Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

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).     

A strange symbiosis: Seismic ray theory and Saturday touch football — Donald V. Helmberger as a graduate advisor

At the end of December of 1978 I was sitting in the office of Caltech Professor Don Helmberger,he was peering out his window towards the San Gabriel Mountains,s...     

RegCM3对东亚环流和中国气候模拟能力的检验

使用RegCM3区域气候模式,嵌套ERA40再分析资料,对东亚地区进行了15年（1987～2001年）时间长度的数值积分试验,分析了模式对东亚平均环流及中国地区气温和降水的模拟。结果表明,模式对东亚平均环流的特征和中国地区降水、地面气温的年、季地理分布和季节变化特征均具有一定的模拟能力,对气温和降水年际变率的模拟也较好。此外模式模拟在测站稀少地区,可以提供局地如降水分布更可靠的信息。模式对气温的模拟存在1-3℃的系统性冷偏差;对中国地区降水地理分布的模拟也存在一定偏差,如对年平均降水的模拟中,降水最大值位置与观测有一定差距,特别是对冬季降水中心的模拟存在较大偏差。模式模拟的夏季降水,在中国北方地区总体偏大100-200 mm,南方总体偏小100-200 mm。模式对地面气温的模拟效果好于降水。     

The Palaeoproterozoic Kristineberg VMS deposit, Skellefte district, northern Sweden. Part II: chemostratigraphy and alteration

The Kristineberg massive sulfide deposit is hosted by metamorphosed volcanic and subvolcanic rocks of the Palaeoproterozoic Skellefte Group. The deposit consists of: (1) two main massive sulfide horizons, the A-ores and B-ores, which dip steeply southwards and are separated by 100–150 m; and (2) the Einarsson Zone, a complex interval of Cu–Au-rich ‘stockwork‘ sulfides and small massive sulfide lenses in altered and deformed rocks near the 1,000 m level. The Einarsson Zone occurs some 20–100 m south of the B-ores. There are no definite younging indicators in the mine sequence. In many areas of the mine, the original host rocks are impossible to identify petrographically due to the abundance of secondary minerals such as quartz, chlorite, muscovite, cordierite, andalusite, phlogopite, pyrite and talc, combined with variably schistose fabrics. Application of immobile-element methods to 600 recent whole-rock chemical analyses has, however, allowed the original rock types to be identified and correlated. Rhyolite X lies immediately north of the A-ore, while andesitic to dacitic to rhyodacitic rocks make up the 100–150 m interval between the A-ore and B-ore, and massive rhyolite A lies immediately south of the B-ore. The felsic rocks are mostly of calc-alkaline affinity, excluding rhyolite X, which is transitional. The mine porphyry, which lies north of the A-ore and forms the marginal phase of the synvolcanic Viterliden Intrusive Complex, is compositionally similar to dacite and rhyodacite. Mass changes calculated for all rock types indicate that most of the volcanic rocks in the mine area are strongly depleted in Na and Ca, and have gained variable amounts of Mg and Fe, whereas Si changes range from negative to positive. Gains in Fe and changes in Si are largest within 5–10 m of the massive sulfide lenses. Cordierite-bearing schists of andesitic to felsic compositions that lie between massive sulfide lenses A and B are not as altered. The Einarsson Zone commonly shows large gains in Fe and Mg, while Si shows large gains to large losses. Immobile-element ratios indicate that very different secondary assemblages in the mine, e.g. andalusite–quartz–muscovite and cordierite–chlorite–talc, can be produced from the same precursor volcanic unit, e.g., rhyolite. Conversely, the same secondary mineral assemblage can be produced from different rocks, e.g. weakly altered andesite and strongly altered rhyolite. The common presence of cordierite + andalusite in the mine area, without anthophyllite, is unusual in the alteration systems of volcanic-hosted massive sulfide deposits, and is proposed to have formed by the metamorphic reaction of the synvolcanic alteration minerals kaolinite and chlorite to produce cordierite. Where kaolinite was in excess of chlorite, andalusite was also formed. We propose that highly acidic alteration fluids locally produced high-Al minerals such as kaolinite that either overprinted, or occurred in place of, a more typical sericite–chlorite–quartz alteration assemblage that otherwise formed near the massive sulfide lenses. Application of lithogeochemical methods to the altered, deformed and metamorphosed Kristineberg rocks has identified specific volcanic contacts with massive sulfide potential, and quantified the effects of synvolcanic hydrothermal alteration. Such an approach can increase the effectiveness of mineral exploration in metamorphosed terrains.     

Review of tufa deposition and palaeohydrological conditions in the White Peak,Derbyshire, UK: implications for Quaternary landscape evolution

This review considers the geological and geomorphological context of tufa barrages that occupy buried valley settings in the Wye catchment, Derbyshire. It describes the potential relationship of the tufa with locations of hypothesised river captures and inception horizon-guided groundwater flow paths. Tufa barrage development is associated with steps in the bedrock, which may be related to knick-point recession during river capture. Broad estimates of valley incision have been calculated from previously dated deposits. These support current interpretations of particularly significant effective base-level lowering during the Anglian and Devensian stages of the Quaternary and have the potential to add to the knowledge of regional uplift histories.     

40Ar/39Ar ages of L4, H5, EL6, and feldspathic ureilitic clasts from the Almahata Sitta polymict ureilite (asteroid 2008 TC3)

The Almahata Sitta (AhS) meteorite consists of disaggregated clasts from the impact of the polymict asteroid 2008 TC₃, including ureilitic (70%–80%) and diverse non-ureilitic materials. We determined the ⁴⁰Ar/³⁹Ar release patterns for 16 AhS samples (3–1500 μg) taken from three chondritic clasts, AhS 100 (L4), AhS 25 (H5), and MS-D (EL6), as well as a clast of ureilitic trachyandesite MS-MU-011, also known as ALM-A, which is probably a sample of the crust of the ureilite parent body (UPB). Based on our analyses, best estimates of the ⁴⁰Ar/³⁹Ar ages (Ma) of the chondritic clasts are 4535 ± 10 (L4), 4537–4555 with a younger age preferred (H5), and 4513 ± 17 (EL6). The ages for the L4 and the H5 clasts are older than the most published ⁴⁰Ar/³⁹Ar ages for L4 and H5 meteorites, respectively. The age for the EL6 clast is typical of older EL6 chondrites. These ages indicate times of argon closure ranging up to 50 Ma after the main constituents of the host breccia, that is, the ureilitic components of AhS, reached the >800°C blocking temperatures of pyroxene and olivine thermometers. We suggest that these ages record the times at which the clasts cooled to the Ar closure temperatures on their respective parent bodies. This interpretation is consistent with the recent proposal that the majority of xenolithic materials in polymict ureilites were implanted into regolith 40–60 Ma after calcium–aluminum-rich inclusion and is consistent with the interpretation that 2008 TC₃ was a polymict ureilite. With allowance for its 10-Ma uncertainty, the 4549-Ma ⁴⁰Ar/³⁹Ar age of ALM-A is consistent with closure within a few Ma of the time recorded by its Pb/Pb age either on the UPB or as part of a rapidly cooling fragment. Plots of age versus cumulative ³⁹Ar release for 10 of 15 samples with ≥5 heating steps indicate minor losses of ⁴⁰Ar over the last 4.5 Ga. The other five such samples lost some ⁴⁰Ar at estimated times no earlier than 3800–4500 Ma bp . Clustering of ages in the low-temperature data for these five samples suggests that an impact caused localized heating of the AhS progenitor ~2.7 Ga ago. In agreement with the published work, 10 estimates of cosmic-ray exposure ages based on ³⁸Ar concentrations average 17 ± 5 Ma but may include some early irradiation.