Atmospheric Reactive Nitrogen Cycle and Stable Nitrogen Isotope Processes: Progresses and Perspectives

Oxidized reactive nitrogen in the atmosphere mainly consists of nitrogen oxides (NO _X =NO+NO₂, NO₃) and nitric acid. The atmospheric cycling of NO _X influences the formation of ozone and hydroxyl radicals that are important for atmospheric oxidation capacity. Nitric acid, the final product of NO _X oxidation, not only is an important component of particulate pollutants, but also has a direct impact on the ecosystem through dry and wet deposition. The stable nitrogen isotope (δ¹⁵N) shows the potential to study reactive nitrogen cycle, and to trace the emission, transport and deposition of reactive nitrogen from local to global scales. Here, we reviewed previous studies using δ¹⁵N to investigate NO _X emission and atmospheric reactive nitrogen cycle, and discuss the uncertainties of δ¹⁵N signatures of different NO _X sources from two aspects: NO _X generation mechanism and NO _X collection methods. We also discussed the nitrogen isotope fractionation and the consequences during the conversions of NO _y molecules. We ended up with discussions on the possibility of using δ¹⁵N to trace NO _X emissions. Although there are still large uncertainties in quantifying and tracing NO _X emissions using nitrogen stable isotopes, such isotope tool is efficient enough to trace reactive nitrogen cycles in the atmosphere. On the basis of this, we proposed that we can combine atmospheric chemistry transmission models with isotope tracers to improve our understanding of regional and global atmospheric reactive nitrogen cycle regarding the fluxes of different emission sources, their atmospheric transformation, etc.     

Genesis of the Xiuwenghala Gold Deposit in the Beishan Orogen,Northwest China: Evidence from Geology,Fluid Inclusion,and H–O–S–Pb Isotopes

The Xiuwenghala gold deposit is located in the Beishan Orogen of the southern Central Asian Orogenic Belt. The vein/lenticular gold orebodies are controlled by Northeast‐trending faults and are hosted mainly in the brecciated/altered tuff and rhyolite porphyry of the Lower Carboniferous Baishan Formation. Metallic minerals include mainly pyrite and minor chalcopyrite, arsenopyrite, galena, and sphalerite, whilst nonmetallic minerals include quartz, chalcedony, sericite, chlorite, and calcite. Hydrothermal alterations consist of silicic, sericite, chlorite, and carbonate. Alteration/mineralization processes comprise three stages: pre‐ore silicic alteration (Stage I), syn‐ore quartz‐chalcedony‐polymetallic sulfide mineralization (Stage II), and post‐ore quartz‐calcite veining (Stage III). Fluid inclusions (FIs) in quartz and calcite are dominated by L‐type with minor V‐type and lack any daughter mineral‐bearing or CO₂‐rich/‐bearing inclusions. From Stages I to III, the FIs homogenized at 240–260°C, 220–250°C, and 150–190°C, with corresponding salinities of 2.9–10.9, 3.2–11.1, and 2.9–11.9 wt.% NaCl eqv., respectively. The mineralization depth at Xiuwenghala is estimated to be relatively shallow (<1 km). FI results indicate that the ore‐forming fluids belong to a low to medium‐temperature, low‐salinity, and low‐density NaCl‐H₂O system. The values decrease from Stage I to III (3.7‰, 1.7–2.4‰, and ?1.7 to 0.9‰, respectively), and a similar trend is found for their values (?104 to ?90‰, ?126 to ?86‰, and ?130 to ?106‰, respectively). This indicates that the fluid source gradually evolved from magmatic to meteoric. δ³⁴S values of the hydrothermal pyrites (?3.0 to 0.0‰; avg. ?1.1‰) resemble those of typical magmatic/mantle‐derived sulfides. Pyrite Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.409–18.767, ²⁰⁷Pb/²⁰⁴Pb = 15.600–15.715, ²⁰⁸Pb^/204Pb = 38.173–38.654) are similar to those of the (sub)volcanic ore host, indicating that the origin of ore‐forming material was mainly the upper crustal (sub)volcanic rocks. Integrating evidence from geology, FIs, and H–O–S–Pb isotopes, we suggest that Xiuwenghala is best classified as a low‐sulfidation epithermal gold deposit.     

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.     

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 .