Micro‐PIXE Geochemical Fingerprinting of Nephrite Neolithic Artifacts from Southwest Bulgaria

Neolithic artifacts made of nephrite, □Ca₂(Fe,Mg)₅Si₈O₂₂(OH)_2, are found at prehistoric settlements in Bulgaria. This study investigates these objects based on particle induced X‐ray emission using a scanning nuclear microprobe (micro‐PIXE technique). Seven nephrite artifacts from the Neolithic sites of Kovachevo, Bulgarchevo and Galabnik in southwest Bulgaria were analyzed to quantify their composition and to establish if a correlation exists between the distribution of major and trace elements, color, impurities, and texture. The nephrite artifacts are tremolite in composition, with a proposed ultrabasic origin. Based on the geochemical data obtained by micro‐PIXE, we divide the artifacts into Group 1 objects from the Kovachevo site and Group 2 objects from the Galabnik and Bulgarchevo sites. The analytical data and microprobe analyses are compared with geochemical data of nephrite from across the globe. The results are in a good agreement with previous electron microprobe and electron paramagnetic resonance (EPR) spectroscopy data. Our study provides a better understanding of the mineralogy and geochemistry of nephrite artifacts and helps to address questions regarding origin and the distribution of such materials in Bulgaria and other Balkan countries.     

Experimental and petrological constraints on local-scale interaction of biotite-amphibole gneiss with H2O-CO2-（K, Na）Cl fluids at middle-crustal conditions： Example from the Limpopo Complex, South Africa

Reaction textures and fluid inclusions in the～2.0 Ga pyroxene-bearing dehydration zones within the Sand River biotite-hornblende orthogneisses（Central Zone of the Limpopo Complex） suggest that the formation of these zones is a result of close interplay between dehydration process along ductile shear zones triggered by H₂O-CO₂-salt fluids at 750—800℃and 5.5—6.2 kbar.partial melting,and later exsolution of residual brine and H₂O-CO₂ fluids during melt crystallization at 650—700℃.These processes caused local variations of water and alkali activity in the fluids,resulting in various mineral assemblages within the dehydration zone.The petrological observations are substantiated by experiments on the interaction of the Sand River gneiss with the H₂O-CO-2-（K,Na）Cl fluids at 750 and 800℃and 5.5 kbar.It follows that the interaction of biotite-amphibole gneiss with H₂O-CO₂-（K.Na）Cl fluids is accompanied by partial melting at 750—800℃.Orthopyroxene-bearing assemblages are characteristic for temperature 800℃and are stable in equilibrium with fluids with low salt concentrations,while salt-rich fluids produce clinopyroxene-bearing assemblages.These observations arc in good agreement with the petrological data on the dehydration zones within the Sand River orthoeneisses.     

柴北缘鱼卡地区中侏罗统石门沟组含煤层段沉积有机相分析

柴达木盆地北缘鱼卡地区中侏罗统石门沟组含煤段中发育有油页岩、煤、碳质泥岩和泥岩等富有机质细粒沉积.为了研究其沉积有机相的类型及煤和油页岩形成的控制因素,本文通过岩心观察、工业分析结合有机地球化学测试分析等方法将含煤段细粒沉积物划分为了类型A(三角洲平原沉积环境)、B(三角洲前缘-浅湖沉积环境)、C1(湖沼非油页岩亚相)及C2(湖沼油页岩亚相)四种类型,其中类型C1沉积物中发育煤,类型C2中发育油页岩,且煤较油页岩具有更高的含油率、水分、挥发分以及发热量值.有机质类型特征方面,沉积有机相类型A、B及C1沉积物有机质类型均为Ⅱ2-Ⅲ型、有机质来源均以陆源和混合来源两种有机质来源为主,而类型C2中主要为Ⅱ2型,以混合有机质来源为主;类型A及C2其沉积物有机质均处于未成熟阶段,而类型B和C1中有机质均处于未成熟-低成熟阶段;有机质保存条件方面,类型A沉积物主要形成于缺氧的淡水环境,类型B主要形成于贫氧-缺氧的淡水-半咸水环境,类型C1形成于贫氧-缺氧的淡水-半咸水环境,而类型C2则主要形成于缺氧的淡水-半咸水环境.其中类型B较类型A,类型C2较类型C1,其沉积物均形成于更为还原且盐度更高的水体环境中.石门沟组含煤段是煤和油页岩的形成层位,稳定的沉积环境、丰富的湖泊有机质来源、良好的保存条件及较少的陆源碎屑的稀释共同促进了类型C2中油页岩的形成,而丰富的陆源植物供给及良好的保存条件则促进了类型C1中煤层的形成.     

A New Appraisal of Sri Lankan BB Zircon as a Reference Material for LA‐ICP‐MS U‐Pb Geochronology and Lu‐Hf Isotope Tracing

A potential zircon reference material (BB zircon) for laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) U‐Pb geochronology and Hf isotope geochemistry is described. A batch of twenty zircon megacrysts (0.5–1.5 cm³) from Sri Lanka was studied. Within‐grain rare earth element (REE) compositions are largely homogeneous, albeit with some variation seen between fractured and homogeneous domains. Excluding fractured cathodoluminescence bright domains, the variation in U content for all analysed crystals ranged from 227 to 368 μg g^?1 and the average Th/U ratios were between 0.20 and 0.47. The Hf isotope composition (0.56–0.84 g/100 g Hf) is homogeneous within and between the grains – mean ¹⁷⁶Hf/¹⁷⁷Hf of 0.281674 ± 0.000018 (2s). The calculated alpha dose of 0.59 × 10¹⁸ g^?1 for a number of BB grains falls within the trend of previously studied, untreated zircon samples from Sri Lanka. Aliquots of the same crystal (analysed by ID‐TIMS in four different laboratories) gave consistent U‐Pb ages with excellent measurement reproducibility (0.1–0.4% RSD). Interlaboratory assessment (by LA‐ICP‐MS) from individual crystals returned results that are within uncertainty equivalent to the TIMS ages. Finally, we report on within‐ and between‐grain homogeneity of the oxygen isotope systematic of four BB crystals (13.16‰ VSMOW).     

Tectonothermal history of the basement rocks in the western zone of the North China Craton and its tectonic implications

The basement of the North China Craton can be divided into the eastern, central and western zones, based on lithological, structural, metamorphic and geochronological data. The western zone comprises two different petrotectonic units: Archaean tonalitic–trondhjemitic–granodioritic (TTG) grey gneisses and metamorphic mafic rocks, and Palaeoproterozoic khondalite series. The former is characterized by isobaric cooling (IBC)-type anticlockwise P–T paths in the north-northwestern part of the zone and near-isothermal decompression (ITD)-type clockwise P–T paths in the eastern part, adjacent to the central zone. On the other hand, the tectonothermal evolution of Palaeoproterozoic khondalite series rocks is characterized exclusively by nearly isothermal decompression following the peak of metamorphism and then cooling, defining clockwise P–T paths. The Archaean TTG gneisses and associated mafic rocks with anticlockwise metamorphic P–T paths reflects an origin related to underplating and intrusion of mantle-derived magmas which may be derived from mantle plumes. They represent a late Archaean continental block in the western part of the North China Craton. The Palaeoproterozoic khondalite series rocks represent passive continental margin deposits. They were metamorphosed and deformed in the late Palaeoproterozoic during the amalgamation of the western continental block with another continental block in the east part of the North China Craton. The ITD-type clockwise P–T–t paths of the Palaeoproterozoic khondalite series rocks record the tectonothermal histories of the collision of the western and eastern continental blocks which resulted in the final assembly of the North China Craton at c. 1800 Ma.     

Do paleoclimate proxies agree? A test comparing 19 late Holocene climate and sea‐ice reconstructions from Icelandic marine and lake sediments

Geochemical, mineralogical and biological indicators preserved in sediments are widely used to reconstruct past climate change, but proxies differ in the degree to which their utility as climate indicators has been validated via laboratory experiments, modern spatial calibrations, or down‐core comparisons with instrumental climate data. Multi‐proxy studies provide another means of evaluating interpretations of proxies. This paper presents a multi‐proxy assessment comparing 19 sub‐centennially resolved late Holocene proxy records, covering the period 300–1900 AD, from seven Icelandic marine and lacustrine core sites. We employ simple statistical comparisons between proxy reconstructions to evaluate their correlations over time and, ultimately, their utility as proxies for regional climate. Proxies examined include oxygen isotopic composition of benthic and planktonic foraminifera, abundance of the sea‐ice biomarker IP₂₅, allochthonous quartz in marine sediments (a proxy for drift ice around Iceland), marine carbonate abundance, total organic carbon concentration, chironomid assemblages, lacustrine biogenic silica and carbon/nitrogen ratios in lake sediments. Most of the examined proxy records, including temperature and sea‐ice proxies, correlate strongly with each other over multi‐centennial timescales, and thus do appear to record changes in regional climate. Copyright © 2011 John Wiley & Sons, Ltd.     

Glassy orthopyroxene granodiorites of the Pannonian Basin: tracers of ultra-high-temperature deep-crustal anatexis triggered by Tertiary basaltic volcanism

Glassy orthopyroxene granodiorite-tonalite (named pincinite after type locality) was described from basaltic lapilli tuffs of the Pliocene maar near Pinciná village in the Slovakian part of the Pannonian Basin. Two pincinite types exhibit a qualitatively similar mineral composition (quartz, An_20–55 plagioclase, intergranular silicic glass with orthopyroxene and ilmenite, ±K-feldspar), but strongly different redox potential and formation PT conditions. Peraluminous pincinite is reduced (6–7% of total iron as Fe³⁺ in corundum-normative intergranular dacitic glass) and contains ilmenite with 8–10 mol% Fe₂O₃ and orthopyroxene dominated by ferrosilite. High-density (up to 0.85 g/cm³) primary CO₂ inclusions with minor H₂, CH₄, H₂S, CO and N₂ (<2 mol% total) are present in Qtz and Plg. Equilibrium PT conditions inferred from the intergranular Opx–Ilm–Glass assemblage and fluid density correspond to 1,170±50°C, 5.6±0.4 kbar, respectively. Metaluminous pincinite is more oxidised (25–27% of total iron as Fe³⁺ in diopside-normative intergranular glass of rhyolite–trachyte–dacite composition) and contains Fe₂O₃-rich ilmenite (17–29 mol%) associated with enstatite. Fluid inclusions are composed of CO₂–H₂O mixtures with up to 38 mol% H₂O. Raman spectroscopy revealed H₂S along with dominant CO₂ in the carbonic phase. Equilibrium PT parameters for the intergranular Opx–Ilm–Glass assemblage correspond to 740±15°C, 2.8±0.1 kbar, respectively. Reducing gas species (<2 mol% total) in the CO₂-inclusions of the peraluminous pincinite resulted from hydrogen diffusion due to fH₂ gradient imposed during decrease of redox potential from the log fO₂ values near QFM during Qtz + Plg growth, to QFM-2 incidental to the superimposed Opx + Ilm assemblage in the intergranular melt. The decrease in oxygen fugacity was recorded also in the metaluminous pincinite, where log fO₂ values changed from ~QFM + 2.6 to QFM + 0.4, but hydrogen diffusion did not occur. Absence of OH-bearing minerals, major and trace element abundances (e.g. REE 300–320, Nb 55–57, Th 4–31, Zr 240–300 ppm, FeO_tot/MgO up to 11), and Sr–O isotope ratios in the pincinites are diagnostic of high-temperature anorogenic magmas originated by dehydration melting of biotite in quartz-feldspathoid crust (⁸⁷Sr/⁸⁶Sr>0.705–0.706, ¹⁸O>9 V-SMOW) around alkali basalt reservoir in depths between 17 and 20 km, and around late stage derivatives of the basalt fractionation, intruding the crust up to depths of 10–11 km. Low water activity in the pincinite parental melt was caused by CO₂-flux from the Tertiary basaltic reservoirs and intrusions. The anatexis leads to generation of a melt-depleted granulitic crust beneath the Pannonian Basin, and the pincinites are interpreted as equivalents of igneous charnockites and enderbites quenched at temperatures above solidus and unaffected by sub-solidus re-equilibration and metamorphic overprint.     

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ⁵⁶Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ⁵⁷Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.     

http://www.sciencedirect.com/science/article/pii/S1674987114000395

The study of fluid inclusions in high-grade rocks is especially challenging as the host minerals have been normally subjected to deformation, recrystallization and fluid-rock interaction so that primary in- clusions, formed at the peak of metamorphism are rare. The larger part of the fluid inclusions found in metamorphic minerals is typically modified during uplift. These late processes may strongly disguise the characteristics of the ＂original＂ peak metamorphic fluid. A detailed microstructural analysis of the host minerals, notably quartz, is therefore indispensable for a proper interpretation of fluid inclusions. Cathodoluminescence （CL） techniques combined with trace element analysis of quartz （EPMA, LA- [CPMS） have shown to be very helpful in deciphering the rock-fluid evolution. Whereas high-grade metamorphic quartz may have relatively high contents of trace elements like Ti and A1, low- temperature re-equilibrated quartz typically shows reduced trace element concentrations. The result- ing microstructures in CL can be basically distinguished in diffusion patterns （along microfractures and grain boundaries）, and secondary quartz formed by dissolution-reprecipitation. Most of these textures are formed during retrograde fluid-controlled processes between ca. 220 and 500 ℃, i.e. the range of semi-brittle deformation （greenschist-facies） and can be correlated with the fluid inclusions. In this way modified and re-trapped fluids can be identified, even when there are no optical features observed under the microscope.     

Adjoint formulation and constraint handling for gradient-based optimization of compositional reservoir flow

An adjoint formulation for the gradient-based optimization of oil–gas compositional reservoir simulation problems is presented. The method is implemented within an automatic differentiation-based compositional flow simulator (Stanford’s Automatic Differentiation-based General Purpose Research Simulator, AD-GPRS). The development of adjoint procedures for general compositional problems is much more challenging than for oil–water problems due to the increased complexity of the code and the underlying physics. The treatment of nonlinear constraints, an example of which is a maximum gas rate specification in injection or production wells, when the control variables are well bottom-hole pressures, poses a particular challenge. Two approaches for handling these constraints are presented—a formal treatment within the optimizer and a simpler heuristic treatment in the forward model. The relationship between discrete and continuous adjoint formulations is also elucidated. Results for four example cases of increasing complexity are presented. Improvements in the objective function (cumulative oil produced) relative to reference solutions range from 4.2 to 11.6 %. The heuristic treatment of nonlinear constraints is shown to offer a cost-effective means for obtaining feasible solutions, which are, in some cases, better than those obtained using the formal constraint handling procedure.