Diffusive equilibrium in thin films provides evidence of suppression of hyporheic exchange and large‐scale nitrate transformation in a groundwater‐fed river

The hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse‐scale (5–10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine‐scale (<1 cm) biogeochemical patterns, especially in near‐surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO₃^?. In this study, we utilised diffusive equilibrium in thin‐films samplers to capture high resolution (cm‐scale) vertical concentration profiles of NO₃^?, SO₄^2?, Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub‐reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin‐films samplers indicate considerable cm‐scale variability in NO₃^? (4.4 ± 2.9 mg N/L), SO₄^2? (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface‐subsurface water mixing in the shallow sediments of our sub‐reach under baseflow conditions. The significance of this is that upwelling NO₃^?‐rich groundwater does not appear to be attenuated in the riverbed sediments at <15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub‐reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper‐seated groundwater fluxes and hydro‐stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub‐reach. © 2015 The Authors. Hydrological Processes Published by John Wiley & Sons Ltd.     

Comparison of the LEW88516 and ALHA77005 martian meteorites: Similar but distinct

Abstract By mineral and bulk compositions, the Lewis Cliff (LEW) 88516 meteorite is quite similar to the ALHA77005 martian meteorite. These two meteorites are not paired because their mineral compositions are distinct, they were found 500 km apart in ice fields with different sources for meteorites, and their terrestrial residence ages are different. Minerals in LEW88516 include: olivine, pyroxenes (low- and high-Ca), and maskelynite (after plagioclase); and the minor minerals chromite, whitlockite, ilmenite, and pyrrhotite. Mineral grains in LEW88516 range up to a few mm. Texturally, the meteorite is complex, with regions of olivine and chromite poikilitically enclosed in pyroxene, regions of interstitial basaltic texture, and glass-rich (shock) veinlets. Olivine compositions range from Fo₆₄ to Fo₇₀, (avg. Fo₆₇), more ferroan and with more variation than in ALHA77005 (Fo₆₉ to Fo₇₃). Pyroxene compositions fall between En₇₇Wo₄ and En₆₅Wo₁₅ and in clusters near En₆₃Wo₉ and En₅₃Wo₃₃, on average more magnesian and with more variation than in ALHA77005. Shock features in LEW88516 range from weak deformation through complete melting. Bulk chemical analyses by modal recombination of electron microprobe analyses, instrumental neutron activation, and radiochemical neutron activation confirm that LEW88516 is more closely related to ALHA77005 than to other known martian meteorites. Key element abundance ratios are typical of martian meteorites, as is its non-chondritic rare earth pattern. Differences between the chemical compositions of LEW88516 and ALHA77005 are consistent with slight differences in the proportions of their constituent minerals and not from fundamental petrogenetic differences. Noble gas abundances in LEW88516, like those in ALHA77005, show modest excesses of ⁴⁰Ar and ¹²⁹Xe from trapped (shock-implanted) gas. As with other ALHA77005 and the shergottite martian meteorites (except EETA79001), noble gas isotope abundances in LEW88516 are consistent with exposure to cosmic rays for 2.5–3 Ma. The absence of substantial effects of shielding from cosmic rays suggest LEW88516 spent this time as an object no larger than a few cm in diameter.     

华北东部地幔改造作用和置换作用:单斜辉石激光探针研究

对山东蒙阴古生代金伯利岩中石榴石方辉橄榄岩、河南鹤壁新生代玄武岩中 铬尖晶石方辉橄榄岩、山东栖霞新生代玄武岩中央晶石二辉橄榄岩和山东山旺新生代 玄武岩中尖晶石（富ＣｐＸ）二辉橄榄岩单斜辉石的常量、微量元素的研究和对比表明：华 北地块古生代稳定存在的克拉通岩石圈地幔在中、新生代其东部被具大洋地幔性质的 显生宙地幔不均匀地发生了置换作用,残存于南北重力梯度带（岩石圈减薄过渡带）上 的鹤壁浅部克拉通地幔除保存有置换作用前改造作用的丰富信息外,也包含有其深部 被置换后的地幔改造作用信息;郯庐断裂带东部栖霞的新生地幔仍保留有较多的大洋 地幔成分特征,而郯庐断裂带内山旺的新生地幔受后续地幔改造作用的影响有向大陆 地幔演化的趋向．发生于华北地块东部中、新生代的岩石圈巨厚减薄作用与地幔的置换 作用有关,由渐进的富ＣＯ_２流体或碳酸岩熔体对岩石圈地幔的交代改造作用以及由此 所引起的熔体抽取作用是完成新生地幔对古老地幔置换作用的关键．郯庐断裂带等岩 石圈深大断裂为地幔改造作用和地幔置换作用提供了良好的通道作用．     

Anaerobic Metabolism in Tidal Freshwater Wetlands: I. Plant Removal Effects on Iron Reduction and Methanogenesis

For energetic reasons, iron reduction suppresses methanogenesis in tidal freshwater wetlands; however, when iron reduction is limited by iron oxide availability, methanogenesis dominates anaerobic carbon mineralization. Plants can mediate this microbial competition by releasing oxygen into the rhizosphere and supplying oxidized iron for iron reducers. We utilized a plant removal experiment in two wetland sites to test the hypothesis that, in the absence of plants, rates of iron reduction would be diminished, allowing methanogenesis to dominate anaerobic metabolism. In both sites, methanogenesis was the primary anaerobic mineralization pathway, with iron reduction dominating only early and late in the growing season in the site with a less organic soil. These patterns were not influenced by the presence of plants, demonstrating that plants were not a key control of microbial metabolism. Instead, we suggest that site conditions, including soil chemistry, and temperature are important controls of the pathways of anaerobic metabolism.     

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The Proterozoic,albitite-hosted,Valhalla uranium deposit,Queensland, Australia: a description of the alteration assemblage associated with uranium mineralisation in diamond drill hole V39

The Valhalla uranium deposit, located 40 km north of Mount Isa, Queensland, Australia, is an albitite-hosted, Mesoproterozoic U deposit similar to albitite-hosted uranium deposits in the Ukraine, Sweden, Brazil and Guyana. Uranium mineralisation is hosted by a thick package of interbedded fine-grained sandstones, arkoses and gritty siltstones that are bound by metabasalts belonging to the ca. 1,780 Ma Eastern Creek Volcanics in the Western Succession of the Mount Isa basin. Alteration associated with U mineralisation can be divided into an early, main and late stage. The early stage is dominated by laminated and intensely altered rock comprising albite, reibeckite, calcite, (titano)magnetite ± brannerite. The main stage of mineralisation is dominated by brecciated and intensely altered rocks that comprise laminated and intensely altered rock cemented by brannerite, apatite, (uranoan)-zircon, uraninite, anatase, albite, reibeckite, calcite and hematite. The late stage of mineralisation comprises uraninite, red hematite, dolomite, calcite, chlorite, quartz and Pb-, Fe-, Cu-sulfides. Brannerite has U–Pb and Pb–Pb ages that indicate formation between 1,555 and 1,510 Ma, with significant Pb loss evident at ca. 1,200 Ma, coincident with the assemblage of Rodinia. The oldest ages of the brannerite overlap with ⁴⁰Ar/³⁹Ar ages of 1,533 ± 9 Ma and 1,551 ± 7 Ma from early and main-stage reibeckite and are interpreted to represent the timing of formation of the deposit. These ages coincide with the timing of peak metamorphism in the Mount Isa area during the Isan Orogeny. Lithogeochemical assessment of whole rock data that includes mineralised and unmineralised samples from the greater Mount Isa district reveals that mineralisation involved the removal of K, Ba and Si and the addition of Na, Ca, U, V, Zr, P, Sr, F and Y. U/Th ratios indicate that the ore-forming fluid was oxidised, whereas the crystal chemistry of apatite and reibeckite within the ore zone suggests that F⁻ and were important ore-transporting complexes. δ¹⁸O values of co-existing calcite and reibeckite indicate that mineralisation occurred between 340 and 380°C and involved a fluid having δ¹⁸O_fluid values between 6.5 and 8.6‰. Reibeckite δD values reveal that the ore fluid had a δD_fluid value between −98 and −54‰. The mineral assemblages associated with early and main stages of alteration, plus δ¹⁸O_fluid and δD_fluid values, and timing of the U mineralisation are all very similar to those associated with Na–Ca alteration in the Eastern Succession of the Mount Isa basin, where a magmatic fluid is favoured for this style of alteration. However, isotopic data from Valhalla is also consistent with that from the nearby Mount Isa Cu deposit where a basinal brine is proposed for the transport of metals to the deposit. Based on the evidence to hand, the source fluids could have been derived from either or both the metasediments that underlie the Eastern Creek Volcanics or magmatism that is manifest in the Mount Isa area as small pegmatite dykes that intruded during the Isan Orogeny.     

A simple analytical method for calculating temperature perturbations in a basin caused by the flow of water through thin, shallow-dipping aquifers

Fluid flow in sedimentary basins can be driven by a variety of mechanisms. Commonly, flow is localized in relatively thin aquifers or structures and often these permeable units may be approximated by a series of straight planar segments with shallow dip. A simple formula is derived that describes temperature perturbations in a straight aquifer segment with shallow dip. The temperature is determined everywhere along the segment if the flow rate and temperature at one point is known. “Daisy chaining” the solutions allows easy calculation of the temperature perturbation in a basin caused by fluid flow through a shallow-dipping network of linear fault and aquifer segments. The approach may find many applications but is here illustrated the a number of examples related to the origin of Mississippi Valley-type PbZn deposits. The cases considered emphasize the “salinity problem” encountered by models that hypothesize these deposits formed as the result of cross-basin hydrological flow.     

Fractional Crystallization and Liquid Immiscibility Processes in the Alkaline-Carbonatite Complex of Juqui (So Paulo, Brazil)

The Juqui circular intrusion, which is Cretaceous in age (130–135Ma), crops out in the Precambrian gneissic basement in Brazilover an area of 14 km2. It consists of olivine clinopyroxen-itecumulates (with minor olivine gabbros) in the northeastern sector(74 vol.%), whereas ijolites-melteigites-urtites (4%) and nephelinesyenites with minor essexites and syenodiorites (21%) outlinesubannular concentric patterns with an Mg-carbonatite core (1%), in the southwestern part of the complex. Petrographical, bulk rock, and mineral compositional trendsindicate that the origin of the complex can be largely accountedfor by shallow-level fractional crystallization of a carbonatedbasanitic parental magma. Such a magma was generated deep inthe subcontinental lithosphere by low-degree partial meltingof a garnet-phlogopite peridotite source. Mass-balance calculations in agreement with field volume estimatespermit definition of several fractionation stages of the magmaticevolution under nearly closed-system conditions, with inwarddevelopment of zonally arranged side-wall cumulates. These stagesinvolved: (1) fractionation from basanite to essexite magma(liquid fraction F = 33–5%) by crystallization of olivineclinopyroxenite plus minor olivine alkali gabbro cumulates;(2) derivation of the least differentiated mafic nepheline syenite(F = 5–5 %) from essexitic magma by subtraction of a syenodioriteassemblage; (3) exsolution of a carbonatite liquid (5%) froma CO₂-enriched mafic nepheline syenite magma, which also underwentcontinuous fractionation giving rise to ijolite-melteigite-urtitecumulates. The proportion of cumulus clinopyroxene and biotiteand intercumulus nepheline and alkali feldspar in these lastrocks, as well as the absence of alkalis in carbonatite, maybe attributed, at least in part, to loss of alkali-rich hydrousfluids released during and after the unmixing formation of thetwo conjugate liquids. The KD values determined for Mg-carbonatite/nepheline syeniteare lower (1–4–2–9) for light rare earth elements(LREE) than for REE from Eu to Yb (4–6–7–8),in contrast to recent experimental results (Hamilton et al.,1989). A possible explanation is that Juquia Mg-carbonatiterepresents an alreadydifferentiated magma, which underwent extensivefractionation of LREE-enriched calcite. In this way, the highvariability of K₀ REE patterns observed in several alkaline-carbonatitecomplexes can also be accounted for. The remarkably constant initial ⁸⁷Sr/⁸⁶Sr ratios (mostly between0–7052 and 0–7057) support the interpretation ofthe intrusion as having been generated by fractrional crystallizationand liquid immiscibility from a common parental magma. Iligherisotopic ratios (0–7060–0–7078), found mainlyin dykes and in the border facies of the intrusion, may be dueto contamination by the gecissic basement.     

Initial volatilization temperatures and average volatilization rates of coal — Their relationship to coal rank and other characteristics

Two thermal parameters, initial volatilization temperature (IVT) and average volatilization rate (AVR), have been determined by thermogravimetric analysis in argon for 38 coal samples ranging in rank from lignite to low-volatile bituminous. Both IVT and AVR are correlated with percent volatile matter and vitrinite reflectance.The IVT values increase gradually from about 250 to 445°C with increasing rank; however, a change in slope is observed in the region of high-volatile bituminous coals (from about 340°C to about 380°C) when IVT's are plotted against percent volatile matter or percent fixed carbon. The changes in slope near 340°C and near 380°C occur at “coalification jumps” recognized on the basis of changes in the optical and chemical character of the macerals. In general, AVR values decrease gradually with increasing rank for the lignite and sub-bituminous coals and for the medium- and low-volatile bituminous coals; however, a sharp increase in AVR occurs in high-volatile bituminous coals. The change in slope of the IVT curves and sharp increase in the AVR values for high-volatile bituminous coals reflect the development of new, higher vapor pressure organic compounds produced during this stage of the coalification process.A plot of AVR vs IVT reveals three regions which correspond to: (1) lignite and sub-bituminous coals; (2) high-volatile bituminous coals; and (3) medium- to low-volatile bituminous coals.