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This paper describes numerous siderite occurrences from Nb-Zr-REY-Ga-enriched beds of tuffaceous mudstone from the Yujingshan borehole, eastern Yunnan, southwestern China. The mineral phases in the samples were identified and characterized through macroscopic observation, XRD (X-ray diffraction) analysis, optical microscopy, and FE-SEM (field emission-scanning electron microscopy). The results show that the siderite occurs in the drill core from depths of 664.07 to 729.21 m, where its content varies from 15.1 to 65.7%, 31.3% on average. Modes of occurrence of authigenic siderite include irregular banded or massive aggregates, discrete fine particles, oolitic aggregates, and double or multi-ring ellipsoid-shaped or rhombohedral aggregates. The mineralogical association with quartz, anatase, ilmenite, chromite, and zircon with sharp-edged outlines, high-temperature cracks and/or corroded embayments, and REE-bearing minerals and geochemical characteristics such as Al 2 O 3 /TiO 2 between 3 and 8, less commonly 8–23.77, indicate that abundant siderite was produced by hydrothermal alteration of airborne volcaniclastic materials. The δ 13C PDB , δ 18O PDB , and δ 18O SMOW values of siderite in the argillized tuff range from −12.56 to −1.32‰, −8.98 to −5.88‰, and 21.60 to 24.80‰, respectively. In the δ 13C PDB - δ 18O SMOW diagram, plots of the studied siderite are distributed between the fields of marine carbonate rocks, sedimentary organic matter, and carbonates of hydrothermal ores. Some siderite from the upper part of the studied borehole is isotopically close to REY carbonates from the Abramovka lignite deposit, Far Eastern Russia, which precipitated from evolved basinal waters mixed with CO 2 from a mantle source. In summary, this indicates a hybrid origin for the studied siderite including carbonate dissolution, dehydroxylation of sedimentary organic matter, and hydrothermal activity. Furthermore, the paleosalinity (Z) and paleotemperature (T) of the ore-forming fluids were calculated based on the age-corrected stable carbon and oxygen isotopic data in the samples. The Z values range from 96.65 to 121.5‰, suggesting the formation of siderite under brackish-water conditions. The T values vary from 19.47 to 47.12 °C, with some sharp fluctuations that may be due to ash falls and/or hydrothermal injections. Overall, our data support the model for critical-metal Nb(Ta)-Zr(Hf)-REY-Ga enrichment in tuffaceous deposits of southwest China including a combination of volcanic activity and terrestrial organic-rich sedimentation under warm and humid conditions, followed by low-temperature alteration evolved from acidic leaching, which is responsible for the Nb-Zr-REY-Ga enrichment, and, subsequently, formation of authigenic siderite with associated quartz, sulfide minerals, and phosphate minerals under reducing neutral/weakly alkaline conditions. • Abundant siderite is documented in the clay-altered tuffaceous horizons. • Fe was primarily derived from airborne pyroclastics. • C and O were sourced from carbonate, organic matter, and hydrotherm. • C-O isotopes show that siderite was affected by seawater and hot fluids. • A genetic model of siderite in Nb-Zr-REY-Ga deposits has been proposed. [ABSTRACT FROM AUTHOR]

Abstract: The Xiangshan U deposit, the largest hydrothermal U deposit in China, is hosted in late Jurassic felsic volcanic rocks although the U mineralization post dates the volcanics by at least 20 Ma. The mineralization coincides with intrusion of local mantle-derived mafic dykes formed during Cretaceous crustal extension in South China. Ore-forming fluids are rich in CO2, and U in the fluid is thought to have been dissolved in the form of UO2 (CO3)2 2− and UO2 (CO3) 3 4− complexes. This paper provides He and Ar isotope data of fluid inclusions in pyrites and C isotope data of calcites associated with U mineralization (pitchblende) in the Xiangshan U deposit. He isotopic compositions range between 0.1 and 2.0Ra (where Ra is the 3He/4He ratio of air=1.39×10−6) and correlates with 40Ar/36Ar; although there is potential for significant 3He production via 6Li(n,α)3H(β)3He reactions in a U deposit (due to abundant neutrons), nucleogenic production cannot account for either the 3He concentration in these fluids, nor the correlations between He and Ar isotopic compositions. It is more likely that the high 3He/4He ratios represent trapped mantle-derived gases. A mantle origin for the volatiles of Xiangshan is consistent with the δ 13C values of calcites, which vary from −3.5‰ to −7.7‰, overlapping the range of mantle CO2. The He, Ar and CO2 characteristics of the ore-forming fluids responsible for the deposit are consistent with mixing between 3He- and CO2-rich mantle-derived fluids and CO2-poor meteoric fluids. These fluids were likely produced during Cretaceous extension and dyke intrusion which permitted mantle-derived CO2 to migrate upward and remobilize U from the acid volcanic source rocks, resulting in the formation of the U deposit. Subsequent decay of U within the fluid inclusions has reduced the 3He/4He ratio, and variations in U/3He result in the range in 3He/4He observed with U/3He ratios in the range 5–17×103 likely corresponding to U concentrations in the fluids <0.2 ppm. [Copyright &y& Elsevier]

Abstract: Carbon isotopic compositions of total organic carbon (TOC) or leaf waxes in soils have been used to reconstruct past changes in the relative abundance of C3 and C4 plants. However, TOC contains organic matter of different source organisms (plants, animals, fungi, bacteria etc.) and its isotopic ratios could be modified during diagenesis since different organic fractions (e.g., carbohydrates, proteins, lipids etc.) have different isotopic ratios and degradation rates. Leaf waxes, on the other hand, are transported by wind and hence represent vegetation input from a large geographic area. We report in this paper a new approach to extract in-situ paleovegetation information from late Quaternary paleosols by determining carbon isotopic compositions of biomarkers derived from aliphatic bio- and geopolymers of plant origin. We show that C9 to C17 n-alkenes derived from aliphatic bio- and geopolymers are the dominant compounds released by flash pyrolysis of insoluble organic matter isolated from the late Quaternary paleosols in the Chinese Loess Plateau. Because the aliphatic polymeric substances are mainly derived from plant leaves, bark and roots, the isotopic signatures of these alkenes, determined using pyrolysis–gas chromatography–isotopic ratio mass spectrometry, reflect in-situ vegetation changes. Our down-core δ 13C data from the Xifeng loess–paleosol profile show significant coherence among biopolymer-derived n-alkenes, leaf wax n-alkanes, and TOC for the past 40 kyr. However, the different amplitudes of the temporal isotopic changes among these data sets are indicative of variability in in-situ and regional vegetation dynamics, organic sources and effect of diagenesis. Our data also imply that below-ground biomass is a major source of soil organic matter in the central China loess sediment. [Copyright &y& Elsevier]

The late Paleozoic ice age (LPIA) during the Carboniferous and Permian (ca. 360–260 Ma) was vegetated Earth's only recorded icehouse-to-greenhouse transition and provides a deep-time perspective for climate-glaciation-environment coevolution and future climate change. During the LPIA, changes in glacial-interglacial cycles have been closely linked to atmospheric p CO 2. In this paper, we investigate the relationship between volcanism and glacial to interglacial climate cycles during the Pennsylvanian to earliest Cisuralian in the Liujiang Coalfield from the North China Plate (NCP). We use integrated data from Zircon U-Pb dating, Hg/TOC ratios and δ13C org to recover temporal trends in volcanic intensity and relate these to fluctuations in the global carbon cycle and atmospheric p CO 2. Four new radiometric dates from tuffaceous claystones provide a precision stratigraphic framework and constrain the succession to ~322 to 301 Ma. Results date the Benxi Formation to the Bashkirian–Moscovian stages of the Carboniferous, and the Taiyuan Formation ranging from the Kasimovian stage of the Carboniferous to the Asselian stage of the Permian. Results from Hg/TOC ratios record four peaks of volcanic intensity from the Bashkirian to the Carboniferous-Permian (C-P) transition period, and two low ebbs during the early-middle Bashkirian and the early-middle Moscovian. Peaks in volcanic intensity coincide with the four negative excursions of δ13C org and correlate with volcanism in the North China Plate and NW Europe, inferring volcanic drivers for the carbon isotope excursions and perturbations in the global carbon cycle. Periods of higher atmospheric p CO 2 correlate to interglacial intervals, the two lower ebbs in p CO 2 correlate with two positive isotope plateaus, while periods of lower atmospheric p CO 2 and cooling correlate with glacial intervals C3 and C4 recognized from other sections globally. Results suggest volcanism to be a significant driver for late Pennsylvanian to earliest Cisuralian shifts in global climates from glacial to interglacial through greenhouse gas emissions and changes to the global carbon cycle. Our results represent an important contribution to the development of an accurate chronostratigraphy for the continental facies of the NCP during the Pennsylvanian and earliest Permian, enabling correlation of volcanic and climate events including glacial and interglacial cycles. [ABSTRACT FROM AUTHOR]