As a powerful tracer in high-temperature geochemistry,Fe isotopes have been studied for their behaviour during fl uid exsolution and evolution related to felsic magma system,but that for carbonatite magma system remai...As a powerful tracer in high-temperature geochemistry,Fe isotopes have been studied for their behaviour during fl uid exsolution and evolution related to felsic magma system,but that for carbonatite magma system remains unknown.Here we study the Fe isotope fractionation behaviour during fenitization–processes that widely occur associated with carbonatite or alkaline intrusions.Nine fenite/carbonatite samples from carbonatite dykes at Bayan Obo area are analyzed for their Fe isotope compositions as well as elemental compositions.Combined with previous reported carbonatite δ^(56)Fe data,the results show that carbonatites range from-0.35‰to 0.28‰,with an average of-0.10‰in δ^(56)Fe values,while fenites range from-0.17‰to 0.30‰,with an average of 0.11‰in δ^(56)Fe values.This indicates that fenitizing fl uids exsolved from carbonatite melts are enriched in heavier Fe isotopes.Such a Fe isotope fractionation trend is diff erent from that for fl uid exsolution from felsic magmatism.δ^(56)Fe values in fenites are negatively correlated with indicators of fenitization intensity such as(Na+K),Ti,Ba,Th,Nb,U or Pb abundances,likely refl ecting that Fe isotopes fractionate during the evolution of the fenitizing fl uids.Thus,Fe isotopes are a valuable tool for tracing fl uid exsolution and evolution relevant to carbonatite magmatism and related metal mineralization.展开更多
Podiform chromitites crop out in ophiolitic harzburgites as pod-like bodies associated with dunite envelopes with various thickness. It is widely accepted that the change of melt compositions caused by melt-rock react...Podiform chromitites crop out in ophiolitic harzburgites as pod-like bodies associated with dunite envelopes with various thickness. It is widely accepted that the change of melt compositions caused by melt-rock reaction, especially an increase in silica content, plays a crucial role in the generation of podiform chromitite(e.g., Arai and Yurimoto, 1994;Zhou et al., 1994). Due to the presence of ultrahigh pressure and highly reduced minerals, the genesis of some podiform chromitites was attributed to some deep processes(e.g., Arai, 2013;Yang et al., 2007). Although much progress has been achieved, the formation mechanism of podiform chromitites are still in dispute. Iron isotope may be a potential tool to give further insight to the issue, given that some high temperature processes, such as partial melting, metasomatism, magma differentiation and redox change, can result in measurable iron isotopic fractionation to different extent(e.g. Chen et al., 2014;Weyer and Ionov, 2007;Zhao et al., 2009). This study investigates the Fe isotope compositions of chromitites and chromite dunites from Dazhuqu and Luobusha ophiolites. For Dazhuqu chromite dunites, δ56 Fe(relative to the standard, IRMM-014) values range from-0.02‰ to 0.11‰ in olivines and from 0.03‰ to 0.08‰ in chromites. Chromites in Dazhuqu chromitites show δ56 Fe values varying from-0.03‰ to 0.02‰. In nodular and densely disseminated chromitites from Luobusha, olivines have δ56 Fe values of olivines and chromites are 0.09–0.35‰ and-0.15–0.08 ‰, respectively. Chromites from Luobusha massive chromitites have δ56 Fe values of 0.07–0.12 ‰. Based on theorical calculations, chromites should be heavier than olivines in Fe isotope compositions ?56 FeOl-Chr ≈-0.08‰ at 1300 ℃ according to the ionic model(e.g., Macris et al., 2015;Sossi and O’Neill, 2017). However, most of our samples, except for two samples, have ?56 FeOl-Chr values that are greater than zero, indicating a disequilibrium inter-mineral Fe isotopic fractionation. There is a positive correlation between Fo and δ56 Fe(or ?56 FeOl-Chr) of olivines but no positive correlation between Mg# and δ56 Fe(or ?56 FeOl-Chr) of chromites. This phenomenon suggests that the Fe isotopic dis-equilibration may be caused by migrating melts in dunitic channels rather than by the sub-solidus Fe-Mg exchange(Xiao et al., 2016;Zhang et al., 2019). Additionally, the wide δ56 Fe range of chromites is similar to those of the subduction-related basalts and boninites, inferring that their parental magmas form in the suprasubduction zone.展开更多
Iron isotopes are important for tracing the magmatic process.The fractionation of iron isotopes in granite is up to 0.55‰.In this study,Wangjiagou(XWJ)granite and Tayueping(XTY)granite in the Xinxian pluton of the We...Iron isotopes are important for tracing the magmatic process.The fractionation of iron isotopes in granite is up to 0.55‰.In this study,Wangjiagou(XWJ)granite and Tayueping(XTY)granite in the Xinxian pluton of the Western Dabie orogen were evaluated.Both the XTY and XWJ granite belong to monzogranites,with high SiO2(74.42-76.82 wt.%)contents.The granites are depleted of Nb and Ti but enriched with Pb and K,and they display negative Eu anomalies(Eu/Eu^(*)=0.40-0.52)on REE plots that are normalized by chondrite.Theδ^(56)Fe values of the XTY granites vary from 0.19±0.03‰to0.27±0.04‰,and theδ^(56)Fe values of the XWJ granites are 0.34±0.02‰and 0.36±0.01‰,respectively.Both the XTY and the XWJ granites belong to highly fractionated granites due to their SI(solidification index),DI(differentiation index),and content of CaO.Evidence from the iron isotopes shows that neither fluid exsolution,alteration,weathering,nor partial melting can explain the enrichment of the heavy iron isotopes.The results modeled using the Rayleigh equation showed that fractional crystallization can produceΔ^(56)Femelt-crystalwith the value of0.08-0.15‰.In conclusion,fractional crystallization was the main factor controlling the fractionation of iron isotopes,and the change of melt composition may also lead to the enrichment of heavy iron isotopes in the residual melt.展开更多
The Kop ophiolite in NE Turkey is a fragment of Neo-Tethyan forearc.It can be mainly divided into a paleo-Moho transition zone(MTZ)in the North and a harzburgitic mantle sequence in the South.Dunites are predominant i...The Kop ophiolite in NE Turkey is a fragment of Neo-Tethyan forearc.It can be mainly divided into a paleo-Moho transition zone(MTZ)in the North and a harzburgitic mantle sequence in the South.Dunites are predominant in the MTZ of the Kop ophiolite,and they are locally interlayered with chromitites and enclose minor bodies of harzburgites near the petrological Moho boundary.Large Fe isotopic variations were observed for magnesiochromite(-0.14‰to 0.06‰)and olivine(-0.12‰to 0.14‰)from the MTZ chromitites,dunites and harzburgites.In individual dunite samples,magnesiochromite usually has lighter Fe isotopic compositions than olivine,which was probably caused by subsolidus Mg-Fe exchange between the two mineral phases.Both magnesiochromite and olivine display an increasing trend ofδ56Fe along a profile from chromitite todunite.This trend reflects continuous fractional crystallization in a magma chamber,which resulted in heavier Fe isotopes concentrated in the evolved magmas.In each cumulative cycle of chromitite and dunite,dunite was formed from relatively evolved melts after massive precipitation of magnesiochromite.Mixing of more primitive and evolved melts in the magma chamber was a potential mechanism for triggering the crystallization of magnesiochromite,generating chromitite layers in the cumulate pile.Before mixing happened,the primitive melts had reacted with mantle harzburgites during their ascendance;whereas the evolved melts may lie on the olivine-chromite cotectic near the liquidus field of pyroxene.Variable degrees of magma mixing and differentiation are expected to generate melts with differentδ56Fe values,accounting for the Fe isotopic variations of the Kop MTZ.展开更多
Here we report iron(Fe) isotopic data of three pure Fe solution standards(IRMM-014, GSB Fe, and NIST3126a) and five widely used geological reference materials(RMs) from the United States Geological Survey and Geologic...Here we report iron(Fe) isotopic data of three pure Fe solution standards(IRMM-014, GSB Fe, and NIST3126a) and five widely used geological reference materials(RMs) from the United States Geological Survey and Geological Survey of Japan obtained on a Neptune Plus multi-collector–inductively coupled plasma–mass spectrometer(MC-ICP-MS) in our laboratory over the past 3 years. The instrumental mass bias was corrected by three independent methods: sample-standard bracketing(SSB),Ni doping + SSB, and ^(57)Fe–^(58)Fe double spike + SSB.Measurements reveal that both the Ni doping and double spike methods helped calibrate short-term fluctuations in mass bias. Collectively, almost all measurements of RMs yielded δ^(56)Fe within ± 0.05 of recommended values,provided that each sample was measured four times on MC-ICP-MS. For the first time, new recommended values for NIST SRM3126a are reported(δ^(56)Fe = 0.363 ± 0.006,2SE, 95% CI; and δ^(57)Fe = 0.534 ± 0.010, 2SE).展开更多
Seafloor hydrothermal chimneys are significant metal resources and have fundamental effects on marine chemistry balance.Previous studies on growth of the chimneys focused on mineral composition and elemental distribut...Seafloor hydrothermal chimneys are significant metal resources and have fundamental effects on marine chemistry balance.Previous studies on growth of the chimneys focused on mineral composition and elemental distribution in chimney walls,but the isotopic composition of different elements and their correlations remain poorly understood.Here,we report lateral Fe and S isotopes from sulfides across a chimney wall in detail from the Deyin-1 hydrothermal field(DHF) on the South Mid-Atlantic Ridge.Pyrite was characterized by increases in both δ34S and δ56Fe from the exterior to the interior within the chimney wall,which is likely related to enhanced S and Fe isotope fractionation between pyrite and fluids derived from the temperature gradient.Furthermore,δ56Fe displayed a well-defined,linear,positive correlation with δ34S in pyrite from the DHF as well as in pyrite from other areas.A model of hydrothermal pyrite formation suggests that,under conditions with uniform hydrothermal fluid,different temperatures and similar pyrite-fluid exchange degrees could result in the observed linear relationships between δ34S and δ56Fe.The regular and coupled Fe-S isotope variations within the chimney wall efficiently constrain the process of hydrothermal sulfide formation.展开更多
It is generally considered that a significant change in oceanic redox conditions occurred during the Ediacaran-Cambrian transition. However, there are currently two major conflicting views on the degree of oxygenation...It is generally considered that a significant change in oceanic redox conditions occurred during the Ediacaran-Cambrian transition. However, there are currently two major conflicting views on the degree of oxygenation of deep water(oxic vs. ferruginous) during this interval. To date, the oxygenation conditions of the Early Cambrian ocean have not been well constrained. The oxygenation magnitude and mechanism of the Early Cambrian ocean could be critical to the significant biological evolution of the "Cambrian Explosion". To constrain the Early Cambrian oceanic redox environment, we conducted an integrated study on iron and sulfur isotopes and redox-sensitive elements(Mo, U, and V) of Lower Cambrian phosphorite deposits from two shallow sections(Meishucun and Gezhongwu) and a deeper water section(Zunyi) from the Yangtze Platform, South China. The near zero δ^(56)Fe values from the two shallow sections studied here reflect oxic conditions in the lower phosphorite deposition. An obvious positive shift in δ^(56)Fe and redox-sensitive element content was observed in the middle parts of the two shallow water sections, which might reflect loss of light iron by dissimilatory iron reduction during early diagenesis under suboxic shallow water in the platform. However, the highly positive δ^(56)Fe values in the deep section could reflect a lower oxidation degree of dissolved Fe(II) under anoxic deep water. The data suggest redox-stratified oceanic conditions during the Early Cambrian, in which completely oxygenated shallow water(platform) coexisted with anoxic deep water(slope). We propose that prolonged upwelling of dissolved organic carbon(DOC)-, Fe(II)- and phosphorus-rich anoxic deep water in a redox-stratified ocean could have increased exchange with the open ocean, resulting in major phosphorite deposition in oxic-suboxic conditions. The progressive oxygenation of the ocean may have facilitated the Early Cambrian biotic diversification.展开更多
基金the National Key R&D Programmes of China(Nos.2019YFA0708604 and 2019YFA0708404)the National Natural Science Foundation of China(No.41773018)the Key Laboratory of Deep-Earth Dynamics of Ministry of Natural Resources(No.J1901-29)。
文摘As a powerful tracer in high-temperature geochemistry,Fe isotopes have been studied for their behaviour during fl uid exsolution and evolution related to felsic magma system,but that for carbonatite magma system remains unknown.Here we study the Fe isotope fractionation behaviour during fenitization–processes that widely occur associated with carbonatite or alkaline intrusions.Nine fenite/carbonatite samples from carbonatite dykes at Bayan Obo area are analyzed for their Fe isotope compositions as well as elemental compositions.Combined with previous reported carbonatite δ^(56)Fe data,the results show that carbonatites range from-0.35‰to 0.28‰,with an average of-0.10‰in δ^(56)Fe values,while fenites range from-0.17‰to 0.30‰,with an average of 0.11‰in δ^(56)Fe values.This indicates that fenitizing fl uids exsolved from carbonatite melts are enriched in heavier Fe isotopes.Such a Fe isotope fractionation trend is diff erent from that for fl uid exsolution from felsic magmatism.δ^(56)Fe values in fenites are negatively correlated with indicators of fenitization intensity such as(Na+K),Ti,Ba,Th,Nb,U or Pb abundances,likely refl ecting that Fe isotopes fractionate during the evolution of the fenitizing fl uids.Thus,Fe isotopes are a valuable tool for tracing fl uid exsolution and evolution relevant to carbonatite magmatism and related metal mineralization.
基金granted by the China Geological Survey(Grant No.121201102000150069)
文摘Podiform chromitites crop out in ophiolitic harzburgites as pod-like bodies associated with dunite envelopes with various thickness. It is widely accepted that the change of melt compositions caused by melt-rock reaction, especially an increase in silica content, plays a crucial role in the generation of podiform chromitite(e.g., Arai and Yurimoto, 1994;Zhou et al., 1994). Due to the presence of ultrahigh pressure and highly reduced minerals, the genesis of some podiform chromitites was attributed to some deep processes(e.g., Arai, 2013;Yang et al., 2007). Although much progress has been achieved, the formation mechanism of podiform chromitites are still in dispute. Iron isotope may be a potential tool to give further insight to the issue, given that some high temperature processes, such as partial melting, metasomatism, magma differentiation and redox change, can result in measurable iron isotopic fractionation to different extent(e.g. Chen et al., 2014;Weyer and Ionov, 2007;Zhao et al., 2009). This study investigates the Fe isotope compositions of chromitites and chromite dunites from Dazhuqu and Luobusha ophiolites. For Dazhuqu chromite dunites, δ56 Fe(relative to the standard, IRMM-014) values range from-0.02‰ to 0.11‰ in olivines and from 0.03‰ to 0.08‰ in chromites. Chromites in Dazhuqu chromitites show δ56 Fe values varying from-0.03‰ to 0.02‰. In nodular and densely disseminated chromitites from Luobusha, olivines have δ56 Fe values of olivines and chromites are 0.09–0.35‰ and-0.15–0.08 ‰, respectively. Chromites from Luobusha massive chromitites have δ56 Fe values of 0.07–0.12 ‰. Based on theorical calculations, chromites should be heavier than olivines in Fe isotope compositions ?56 FeOl-Chr ≈-0.08‰ at 1300 ℃ according to the ionic model(e.g., Macris et al., 2015;Sossi and O’Neill, 2017). However, most of our samples, except for two samples, have ?56 FeOl-Chr values that are greater than zero, indicating a disequilibrium inter-mineral Fe isotopic fractionation. There is a positive correlation between Fo and δ56 Fe(or ?56 FeOl-Chr) of olivines but no positive correlation between Mg# and δ56 Fe(or ?56 FeOl-Chr) of chromites. This phenomenon suggests that the Fe isotopic dis-equilibration may be caused by migrating melts in dunitic channels rather than by the sub-solidus Fe-Mg exchange(Xiao et al., 2016;Zhang et al., 2019). Additionally, the wide δ56 Fe range of chromites is similar to those of the subduction-related basalts and boninites, inferring that their parental magmas form in the suprasubduction zone.
基金National Natural Science Foundation of ChinaGrant/Award number:41972169The priority academic program development of Jiangsu Higher Education on Institutions(2018–2021)。
文摘Iron isotopes are important for tracing the magmatic process.The fractionation of iron isotopes in granite is up to 0.55‰.In this study,Wangjiagou(XWJ)granite and Tayueping(XTY)granite in the Xinxian pluton of the Western Dabie orogen were evaluated.Both the XTY and XWJ granite belong to monzogranites,with high SiO2(74.42-76.82 wt.%)contents.The granites are depleted of Nb and Ti but enriched with Pb and K,and they display negative Eu anomalies(Eu/Eu^(*)=0.40-0.52)on REE plots that are normalized by chondrite.Theδ^(56)Fe values of the XTY granites vary from 0.19±0.03‰to0.27±0.04‰,and theδ^(56)Fe values of the XWJ granites are 0.34±0.02‰and 0.36±0.01‰,respectively.Both the XTY and the XWJ granites belong to highly fractionated granites due to their SI(solidification index),DI(differentiation index),and content of CaO.Evidence from the iron isotopes shows that neither fluid exsolution,alteration,weathering,nor partial melting can explain the enrichment of the heavy iron isotopes.The results modeled using the Rayleigh equation showed that fractional crystallization can produceΔ^(56)Femelt-crystalwith the value of0.08-0.15‰.In conclusion,fractional crystallization was the main factor controlling the fractionation of iron isotopes,and the change of melt composition may also lead to the enrichment of heavy iron isotopes in the residual melt.
文摘The Kop ophiolite in NE Turkey is a fragment of Neo-Tethyan forearc.It can be mainly divided into a paleo-Moho transition zone(MTZ)in the North and a harzburgitic mantle sequence in the South.Dunites are predominant in the MTZ of the Kop ophiolite,and they are locally interlayered with chromitites and enclose minor bodies of harzburgites near the petrological Moho boundary.Large Fe isotopic variations were observed for magnesiochromite(-0.14‰to 0.06‰)and olivine(-0.12‰to 0.14‰)from the MTZ chromitites,dunites and harzburgites.In individual dunite samples,magnesiochromite usually has lighter Fe isotopic compositions than olivine,which was probably caused by subsolidus Mg-Fe exchange between the two mineral phases.Both magnesiochromite and olivine display an increasing trend ofδ56Fe along a profile from chromitite todunite.This trend reflects continuous fractional crystallization in a magma chamber,which resulted in heavier Fe isotopes concentrated in the evolved magmas.In each cumulative cycle of chromitite and dunite,dunite was formed from relatively evolved melts after massive precipitation of magnesiochromite.Mixing of more primitive and evolved melts in the magma chamber was a potential mechanism for triggering the crystallization of magnesiochromite,generating chromitite layers in the cumulate pile.Before mixing happened,the primitive melts had reacted with mantle harzburgites during their ascendance;whereas the evolved melts may lie on the olivine-chromite cotectic near the liquidus field of pyroxene.Variable degrees of magma mixing and differentiation are expected to generate melts with differentδ56Fe values,accounting for the Fe isotopic variations of the Kop MTZ.
基金supported by the National Natural Science Foundation of China(41473016)the State Key Laboratory of Geological Processes and Mineral Resources
文摘Here we report iron(Fe) isotopic data of three pure Fe solution standards(IRMM-014, GSB Fe, and NIST3126a) and five widely used geological reference materials(RMs) from the United States Geological Survey and Geological Survey of Japan obtained on a Neptune Plus multi-collector–inductively coupled plasma–mass spectrometer(MC-ICP-MS) in our laboratory over the past 3 years. The instrumental mass bias was corrected by three independent methods: sample-standard bracketing(SSB),Ni doping + SSB, and ^(57)Fe–^(58)Fe double spike + SSB.Measurements reveal that both the Ni doping and double spike methods helped calibrate short-term fluctuations in mass bias. Collectively, almost all measurements of RMs yielded δ^(56)Fe within ± 0.05 of recommended values,provided that each sample was measured four times on MC-ICP-MS. For the first time, new recommended values for NIST SRM3126a are reported(δ^(56)Fe = 0.363 ± 0.006,2SE, 95% CI; and δ^(57)Fe = 0.534 ± 0.010, 2SE).
基金supported by the Strategic Priority Research Program (B) of Chinese Academy of Sciences (XDB42000000)the National Natural Science Foundation of China (41806061)+3 种基金the National Key Research & Development Program of China (2016YFC0600408)the Strategic Priority Research Program (A) of the Chinese Academy of Sciences (XDA22050103)the Taishan Scholar Program of Shandong (ts201712075)the AoShan Talents Cultivation Program supported by Qingdao Pilot National Laboratory for Marine Science and Technology (2017ASTCPOS07)。
文摘Seafloor hydrothermal chimneys are significant metal resources and have fundamental effects on marine chemistry balance.Previous studies on growth of the chimneys focused on mineral composition and elemental distribution in chimney walls,but the isotopic composition of different elements and their correlations remain poorly understood.Here,we report lateral Fe and S isotopes from sulfides across a chimney wall in detail from the Deyin-1 hydrothermal field(DHF) on the South Mid-Atlantic Ridge.Pyrite was characterized by increases in both δ34S and δ56Fe from the exterior to the interior within the chimney wall,which is likely related to enhanced S and Fe isotope fractionation between pyrite and fluids derived from the temperature gradient.Furthermore,δ56Fe displayed a well-defined,linear,positive correlation with δ34S in pyrite from the DHF as well as in pyrite from other areas.A model of hydrothermal pyrite formation suggests that,under conditions with uniform hydrothermal fluid,different temperatures and similar pyrite-fluid exchange degrees could result in the observed linear relationships between δ34S and δ56Fe.The regular and coupled Fe-S isotope variations within the chimney wall efficiently constrain the process of hydrothermal sulfide formation.
基金the National Basic Research Program of China (No. 2014CB440906)the National Natural Science Foundation of China (Nos. 41273024, 41573011)+2 种基金Youth Innovation Promotion Association CAS, "West Light" of CAS, the 12th Five-Year Plan project of the State Key Laboratory of Ore Deposit Geochemistry, CAS (No. SKLODG-ZY125-07)MLR Public Benefit Research Foundation (No. 201411044)China Geological Survey Foundation (No. 1212011120354)
文摘It is generally considered that a significant change in oceanic redox conditions occurred during the Ediacaran-Cambrian transition. However, there are currently two major conflicting views on the degree of oxygenation of deep water(oxic vs. ferruginous) during this interval. To date, the oxygenation conditions of the Early Cambrian ocean have not been well constrained. The oxygenation magnitude and mechanism of the Early Cambrian ocean could be critical to the significant biological evolution of the "Cambrian Explosion". To constrain the Early Cambrian oceanic redox environment, we conducted an integrated study on iron and sulfur isotopes and redox-sensitive elements(Mo, U, and V) of Lower Cambrian phosphorite deposits from two shallow sections(Meishucun and Gezhongwu) and a deeper water section(Zunyi) from the Yangtze Platform, South China. The near zero δ^(56)Fe values from the two shallow sections studied here reflect oxic conditions in the lower phosphorite deposition. An obvious positive shift in δ^(56)Fe and redox-sensitive element content was observed in the middle parts of the two shallow water sections, which might reflect loss of light iron by dissimilatory iron reduction during early diagenesis under suboxic shallow water in the platform. However, the highly positive δ^(56)Fe values in the deep section could reflect a lower oxidation degree of dissolved Fe(II) under anoxic deep water. The data suggest redox-stratified oceanic conditions during the Early Cambrian, in which completely oxygenated shallow water(platform) coexisted with anoxic deep water(slope). We propose that prolonged upwelling of dissolved organic carbon(DOC)-, Fe(II)- and phosphorus-rich anoxic deep water in a redox-stratified ocean could have increased exchange with the open ocean, resulting in major phosphorite deposition in oxic-suboxic conditions. The progressive oxygenation of the ocean may have facilitated the Early Cambrian biotic diversification.