Biotransformation of two-line silica-ferrihydrite by a dissimilatory Fe(III)-reducing bacterium: formation of carbonate green rust in the presence of phosphate

The reductive biotransformation of two Si-ferrihydrite coprecipitates (1 and 5 mole % Si) by Shewanella putrefaciens, strain CN32, was investigated in 1,4-piperazinediethanesulfonic acid-buffered media (pH ∼7) with lactate as the electron donor. Anthraquinone-2,6-disulfonate, an electron shuttle, was present in the media. Experiments were performed without and with PO₄³⁻ (P) (1 to 20 mmol/L) in media containing 50 mmol/L Fe. Our objectives were to define the combined effects of SiO₄⁴⁻ (Si) and P on the bioreducibility and biomineralization of ferrihydrites under anoxic conditions. Iron reduction was measured as a function of time, solids were characterized by powder X-ray diffraction and Mössbauer spectroscopy, and aqueous solutions were analyzed for Si, P, Cl⁻ and inorganic carbon. Both of the ferrihydrites were rapidly reduced regardless of the Si and P content. Si concentration had no effect on the reduction rate or mineralization products. Magnetite was formed in the absence of P whereas carbonate green rust GR(CO₃²⁻) ([Fe_(6−x)^IIFe^III_x(OH)₁₂]^x+(CO₃²⁻)_0.5x · yH₂O) and vivianite [Fe₃(PO₄)₂ · 8H₂O], were formed when P was present. GR(CO₃²⁻) dominated as a mineral product in samples with <4 mmol/L P. The Fe(II)/Fe(III) ratio of GR(CO₃²⁻) varied with P concentration; the ratio was 2 in 1 mmol/L P and approached 1 with 4- and 10 mmol/L P. Green rust appeared to form by solid-state transformation of ferrihydrite. Media P and Si concentration dictated the mechanism of transformation. In the 1 mole % Si coprecipitate with 1 mmol/L P, an intermediate Fe(II)/Fe(III) phase with structural Fe(II) slowly transformed to GR with time. In contrast, when ferrihydrite contained more Si (5 mole %) and/or contained higher P (4 mmol/L), sorbed Fe(II) and residual ferrihydrite together transformed to GR. Despite similar chemistries, P was shown to have a profound effect on extent of ferrihydrite reduction and biotransformations while that of Si was minimal.     

Impact of highly basic solutions on sorption of Cs to subsurface sediments from the Hanford site, USA

The effect of caustic NaNO₃ solutions on the sorption of ¹³⁷Cs to a Hanford site micaceous subsurface sediment was investigated as a function of base exposure time (up to 168 d), temperature (10°C or 50°C), and NaOH concentration (0.1 mol/L to 3 mol/L). At 10°C and 0.1 M NaOH, the slow evolution of [Al]_aq was in stark contrast to the rapid increase and subsequent loss of [Al]_aq observed at 50°C (regardless of base concentration). Exposure to 0.1 M NaOH at 10°C for up to 168 d exhibited little if any measurable effect on sediment mineralogy, Cs⁺ sorption, or Cs⁺ selectivity; sorption was well described with a two-site ion exchange model modified to include enthalpy effects. At 50°C, dissolution of phyllosilicate minerals increased with [OH]. A zeolite (tetranatrolite; Na₂Al₂Si₃O₁₀·2H₂O) precipitated in 0.1 M NaOH after about 7 days, while an unnamed mineral phase (Na₁₄Al₁₂Si₁₃O₅₁·6H₂O) precipitated after 4 and 2 days of exposure to 1 M and 3 M NaOH solutions, respectively. Short-term (16 h) Cs⁺ sorption isotherms (10⁻⁹-10⁻² mol/L) were measured on sediment after exposure to 0.1 M NaOH for 56, 112, and 168 days at 50°C. There was a trend toward slightly lower conditional equilibrium exchange constants (Δlog _Na^CsK_c ∼ 0.25) over the entire range of surface coverage, and a slight loss of high affinity sites (15%) after 168 days of pretreatment with 0.1 M base solution. Cs⁺ sorption to sediment over longer times was also measured at 50°C in the presence of NaOH (0.1 M, 1 M, and 3 M NaOH) at Cs⁺ concentrations selected to probe a range of adsorption densities. Model simulations of Cs⁺ sorption to the sediment in the presence of 0.1 M NaOH for 112 days slightly under-predicted sorption at the lower Cs⁺ adsorption densities. At the higher adsorption densities, model simulations under-predicted sorption by 57%. This under-prediction was surmised to be the result of tetranatrolite precipitation, and subsequent slow Na → Cs exchange. At higher OH concentrations, Cs⁺ sorption in the presence of base for 112 days was unexpectedly equal to, or greater than that expected for pristine sediment. The precipitation of secondary phases, coupled with the fairly unique mica distribution and quantity across all size-fractions in the Hanford sediment, appears to mitigate the impact of base dissolution on Cs⁺ sorption.     

西秦岭勉略带陆内构造变形研究

秦岭造山带勉略缝合带是古特提斯洋盆向北俯冲形成的华北与华南最后拼接带。这个主缝合带俯冲-碰撞过程中以由北向南的一系列韧性逆冲推覆构造为特征,形成由前泥盆系、泥盆-石炭系和蛇绿混杂岩等不同构造岩片叠置的复杂构造带,碰撞时代从245Ma一直延续到230Ma左右。最近,作者对勉略缝合带内发育的韧性和脆性左行走滑剪切变形进行了研究,结果表明这些顺造山带的左行韧性走滑剪切变形带的变形时代为223±2Ma,与碰撞后花岗岩所确定的碰撞后构造环境的起始时间(225Ma)一致,显示这些韧性走滑剪切变形带是勉略带陆内变形初期变形产物。亦即华北、扬子大陆碰撞之后很快就转入陆内变形阶段,并且是以顺造山带的侧向走滑位移为主要变形方式。勉略带内顺造山带的脆性左行走滑断层的发育,表明这种顺造山带的侧向位移过程从深部到地壳浅层是一致的。因此,大陆碰撞在直接碰撞之后很快转变为顺造山带的侧向走滑位移为主的陆内变形,这种位移可能表现为两个大陆碰撞后的相对走滑,或是碰撞带中强烈变形部分顺造山带的侧向挤出,从而消减了正向碰撞所造成的地壳缩短和增厚。     

内蒙古鸡冠山斑岩钼矿床成矿时代和成矿流体研究

内蒙古鸡冠山钼矿床是西拉沐伦钼成矿带上的典型斑岩矿床。矿床产于火山侵入杂岩中,矿化类型以细脉浸染状矿化为主。对矿床5件辉钼矿样品进行了铼-锇同位素分析,获得了151.1±1.3Ma的等时线年龄,表明成矿作用发生在晚侏罗世。成矿作用可划分为三个阶段:早阶段为石英-黄铁矿阶段,发育乳白色石英和粗粒浸染状黄铁矿;中阶段包括早期石英-多金属硫化物亚阶段和晚期石英-萤石-金属硫化物亚阶段;晚阶段为石英-碳酸盐细脉,穿切早、中阶段脉体和矿物组合。鸡冠山钼矿床流体包裹体岩相学研究表明,与成矿有关的包裹体主要有六种类型:富液相、富气相、含子晶多相、含CO2三相、纯CO2及纯液相包裹体。其中,早阶段以富气和富CO2包裹体为主,中阶段多种包裹体共存,晚阶段则主要为富液包裹体。冷热台显微测温和激光拉曼显微探针(LRM)成分分析结果表明,早阶段石英中原生包裹体的均一温度480℃,盐度最高66.75%NaCleqv,包裹体气相成分富含水和CO2,液相成分则以水为主,子晶矿物有石盐、黄铜矿以及指示氧化条件的赤铁矿等,同时也说明成矿流体是富含成矿金属元素的。中阶段早期石英中的流体包裹体均一温度为320～480℃,晚期石英和萤石中的流体包裹体的均一温度为180～320℃。中阶段流体盐度介于4.65%～56.76%NaCleqv。中阶段包裹体含石盐、方解石、黄铜矿、赤铁矿等子矿物,富气相、富液相与含子晶多相包裹体共存,且具有相近的均一温度,而盐度相差悬殊,指示流体发生了沸腾。晚阶段流体的温度降低至100～180℃,盐度则低于10.86%NaCleqv,流体包裹体成分主要为水。鸡冠山钼矿成矿流体演化从早至晚为:从早阶段高温、高盐度、高氧逸度、富CO2、富成矿物质以岩浆热液为主成矿流体,演化至晚期低温、低盐度、无子晶、贫CO2、以大气降水为主的流体。沸腾作用是鸡冠山钼矿形成的重要机制。     

东秦岭石窑沟斑岩钼矿床地质特征及辉钼矿Re-Os年龄

在东秦岭钼成矿带最近探明的石窑沟大型钼矿床位于近东西向马超营断裂带与北东向石窑沟-焦园断裂带的交汇部位,获得钼金属储量10余万吨,平均品位0.068%。钼矿化呈细脉-网脉状分布于花岗斑岩体及其围岩熊耳群火山岩中,与矿化有关的围岩蚀变有钾长石化、硅化、绢云母化、黄铁矿化等,具有斑岩型钼矿床的一些基本特点。在矿床中选取5件不同矿化类型的辉钼矿样品,采用ICP-MS法进行Re-Os同位素定年,获得模式年龄131.3±2.4～134.3±2.6Ma,等时线年龄135.2±1.8Ma(MSWD=0.18),形成于早白垩世,与豫西熊耳山地区雷门沟、鱼池岭等钼矿床形成时代相近。据辉钼矿Re含量(8.242×10-6～30.24×10-6)推测,矿床成矿物质主要来自于下地壳。矿床为东秦岭-大别山地区中生代第三期钼成矿作用产物,形成于早白垩世中国东部岩石圈伸展环境。     

Microscale controls on the fate of contaminant uranium in the vadose zone, Hanford Site, Washington

An alkaline brine containing uranyl (UO₂²⁺) leaked to the thick unsaturated zone at the Hanford Site. We examined samples from this zone at microscopic scale to determine the mode of uranium occurrence—microprecipitates of uranyl (UO₂²⁺) silicate within lithic-clast microfractures—and constructed a conceptual model for its emplacement, which we tested using a model of reactive diffusion at that scale. The study was driven by the need to understand the heterogeneous distribution of uranium and the chemical processes that controlled it. X-ray and electron microprobe imaging showed that the uranium was associated with a minority of clasts, specifically granitic clasts occupying less than four percent of the sediment volume. XANES analysis at micron resolution showed the uranium to be hexavalent. The uranium was precipitated in microfractures as radiating clusters of uranyl silicates, and sorbed uranium was not observed on other surfaces. Compositional determinations of the 1-3 μm precipitates were difficult, but indicated a uranyl silicate. These observations suggested that uranyl was removed from pore waters by diffusion and precipitation in microfractures, where dissolved silica within the granite-equilibrated solution would cause supersaturation with respect to sodium boltwoodite. This hypothesis was tested using a reactive diffusion model operating at microscale. Conditions favoring precipitation were simulated to be transient, and driven by the compositional contrast between pore and fracture space. Pore-space conditions, including alkaline pH, were eventually imposed on the microfracture environment. However, conditions favoring precipitation were prolonged within the microfracture by reaction at the silicate mineral surface to buffer pH in a solubility limiting acidic state, and to replenish dissolved silica. During this time, uranyl was additionally removed to the fracture space by diffusion from pore space. Uranyl is effectively immobilized within the microfracture environment within the presently unsaturated Vadose Zone.     

Fluorescence spectroscopy of U(VI)-silicates and U(VI)-contaminated Hanford sediment

Time-resolved U(VI) laser fluorescence spectra (TRLFS) were recorded for a series of natural uranium-silicate minerals including boltwoodite, uranophane, soddyite, kasolite, sklodowskite, cuprosklodowskite, haiweeite, and weeksite, a synthetic boltwoodite, and four U(VI)-contaminated Hanford vadose zone sediments. Lowering the sample temperature from RT to ∼ 5.5 K significantly enhanced the fluorescence intensity and spectral resolution of both the minerals and sediments, offering improved possibilities for identifying uranyl species in environmental samples. At 5.5 K, all of the uranyl silicates showed unique, well-resolved fluorescence spectra. The symmetric O = U = O stretching frequency, as determined from the peak spacing of the vibronic bands in the emission spectra, were between 705 to 823 cm⁻¹ for the uranyl silicates. These were lower than those reported for uranyl phosphate, carbonate, or oxy-hydroxides. The fluorescence emission spectra of all four sediment samples were similar to each other. Their spectra shifted minimally at different time delays or upon contact with basic Na/Ca-carbonate electrolyte solutions that dissolved up to 60% of the precipitated U(VI) pool. The well-resolved vibronic peaks in the fluorescence spectra of the sediments indicated that the major fluorescence species was a crystalline uranyl mineral phase, while the peak spacing of the vibronic bands pointed to the likely presence of uranyl silicate. Although an exact match was not found between the U(VI) fluorescence spectra of the sediments with that of any individual uranyl silicates, the major spectral characteristics indicated that the sediment U(VI) was a uranophane-type solid (uranophane, boltwoodite) or soddyite, as was concluded from microprobe, EXAFS, and solubility analyses.     

Chromium speciation and mobility in a high level nuclear waste vadose zone plume

Radioactive core samples containing elevated concentrations of Cr from a high level nuclear waste plume in the Hanford vadose zone were studied to asses the future mobility of Cr. Cr(VI) is an important subsurface contaminant at the Hanford Site. The plume originated in 1969 by leakage of self-boiling supernate from a tank containing REDOX process waste. The supernate contained high concentrations of alkali (NaOH ≈ 5.25 mol/L), salt (NaNO₃/NaNO₂ >10 mol/L), aluminate [Al(OH)₄⁻ = 3.36 mol/L], Cr(VI) (0.413 mol/L), and ¹³⁷Cs⁺ (6.51 × 10⁻⁵ mol/L). Water and acid extraction of the oxidized subsurface sediments indicated that a significant portion of the total Cr was associated with the solid phase. Mineralogic analyses, Cr valence speciation measurements by X-ray adsorption near edge structure (XANES) spectroscopy, and small column leaching studies were performed to identify the chemical retardation mechanism and leachability of Cr. While X-ray diffraction detected little mineralogic change to the sediments from waste reaction, scanning electron microscopy (SEM) showed that mineral particles within 5 m of the point of tank failure were coated with secondary, sodium aluminosilicate precipitates. The density of these precipitates decreased with distance from the source (e.g., beyond 10 m). The XANES and column studies demonstrated the reduction of 29-75% of the total Cr to insoluble Cr(III), and the apparent precipitation of up to 43% of the Cr(VI) as an unidentified, non-leachable phase. Both Cr(VI) reduction and Cr(VI) precipitation were greater in sediments closer to the leak source where significant mineral alteration was noted by SEM. These and other observations imply that basic mineral hydrolysis driven by large concentrations of OH⁻ in the waste stream liberated Fe(II) from the otherwise oxidizing sediments that served as a reductant for CrO₄²⁻. The coarse-textured Hanford sediments contain silt-sized mineral phases (biotite, clinochlore, magnetite, and ilmenite) that are sources of Fe(II). Other dissolution products (e.g., Ba²⁺) or Al(OH)₄⁻ present in the waste stream may have induced Cr(VI) precipitation as pH moderated through mineral reaction. The results demonstrate that a minimum of 42% of the total Cr inventory in all of the samples was immobilized as Cr(III) and Cr(VI) precipitates that are unlikely to dissolve and migrate to groundwater under the low recharge conditions of the Hanford vadose zone.     

Petrologic constraints on rift-zone processes

The Puu Oo eruption in the middle of Kilauea volcano's east rift zone provides an excellent opportunity to utilize petrologic constraints to interpret rift-zone processes. Emplacement of a dike began 24 hours before the start of the eruption on 3 January 1983. Seismic and geodetic evidence indicates that the dike collided with a magma body in the rift zone. Most of the lava produced during the initial episode of the Puu Oo eruption is of hybrid composition, with petrographic and geochemical evidence of mixing magmas of highly evllved and more mafic compositions. Some olivine and plagioclase grains in the hybrid lavas show reverse zoning. Whole-rock compositional variations are linear even for normally compatible elements like Ni and Cr. Leastsquares mixing calculations yield good residuals for major and trace element analyses for magma mixing. Crystal fractionation calculations yield unsatisfactory residuals. The highly evolved magma is similar in composition to the lava from the 1977 eruption and, at one point, vents for these two eruptions are only 200 m apart. Possibly both the 1977 lava and the highly evolved component of the episode 1 Puu Oo lava were derived from a common body of rift-zone-stored magma. The more mafic mixing component may be represented by the most mafic lava from the January 1983 eruption; it shows no evidence of magma mixing. The dike that was intruded just prior to the start of the Puu Oo eruption may have acted as a hydraulic plunger causing mixing of the two rift-zone-stored magmas.