New age constraints on the western Betic intramontane basins: A late Tortonian closure of the Guadalhorce Corridor?

Several gateways connected the Mediterranean with the Atlantic during the late Miocene but the timing of closure and therefore their role prior to and during the Messinian Salinity Crisis (5.97–5.33 Ma) is still under debate. The timing of closure of the Guadalhorce Corridor is especially disputed as the common lack of marine microfossils hampers precise age determination. Here we present new biostratigraphic age constraints on the sediments of the Ronda, Antequera and Arcos regions, which formed the northern part of the Guadalhorce Corridor. The general presence of Globorotalia menardii 4 in the youngest deep‐marine sediments of all three regions indicates a late Tortonian age, older than 7.51 Ma. We conclude that the Guadalhorce Corridor closed during the late Tortonian, well before the onset of the Messinian Salinity Crisis and that the late Tortonian tectonic uplift of the eastern Betics extended into the western Betics.     

Defining the Potential of Nanoscale Re‐Os Isotope Systematics Using Atom Probe Microscopy

Atom probe microscopy (APM) is a relatively new in situ tool for measuring isotope fractions from nanoscale volumes (< 0.01 μm³). We calculate the theoretical detectable difference of an isotope ratio measurement result from APM using counting statistics of a hypothetical data set to be ± 4δ or 0.4% (2s). However, challenges associated with APM measurements (e.g., peak ranging, hydride formation and isobaric interferences), result in larger uncertainties if not properly accounted for. We evaluate these factors for Re‐Os isotope ratio measurements by comparing APM and negative thermal ionisation mass spectrometry (N‐TIMS) measurement results of pure Os, pure Re, and two synthetic Re‐Os‐bearing alloys from Schwander et al. (2015, Meteoritics and Planetary Science, 50, 893) [the original metal alloy (HSE) and alloys produced by heating HSE within silicate liquid (SYN)]. From this, we propose a current best practice for APM Re‐Os isotope ratio measurements. Using this refined approach, mean APM and N‐TIMS ¹⁸⁷Os/¹⁸⁹Os measurement results agree within 0.05% and 2s (pure Os), 0.6–2% and 2s (SYN) and 5–10% (HSE). The good agreement of N‐TIMS and APM ¹⁸⁷Os/¹⁸⁹Os measurements confirms that APM can extract robust isotope ratios. Therefore, this approach permits nanoscale isotope measurements of Os‐bearing alloys using the Re‐Os geochronometer that could not be measured by conventional measurement principles.     

Fire and vegetation change during the Early Pleistocene in southeastern Australia

Early Pleistocene vegetation in upland southeastern Australia included diverse rainforests and sclerophyll forests, which alternated on precessional timescales. The nature and timing of transitions between these biomes, and the role of fire in maintaining or driving transitions between them, are uncertain. Here we present a high‐resolution pollen record from Stony Creek Basin, a small Early Pleistocene palaeolake in southeastern Australia. The pollen record documents a pattern of vegetation change, over ca. 10 ka at ca. 1590–1600 ka, between sclerophyll forests, dominated by Eucalyptus, Callitris (Cupressaceae) or Casuarinaceae, and rainforests dominated by either angiosperms or conifers of the family Podocarpaceae. Transitions between these biomes typically occurred within ca. 1–2 ka. The associated charcoal record suggests that greatest biomass combustion occurred when local vegetation was dominated by Eucalyptus, and the least biomass combustion occurred when local vegetation was dominated by Podocarpaceae. However, local fires burnt in both sclerophyll and angiosperm‐dominated rainforest vegetation, at least once every several centuries. Fire was very rare (less than about one fire per millennium) only when the local vegetation was rainforest dominated by Podocarpaceae. This suggests that fire was an irregular presence in both sclerophyll‐ and angiosperm‐dominated rainforest biomes during the late Neogene, though was largely absent in Podocarpaceae‐dominated rainforests. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

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.