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 wer...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.展开更多
The use of lead, some of which is characterized by a highly radiogenic signature, sharply distinguishes Bronze Age China from the rest of Eurasia. Scholars have long hypothesized that silver can offer an independent p...The use of lead, some of which is characterized by a highly radiogenic signature, sharply distinguishes Bronze Age China from the rest of Eurasia. Scholars have long hypothesized that silver can offer an independent proxy to characterize lead minerals. The summary of silver distribution associated with Shang and Western Zhou bronzes in this paper reveals an important difference between the south(Sanxingdui, Hanzhong, Jinsha, Panlongcheng, Xin’gan) and the Central Plains. Correlating silver with lead content as well as with the isotopic signature indicates that south China and the Central Plains had different lead sources during the late Shang period, and also that the highly radiogenic and common lead used at Anyang come from geochemical environments which cannot be distinguished by the level of silver.展开更多
The Sinongduo mining region includes two types of mineralizations:the epithermal and the carbonate-hosted PbZn-Ag deposits.Despite being studied for many years,the ore formation process and genesis of the carbonate-ho...The Sinongduo mining region includes two types of mineralizations:the epithermal and the carbonate-hosted PbZn-Ag deposits.Despite being studied for many years,the ore formation process and genesis of the carbonate-hosted Pb-Zn-Ag deposits remain poorly understood.The Pb-Zn-Ag ore bodies occur as veins and are hosted by limestone and dolostone of the Permian Xiala Formation.Three sulfide mineralization substages have been identified at the Sinongduo carbonatehosted deposit.Indium coupled with Cu,Co and Sn was incorporated into sphalerite as substitutions:2Zn^(2+)?Cu^(+)+In^(3+),(3n/2+1)Zn^(2+)?Co^(2+)+n In^(3+)or(2n+1)Zn^(2+)?Co^(2+)+n(Cu^(+)+In^(3+))(n>1)and 4Zn^(2+)?Sn2++2In^(3+).Sphalerite and pyrite in the mineralization stage displayδ^(34)S values in a narrow range of+5.7‰to+11.3‰,which are similar to those of Palaeocene igneous rocks,indicative of a magmatic source of sulfur.We present systematic carbon-hydrogen-oxygen isotope results that further support a magmatic source for the ore-forming fluids that were influenced by meteoric water.Furthermore,the Pb isotope compositions of sulfide minerals in the Sinongduo carbonate-hosted deposit overlap with the values of coeval Linzizong volcanic rocks and are similar to those of Indian Ocean sediments,indicating upper crustal sources of metals.We conclude that the Sinongduo carbonate-hosted Pb-Zn-Ag deposit is a medium-to low-temperature magmatic-hydrothermal deposit related to Linzizong magmatism.展开更多
The Baiyun deposit is a large gold deposit at the western end of the Liaoji rift zone in Liaoning Province, which has produced both auriferous quartz-vein type and altered-rock type mineralization. The ore bodies are ...The Baiyun deposit is a large gold deposit at the western end of the Liaoji rift zone in Liaoning Province, which has produced both auriferous quartz-vein type and altered-rock type mineralization. The ore bodies are mainly hosted in schist from the Gaixian Formation of the Liaohe Group. A detailed field geological survey showed that the quartz-vein type gold ore bodies are distributed in the near EW-trending and occur in the extensional tectonic space of schist in the Gaixian Formation, and the altered-rock type gold ore bodies are distributed in the near EW-trending structural belt and occur near in the Gaixian Formation of biotite schist, biotite granulite, marble and the upper footwall of dike. To further elucidate the source of ore-forming fluid and material in the Baiyun gold deposit, the H-O isotopes for quartz, S and Pb isotopes, in-situ trace elements for sulfides from quartz-vein and altered-rock type mineralization were studied. The H-O isotopic δD_(V-SMOW) and δ^(18)O_(H2O) values of the auriferous quartz range were from-88.8‰ to-82.2‰ and-1.95‰ to 4.85‰, respectively, suggests that the ore-forming fluids were mainly magmatic water with minor meteoric water. The distribution ranges of in-situ S isotopic compositions of Au-bearing pyrite in the quartz-vein type and altered-rock type ores were-8.38‰–-10.47‰(with average values of-7.89‰) and 11.38‰– 17.52‰(with average values of 11.55‰), respectively, indicating that the S isotopic compositions of the two ore types were clearly different. The in-situ Pb isotopic ratios changed almost uniformly, which showed that they had the same lead isotopic source. Based on the analysis of S and Pb isotopic compositions, the metallogenic materials in the Baiyun gold deposit were primarily from deep magma, and some wall rock materials may have been mixed in the metallogenic process. Co/Ni diagram shows that most Au-bearing pyrites have magmatic-hydrothermal or sedimentary alteration properties, and Au/As ratios were between 0.001 and 0.828(the average value was 0.07), indicating that the ore-forming fluid in the Baiyun gold deposit may have been deep magma. Combining the geological, trace element, and isotopic data, as well as data from previous studies, we propose that the Baiyun gold deposit is a magmatic-hydrothermal ore deposit.展开更多
The Zaibian mafic-ultramafic rock is located in the transitional zone of the Yangtze craton and south China fold system,where is the southwest of Jiangnan orogenic belt(Zeng et al.,2003;Wang et al.,in press).
基金supported by National Natural Science Foundation of China (NSFC) projects (41703012)Qinghai Science and Technology projects (2018-ZJ-956Q)+2 种基金the supports of the Strategic Priority Research Program (B) of CAS (XDB18010100, XDB41000000)pre-research Project on Civil Aerospace Technologies No. D020202 funded by the Chinese National Space AdministrationNSFC projects (41530210)。
文摘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.
基金This work has been partially supported by European Research Council Horizon 2020 Advanced Project FLAME(ERC AdG 670010Flow of Metal Across Eurasia).
文摘The use of lead, some of which is characterized by a highly radiogenic signature, sharply distinguishes Bronze Age China from the rest of Eurasia. Scholars have long hypothesized that silver can offer an independent proxy to characterize lead minerals. The summary of silver distribution associated with Shang and Western Zhou bronzes in this paper reveals an important difference between the south(Sanxingdui, Hanzhong, Jinsha, Panlongcheng, Xin’gan) and the Central Plains. Correlating silver with lead content as well as with the isotopic signature indicates that south China and the Central Plains had different lead sources during the late Shang period, and also that the highly radiogenic and common lead used at Anyang come from geochemical environments which cannot be distinguished by the level of silver.
基金jointly supported by the National Key Research and Development Program of China(2022YFC2905001)the National Natural Science Foundation(42230813)。
文摘The Sinongduo mining region includes two types of mineralizations:the epithermal and the carbonate-hosted PbZn-Ag deposits.Despite being studied for many years,the ore formation process and genesis of the carbonate-hosted Pb-Zn-Ag deposits remain poorly understood.The Pb-Zn-Ag ore bodies occur as veins and are hosted by limestone and dolostone of the Permian Xiala Formation.Three sulfide mineralization substages have been identified at the Sinongduo carbonatehosted deposit.Indium coupled with Cu,Co and Sn was incorporated into sphalerite as substitutions:2Zn^(2+)?Cu^(+)+In^(3+),(3n/2+1)Zn^(2+)?Co^(2+)+n In^(3+)or(2n+1)Zn^(2+)?Co^(2+)+n(Cu^(+)+In^(3+))(n>1)and 4Zn^(2+)?Sn2++2In^(3+).Sphalerite and pyrite in the mineralization stage displayδ^(34)S values in a narrow range of+5.7‰to+11.3‰,which are similar to those of Palaeocene igneous rocks,indicative of a magmatic source of sulfur.We present systematic carbon-hydrogen-oxygen isotope results that further support a magmatic source for the ore-forming fluids that were influenced by meteoric water.Furthermore,the Pb isotope compositions of sulfide minerals in the Sinongduo carbonate-hosted deposit overlap with the values of coeval Linzizong volcanic rocks and are similar to those of Indian Ocean sediments,indicating upper crustal sources of metals.We conclude that the Sinongduo carbonate-hosted Pb-Zn-Ag deposit is a medium-to low-temperature magmatic-hydrothermal deposit related to Linzizong magmatism.
基金supported by theNational Key Research and Development Program(No.2018YFC0603806)the Geological Surveying Project of China Geological Survey(No.DD20190166).
文摘The Baiyun deposit is a large gold deposit at the western end of the Liaoji rift zone in Liaoning Province, which has produced both auriferous quartz-vein type and altered-rock type mineralization. The ore bodies are mainly hosted in schist from the Gaixian Formation of the Liaohe Group. A detailed field geological survey showed that the quartz-vein type gold ore bodies are distributed in the near EW-trending and occur in the extensional tectonic space of schist in the Gaixian Formation, and the altered-rock type gold ore bodies are distributed in the near EW-trending structural belt and occur near in the Gaixian Formation of biotite schist, biotite granulite, marble and the upper footwall of dike. To further elucidate the source of ore-forming fluid and material in the Baiyun gold deposit, the H-O isotopes for quartz, S and Pb isotopes, in-situ trace elements for sulfides from quartz-vein and altered-rock type mineralization were studied. The H-O isotopic δD_(V-SMOW) and δ^(18)O_(H2O) values of the auriferous quartz range were from-88.8‰ to-82.2‰ and-1.95‰ to 4.85‰, respectively, suggests that the ore-forming fluids were mainly magmatic water with minor meteoric water. The distribution ranges of in-situ S isotopic compositions of Au-bearing pyrite in the quartz-vein type and altered-rock type ores were-8.38‰–-10.47‰(with average values of-7.89‰) and 11.38‰– 17.52‰(with average values of 11.55‰), respectively, indicating that the S isotopic compositions of the two ore types were clearly different. The in-situ Pb isotopic ratios changed almost uniformly, which showed that they had the same lead isotopic source. Based on the analysis of S and Pb isotopic compositions, the metallogenic materials in the Baiyun gold deposit were primarily from deep magma, and some wall rock materials may have been mixed in the metallogenic process. Co/Ni diagram shows that most Au-bearing pyrites have magmatic-hydrothermal or sedimentary alteration properties, and Au/As ratios were between 0.001 and 0.828(the average value was 0.07), indicating that the ore-forming fluid in the Baiyun gold deposit may have been deep magma. Combining the geological, trace element, and isotopic data, as well as data from previous studies, we propose that the Baiyun gold deposit is a magmatic-hydrothermal ore deposit.
基金National Basic Research Program of China(No.2007CB411402)Cooperation Program of Institute of Geochemistry and Guizhou Geology and Minerals Bureau 102 Geology Group
文摘The Zaibian mafic-ultramafic rock is located in the transitional zone of the Yangtze craton and south China fold system,where is the southwest of Jiangnan orogenic belt(Zeng et al.,2003;Wang et al.,in press).
