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1.
狮泉河蛇绿混杂岩带的结构、性质、形成时间及与班-怒带的时空演化关系是青藏高原大地构造划分中亟待解决的问题。通过系统的地质调查工作,证实狮泉河带内存在完整的蛇绿岩带,并首次将其划分为4个蛇绿岩亚带,相互之间由3个呈平行分布的岛弧链分隔,从而构成一个早白垩世的多岛弧盆系统。狮泉河带闭合过程为岛弧造山过程,俯冲极向主要向北,构成冈底斯-腾冲陆块和喀喇昆仑-南羌塘-左贡陆块之间的晚燕山期结合带;它与班-怒带在时间上具有继承性,空间上由北向南迁移,并部分重叠,反映了由班-怒带向狮泉河带的转化是一种接力式的。上述发现对青藏高原大地构造单元划分、新特提斯洋构造演化的研究具有重要意义。  相似文献   

2.
刘福来  刘平华 《岩石学报》2009,25(9):2113-2131
北苏鲁仰口地区出露超高压的变辉长岩.锆石阴极发光图像和其内部矿物包体激光拉曼测试的联合研究结果表明,变辉长岩锆石具有弱发光效应的岩浆韵律环带的核和被改造的强发光效应的边.岩浆韵律环带的核部保存大量而复杂的矿物包体,包括普通辉石(Cpx)+斜方辉石(Opx)+斜长石(P1)+石英(Qtz)+黑云母(Bt)+钛铁矿(Ilm)+磷灰石(Ap);边部保存的矿物包体则相对较少,包括普通辉石(Cpx)+斜方辉石(Opx)+斜长石(Pl)+磷灰石(Ap).尽管岩浆韵律环带核部的稀土元素总合量比被改造的锆石边部明显偏高,但二者稀土元素配分模式具有明显的相似性,主要表现为轻稀土相对亏损,而重稀土明显富集,相应的(La/Yb)N=0.00015~0.00039,并具有明显的负Eu异常(Eu/Eu*=0.20~0.26)、相对明显的正Ce异常(Ce/Ce*=71.5~147.4)和较高的Th/U比值(1.97~2.69).上述特征表明,仰口地区变辉长岩中的锆石均为继承性的岩浆锆石,而没有新生的变质锆石.LA-(MC)-ICP-MS锆石原位U-Pb定年和Lu-Hf同位素分析结果表明,两件锆石样品Y1和Y2的年龄数据所构成的不一致线显示了十分接近的上交点和下交点年龄.其上交点年龄分别为785±15Ma(2σ)和784±12Ma(2σ),应代表原岩的形成时代,表明变辉长岩的原岩与Rodinia超大陆裂解的岩浆事件存在密切的成因关系;而下交点年龄分别为226±24Ma(2σ)和228±26Ma(2σ),与苏鲁其它类型超高压岩石中含柯石英锆石微区记录的变质年龄十分吻合,应代表变辉长岩的超高压变质时代.岩浆结晶锆石的核部具有明显偏高的176Lu/177Hf(0.00044~0.00291)和176Yh/177Hf(0.0165~0.1168)比值,而176Hf/177Hf比值变化于0.281956~0.282048之间,相应的εHf(t)=-8.5~-14.0,tDM2=2.03~2.32Ga,表明仰口地区变辉长岩的原岩起源于古元古代时期的富集地幔或发生部分熔融的下地壳残留体.被改造的岩浆结晶锆石的边部则具有明显偏低的176Lu/177Hf(0.00029~0.00060)和176Yh/177Hf(0.0112~0.0200)比值,而176Hf/177Hf(t)比值变化于0.281953~0.282002之间,相应的εHf(t)=-10.2~-11.9,tDM2=2.12~2.21Ga.与岩浆结晶锆石核部相比,被改造的岩浆锆石边部的176Lu/177Hf、176Yb/177Hf、176Hf/177Hf(t)比值和εHf(t)和tDM2值的变化范围更小,表明中-新三叠纪的超高压变质作用使岩浆结晶锆石边部的Lu-Hf同位素体系发生调整,更趋向于均一化.  相似文献   

3.
Various sedimentary sequences of the Himalaya reflecting different tectonic cycles when compared with the ages of (i) unconformity, (ii) pre-Tertiary metamorphism, (iii) granites and (iv) pre-Tertiary deformations point to following pre-Tertiary Orogenies: (i) Sundernagar (Middle Precambrian), (ii) Shali (Vendian), (iii) Jasim-Kurgiakh (Ordovician), (iv) Blaini-Thidsi (Upper Paleozoic) and (v) Tal-Chikkim (Middle-Upper Cretaceous). Besides these, minor impulses identifiable are: (i) Bandel-2 (Middle Riphean), (ii) Tangze (Devonian), (iii) Infra Krol (Upper Permian), (iv) Tandi (? Callovian) and (v) Krol (Upper Jurassic - Lower Cretaceous). Due to paucity of deformation structures related to these earth movements, it is suggested that these were either (i) mainly epeirogenic, (ii) feebly orogenic or (iii) they produced folds which were coaxial with subsequent Himalayan folds hence indistinguishable from the latter.  相似文献   

4.
The present research is an attempt to assess the Barakar Formation of the Raniganj Gondwana Basin, India, in the frame of fluvio-marine (estuarine) depositional systems using sequence stratigraphic elements. Analysis of predominant facies associations signify deposition in three sub-environments: (i) a river-dominated bay-head delta zone in the inner estuary, with transition from braided fluvial channels (FA-B1) to tide-affected meandering fluvial channels and flood plains (FA-B2) in the basal part of the succession; (ii) a mixed energy central basin zone, which consists of transitional fluvio-tidal channels (FA-B2), tidal flats, associated with tidal channels and bars (FA-B3) in the middle-upper part of the succession; and (iii) a wave-dominated outer estuary (coastal) zone (FA-B4 with FA-B3) in the upper part of the succession. Stacked progradational (P1, P2)–retrogradational (R1, R2) successions attest to one major base level fluctuation, leading to distinct transgressive–regressive (T–R) cycles with development of initial falling stage systems tract (FSST), followed by lowstand systems tract (LST) and successive transgressive systems tracts (TST-1 and TST-2). Shift in the depositional regime from regressive to transgressive estuarine system in the early Permian Barakar Formation is attributed to change in accommodation space caused by mutual interactions of (i) base level fluctuations in response to climatic amelioration and (ii) basinal tectonisms (exhumation/sagging) related to post-glacial isostatic adjustments in the riftogenic Gondwana basins.  相似文献   

5.
The mechanisms of abiotic sequestration of Se(VI) and Se(IV) on a sample of coal waste rock collected from the Elk Valley, Canada and on three pure mineral species (i.e., siderite, pyrite, and sphalerite) present in coal waste rock were assessed using sterile batch testing under water-saturated, anoxic conditions. Only siderite removed measurable Se(VI) from the test solutions with ~90% removal after 100 d attributed to initial adsorption to the siderite surface as Se(VI) and subsequent reduction to Se(IV) and Se(0). In contrast to Se(VI), all samples removed Se(IV) from the aqueous solutions. The rate of Se(IV) removal was pyrite > siderite > waste rock > sphalerite. The waste rock sample removed Se(IV) from solution in two stages: up to ~40% of the aqueous Se(IV) was rapidly removed (by day 1) followed by slower removal of Se(IV) with up to ~97% removal after 99 d. Se(IV) removal is attributed to the adsorption of Se(IV) and subsequent reduction to Se(0) onto the siderite and pyrite phases of the waste rock. The initial (1 d) removal of Se(IV) by waste rock was characterized using a distribution coefficient (Kd) of 15.5 L/kg. Longer-term Se(IV) removal was fitted with zero and first order removal rates. The removal of Se(IV) by sphalerite was minor and deemed to have a minimal effect on Se sequestration in the waste rock. Desorption tests on waste rock showed that the fraction of sequestered Se susceptible to desorption decreased with time as adsorbed Se(IV) was reduced to insoluble Se(0). These findings show that abiotic Se sequestration can occur in saturated, anoxic zones in coal waste rock dumps.  相似文献   

6.
Ce(IV)-Ce(III) and Fe(III)-Fe(II) redox equilibria in Ca-Mg-Al-silicate melts have been individually measured with respect to the base composition, melt temperature, imposed oxygen fugacity, and multivalent element concentration (up to about 1.5 wt%). The mutual interaction of these two redox couples has been studied in analogous glasses which simultaneously contained iron and cerium. Analyses of Fe(III) concentrations in iron-cerium glasses by electron paramagnetic resonance and optical absorption spectroscopy indicate that Ce(IV) is stoichiometrically reduced by Fe(II) in the melt to produce Fe(III) and Ce(III) and that Ce(III)-O-Fe(III) complexes are formed in the melt. Consequently, it is concluded that cerium exists only as Ce(III) in basaltic magmas; cerium anomalies cannot be ascribed to the stabilization of Ce(IV) in magmas.  相似文献   

7.
The distribution behavior of tellurium (Te) between soil and water in a synthetic soil-water system was studied coupled with the speciation of Te both in soil and water phases by using X-ray absorption fine structure (XAFS) spectroscopy and a high-performance liquid chromatography connected to an ICP-MS (HPLC-ICP-MS), respectively. The results were compared with a similar data set for Se, which was simultaneously obtained in this study. The oxidation states and host phases of Te and Se in the soil samples were given by XAFS, while the oxidation states in water were given by HPLC-ICP-MS. It was found that both Te and Se in soil are mainly associated with Fe(III) hydroxides under oxic conditions. From the EXAFS analyses, the outer-sphere complex is important for the Se(VI) sorbed on Fe(III) hydroxides in soils, while Se(IV), Te(IV), and Te(VI) form inner-sphere complexes. Under reducing condition, it was found that Te(0) and Se(0) species were formed and that Se was more readily reduced to Se(0) than Te, as is predicted from their Eh-pH diagrams. The reduction process from hexavalent to zerovalent species was different between Se and Te, that is, the direct reduction from Se(VI) to Se(0) was observed for Se, while Te was reduced stepwise from Te(VI) to Te(0) via Te(IV). In terms of the distribution between soil and water, Se distribution to water was much higher than that of Te under wide redox conditions. For Se, selenate is the predominant species in water even under reducing condition due to the much higher solubility of Se(VI) than Se(IV). Furthermore, a much smaller distribution of Te in water was primarily due to the larger affinities of Te(IV) and Te(VI) to Fe(III) hydroxides than Se(VI), which originates from the formation of the inner-sphere complexes of Te(IV) and Te(VI) to Fe(III) hydroxides.  相似文献   

8.
传统型铂族矿产,系指与镁铁质岩浆成矿作用有关的铂族矿产资源。华力西运动时期,扬子地台西南缘沿超壳深断裂带发生的大陆裂谷作用,为来自上地幔的镁铁质(拉斑玄武岩质)岩浆的上涌和侵位提供了极为有利的前提条件。含铂基性超基性岩的时空分布,受到大陆裂谷作用的主要发生发展时期和裂谷活动带的控制。通过对典型矿床特征及其成矿作用的探讨,论述了扬子地台西南缘主要的铂族矿床类型;并从四维成矿的角度,阐述了对区域成矿规律的一些基本认识。  相似文献   

9.
我国海南岛及南海诸岛沿岸,广泛发育海滩岩。1980年我队赴海南岛考察现代沉积时,对海滩岩的分布、岩性特征及其与周围环境的关系进行了观察和采样。样品采自崖县鹿回头三亚湾水尾岭海蚀崖、西洲岛、小东海、东瑁岛、西瑁岛、天涯海角,乐东县莺歌海,文昌县渔业等地(图1)。有关的地质、地貌及岩性特征等,已有许多描述,对海滩岩的岩石学及成岩作用也有许多研究。本文侧重探讨海滩岩的胶结作用及与成岩环境的关系。  相似文献   

10.
High-grade exotic blocks in the Franciscan Complex at Jenner, California, show evidence for polydeformation/metamorphism, with eight distinct stages. Two parallel sets of mineral assemblages [(E) eclogite, and (BS) laminated blueschist] representing different bulk chemistry were identified. Stage 1, recorded by parallel aligned inclusions (S1) of crossite + omphacite + epidote + ilmenite + titanite + quartz (E), and glaucophane + actinolite + epidote + titanite (BS) in the central parts of zoned garnets, represents the epidote blueschist facies. The onset of a second stage (stage 2) is represented by a weak crenulation of S1 and growth of garnet. This stage develops a well-defined S2 foliation of orientated barroisite + epidote + titanite (E), or subcalcic actinolite + epidote + titanite (BS) at c. 90d? to S1, with syntectonic growth of garnet, defining the (albite-)epidote-amphibolite facies. A third stage, with aligned inclusions of glaucophane + (subcalcic) actinolite + phengite parallel to S2 in the outermost rims of large garnet grains, is assigned to the transitional (albite-)epidote-amphibolite/(garnet-bearing) epidote blueschist facies. The fourth stage represents the peak metamorphism, and was identified by unorientated matrix minerals in the least retrograded samples. In this stage the mineral assemblages garnet + omphacite + glaucophane + phengite (E) and garnet + winchite + phengite + epidote (BS) both represent the eclogite facies. Stage 5 is represented by the retrogression of eclogite facies assemblages to the epidote blueschist facies assemblages crossite/glaucophane + garnet + omphacite + epidote + phengite (E), and glaucophane + actinolite + epidote + phengite (BS), with the development of an S5 foliation subparallel to S2. Stage 6 represents a crenulation of S5, with the development of a well-defined S6 crenulation cleavage wrapping around relics of the eclogite facies assemblages. This crenulation cleavage is further weakly crenulated during a D7 event. Post-D7 (stage 8) is recorded by the growth of lawsonite + chlorite ± actinolite replacing garnet, and by veins of lawsonite + pumpellyite + aragonite and phengite + apatite. The different, yet coeval, mineral parageneses observed in rock types (E) and (BS) are probably due to differences in bulk chemistry. The metamorphic evolution from stage 1 to stage 8 seems to have been broadly continuous, following an anticlockwise P-Tpath: (1) epidote blueschist (garnet-free) to (2) (albite-)epidote-amphibolite to (3) transitional epidote blueschist (garnet-bearing)/(albite-)epidote-amphibolite to (4) eclogite to (5) epidote blueschist (garnet-bearing) to (6-7) epidote blueschist (garnet-free) facies to (8) lawsonite + pumpellyite + aragonite-bearing assemblages. This anticlockwise P-T path may have resulted from a decreasing geothermal gradient with time in the Mesozoic subduction zone of California at early or pre-Franciscan metamorphism.  相似文献   

11.
塔深1井寒武系白云岩储层同位素流体地球化学示踪   总被引:3,自引:0,他引:3  
通过对塔里木盆地沙雅隆起阿克库勒凸起东部塔深1井寒武系白云岩岩石学特征及成岩成因分析,影响塔深1井寒武系地层流体改变主要成岩有准同生期、埋藏期和后期热液改造期等.塔深1井寒武系白云岩及充填孔、洞、缝内方解石的氧、碳、锶同位素地球化学特征表明:准生期白云岩δ~(13)C_(PDB)值(0.9‰~1.8‰)偏正、δ~(18)C_(PDB)值(-10.1‰~-4.2‰)偏负反映准同生期泥微晶白云石成因属于高盐度的海水使得碳酸盐泥发生白云石化;埋藏期白云岩碳、氧随重结晶作用加强,白云岩晶粒由细向粗变化值随埋深增加,由于同位素分馏作用而偏负,δ~(18)C_(PDB)值(-10.02‰~-5.7‰)呈明显的下降,但δ~(13)C_(PDB)值(-1.4‰~0‰)组成变化不大;后期热液白云岩在热液作用下δ~(18)C_(PDB)值普遍低于-10‰(δ~(18)C_(PDB)/‰-13.1~-9.4,δ~(13)C_(PDB)/‰-2~-0.647);基质方解石δ~(18)C_(PDB)值为-10.1‰~-10.13‰,δ~(13)C_(PDB)值为-1.48‰~-1.62‰;充填孔洞缝粗-巨晶方解石δ~(18)C_(PDB)值为-10.89‰~-14.28‰,δ~(13)C_(PDB)值为-2‰~-3.09‰,反映准同生期→埋藏期→后期热液晶粒大小由泥微晶→细晶→中晶→粗晶氧碳同位素值逐渐变小偏负,据~(87)Sr/~(86)Sr(0.707 284~0.746 888)值均远高于现今海洋中海水的锶同位素组成(0.708)及围岩的锶同位素(0.707 284),说明鞍形白云石以及方解石结晶时的孔隙流体不是残余在岩石孔隙中的同生期海水,而是外来的富含锶的流体,也就是深部热液流体.渗透回流白云石化、埋藏白云石化和高温热液白云石化等特征表明白云岩形成于超盐度、埋藏和高温热液等3种不同的环境,因此影响储层形成与分布,从而影响对白云岩的勘探.  相似文献   

12.
Manganese (oxy)hydroxides (MnOX) play important roles in the oxidation and mobilization of toxic As(III) in natural environments. Abiotic oxidation of Mn(II) to MnOX in the presence of Fe minerals has been proved to be an important pathway in the formation of Mn(III, IV) (oxy)hydroxides. However, interactions between Mn(II) and As(III) in the presence of Fe minerals are still poorly understood. In this study, abiotic oxidation of Mn(II) on lepidocrocite, and its effect on the oxidation and mobilization of As(III) were investigated. The results show that MnOX species are detected on lepidocrocite and their contents increase with increasing pH values ranging from 7.5 to 8.4. After 10 days, an MnOx component, groutite (α-MnOOH) was found on lepidocrocite. During the simultaneous oxidation of Mn(II) and As(III), and the As(III) pre-adsorbed processes, the presence and oxidation of Mn(II) significantly promotes the removal of soluble As(III). In addition, MnOx formed on lepidocrocite also contributes to the oxidation of soluble and adsorbed As(III) to As(V), the latter being subsequently released into solution. In the process where Mn(II) is pre-adsorbed on lepidocrocite, less As(III) is removed, given that the active sites occupied by MnOx inhibit the adsorption of As(III). In all experiments, the removal percentages of As(III) and the release of As(V) are correlated positively with pH values and initial concentrations of Mn(II), although they are not apparent in the Mn(II) pre-adsorbed system.  相似文献   

13.
塔里木盆地北部丘里塔格群(寒武系至奥陶系)白云岩的成因   总被引:17,自引:2,他引:17  
叶德胜 《沉积学报》1992,10(4):77-86
本文通过详细岩石学及地球化学研究,探讨了塔里木盆地丘里塔格群(寒武至奥陶系)白云岩的成因。研究表明藻纹层白云岩、微晶白云岩及颗粒白云岩中的颗粒为近地表准同生白云化的产物。结晶白云岩(细晶以上)及颗粒白云岩中的中粗晶白云岩胶结物是深埋藏成岩环境的产物。并对埋藏白云化的镁离子来源及搬运机理进行了探讨。  相似文献   

14.
Analytical methods used for determining dissolved Fe(II) often yield inaccurate results in the presence of high Fe(III) concentrations. Accurate analysis of Fe(II) in solution when it is less than 1% of the total dissolved Fe concentration (FeT) is sometimes required in both geochemical and environmental studies. For example, such analysis is imperative for obtaining the ratio Fe(II)/Fe(III) in rocks, soils and sediments, for determining the kinetic constants of Fe(II) oxidation in chemical or biochemical systems operating at low pH, and is also important in environmental engineering projects, e.g. for proper control of the regeneration step (oxidation of Fe(II) into Fe(III)) applied in ferric-based gas desulphurization processes. In this work a method capable of yielding accurate Fe(II) concentrations at Fe(II) to FeT ratios as low as 0.05% is presented. The method is based on a pretreatment procedure designed to separate Fe(II) species from Fe(III) species in solution without changing the original Fe(II) concentration. Once separated, a modified phenanthroline method is used to determine the Fe(II) concentration, in the virtual absence of Fe(III) species. The pretreatment procedure consists of pH elevation to pH 4.2–4.65 using NaHCO3 under N2(g) environment, followed by filtration of the solid ferric oxides formed, and subsequent acidification of the Fe(II)-containing filtrate. Accuracy of Fe(II) analyses obtained for samples (Fe(II)/FeT ratios between 2% and 0.05%) to which the described pretreatment was applied was >95%. Elevating pH to above 4.65 during pretreatment was shown to result in a higher error in Fe(II) determination, likely resulting from adsorption of Fe(II) species and their removal from solution with the ferric oxide precipitate.  相似文献   

15.
INTRODUCTION The properties of phosphor usedin a plasma dis-play panel (PDP) affect the performance of the PDP(Okazaki et al .,2000 ; Rao and Devine ,2000) . Theluminescent properties of the phosphor are decided bythe morphology ,particle size and size distribution ofthe powder ,sothe requirements for the powder mor-phology are high in a color PDP which belongs to ahigh resolution display apparatus (I m et al .,2005 ;Yang et al ., 2005) . Studies have shown that withsmall particle si…  相似文献   

16.
Uranium(VI), which is often elevated in granitoidic groundwaters, is known to adsorb strongly to Fe (hydr)oxides under certain conditions. This process can be used in water treatment to remove U(VI). To develop a consistent geochemical model for U(VI) adsorption to ferrihydrite, batch experiments were performed and previous data sets reviewed to optimize a set of surface complexation constants using the 3-plane CD-MUSIC model. To consider the effect of dissolved organic matter (DOM) on U(VI) speciation, new parameters for the Stockholm Humic Model (SHM) were optimized using previously published data. The model, which was constrained from available X-ray absorption fine structure (EXAFS) spectroscopy evidence, fitted the data well when the surface sites were divided into low- and high-affinity binding sites. Application of the model concept to other published data sets revealed differences in the reactivity of different ferrihydrites towards U(VI). Use of the optimized SHM parameters for U(VI)-DOM complexation showed that this process is important for U(VI) speciation at low pH. However in neutral to alkaline waters with substantial carbonate present, Ca–U–CO3 complexes predominate. The calibrated geochemical model was used to simulate U(VI) adsorption to ferrihydrite for a hypothetical groundwater in the presence of several competitive ions. The results showed that U(VI) adsorption was strong between pH 5 and 8. Also near the calcite saturation limit, where U(VI) adsorption was weakest according to the model, the adsorption percentage was predicted to be >80%. Hence U(VI) adsorption to ferrihydrite-containing sorbents may be used as a method to bring down U(VI) concentrations to acceptable levels in groundwater.  相似文献   

17.
We report on a paramagnetic anisotropy study of three layered phyllosilicates. The mineral samples were characterized through X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). Based on EPR measurements of samples oriented parallel or perpendicular to the magnetic field lines, we show how the substitutional iron is transformed from Fe(II) (biotite) into Fe(III) (muscovite and kaolinite) species and from axial Fe(III) coordination sites (muscovite) to rhombic (kaolinite) sites in response to weathering.  相似文献   

18.
杨刚  杜安道  陈江峰 《地学前缘》2004,11(2):445-452
1 90 Pt通过α衰变生成1 86Os ,目前采用的衰变常数λ =1 .5 4 2× 1 0 -1 2 a-1 是由诺里尔斯克矿床的Pt Os等时线确定的。IIAB群铁陨石的1 90 Pt 1 86Os等时线年龄为 (4 2 90± 2 84 )Ma(2σ) ,说明Pt Os定年方法可能主要适合于古老样品。Pt Os体系的示踪研究以夏威夷现代地幔柱和诺里尔斯克矿床 (与西伯利亚地幔柱有关 )等为例 ,夏威夷苦橄岩的N(1 86Os) /N(1 88Os)值为 0 .1 1 98339~ 0 .1 1 985 2 6 ,γ(Os)为 1 .2 3~ 9.0 6 ,诺里尔斯克矿石的N(1 86Os) /N(1 88Os)为 0 .1 1 984 9,γ(Os)为 8,这种1 86Os/ 1 88Os 1 87Os/ 1 88Os双异常现象揭示了地幔柱物质中有来自地球外核的Os的贡献 ,这是迄今为止Pt Os体系对地球科学研究的最大贡献。Pt Os体系在壳源岩石方面的研究以肖德贝里Cu Ni硫化物矿床为例。研究支持肖德贝里的矿石主要来自地壳的结论 ,并可用二元混合模型 (太古宙苏必利尔省和元古宙Huronian省的沉积变质岩 )来解释其1 87Os/ 1 88Os同位素组成。但是该矿区的某些矿床的1 86Os/ 1 88Os比值偏高 ,需要有古老的Pt/Os比高的镁铁质岩的加入来解释  相似文献   

19.
The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, “dead-end” U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).  相似文献   

20.
The kaolin industry has shown a phenomenal growth record from 1930 to the present and there is no indication that this growth will not continue. Innovative and efficient process developments enabled the kaolin industry to wet process over 5,000,000 tons in 1978 in Georgia and over 3,000,000 tons in the Cornwall district of southwestern England. These two regions supply the major tonnage of paper coating clays for the world's paper industry. The more important process developments are listed as follows: (1) development of chemicals for dispersion and flocculation; (2) continuous blungers to slurry the kaolin at the mine; (3) (continuous degritting by rake classifiers and hydrocyclones; (4) transport of kaolin slurry through pipelines from mine to plant; (5) continuous centrifuges for particle separation into coarse, medium, and fine sizes (6) chemical leaching of iron to improve brightness and color, (7) dewatering to high solids by: (a) continuous rotary vacuum filters; (b) automated plate and frame filter presses; (c) tube presses; (d) high speed contrifuges; (8) spray drying to low moisture and spherical shape to permit bulk hopper car shipments; (9) flotation to remove iron and titanium impurities to improve brightness and whiteness; (10) slurry clay shipments at 70 percent solids in tank cars; (11) high gradient magnetic separation to improve brightness and whiteness and to utilize marginal deposits; (12) delamination to utilize course kaolin stacks to make an improved product; (13) pugging and working the kaolin to improve viscosity; (14) a new development — dewatering to 80 to 85 percent solids using electrophoresis.Each of these developments is described and the future need to develop an efficient process to significantly lower the viscosity of high viscosity kaolins is discussed.  相似文献   

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