Theoretical study of kinetic isotope effects for vacancy diffusion of impurity in solids

Theoretical studies of the diffusionalisotope effect in solids are still stuck in the 1960s and 1970s.With the development of high spatial resolution mass spectrometers,isotopic data of mineral grains are rapidly accumulated.To dig up information from these data,molecularlevel theoretical models are urgently needed.Based on the microscopic definition of the diffusion coe fficient(D),a new theoretical framework for calculating the diffusional isotope effect(DIE(v))(intermsofD*/D)forvacancy-mediated impurity diffusion in solids is provided based on statistical mechanics formalism.The newly derived equation shows that theDIE(v)can be easily calculated as long as the vibration frequencies of isotope-substituted solids are obtained.The calculatedDIE(v)values of^(199)Au/^(195)Au and^(60)Co/^(57)Co during diffusion in Cu and Au metals are all within 1%of errors compared to the experimental data,which shows that this theoretical model is reasonable and precise.

REE and C-O Isotopic Geochemistry of Calcites from the World-class Huize Pb-Zn Deposits,Yunnan,China:Implications for the Ore Genesis

The world-class Huize Pb-Zn deposits of Yunnan province,in southwestern China,located in the center of the Sichuan-Yunnan-Guizhou Pb-Zn polymetallic metallogenic province,has Pb＋Zn reserves of more than 5 million tons at Pb＋Zn grade of higher than 25%and contains abundant associated metals,such as Ag,Ge,Cd,and Ga.The deposits are hosted in the Lower Carboniferous carbonate strata and the Permian Emeishan basalts which distributed in the northern and southwestern parts of the orefield.Calcite is the only gangue mineral in the primary ores of the deposits and can be classified into three types,namely lumpy,patch and vein calcites in accordance with their occurrence.There is not intercalated contact between calcite and ore minerals and among the three types of calcite,indicating that they are the same ore-forming age with different stages and its forming sequence is from lumpy to patch to vein calcites. This paper presents the rare earth element（REE） and C-O isotopic compositions of calcites in the Huize Pb-Zn deposits.From lumpy to patch to vein calcites,REE contents decrease as LREE/ HREE ratios increase.The chondrite-normalized REE patterns of the three types of calcites are characterized by LREE-rich shaped,in which the lumpy calcite shows（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〈1,the patch calcite has（La）_N〈（Ce）_N〈（Pr）_N≈（Nd）_N with Eu/Eu~＊〉1,and the vein calcite displays（La）_N〉（Ce）_N〉（Pr）_N〉（Nd）_N with Eu/Eu~＊〉1.The REE geochemistry of the three types of calcite is different from those of the strata of various age and Permian Emeishan basalt exposed in the orefield.Theδ^（13） C_（PDb） andδ^（18）O_（Smow） values of the three types of calcites vary from-3.5‰to-2.1‰and 16.7‰to 18.6‰,respectively,falling within a small field between primary mantle and marine carbonate in theδ^（13）C_（PDb） vsδ^（18）O_（Smow） diagram. Various lines of evidence demonstrate that the three types of calcites in the deposits are produced from the same source with different stages.The ore-forming fluids of the deposits resulted from crustal -mantle mixing processes,in which the mantle-derived fluid components might be formed from degassing of mantle or/and magmatism of the Permian Emeishan basalts,and the crustal fluid was mainly provided by carbonate strata in the orefield.The ore-forming fluids in the deposits were homogenized before mineralization,and the ore-forming environment varied from relatively reducing to oxidizing.

Depositional Environment and Lithofacies Analyses of Eocene Lacustrine Shale in the Bohai Bay Basin:Insights from Mineralogy and Elemental Geochemistry

The effect of various depositional parameters including paleoclimate,paleosalinity and provenance,on the depositional mechanism of lacustrine shale is very important in reconstructing the depositional environment.The classification of shale lithofacies and the interpretation of shale depositional environment are key features used in shale oil and gas exploration and development activity.The lower 3rd member of the Eocene Shahejie Formation(Es_(3)^(x)shale)was selected for this study,as one of the main prospective intervals for shale oil exploration and development in the intracratonic Bohai Bay Basin.Mineralogically,it is composed of quartz(avg.9.6%),calcite(avg.58.5%),dolomite(avg.7%),pyrite(avg.3.3%)and clay minerals(avg.20%).An advanced methodology(thin-section petrography,total organic carbon and total organic sulfur contents analysis,X-ray diffraction(XRD),X-ray fluorescence(XRF),field-emission scanning electron microscopy(FE-SEM))was adopted to establish shale lithofacies and to interpret the depositional environment in the lacustrine basin.Six different types of lithofacies were recognized,based on mineral composition,total organic carbon(TOC)content and sedimentary structures.Various inorganic geochemical proxies(Rb/Sr,Ca/(Ca+Fe),Ti/Al,Al/Ca,Al/Ti,Zr/Rb)have been used to interpret and screen variations in depositional environmental parameters during the deposition of the Es_(3)^(x)shale.The experimental results indicate that the environment during the deposition of the Es_(3)^(x)shale was warm and humid with heightened salinities,moderate to limited detrital input,higher paleohydrodynamic settings and strong oxygen deficient(reducing)conditions.A comprehensive depositional model of the lacustrine shale was developed.The interpretations deduced from this research work are expected to not only expand the knowledge of shale lithofacies classification for lacustrine fine-grained rocks,but can also offer a theoretical foundation for lacustrine shale oil exploration and development.

Depth profiling of arsenian pyrite in Carlin-type ores through wet chemistry

Enrichment of As and Au at the overgrowth rims of arsenian pyrite is a distinctive feature of Carlin-type gold ores.Revealing distribution of such key elements in high resolution is of fundamental importance yet often proves challenging.In this study,repeated non-oxidative acid etching of ore samples from Shuiyindong gold deposit was applied to enable elemental depth profiling of goldbearing arsenian pyrite grains.ICP-OES and AAS were used to determine the dissolved Fe,As,and Au concentrations in each of the etching solutions,and XPS was carried out to exam the etched mineral surfaces.In contrast to conventional ion beam etching that may cause substantial sample damage,our acid etching method does not seem to significantly alter the composition and chemical state of the samples.The etched depths directly converted from the measured elemental concentrations can reproducibly reach a very high resolution of~1 nm,and can be conveniently controlled through varying the etching time.While the Fe and As depth profiles consistently reflect the surface oxidation property of arsenian pyrite,the Au profile displaying an obvious upward trend reveals the ore fluid evolution at the late stage of mineralization.Based on our experimental results,we demonstrate that our wet chemistry method is capable of effective depth profiling of gold ore and perhaps other geological samples,with advantages surpassing many instrumental techniques including negligible sample damage,nanoscale resolution as well as isotropic etching.

Trace Element Geochemistry of Magnetite from the Fe(-Cu) Deposits in the Hami Region, Eastern Tianshan Orogenic Belt, NW China

Laser ablation–inductively coupled plasma–mass spectrometry（LA–ICP–MS） was used to determine the trace element concentrations of magnetite from the Heifengshan, Shuangfengshan, and Shaquanzi Fe（–Cu） deposits in the Eastern Tianshan Orogenic Belt. The magnetite from these deposits typically contains detectable Mg, Al, Ti, V, Cr, Mn, Co, Ni, Zn and Ga. The trace element contents in magnetite generally vary less than one order of magnitude. The subtle variations of trace element concentrations within a magnetite grain and between the magnetite grains in the same sample probably indicate local inhomogeneity of ore–forming fluids. The variations of Co in magnetite between samples are probably due to the mineral proportion of magnetite and pyrite. Factor analysis has discriminated three types of magnetite： Ni–Mn–V–Ti（Factor 1）, Mg–Al–Zn（Factor 2）, and Ga– Co（Factor 3） magnetite. Magnetite from the Heifengshan and Shuangfengshan Fe deposits has similar normalized trace element spider patterns and cannot be discriminated according to these factors. However, magnetite from the Shaquanzi Fe–Cu deposit has affinity to Factor 2 with lower Mg and Al but higher Zn concentrations, indicating that the ore–forming fluids responsible for the Fe–Cu deposit are different from those for Fe deposits. Chemical composition of magnetite indicates that magnetite from these Fe（–Cu） deposits was formed by hydrothermal processes rather than magmatic differentiation. The formation of these Fe（–Cu） deposits may be related to felsic magmatism.

Study on the evolution of ore-formation fluids for Au-Sb ore deposits and the mechanism of Au-Sb paragenesis and differentiation in the southwestern part of Guizhou Province, China

Ore deposits (occurrences) of Au, As, Sb, Hg, etc. distributed in Southwest Guizhou constitute the important portion of the low-temperature metallogenic domain covering a large area in Southwest China, with the Carlin-type Au and Sb deposits being the most typical ones. In this paper the Au and Sb ore deposits are taken as the objects of study. Through the petrographic analysis, microthermomitric measurement and Raman spectrophic analysis of fluid inclusions in gangue minerals and research on the S and C isotopic compositions in the gold ore deposits we can reveal the sources of ore-forming materials and ore-forming fluids and the rules of ore fluid evolution. Ore deposits of Au, Sb, etc. are regionally classified as the products of ore fluid evolution, and their ore-forming materials and ore fluids were probably derived mainly from the deep interior of the Earth. Fluid inclusion studies have shown that the temperatures of Au mineralization are within the range of 170-361℃,the salinities are 0.35 wt%-8 wt% NaCl eq.; the temperatures of Sb mineralization are 129.4-214℃ and the salinities are 0.18 wt%- 3.23 wt% NaCl eq.; the ore-forming fluid temperatures and salinities tend to decrease progressively. In the early stage (Au metallogenic stage) the ore-forming fluids contained large amounts of volatile components such as CO2, CH4, N2 and H2S, belonging to the H2O-CO2-NaCl fluid system; in the late stage (Sb metallogenic stage) the ore-forming fluids belong to the Sb-bearing H2O-NaCl system. The primitive ore-forming fluids may have experienced at least two processes of immiscibility: (1) when early ore-bearing hydrothermal solutions passed through rock strata of larger porosity or fault broken zones, CO2, CH4, N2 would escape from them, followed by the release of pressure, resulting in pressure release and boiling of primitive homogenous fluids, thereafter giving rise to their phase separation, thus leading to Au unloading and mineralization; and (2) in the late stage (Sb metallogenic stage ) a large volume of meteoric water was involved in the ore-forming fluids, leading to fluid boiling as a result of their encounter, followed by the drop of fluid temperature. As a result, the dissolubility of Sb decreased so greatly that Sb was enriched and precipitated as ores. Due to differences in physic-chemical conditions between Au and Sb precipitates, Au and Sb were respectively precipitated in different structural positions, thus creating such a phenomenon of Au/Sb paragenesis and differentiation in space.

In-situ analysis and genetic investigation of Li-bearing minerals in McDermitt clay-type lithium deposit,Nevada,USA

Clay-type Li deposits are poised to play a pivotal role in addressing the surging global demand for Li.The McDermitt clay-type Li deposit,located in Nevada,is the largest Li deposit in the United States,with Li hosted by a clay-rich sequence of smectite-dominated intervals and illite-dominated intervals,respectively.However,the occurrence of Li and the genesis of Li-bearing minerals within smectite-dominated intervals have not been thoroughly investigated in previous research.Here,we studied the mineralogy,the in-situ Li distribution,and the bonding environments of Li within the smectite intervals using a combination of instru-mental techniques including scanning electron microscope,transmission electron microscope,time-of-flight secondary ion mass spectrometry,and nuclear magnetic resonance.Our results indicate that the smectite exhibits low crystallinity characteristics of lacustrine clay authigenesis and is com-monly found tofill the interstices among volcanic minerals or envelop them;Li is mainly hosted by Mg-smectite rather than the volcanic minerals.Within the tuffaceous sediment samples,the volcanic glass has undergone a transformation,resulting in its complete disappearance and alteration into clay minerals.Owing to the octahedral sites of Mg-smectite bounded in Li,it is referred to be hectorite.We interpret that the hectorite’s precipitation occurs in a high saline-alkaline water environment,a result of McDermitt tuffdissolution.This conclusion can be supported by the coexistence of spherulitic calcite and hectorite.Overall,this study confirms hectorite as the main Li-bearing mineral and increases the understanding of the genetic model of hectorite formation in intracontinental caldera basins.

Geology and sulfur isotope geochemistry of Dafulou tin-polymetallic deposit in Dachang orefield, Guangxi, China

No. 22 ore of Dafulou deposit was systematically analyzed for sulfur isotopes. The results show that the δ34S values of sulfide minerals, ranging from 0.154 to +0.218% and with an average value of +0.114 1%, are mostly positive and characterized by rich sulfur(S) content. This suggests that the sulfur of the Dafulou ore deposit is derived from magma and relates to the Longxianggai concealed granite, which points to the important role of magma during mineralization and implyies the product of the active continental margin. By comparison between the Dafulou and the Kengma tin deposit, significant differences exist in the sulfur isotope composition. In the Kengma deposit, the sulfur isotope composition is characterized by the high negative value, which is different from the Dafulou tin-polymetallic deposit. The difference of the enrichment and fractionation of the sulfur isotope is the synthesized result of the metallogenic conditions. It also has the difference in the metallogenic environment and metallogenic characteristics of the deposit in the same ore belt.

The occurrence state of vanadium in the black shale-hosted vanadium deposits in Shangling of Guangxi Province, China

The Shangling vanadium deposit, which occurs in the Lower Devonian Tangding formation black rock series strata, has V2O5 reserves of more than 1.5 million tons and prospective reserves of more than 2 million tons. Preliminary studies on the occurrence state of vanadium(V) in this deposit have been conducted by artificial heavy minerals concentrates, leaching experiments, scanning and transmission electron microscopy and X-ray powder diffraction.These experiments have revealed no independent vanadium mineral occurrences in the Shangling vanadium deposit and the percentages of water-soluble vanadium, hydrochloric acid soluble vanadium and HF soluble vanadium were1.93 %, 21.42 % and 76.47 %, respectively. Based on our data and earlier research, we estimate that the valences state of V absorbed onto the surface of organic matter or clastic particles are +5 and +4, accounting for 10.00 % and13.35 % of the total amount of V, respectively and the valences state of V that exist in the octahedral crystal lattice of authigenic illite include +3 and +4, accounting for71.64 % and 4.83 % of the total amount of V, respectively.By calculating the correlation between the total organic carbon and V, we infer that after deposition and before entering the crystal lattice of illite, V occurs in the form of humate complex or is adsorbed by organic matter. About4.24 % of the Al is in the octahedral crystal lattice of illite,which was replaced by the vanadium under the metallogenic environments of Shanglin.

Study on the occurrence state of indium in sphalerite of Dulong Sn–Zn–In polymetallic deposit,Southwest China

The Dulong deposit,located in the Laojunshan area of southeastern Yunnan,China,is an important polymetallic deposit due to its high reserves of tin,zinc,and indium.The occurrence state of indium is critical for understanding its supernormal enrichment mechanism.Previous studies investigated the occurrence state of indium(including the valence state)based on the indium content in sphalerite and the correlation between metal concentrations.However,more evidence is needed to better constrain indium occurrence at the micro-,nano-,or even atomic scale.In this study,EPMA-FIB-SEM-TEM and XPS techniques were employed to investigate the indium distribution characteristics and occurrence state in sphalerite from the Dulong Sn–Zn–In polymetallic deposit.The maximum concentration of indium in the indium-rich sphalerite samples is 0.37%,and the results of the EPMA analysis showed a relatively homogeneous distribution of indium in sphalerite.The FIB-SEM-TEM results demonstrated that the lattice stripes of sphalerite were periodically and continuously distributed at the nanoscale,confirming that sphalerite in the deposit was an excellent single crystal structure,and the peak heights of the various characteristic peaks of indium in the EDX spectra were relatively close to each other,with no distinct peaks of high indium content.In addition,the XPS results indicate that the element valence state of indium in sphalerite is In^(3+),and it combines with S^(2-)to form a bond.These results indicate that indium in sphalerite of the Dulong deposit is uniformly distributed at both the micro-and nanoscale,and there is no indium-independent mineral.In^(3+)enters the crystal lattice of sphalerite by replacing Zn2+in the form of isomorphic substitution.

Geology and C-O isotope geochemistry of carbonate-hosted Pb-Zn deposits, NW Guizhou Province, SW China

The Pb-Zn metallogenic district in NW Guizhou Province is an important part of the Yun-nan-Sichuan-Guizhou Pb-Zn metallogenic province, and also is one of the most important Pb-Zn producers in China. The hosting rocks of the Pb-Zn deposits are Devonian to Permian carbonate rocks, and the basement rocks are meta-sedimentary and igneous rocks of the Proterozoic Kunyang and Huili groups. The ore minerals are composed of sphalerite, galena and pyrite, and the gangue minerals are include calcite and dolomite. Geology and C-O isotope of these deposits were studied in this paper. The results show that δ13C and δ18O values of hydrothermal calcite, altered wall rocks-dolostone, sedimentary calcite and hosting carbonate rocks range from -5.3‰ to -0.6 ‰ (mean -3.4‰) and +11.3‰ to +20.9 ‰ (mean +17.2‰), -3.0‰ to +0.9 ‰ (mean -1.3‰) and +17.0‰ to +20.8‰ (mean +19.7‰), +0.6‰ to +2.5 ‰ (mean +1.4‰) and +23.4‰ to +26.5 ‰ (mean +24.6‰), and -1.8‰ to +3.9‰ (mean +0.7‰) and +21.0‰ to +26.8‰ (mean +22.9‰), respectively, implying that CO2 in the ore-forming fluids was mainly a result of dissolution of Devonian and Carboniferous carbonate rocks. However, it is difficult to evaluate the contribution of sediment de-hydroxylation. Based on the integrated analysis of geology, C and O isotopes, it is believed that the ore-forming fluids of these carbonate-hosted Pb-Zn deposits in this area were derived from multiple sources, including hosting carbonate rocks, Devonian to Permian sedimentary rocks and basement rocks (the Kun-yang and Huili groups). Therefore, the fluids mixing is the main precipitation mechanism of the Pb-Zn deposit in this province.

Helium, lead and sulfur isotope geochemistry of the Gejiu Sn-polymetallic ore deposit and the s ources of ore-forming materials

Studies on the helium, lead and sulfur isotopic composition were performed of the Gejiu super-large Sn-polymetallic ore deposit. The results indicated that the ore-forming materials came from different sources and the deposit is a product of superimposed mineralization. The deposit is characterized by multi-source and multi-period mineralization, which experienced submarine hydrothermal deposition and Late Yanshanian magmatic hydrothermal mineralization. It is held that the Gejiu super-large Sn-polymetallic ore deposit is a multi-genesis deposit.

Rare earth element(REE) geochemistry of different colored fluorites from the Baoshan Cu–Pb–Zn deposit, Southern Hunan,South China

The Baoshan Cu–Pb–Zn deposit, located in the central part of the Qin–Hang belt in South China, is closely related to the granodiorite-porphyry. However, the characteristics and the source of the ore-forming fluid are still ubiquitous. According to the crosscutting relationships between veinlets and their mineral assemblages, three stages of hydrothermal mineralization in this deposit were previously distinguished. In this contribution, two different colored fluorites from the major sulfide mineralization stage are recognized:(1) green fluorites coexisting with Pb–Zn ores;and(2) violet fluorites coexisting with pyrite ores. Y/Ho ratios verify the green fluorites and violet fluorites were co-genetic. The fluorites display elevated(La/Yb)Nratios, which decrease from 1201 to 5710 for green fluorites to 689–1568 for violet fluorites, indicating that they precipitated at the early hydrothermal sulfide stage,and Pb–Zn ores crystallized earlier than pyrite ores. The similar Tb/La ratios of the fluorites also indicate that they precipitated at an early stage within a short time. From the green fluorites to violet fluorites, the total rare earth element(ΣREE)concentrationsdecreasefrom1052–1680 ppm to 148–350 ppm, indicating that the green fluorites precipitated from a more acidic fluid. The Eu/Eu*ratios increase from 0.17 to 0.30 for green fluorites to0.29–0.48 for violet fluorites, and the Ce/Ce* ratios decrease from 1.08–1.13 to 0.93–1.11, suggesting a gradual increase in oxygen fugacity(fO_(2)) and pH value of the mineralization fluid. Though the fluorites display similar REE patterns to the granodiorite-porphyry and limestone,the ΣREE concentrations of the fluorites are significantly higher than those of limestone and the granodiorite-porphyry, suggesting that an important undetected non-magmatic source is involved to provide sufficient REE for fluorites. The most plausible mechanism is fluid mixing between magma fluid and an undetected non-magmatic fluid.

Trace elements in magmatic and hydrothermal quartz:Implications on the genesis of the Xingluokeng Tungsten Deposit,South China

The Xingluokeng deposit is the largest gran-ite-related tungsten deposit within the Wuyi metallogenic belt in South China.The Xingluokeng intrusion primarily consists of porphyritic biotite granite,biotite granite,andfine-grained granite.The deposit is represented by veinlet-disseminated mineralization with K-feldspathization and biotitization,alongside quartz-vein mineralization with gre-isenization and sericitization.This study investigates in-situ analyses of quartz compositions from both the intrusion and hydrothermal veinlets and veins.Trace element correlations indicate that trivalent Al^(3+)and Fe^(3+)replace Si^(4+)within the quartz lattice,with monovalent cations(such as Li^(+),Na^(+),and K^(+))primarily serving as charge compensators.Low Ge/Al ratios(<0.013)of quartz from granites suggest a mag-matic origin.The low Al/Ti and Ge/Ti ratios,accompanied by high Ti contents in quartz,suggest that the porphyritic biotite granite and biotite granite are characterized by rela-tively low levels of differentiation and high crystallization temperatures.In contrast,thefine-grained granite exhibits a higher degree of fractionation,lower crystallization tem-peratures,and a closer association with tungsten miner-alization.Ti contents in quartz from quartz veins indicate Qz-Ⅰformed at temperatures above 400°C,while Qz-Ⅱto Qz-Ⅴformed at temperatures below 350°C.Variations in different generations of quartz,as indicated by Al content and(Al+Fe)/(Li+Na+K)ratio,suggest that Qz-Ⅰprecipi-tated from a less acidicfluid with a stable pH,whereas Qz-Ⅱto Qz-Ⅴoriginated from a more acidicfluid with notable pH variations.Consequently,alkaline alteration and acidic alteration supplied the essential Ca and Fe for the precipita-tion of scheelite and wolframite,respectively,highlighting a critical mechanism in tungsten mineralization at the Xin-gluokeng deposit.

The lithology and composition of lunar mantle modified by ilmenite bearing cumulate:A thermodynamic model

Due to their high density,the ilmenite-bearing cumulates(IBC)(with or without KREEP)formed during the late-stage lunar magma ocean solidification are thought to sink into the underlying lunar mantle and trigger lunar mantle overturn.Geophysical evidence implied that IBC may descend deep inside the Moon and remain as a partially molten layer at the core-mantle boundary(CMB).However,partial melting may have occurred on the mixed mantle cumulates during the sinking of IBC/KREEP and the silicate melt may be positively buoyant,thus preventing the IBC/KREEP layer from sinking to the CMB.Here,we perform thermodynamic simulation on the stability of lunar mantle cumulates at different depths mixed with different amounts of IBC/KREEP from an updated LMO model.The modeling results suggest that the sinking of IBC/KREEP will cause at least 5 wt%partial melting in the shallow(~120 km)and a much larger degree of partial melting in the deep lunar mantle(~420 km).Due to the density contrast with the surrounding mantle,IBC/KREEP-bearing melts could potentially decouple under certain conditions.The modified lunar mantle by sinking of IBC/KREEP can better explain the formation of different kinds of lunar basaltic magma than the primary lunar mantle formed through differentiation of lunar magma ocean.Sinking of IBC/KREEP back into the lunar mantle may introduce plagioclase,clinopyroxene,garnet,and incompatible radioactive elements into the deep lunar mantle,which will further affect the thermal and chemical evolution of the lunar interior.

Rebuilding the theory of isotope fractionation for evaporation of silicate melts under vacuum condition

Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations of laboratory experiments due to its oversimplified assumptions.Here,we point out that the Hertz-Knudsen-equation-based theory is incomplete for silicate melt evaporation cases and can only be used for situations where the vaporized species is identical to the one in the melt.We propose a new model designed for silicate melt evaporation under vacuum.Our model considers multiple steps including mass transfer,chemical reaction,and nucleation.Our derivations reveal a kinetic isotopic fractionation factor(KIFF orα)αour model=[m(^(1)species)/m(^(2)species)]^(0.5),where m(species)is the mass of the reactant of reaction/nucleation-limiting step or species of diffusion-limiting step and superscript 1 and 2 represent light and heavy isotopes,respectively.This model can eff ectively reproduce most reported KIFFs of laboratory experiments for various elements,i.e.,Mg,Si,K,Rb,Fe,Ca,and Ti.And,the KIFF-mixing model referring that an overall rate of evaporation can be determined by two steps jointly can account for the eff ects of low P_(H2)pressure,composition,and temperature.In addition,we find that chemical reactions,diffusion,and nucleation can control the overall rate of evaporation of silicate melts by using the fitting slope in ln(−ln f)versus ln(t).Notably,our model allows for the theoretical calculations of parameters like activation energy(E_(a)),providing a novel approach to studying compositional and environmental eff ects on evaporation processes,and shedding light on the formation and evolution of the proto-solar and Earth-Moon systems.

Nuclear volume effects in kinetic isotope fractionation:A case study of mercury oxidation by chlorine species

It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the effect of the NVE on these kinetic processes is not known.The total fractionations(MDFs+NVEinduced MIFs)of several representative Hg-incorporated substances were selected and calculated with ab initio calculations in this work for both equilibrium and kinetic processes.NVE-induced MIFs were calculated with scaled contact electron densities at the nucleus through systematic evaluations of their accuracy and errors using the Gaussian09 and DIRAC19 packages(named the electron density scaling method).Additionally,the NVE-induced kinetic isotope effect(KIE)of Hg isotopes are also calculated with this method for several representative Hg oxidation reactions by chlorine species.Total KIEs for 202 Hg/^(198)Hg ranging from−2.27‰to 0.96‰are obtained.Three anomalous^(202)Hg-enriched KIEs(δ^(202)Hg/^(198)Hg=0.83‰,0.94‰,and 0.96‰,)caused by the NVE are observed,which are quite different from the classical view(i.e.,light isotopes react faster than the heavy ones).The electron density scaling method we developed in this study can provide an easier way to calculate the NVE-induced KIEs for heavy isotopes and serve to better understand the fractionation mechanisms of mercury isotope systems.

Correction:The escape mechanisms of the proto-atmosphere on terrestrial planets:“boil-off”escape,hydrodynamic escape and impact erosion

In the original publication of the article,the affiliation“College of Earth and Planetary Sciences,University of Chinese Academy of Sciences,Beijing,People’s Republic of China”for author Ziqi Wang was missing and included in this correction article.

Application of low-temperature thermochronology on ore deposits preservation framework in South China:a review

South China can be divided into four metallogenic belts:The Middle-Lower Yangtze Metallogenic Belt(MLYB),Qinzhou-Hangzhou Metallogenic Belt(QHMB),Nanling Metallogenic Belt(NLMB),and Wuyi Metallogenic Belt(WYMB).The major mineralization in the four metallogenic belts is granite-related Cu–Au–Mo and porphyrite Fe-apatite,porphyry Cu(Au),and epithermal Pb–Zn–Ag,hydrothermal Cu–Au–Pb–Zn–Ag,and granite-related skarn-type and quartz-veins W–Sn,respectively.Low-temperature thermochronology,including fissiontrack and U-Th/He dating,has been widely used to constrain tectonic thermal evolution and ore deposits preservation.Understanding fission-track annealing and He diffusion kinetics in accessory minerals,such as zircon and apatite,is essential for dating and applications.In this study,previous zircon fission-track(ZFT)and apatite fission-track(AFT)ages in South China were collected.The result shows that the ZFT ages are mainly concentrated at140–90 Ma,and the AFT ages are mainly distributed at70–40 Ma.The age distribution and inversion temperature–time paths reveal heterogeneous exhumation histories in South China.The MLYB experienced Late CretaceousCenozoic extremely slow exhumation after rapid cooling in the Early Cretaceous.The northern QHMB(i.e.from southern Anhui province to the Hangzhou Bay)had a relatively faster rate of uplifting and denudation than the southern QHMB in the Cretaceous.Subsequently,the northern QHMB rapidly exhumed,while the continuously slow exhumation operated the southern QHMB in the Cenozoic.The southern NLMB had a more rapid cooling rate than the northern NLMB during the Cretaceous time,and the whole NLMB experienced rapid cooling in the Cenozoic,except that the southern Hunan province had the most rapid cooling rate.The WYMB possibly had experienced slow exhumation since the Late Cretaceous.The exhumation thickness of the four metallogenic belts since90 Ma is approximately calculated as follows:the MLYB≤3.5 km,the northern QHMB concentrated at3.5–5.5 km,and the southern QHMB usually less than3.5 km,the NLMB 4.5–6.5 km and the WYMB<3.5 km.The exhumation thickness of the NLMB is corresponding to the occurrence of the world-class W deposits,which were emplaced into a deeper depth of 1.5–8 km.As such,we infer that the uplifting and denudation processes of the four metallogenic belts have also played an important role in dominated ore deposits.

Source characteristics and genesis of Sb mineralization from the Au and Sb deposits of the Youjiang Basin,SW China:constraints from stibnite trace element and isotope geochemistry

The Youjiang Basin is characterized by a wide distribution of Au and Sb deposits.These deposits are mainly hosted by sedimentary rocks from Cambrian to Triassic and are structurally controlled by faults and folds.Three types of Sb mineralization can be distinguished based on geologic characteristics,economic metals,and mineral associations.The first type is dominated by Sb mineralization but contains minor or little Au,similar to the large Qinglong deposit.The second type has a spatial association with the gold deposit but formed independent Sb mineralization,reminiscent of the Badu deposit.In the third type,Sb generally formed as an accompanying element in the Carlin-type gold deposit,and stibnite occurred as euhedral crystals filling the open space and faults in the late stage of gold mineralization,analogous to the Yata deposit.Trace element concentrations and sulfur isotopic ratio of stibnite,and oxygen isotope of stibnite bearing quartz were analyzed to infer the ore source(s)for Sb mineralization and genesis.To distinguish the various types of stibnite mineralization between the deposits,Cu,Pb,and As have recognized most diagnostic,with an elevated concentration in Au and Au-Sb deposits and depleted in Sb deposit.Theδ34S isotopic composition of stibnite samples from three deposits show a wide variation,ranging from-6.6%to+17.45%.Such isotopic values may indicate the sedimentary sulfur source,introduced by fluid–rock interaction.On the other hand,fluid mixing of several end members cannot be excluded.The calculatedδ18O isotopic data of Sb-bearing quartz show the initial ore fluid in Au and Au-Sb deposits most likely have a magmatic or metamorphic origin that enriched during fluid–rock interaction,and Sb deposit characterized by initial meteoric water.From these data,we proposed that different lithologies,fluid–rock interaction,fluid pathways,and different ore fluids controlled the compositional evolution of fluids,which might be the main reason for the diversity of Au or Sb mineralization.