In Situ U‐Th‐Pb Dating and Sr‐Nd Isotope Analysis of Bastnäsite by LA‐(MC)‐ICP‐MS

Bastnäsite is the end member of a large group of carbonate–fluoride minerals with the common formula (REE) CO₃F·CaCO₃. This group is generally widespread and, despite never occurring in large quantities, represents the major economic light rare earth element (LREE) mineral in deposits related to carbonatite and alkaline intrusions. Since bastnäsite is easily altered and commonly contains inclusions of earlier‐crystallised minerals, in situ analysis is considered the most suitable method to measure its U‐Th‐Pb and Sr‐Nd isotopic compositions. Electron probe microanalysis and laser ablation (multi‐collector) inductively coupled plasma‐mass spectrometry of forty‐six bastnäsite samples from LREE deposits in China, Pakistan, Sweden, Mongolia, USA, Malawi and Madagascar indicate that this mineral typically has high Th and LREE and moderate U and Sr contents. Analysis of an in‐house bastnäsite reference material (K‐9) demonstrated that precise and accurate U‐Th‐Pb ages could be obtained after common Pb correction. Moreover, the Th‐Pb age with its high precision is preferable to the U‐Pb age because most bastnäsites have relatively high Th rather than U contents. These results will have significant implications for understanding the genesis of endogenous ore deposits and formation processes related to metallogenic geochronology research.     

Basaltic and Solution Reference Materials for Iron,Copper and Zinc Isotope Measurements

Iron, Cu and Zn stable isotope systems are applied in constraining a variety of geochemical and environmental processes. Secondary reference materials have been developed by the Institute of Geology, Chinese Academy of Geological Sciences (CAGS), in collaboration with other participating laboratories, comprising three solutions (CAGS‐Fe, CAGS‐Cu and CAGS‐Zn) and one basalt (CAGS‐Basalt). These materials exhibit sufficient homogeneity and stability for application in Fe, Cu and Zn isotopic ratio determinations. Reference values were determined by inter‐laboratory analytical comparisons involving up to eight participating laboratories employing MC‐ICP‐MS techniques, based on the unweighted means of submitted results. Isotopic compositions are reported in per mil notation, based on reference materials IRMM‐014 for Fe, NIST SRM 976 for Cu and IRMM‐3702 for Zn. Respective reference values of CAGS‐Fe, CAGS‐Cu and CAGS‐Zn solutions are as follows: δ⁵⁶Fe = 0.83 ± 0.07 and δ⁵⁷Fe = 1.20 ± 0.13, δ⁶⁵Cu = 0.57 ± 0.06, and δ⁶⁶Zn = ?0.79 ± 0.12 and δ⁶⁸Zn = ?1.65 ± 0.24, respectively. Those of CAGS‐Basalt are δ⁵⁶Fe = 0.15 ± 0.07, δ⁵⁷Fe = 0.22 ± 0.10, δ⁶⁵Cu = 0.12 ± 0.08, δ⁶⁶Zn = 0.17 ± 0.13, and δ⁶⁸Zn = 0.34 ± 0.26 (2s).     

Age and metal source of orogenic gold deposits in Southeast Guizhou Province,China: Constraints from Re-Os and He-Ar isotopic evidence

The orogenic gold deposits in Southeast Guizhou are an important component of the Xuefeng polymetallic ore belt and have significant exploration potential, but geochronology research on these gold deposits is scarce. Therefore, the ore genetic models are poorly constrained and remain unclear. In the present study, two important deposits(Pingqiu and Jinjing) are investigated, including combined Re-Os dating and the He-Ar isotope study of auriferous arsenopyrites. It is found that the arsenopyrites from the Pingqiu gold deposit yielded an isochron age of 400 ± 24 Ma,with an initial ~(187)Os/~(188)Os ratio of 1.24 ± 0.57(MSWD = 0.96). An identical isochron age of 400 ± 11 Ma with an initial ~(187)Os/~(188)Os ratio of 1.55 ± 0.14(MSWD = 0.34) was obtained from the Jinjing deposit. These ages correspond to the regional Caledonian orogeny and are interpreted to represent the age of the main stage ore. Both initial ~(187)Os ratios suggest that the Os was derived from crustal rocks. Combined with previous rare earth element(REE), trace elements, Nd-Sr-S-Pb isotope studies on scheelite, inclusion fluids with other residues of gangue quartz, and sulfides from other gold deposits in the region, it is suggested that the ore metals from Pingqiu and Jinjing were sourced from the Xiajiang Group. The He and Ar isotopes of arsenopyrites are characterized by ~3 He/~4 He ratios ranging from 5.3 × 10~(-4) Ra to 2.5 × 10~(-2) Ra(Ra = 1.4 × 10~(-6), the ~3 He/~4 He ratio of air), 40 Ar=/~4 He ratios from 0.64 × 10~(-2) to 15.39×10~(-2), and ~(40)Ar/~(36)Ar ratios from 633.2 to 6582.0. Those noble gas isotopic compositions of fluid inclusions also support a crustal source origin,evidenced by the Os isotope. Meanwhile, recent noble gas studies suggest that the amount of in situ radiogenic ~4 He generated should not be ignored, even when Th and U are present at levels of only a few ppm in host minerals.     

Zircon U-Pb-Hf constraints from Gongga Shan granites on young crustal melting in eastern Tibet

The Gongga Shan batholith is a complex granitoid batholith on the eastern margin of the Tibetan Plateau with a long history of magmatism spanning from the Triassic to the Pliocene. Late Miocene-Pliocene units are the youngest exposed crustal melts within the entire Asian plate of the Tibetan Plateau.Here, we present in-situ zircon Hf isotope constraints on their magmatic source, to aid the understanding of how these young melts were formed and how they were exhumed to the surface. Hf isotope signatures of Eocene to Pliocene zircon rims(ε_Hf(t)=-4 to +4), interpreted to have grown during localised crustal melting, are indicative of melting of a Neoproterozoic source region, equivalent to the nearby exposed Kangding Complex. Therefore, we suggest that Neoproterozoic crust underlies this region of the Songpan-Ganze terrane, and sourced the intrusive granites that form the Gongga Shan batholith. Localised young melting of Neoproterozoic lower or middle crust requires localised melt-fertile lithologies. We suggest that such melts may be equivalent to seismic and magnetotelluric low-velocity and high-conductivity zones or "bright spots" imaged across much of the Tibetan Plateau. The lack of widespread exposed melts this age is due either to the lack of melt-fertile rocks in the middle crust, the very low erosion level of the Tibetan plateau, or to a lack of mechanism for exhuming such melts. For Gongga Shan, where some melting is younger than nearby thermochronological ages of low temperature cooling, the exact process and timing of exhumation remains enigmatic, but their location away from the Xianshuihe fault precludes the fault acting as a conduit for the young melts. We suggest that underthrusting of dry granulites of the lower Indian crust(Archaean shield) this far northeast is a plausible mechanism to explain the uplift and exhumation of the eastern Tibetan Plateau.     

Paleoproterozoic volcanic rocks in the southern margin of the North China Craton,central China:Implications for the Columbia supercontinent

The volcanic rocks of the Xiong'er Group are situated in the southern margin of the North China Craton(NCC).Research on the Xiong er Group is important to understand the tectonic evolution of the NCC and the Columbia supercontinent during the Paleoproterozoic.In this study,to constrain the age of the Xiong'er volcanic rocks and identify its tectonic environment,we report zircon LA-ICP-MS data with Hf isotope,whole-rock major and trace element compositions and Sr-Nd-Pb-Hf isotopes of the volcanic rocks of the Xiong'er Group.The Xiong'er volcanic rocks mainly consist of basaltic andesite,andesite.dacite and rhyolite,with minor basalt.Our new sets of data combined with those from previous studies indicate that Xiong'er volcanism should have lasted from 1827 Ma to 1746 Ma as the major phase of the volcanism.These volcanics have extremely low MgO.Cr and Ni contents,are enriched in LREEs and LILEs but depleted in HFSEs(Nb,Ta,and Ti),similar to arc-related volcanic rocks.They are characterized by negative zircon ε_(Hf)_(t) values of-17.4 to 8.8,whole-rock initial ~(87)Sr/~(86)Sr values of 0.7023 to 0.7177 andε_(Nd)(t) values of-10.9 to 6.4.and Pb isotopes(~(206)Pb/~(204)Pb =14.366-16.431,~(207)Pb/~(204)Pb =15.106-15.371,~(208)Pb/~(204)Pb= 32.455-37.422).The available elemental and Sr-Nd-Pb-Hf isotope data suggest that the Xiong'er volcanic rocks were sourced from a mantle contaminated by continental crust.The volcanic rocks of the Xiong'er Group might have been generated by high-degree partial melting of a lithospheric mantle that was originally modified by oceanic subduction in the Archean.Thus,we suggest that the subduction-modified lithospheric mantle occurred in an extensional setting during the breakup of the Columbia supercontinent in the Late Paleoproterozoic,rather than in an arc setting.     

硫氧同位素示踪污染物来源在济南岩溶水中的应用

近年来,济南岩溶水硫酸盐浓度逐年升高,为了对硫酸盐污染区域实施有效的防治措施,保障饮用水安全,识别硫酸盐的污染来源极其重要。在系统分析研究区水文地质条件的基础上,根据实际的采样测试数据,采用硫、氧(S、O)双同位素示踪技术,分析识别了济南趵突泉泉域硫酸盐的主要污染来源,并通过IsoSource质量守恒模型,估算了硫酸盐各污染来源的贡献率。结果表明: 泉域内硫酸盐主要污染来源有大气沉降、污水和土壤; 大气沉降来源贡献率最大,均值达到53.9%; 其次是污水来源,均值为31%; 土壤来源贡献率最小,均值为15.1%。该研究为北方岩溶区地下水硫酸盐来源的定量研究提供了一种新方法,为济南趵突泉泉域硫酸盐污染防治提供了科学依据。     

Origin of sulphate in the unsaturated zone and groundwater of a loess aquifer

The use of the sulphate mass balance (SMB) between precipitation and soil water as a supplementary method to estimate the diffuse recharge rate assumes that the sulphate in soil water originated entirely from atmospheric deposition; however, the origin of sulphate in soil and groundwater is often unclear, especially in loess aquifers. This study analysed the sulphur (δ³⁴S-SO₄) and oxygen (δ¹⁸O-SO₄) isotopes of sulphate in precipitation, water-extractable soil water, and shallow groundwater samples and used these data along with hydrochemical data to determine the sources of sulphate in the thick unsaturated zone and groundwater of a loess aquifer. The results suggest that sulphate in groundwater mainly originated from old precipitation. When precipitation percolates through the unsaturated zone to recharge groundwater, sulphates were rarely dissolved due to the formation of CaCO₃ film on the surface of sulphate minerals. The water-extractable sulphate in the deep unsaturated zone (>10 m) was mainly derived from the dissolution of evaporite minerals and there was no oxidation of sulphide minerals during the extraction of soil water by elutriating soil samples with deionized water. The water-extractable concentration of SO₄ was not representative of the actual SO₄ concentration in mobile soil water. Therefore, the recharge rate cannot be estimated by the SMB method using the water-extractable concentration of SO₄ in the loess areas. This study is important for identifying sulphate sources and clarifying the proper method for estimating the recharge rate in loess aquifers.     

Late Quaternary vegetation and climate dynamics in central-eastern Brazil: insights from a ~35k cal a bp peat record in the Cerrado biome

The late Quaternary evolution of central-eastern Brazil has been under-researched. Questions remain as to the origin of the Cerrado, a highly endangered biome, and other types of vegetation, such as the Capões – small vegetation islands of semi-deciduous and mountain forests. We investigated the factors that influenced the expansion and contraction of the Cerrado and Capões during the late Quaternary (last ~35 ka), using a multi-proxy approach: stable isotopes (δ¹³C, δ¹⁵N), geochemistry, pollen and multivariate statistics derived from a peat core (Pinheiro mire, Serra do Espinhaço Meridional). Five major shifts in precipitation, temperature, vegetation and landscape stability occurred at different timescales. Our study revealed that changes in the South Atlantic Convergence Zone (SACZ) seem to have been coeval with these shifts: from the Late Glacial Maximum to mid-Holocene the SACZ remained near (~29.6 to ~16.5k cal a bp ) and over (~16.5 to ~6.1 k cal a bp ) the study area, providing humidity to the region. This challenges previous research which suggested that climate was drier for this time period. At present, the Capões are likely to be a remnant of a more humid climate; meanwhile, the Cerrado biome seems to have stablished in the late Holocene, after ~3.1 k cal a bp .     

Local meteoric water lines describe extratropical precipitation

Stable water isotopes δ¹⁸O and δ²H are used to investigate precipitation trends and storm dynamics to advance knowledge of precipitation patterns in a warming world. Herein, δ¹⁸O and δ²H were used to determine the relationship between extratropical cyclonic precipitation and local meteoric water lines (LMWLs) in the eastern Ohio Valley and the eastern United States. Precipitation volume weighted and unweighted central Ohio LMWLs, created with samples collected during 2012–2018, showed that temperature had the greatest effect on precipitation isotopic composition. HYSPLIT back trajectory modelling showed that precipitation was primarily derived from a mid-continental moisture source. Remnants of major hurricanes were collected as extratropical precipitation during the 2012–2018 sampling period in central Ohio. Extratropical precipitation samples were not significantly different from the samples that created the central Ohio LMWL. Six additional LMWLs were derived from United States Geological Survey (USGS) Atmospheric Integrated Research Monitoring Network (AIRMoN) samples collected in Pennsylvania, Delaware, Tennessee, Vermont, New Hampshire, and Oxford, Ohio. Meteoric water lines describing published samples from Superstorm Sandy, plotted with these AIRMoN LMWLs, showed isotopic composition of Superstorm Sandy precipitation was commonly more depleted than the average isotopic composition at the mid-latitude locations. Meteoric water lines describing the Superstorm Sandy precipitation were not significantly different in slope from LMWLs generated within 300 km of the USGS AIRMoN site. This finding, which was observed across the eastern Ohio Valley and eastern United States, demonstrated a consistent precipitation δ²H–δ¹⁸O relationship for extratropical cyclonic and non-cyclonic events. This work also facilitates the analysis of storm development based on the relationship between extratropical event signature and the LMWL. Analysis of extratropical precipitation in relation to LMWLs along storm tracks allows for stronger development of precipitation models and understanding of which climatic and atmospheric factors determine the isotopic composition of precipitation.