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.     

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.     

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.     

Searching for (un)sustainabilty in pangasius aquaculture: A political economy of quality in European retail

Drawing on a political economy of food quality, this paper investigates the main sources of uncertainty over the environmental sustainability of Vietnamese pangasius catfish in European markets and how retailers subsequently respond to these uncertainties. Based on media survey and interviews with supermarket retailers across Europe between 2008 and 2010, the analysis focuses on the claims and counterclaims over the sustainability of pangasius aquaculture, how retailers have dealt with the uncertainty these claims have engendered about the fish, and what effect this uncertainty has had on the potential of marketing ‘sustainable pangasius’ in European supermarkets. The paper concludes that successful claims around new food qualities like sustainability by retailers are dependent on the ability of regulatory networks to overcome any perceived illegitimacy of imported products in the face of continuing uncertainty and the wider politics of market protectionism.     

Gold solubility in oxidized and reduced, water-saturated mafic melt

We have performed experiments to evaluate Au solubility in natural, water-saturated basaltic melts as a function of oxygen fugacity. Experiments were carried out at 1000 °C and 200 MPa, and oxygen fugacity was controlled at the fayalite-magnetite-quartz (FMQ) oxygen fugacity buffer and FMQ + 4. All experiments were saturated with a metal-chloride aqueous solution loaded initially as a 10 wt% NaCl eq. fluid. The stable phase assemblage at FMQ consists of basalt melt, olivine, clinopyroxene, a single-phase aqueous fluid, and metallic Au. The stable phase assemblage at FMQ + 4 consists of basalt melt, clinopyroxene, magnetite-spinel solid solution, a single-phase aqueous fluid, and metallic Au. Silicate glasses (i.e., quenched melt) and their contained crystalline material were analyzed by using both electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Measured Au concentrations in the quenched melt range from 4.8 μg g⁻¹ to 0.64 μg g⁻¹ at FMQ + 4, and 0.54 μg g⁻¹ to 0.1 μg g⁻¹ at FMQ. The measured solubility of Au in olivine and clinopyroxene was consistently below the LA-ICP-MS limit of detection (i.e., 0.1 μg g⁻¹). These melt solubility data place important limitations on the dissolved Au content of water-saturated, Cl- and S-bearing basaltic liquids at geologically relevant fO₂ values. The new data are compared to published, experimentally-determined values for Au solubility in dry and hydrous silicate liquids spanning the compositional range from basalt to rhyolite, and the effects of melt composition, oxygen fugacity, pressure and temperature are discussed.     

Geochemical studies in the drainage basin of the Rio Vouga,Portugal. IV. Impact of land use on the hydrogeochemistry of natural waters in the Vouzela region

A hydrogeochemical study of the impact of land use on the composition of natural waters in the Vouzela region in northern Portugal was carried out during the summer of 1983. Water samples were collected from spring and major streams in the area and analyzed for major constituents and some trace elements. Analysis of variance and subsequent pairwise contrast tests demonstrated that waters from agricultural areas are significantly enriched in constiluents such as Na, K, Ca, Mg, Sr, Cl, SO₄, and NO₃. High concentrations of these ions in agricultural areas are the result of both the application of fertilizers and enhanced evaporation by the intensive irrigation of agricultural lands. Constitutents such as H₄SiO₄, HCO₃, F, and probably Li, which are typically related to mineral weathering, were not affected by land use. In waters from forested areas the concentration of most constituents was about 20% higher than in waters from uncultivated areas with mainly a grass cover. This reflects the difference in the evapotranspiration of these two vegetation types. The chemistry of the Rio Zela clearly reflects differences in land use in the Rio Zela valley.