Multiple metal sources in polymetallic W-Sn ore deposits revealed by mercury stable isotopes

Granite-related W-Sn ore systems are commonly associated with coeval Pb-Zn mineralization. It remains unclear whether these metals are derived from the same sources or not. Mercury(Hg) is a common minor component in such systems. Hg isotopes undergo unique mass-independent fractionation(expressed as Δ^(199)Hg values), which is mainly generated during Hg photochemical reactions on Earth's surface and not affected by magmatic-hydrothermal processes, offering an excellent opportunity to trace metal sources in hydrothermal systems. We observed near-zero Δ^(199)Hg values in wolframite(-0.10‰ to0.08‰, n=11), and in skarn-(-0.17‰ to 0.12‰, n=48) and greisen-type(-0.12‰ to 0.10‰, n=11) bulk tin-tungsten ore from eight major ore deposits in South China. These values are identical to those of coeval highly evolved granites(-0.13‰ to 0.12‰,n=49), supporting that Hg in W-Sn ores were sourced from granite. However, sulfides(e.g., pyrite, chalcopyrite, arsenopyrite,galena, and sphalerite) in these deposits exhibit negative to near-zero Δ^(199)Hg values(-0.42‰ to 0.09‰, n=124), which indicates a contribution of Hg and by inference other metals from both Precambrian basement rocks(Δ^(199)Hg<0) and ore-related granites.The study demonstrates that multiple sources of metals were involved in the formation of the polymetallic W-Sn deposits, and further highlights that extraction of metals from basement rocks may be a critical control on the formation of economically important mineralization of base metal sulfides(e.g., Pb, Zn) in granite-related magmatic-hydrothermal systems.

Applications of mercury stable isotopes for tracing volcanism in the geologic record

Mercury(Hg)enrichments in ancient sediments have been used as a proxy of volcanism,especially large igneous province(LIP)eruptions.However,considering the existence of other potential Hg sources besides volcanoes and the diverse factors(e.g.,organic matters,clay minerals,sulfide minerals and Fe oxides)that can affect Hg sequestration,there are considerable uncertainties to simply regard sedimentary Hg anomalies as signatures of volcanic activities.Mercury stable isotopes,a promising tool for tracing the origins and transformations of Hg,have been increasingly used for determining the causes of Hg spikes and understanding the geochemical behavior of Hg in the geologic record.To date,lots of researches have applied Hg concentrations and Hg isotopes to identify LIP volcanisms linking with significant geological events such as mass extinctions,ocean anoxic events and other environmental perturbations that mainly occurred in the Phanerozoic.However,the results in previous studies clearly show that not all Hg enrichments are derived from volcanic inputs,which emphasize the need for more caution in using Hg as a fingerprint of volcanism.With a better understanding of Hg isotopes in the future,there will be important implications for Hg isotopes to reconstruct volcanic activities in the rock records and their impacts on biological evolution.

Atmospheric particle-bound mercury in the northern Indo-Gangetic Plain region:Insights into sources from mercury isotope analysis and influencing factors

Lumbini is a world heritage site located in the southern plains region of Nepal, and is regarded as a potential site for evaluating transboundary air pollution due to its proximity to the border with India. In this study, 82 aerosol samples were collected between April 2013 and July 2014 to investigate the levels of particulate-bound mercury(PBM) and the corresponding seasonality, sources, and influencing factors.The PBM concentration in total suspended particulate(TSP) matter ranged from 6.8 pg m^(-3) to351.7 pg m^(-3)(mean of 99.7 ± 92.6 pg m^(-3)), which exceeded the ranges reported for remote and rural sites worldwide. The Hg content(PBM/TSP) ranged from 68.2 ng g^(-1) to 1744.8 ng g^(-1)(mean of 446.9 ±312.7 ng g^(-1)), indicating anthropogenic enrichment. The PBM levels were higher in the dry season(i.e.,winter and the pre-monsoon period) than in the wet season(i.e., the monsoon period). In addition, the δ^(202) Hg signature indicated that waste/coal burning and traffic were the major sources of Hg in Lumbini during the pre-monsoon period. Meanwhile, precipitation occurring during photochemical processes in the atmosphere may have been responsible for the observed Δ^(199) Hg values in the aerosol samples obtained during the monsoon period. The PBM concentration was influenced mostly by the resuspension of polluted dust during dry periods and crop residue burning during the post-monsoon period. The estimated PBM deposition flux at Lumbini was 15.7 lg m^(-2) yr^(-1). This study provides a reference dataset of atmospheric PBM over a year, which can be useful for understanding the geochemical cycling of Hg in this region of limited data.

Significant Mercury Isotope Anomalies in Hydrothermal Altered Coals from the Huaibei Coalfield,China

Igneous intrusion into coal-bearing strata can cause an abrupt increase of temperature-pressure and trigger hydrothermal circulation at the igneous rock-coal contact zone. The conductive heat of intruded lnagma and convective migration of secondary hydrothermal fluids have been observed to significantly alter the concentrations and modes of occurrence of mercury （Hg） in thermally-intruded coals.

Equilibrium mercury and lead isotope fractionation caused by nuclear volume effects in crystals

To investigate equilibrium mercury(Hg)and lead(Pb)isotope fractionation caused by the nuclear volume effect(NVE)in crystals,the electron densities at nuclei(i.e.,|Ψ(0)|2)for Hg-or Pb-bearing crystalline compounds were investigated by using the relativistic spin orbit zeroth-order regular approximation(ZORA)method with a three-dimensional periodic boundary condition based on the density functional theory(DFT).Many isotope fractionation factors of crystalline compounds are provided for the first time.Our results show,even at1000℃,NVE-driven Hg and Pb isotope fractionation are meaningfully large,i.e.,range from 0.12‰to 0.49‰(202Hg/^(198)Hg),from-0.20‰to 0.17‰(208Pb/^(206)Pb)and from-0.08‰to 0.06‰(207Pb/^(206) Pb)relative to Hg0 vapor and Pb0 vapor,respectively.Specifically,the fractionations range from-0.06‰to-0.20‰(208Pb/^(206)Pb)and from-0.02‰to-0.08‰(207Pb/^(206)Pb)for Pb2+-bearing species,from 0.10‰to 0.17‰(208Pb/^(206)Pb)and from 0.04‰to 0.06‰(207Pb/^(206)Pb)for Pb4+-bearing species in crystals.All calculated Hg-bearing species in crystals will enrich heavier isotope(202Hg)relative to Hg0 vapor.Meanwhile,Pb4+-bearing species enrich heavier Pb isotopes(208Pb and 207Pb)than Pb^(2+)-bearing species in crystals,which the enrichment can be up to 0.37‰(208-Pb/^(206)Pb)and 0.14‰(207Pb/^(206)Pb)at 1000℃,due to their NVEs are in opposite directions.The NVE-driven MIFs of Hg isotopes,which are compared to the Hg202-Hg198baseline,are up to-0.158‰(ΔNV199Hg),-0.024‰(ΔNV200Hg)and-0.094‰(ΔNV201Hg)relative to Hg0 vapor at5000 C.For all studied Hg-bearing species in crystals,the MIFs of two odd-mass isotopes(i.e.,ΔNV199Hg andΔNV201Hg)will be changed proportionally and their ratio(i.e.,ΔNV199Hg/ΔNV201Hg)will be a constant 1.67.The NVE can also cause mass-independent fractionations for 207Pb and 204 Pb compared to the baseline of 208Pb and 206Pb.The largest NVEdriven MIFs are 0.043‰(ΔNV207Pb)and-0.040‰(ΔNV204Pb)among all the studied species relative to Pb0 vapor at 5000 C.The magnitudes of odd-mass isotope MIF(ΔNV207Pb)and even-mass isotope MIF(ΔNV204Pb)are almost the same but with opposite signs,leading to the MIF ratio of them(i.e.,ΔNV207Pb/ΔNV204Pb)is-1.08.

Comparison of two pretreatment methods for mercury stable isotope analysis in Antarctic moss

Mercury （Hg） stable isotope analysis can provide new insight for understanding the biogeochemistry and sources of Hg in the polar regions. To completely extract the low contents of Hg in polar samples and to avoid isotopic fractionation during the sample preparation stage, an effective and reliable pretreatment method is needed. In this work, two different pretreatment methods were compared for measuring Hg stable isotopes in Antarctic moss samples. One method was acid digestion （HNO3 ： H2O2=5 ： 3, v/v） and the second was a combustion-trapping treatment with a trapping solution （HNO3：HCl=2：1, v/v）. There were no significant differences in the analytical results obtained with the two methods. The overall mean values and uncertainties of total Hg （THg） and the isotopic compositions of Hg in the referenced materials were all in good agreement with the certified and reported values, indicating that both methods were accurate and applicable. Acid digestion is highly efficient, while the combustion-trapping method can be used to treat samples with low Hg content. The proposed methods were successfully used to determine the Hg isotopic compositions in moss samples collected from the Antarctic.

Roller-coaster atmospheric-terrestrial-oceanic-climatic system during Ordovician-Silurian transition:Consequences of large igneous provinces

The Ordovician-Silurian transition(OST)hosted profound and frequent changes in the atmospheric-terres trial-oceanic-climatic system(ATOCS).Previous studies have found contrasting stages for such changes,primarily based on hiatus-interrupted sections.However,the dominant driving factors and mechanisms reconciling such frequent changes remain controversial.Mercury isotopes,which undergo both massdependent and mass-independent fractionation,can provide critical insights into the deep-time ATOCSs,especially for those impacted by large igneous provinces(LIPs)events.Here,we build a highresolution multi-proxy record of Hg(concentrations and isotopic compositions)combined with organic carbon isotopes(δ^(13)Corg)and whole-rock geochemical data(including trace elements and phosphorus)from continuous cores in the Yangtze Platform,South China.Our data,combined with reported ones,indicate the occurrence of LIP eruptions against localized volcanism,and four successive,yet contrasting stages of ATOCSs during the OST.Moreover,we identified the coupling between two-pulse LIP magmatism and extreme ATOCSs,each with special pCO_(2),weathering rate,primary productivity,redox condition,climatic mode,and biotic evolution.For stage I,the first pulse of LIP magmatism triggered global warming,enhanced terrestrial weathering,oceanic acidification,eutrophication,anoxia,P recycling,and thereby widespread deposition of black shales.During stage II,the Hirnantian glaciation and oxygenation arose from the intense chemical weathering and black shale deposition of stage I;slashed terrestrial weathering and oceanic oxygenation facilitated CO_(2) accumulation.In stage III,another pulse of LIP magmatism triggered the de-glaciation,and the ATOCS was largely similar to that of stage I.This led to another round of oxygenation and positive d13Corg excursion in stage IV.Compared with the environmental pressure by the peculiar ATOCS of each stage,their transitions might have been more devastating in triggering the prolonged Late Ordovician Mass Extinction(LOME).Moreover,limited biotic recovery was possible in the later portion of stages I and III.The multi-proxy study of continuous strata of the OST provides an excellent framework for better illuminating LIPs’essential role in driving the“roller-coaster”behavior of the ATOCS and thus biotic crisis during the pivotal period of the OST.