various isotopes (K_ads) and not by sorption kinetics. A fractionation factor α_57/54 of 1.001 fits the observed fractionation.     

Reverse Weathering in River-dominated Marginal Seas

In estuarine regions and marginal seas, reverse weathering refers to the formation of authigenic aluminosilicate and carbonate minerals promoted by large inputs of terrestrial weathering products and intense remineralization of Sedimentary Organic Carbon (SOC), which is opposite to land weathering process. Compared with the process in open ocean, the formation of authigenic aluminosilicate and carbonate minerals caused by reverse weathering in estuarine regions and marginal seas is rather rapid, playing an important role in the maintenance of ocean acidity and elements cycles. At present, there are two research methods regarding the reverse weathering process, i.e., direct observation and chemical detection. The first method is used to study the structure and chemical composition of authigenic minerals and the second is mainly used to do quantified studies of authigenic minerals. The reverse weathering is very important to the cycles of Si, C, major ions (F^-, Li⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺), and alkali metal cations (Fe, Mn and Al) in marine environments, which promotes the burial of these elements in marine sediments. Due to large inputs of weathering products rich in Fe, Mn and Al oxides, precipitation of labile OC and biogenic silica, intense remineralization process and suboxic/anoxic conditions, estuarine and marginal seas are suitable sites for reverse weathering studies. The reverse weathering studies in sub-tropical and temperate estuaries should be emphasized in the future.     

Transformation of magnetite to hematite and its influence on the dissolution of iron oxide minerals

Deformed rocks of the Itabira Iron Formation (itabirites) in Brazil show microstructural evidence of pressure solution of quartz and iron oxides; it appears that magnetite was dissolved and hematite precipitated. The dissolution of magnetite seems to be related to its transformation to hematite by oxidation of Fe²⁺ to Fe³⁺. The transformation of magnetite to hematite occurs along {111} planes, and results in the development of hematite domains along {111} that are parallel to the foliation. The difference in volume created by the transformation of magnetite to hematite and the shear stress acting on the interphase boundaries allow fluids to migrate along these planes. The dissolution of magnetite involves the hydrolyzation of the Fe²⁺—O bonds at interphase boundaries of high normal stress. The high fugacity of oxygen in the fluid phase promotes the reaction of Fe²⁺ (in solution) with oxygen. Fe²⁺ ions oxidize to Fe³⁺ and precipitate as hematite platelets with their longest axes oriented parallel to the direction of maximum stretching. The transformation of magnetite to hematite during deformation plays an important role in the fabric evolution of the iron formation rocks. The transformation along {111} creates planes of weakness that facilitate fracturing. The fracturing plus the dissolution result in a reduction of magnetite grain size, and the oriented precipitation results in layers of hematite platelets. These processes produce a new fabric characterized by a penetrative foliation and lineation.     

Biomineralization of lepidocrocite and goethite by nitrate-reducing Fe(II)-oxidizing bacteria: Effect of pH, bicarbonate, phosphate, and humic acids

Fe(III) solid phases are the products of Fe(II) oxidation by Fe(II)-oxidizing bacteria, but the Fe(III) phases reported to form within growth experiments are, at times, poorly crystalline and therefore difficult to identify, possibly due to the presence of ligands (e.g., phosphate, carbonate) that complex iron and disrupt iron (hydr)oxide precipitation. The scope of this study was to investigate the influences of geochemical solution conditions (pH, carbonate, phosphate, humic acids) on the Fe(II) oxidation rate and Fe(III) mineralogy. Fe(III) mineral characterization was performed using ⁵⁷Fe-Mössbauer spectroscopy and μ-X-ray diffraction after oxidation of dissolved Fe(II) within Mops-buffered cell suspensions of Acidovorax sp. BoFeN1, a nitrate-reducing, Fe(II)-oxidizing bacterium. Lepidocrocite (γ-FeOOH) (90%), which also forms after chemical oxidation of Fe(II) by dissolved O₂, and goethite (α-FeOOH) (10%) were produced at pH 7.0 in the absence of any strongly complexing ligands. Higher solution pH, increasing concentrations of carbonate species, and increasing concentrations of humic acids promoted goethite formation and caused little or no changes in Fe(II) oxidation rates. Phosphate species resulted in Fe(III) solids unidentifiable to our methods and significantly slowed Fe(II) oxidation rates. Our results suggest that Fe(III) mineralogy formed by bacterial Fe(II) oxidation is strongly influenced by solution chemistry, and the geochemical conditions studied here suggest lepidocrocite and goethite may coexist in aquatic environments where nitrate-reducing, Fe(II)-oxidizing bacteria are active.