Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive
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摘要
Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater.Mg isotopes are significantly(up to 5%)fractionated during carbonate precipitation by preferential incorporation of ~(24)Mg,while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of~( 26)Mg.Thus,the marine Mg cycle could be reflected by seawater Mg isotopic composition(δ~(26)Mg_(sw)),which might be recorded in marine carbonate.However,carbonates are both texturally and compositionally heterogeneous,and it is unclear which carbonate component is the most reliable for reconstructing δ~(26)Mg_(sw).In this study,we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China.Based on petrographic studies,four carbonate components were recognized:micrite,marine cement,brachiopod shell,and mixture.The four components had distinct δ~(26)Mg:(1)micrite samples ranged from -2.86% to -2.97%;(2)pure marine cements varied from -3.40% to -3.54%,while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range(-3.27% to-3.75%);(3)values for the mixture component were-3.17% and -3.49%;and (4)brachiopod shells ranged from -2.20% to -3.07%,with the thickened hinge area enriched in ~( 24)Mg.Due to having multiple carbonate sources,neither the micrite nor the mixture component could be used to reconstruct δ~(26)Mg_(sw).In addition,the marine cement was homogenous in Mg isotopes,but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ~(26)Mg_(sw).Furthermore,brachiopod shells had heterogeneous C and Mg isotopes,suggesting a significant vital effect during growth.Overall,the heterogeneous δ~(26)Mg of the Huangjin limestone makes it difficult to reconstruct δ~(26)Mg_(sw)using bulk carbonate/calcareous sediments.Finally,δ~(26)Mg_(sw)was only slightly affected by the faunal composition of carbonate-secreting organisms,even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range(0.2%–4.8%)of fractionation during biogenic carbonate formation.
Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater.Mg isotopes are significantly(up to 5%)fractionated during carbonate precipitation by preferential incorporation of ~(24)Mg,while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of~( 26)Mg.Thus,the marine Mg cycle could be reflected by seawater Mg isotopic composition(δ~(26)Mg_(sw)),which might be recorded in marine carbonate.However,carbonates are both texturally and compositionally heterogeneous,and it is unclear which carbonate component is the most reliable for reconstructing δ~(26)Mg_(sw).In this study,we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China.Based on petrographic studies,four carbonate components were recognized:micrite,marine cement,brachiopod shell,and mixture.The four components had distinct δ~(26)Mg:(1)micrite samples ranged from -2.86% to -2.97%;(2)pure marine cements varied from -3.40% to -3.54%,while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range(-3.27% to-3.75%);(3)values for the mixture component were-3.17% and -3.49%;and (4)brachiopod shells ranged from -2.20% to -3.07%,with the thickened hinge area enriched in ~( 24)Mg.Due to having multiple carbonate sources,neither the micrite nor the mixture component could be used to reconstruct δ~(26)Mg_(sw).In addition,the marine cement was homogenous in Mg isotopes,but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ~(26)Mg_(sw).Furthermore,brachiopod shells had heterogeneous C and Mg isotopes,suggesting a significant vital effect during growth.Overall,the heterogeneous δ~(26)Mg of the Huangjin limestone makes it difficult to reconstruct δ~(26)Mg_(sw)using bulk carbonate/calcareous sediments.Finally,δ~(26)Mg_(sw)was only slightly affected by the faunal composition of carbonate-secreting organisms,even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range(0.2%–4.8%)of fractionation during biogenic carbonate formation.
Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from seawater.Mg isotopes are significantly(up to 5%)fractionated during carbonate precipitation by preferential incorporation of ~(24)Mg,while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of~( 26)Mg.Thus,the marine Mg cycle could be reflected by seawater Mg isotopic composition(δ~(26)Mg_(sw)),which might be recorded in marine carbonate.However,carbonates are both texturally and compositionally heterogeneous,and it is unclear which carbonate component is the most reliable for reconstructing δ~(26)Mg_(sw).In this study,we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous Huangjin Formation in South China.Based on petrographic studies,four carbonate components were recognized:micrite,marine cement,brachiopod shell,and mixture.The four components had distinct δ~(26)Mg:(1)micrite samples ranged from -2.86% to -2.97%;(2)pure marine cements varied from -3.40% to -3.54%,while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range(-3.27% to-3.75%);(3)values for the mixture component were-3.17% and -3.49%;and (4)brachiopod shells ranged from -2.20% to -3.07%,with the thickened hinge area enriched in ~( 24)Mg.Due to having multiple carbonate sources,neither the micrite nor the mixture component could be used to reconstruct δ~(26)Mg_(sw).In addition,the marine cement was homogenous in Mg isotopes,but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ~(26)Mg_(sw).Furthermore,brachiopod shells had heterogeneous C and Mg isotopes,suggesting a significant vital effect during growth.Overall,the heterogeneous δ~(26)Mg of the Huangjin limestone makes it difficult to reconstruct δ~(26)Mg_(sw)using bulk carbonate/calcareous sediments.Finally,δ~(26)Mg_(sw)was only slightly affected by the faunal composition of carbonate-secreting organisms,even though biogenic carbonate accounts for more than 90% of marine carbonate production in Phanerozoic oceans and there is a wide range(0.2%–4.8%)of fractionation during biogenic carbonate formation.
引文
Azmy K,Lavoie D,Wang Z,Brand U,Al-Aasm I,Jackson S,Girard I(2013)Magnesium-isotope and REE compositions of Lower Ordovician carbonates from eastern Laurentia:implications for the origin of dolomites and limestones.Chem Geol 356:64-75
Barbin V,Ramseyer K,Debenay JP,Schein E,Roux M,Decrouez D(1991)Cathodoluminescence of recent biogenic carbonates:an enviromental and ontogenetic fingerprint.Geol Mag 128:19-26
Beinlich A,Mavromatis V,Austrheim H,Oelkers EH(2014)Intermineral Mg isotope fractionation during hydrothermal ultramafic rock alteration-implications for the global Mg-cycle.Earth Planet Sci Lett 392:166-176
Brand U et al(2015)Carbon isotope composition in modern brachiopod calcite:a case of equilibrium with seawater?Chem Geol 411:81-96
Budd DA,Hammes U,Ward WB(2000)Cathodoluminescence in calcite cements:new insights on Pb and Zn sensitizing,Mn activation,and Fe quenching at low trace-element concentrations.J Sediment Res 70:217-226
Chang VTC,Williams RJP,Makishima A,Belshawl NS,O’Nions RK(2004)Mg and Ca isotope fractionation during Ca CO3biomineralisation.Biochem Biophys Res Commun 323:79-85
Chen Z,Sun Y(2013)Discovery of color patterned Cranaena(Brachiopoda)from the lower Carboniferous Huangjin Formation in Guilin of Guangxi with a brief comment on its geological and stratigraphic distribution.J Palaeogeogr 15:797-810
Derry LA(2010)On the significance of d13C correlations in ancient sediments.Earth Planet Sci Lett 296:497-501
Elderfield H,Schultz A(1996)Mid-ocean ridge hydrothermal fluxes and the chemical composition of the ocean.Annu Rev Earth Planet Sci 24:191-224
Fantle MS,Higgins J(2014)The effects of diagenesis and dolomitization on Ca and Mg isotopes in marine platform carbonates:implications for the geochemical cycles of Ca and Mg.Geochim Cosmochim Acta 142:458-481
Folk R(1959)Practical petrographic classification of limestones.AAPG Bull 43:1-38
Gallagher KL,Dupraz C,Visscher PT(2014)Two opposing effects of sulfate reduction on carbonate precipitation in normal marine,hypersaline,and alkaline environments:COMMENT.Geology42:e313-e314
Galy A,Bar-Matthews M,Halicz L,O’Nions RK(2002)Mg isotopic composition of carbonate:insight from speleothem formation.Earth Planet Sci Lett 201:105-115
Galy A et al(2003)Magnesium isotope heterogeneity of the isotopic standard SRM980 and new reference materials for magnesiumisotope-ratio measurements.J Anal At Spectrom 18:1352-1356
Geske A,Zorlu J,Richter DK,Buhl D,Niedermayr A,Immenhauser A(2012)Impact of diagenesis and low grade metamorphosis on isotope(d26Mg,d13C,d18O and87Sr/86Sr)and elemental(Ca,Mg,Mn,Fe and Sr)signatures of Triassic sabkha dolomites.Chem Geol 332-333:45-64
Hance L,Hou H,Vachard D(2011)Upper Famennian to Visean Foraminifers and some carbonate Microproblematica from South China-Hunan,Gruangxi and Guizhou.Geological Publishing House,Beijing
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Higgins JA,Schrag DP(2010)Constraining magnesium cycling in marine sediments using magnesium isotopes.Geochim Cosmochim Acta 74:5039-5053
Higgins JA,Schrag DP(2015)The Mg isotopic composition of Cenozoic seawater-evidence for a link between Mg-clays,seawater Mg/Ca,and climate.Earth Planet Sci Lett 416:73-81
Hippler D,Buhl D,Witbaard R,Richter DK,Immenhauser A(2009)Towards a better understanding of magnesium-isotope ratios from marine skeletal carbonates.Geochim Cosmochim Acta73:6134-6146
Holland HD(2005)Sea level,sediments and the composition of seawater.Am J Sci 305:220-239
Huang K-J et al(2015)Magnesium isotopic compositions of the Mesoproterozoic dolostones:implications for Mg isotopic systematics of marine carbonate.Geochim Cosmochim Acta164:333-351
Immenhauser A,Buhl D,Richter D,Niedermayr A,Riechelmann D,Dietzel M,Schulte U(2010)Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave-field study and experiments.Geochim Cosmochim Acta 74:4346-4364
Jacobsen SB,Kaufman AJ(1999)The Sr,C and O isotopic evolution of Neoproterozoic seawater.Chem Geol 161:37-57
Jacobson AD,Zhang Z,Lundstrom C,Huang F(2010)Behavior of Mg isotopes during dedolomitization in the Madison Aquifer,South Dakota.Earth Planet Sci Lett 297:446-452
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Knauth LP,Kennedy MJ(2009)The late Precambrian greening of the Earth.Nature 460:728-732
Li C et al(2012)Evidence for a redox stratified Cryogenian marine basin,Datangpo Formation,South China.Earth Planet Sci Lett331-332:246-256
Machel HG(1985)Cathodoluminescence in calcite and dolomite and its chemical interpretation.Geosci Canada 12:1-9
Mackenzie FT,Morse JW(1992)Sedimentary carbonates through Phanerozoic time.Geochim Cosmochim Acta 56:3281-3295
Meister P(2013)Two opposing effects of sulfate reduction on carbonate precipitation in normal marine,hypersaline,and alkaline environments.Geology 41:499-502
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Peng Y et al(2016)Constraining dolomitization by Mg isotopes:a case study from partially dolomitized limestones of the middle Cambrian Xuzhuang Formation,North China.Geochem Geophys Geosyst.doi:10.1002/2015gc006057
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Pinilla C,Blanchard M,Balan E,Natarajan SK,Vuilleumier R,Mauri F(2015)Equilibrium magnesium isotope fractionation between aqueous Mg2?and carbonate minerals:insights from path integral molecular dynamics.Geochim Cosmochim Acta163:126-139
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Beinlich A,Mavromatis V,Austrheim H,Oelkers EH(2014)Intermineral Mg isotope fractionation during hydrothermal ultramafic rock alteration-implications for the global Mg-cycle.Earth Planet Sci Lett 392:166-176
Brand U et al(2015)Carbon isotope composition in modern brachiopod calcite:a case of equilibrium with seawater?Chem Geol 411:81-96
Budd DA,Hammes U,Ward WB(2000)Cathodoluminescence in calcite cements:new insights on Pb and Zn sensitizing,Mn activation,and Fe quenching at low trace-element concentrations.J Sediment Res 70:217-226
Chang VTC,Williams RJP,Makishima A,Belshawl NS,O’Nions RK(2004)Mg and Ca isotope fractionation during Ca CO3biomineralisation.Biochem Biophys Res Commun 323:79-85
Chen Z,Sun Y(2013)Discovery of color patterned Cranaena(Brachiopoda)from the lower Carboniferous Huangjin Formation in Guilin of Guangxi with a brief comment on its geological and stratigraphic distribution.J Palaeogeogr 15:797-810
Derry LA(2010)On the significance of d13C correlations in ancient sediments.Earth Planet Sci Lett 296:497-501
Elderfield H,Schultz A(1996)Mid-ocean ridge hydrothermal fluxes and the chemical composition of the ocean.Annu Rev Earth Planet Sci 24:191-224
Fantle MS,Higgins J(2014)The effects of diagenesis and dolomitization on Ca and Mg isotopes in marine platform carbonates:implications for the geochemical cycles of Ca and Mg.Geochim Cosmochim Acta 142:458-481
Folk R(1959)Practical petrographic classification of limestones.AAPG Bull 43:1-38
Gallagher KL,Dupraz C,Visscher PT(2014)Two opposing effects of sulfate reduction on carbonate precipitation in normal marine,hypersaline,and alkaline environments:COMMENT.Geology42:e313-e314
Galy A,Bar-Matthews M,Halicz L,O’Nions RK(2002)Mg isotopic composition of carbonate:insight from speleothem formation.Earth Planet Sci Lett 201:105-115
Galy A et al(2003)Magnesium isotope heterogeneity of the isotopic standard SRM980 and new reference materials for magnesiumisotope-ratio measurements.J Anal At Spectrom 18:1352-1356
Geske A,Zorlu J,Richter DK,Buhl D,Niedermayr A,Immenhauser A(2012)Impact of diagenesis and low grade metamorphosis on isotope(d26Mg,d13C,d18O and87Sr/86Sr)and elemental(Ca,Mg,Mn,Fe and Sr)signatures of Triassic sabkha dolomites.Chem Geol 332-333:45-64
Hance L,Hou H,Vachard D(2011)Upper Famennian to Visean Foraminifers and some carbonate Microproblematica from South China-Hunan,Gruangxi and Guizhou.Geological Publishing House,Beijing
Hardie LA(1996)Secular variation in seawater chemistry:an explanation for the coupled secular variation in the mineralogies of marine limestones and potash evaporites over the past 600 my.Geology 24:279-283
Higgins JA,Schrag DP(2010)Constraining magnesium cycling in marine sediments using magnesium isotopes.Geochim Cosmochim Acta 74:5039-5053
Higgins JA,Schrag DP(2015)The Mg isotopic composition of Cenozoic seawater-evidence for a link between Mg-clays,seawater Mg/Ca,and climate.Earth Planet Sci Lett 416:73-81
Hippler D,Buhl D,Witbaard R,Richter DK,Immenhauser A(2009)Towards a better understanding of magnesium-isotope ratios from marine skeletal carbonates.Geochim Cosmochim Acta73:6134-6146
Holland HD(2005)Sea level,sediments and the composition of seawater.Am J Sci 305:220-239
Huang K-J et al(2015)Magnesium isotopic compositions of the Mesoproterozoic dolostones:implications for Mg isotopic systematics of marine carbonate.Geochim Cosmochim Acta164:333-351
Immenhauser A,Buhl D,Richter D,Niedermayr A,Riechelmann D,Dietzel M,Schulte U(2010)Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave-field study and experiments.Geochim Cosmochim Acta 74:4346-4364
Jacobsen SB,Kaufman AJ(1999)The Sr,C and O isotopic evolution of Neoproterozoic seawater.Chem Geol 161:37-57
Jacobson AD,Zhang Z,Lundstrom C,Huang F(2010)Behavior of Mg isotopes during dedolomitization in the Madison Aquifer,South Dakota.Earth Planet Sci Lett 297:446-452
James NP,Choquette PW(1983)Diagenesis 6.Limestones-the sea floor diagenetic environment.Geosci Can 10:162-179
Kaz′mierczak J,Coleman ML,Gruszczyn′ski M,Kempe S(1996)Cyanobacterial key to the genesis of micritic and peloidal limestones in ancient seas.Acta Palaeontol Pol 41:319-338
Knauth LP,Kennedy MJ(2009)The late Precambrian greening of the Earth.Nature 460:728-732
Li C et al(2012)Evidence for a redox stratified Cryogenian marine basin,Datangpo Formation,South China.Earth Planet Sci Lett331-332:246-256
Machel HG(1985)Cathodoluminescence in calcite and dolomite and its chemical interpretation.Geosci Canada 12:1-9
Mackenzie FT,Morse JW(1992)Sedimentary carbonates through Phanerozoic time.Geochim Cosmochim Acta 56:3281-3295
Meister P(2013)Two opposing effects of sulfate reduction on carbonate precipitation in normal marine,hypersaline,and alkaline environments.Geology 41:499-502
Mii HS,Grossman EL,Yancey TE(1997)Stable carbon and oxygen isotope shifts in Permian seas of West Spitsbergen;global change or diagenetic artifact?Geology 25:227-230
Mii HS,Grossman EL,Yancey TE(1999)Carboniferous isotope stratigraphies of North America:implications for Carboniferous paleoceanography and Mississippian glaciation.Geol Soc Am Bull 111:960-973
Mii HS,Grossman EL,Yancey TE,Chuvashov B,Egorov A(2001)Isotopic records of brachiopod shells from the Russian Platform-evidence for the onset of mid-Carboniferous glaciation.Chem Geol 175:133-147
Munnecke A,Samtleben C(1996)The formation of micritic limestones and the development of limestone-marl alternations in the Silurian of Gotland,Sweden.Facies 34:159-176
Opfergelt S,Georg RB,Delvaux B,Cabidoche YM,Burton KW,Halliday AN(2012)Mechanisms of magnesium isotope fractionation in volcanic soil weathering sequences,Guadeloupe.Earth Planet Sci Lett 341-344:176-185
Parkinson D,Curry GB,Cusack M,Fallick AE(2005)Shell structure,patterns and trends of oxygen and carbon stable isotopes in modern brachiopod shells.Chem Geol 219:193-235
Peng Y et al(2016)Constraining dolomitization by Mg isotopes:a case study from partially dolomitized limestones of the middle Cambrian Xuzhuang Formation,North China.Geochem Geophys Geosyst.doi:10.1002/2015gc006057
Pierson BJ(1981)The control of cathodoluminescence in dolomite by iron and manganese.Sedimentology 28:601-610
Pinilla C,Blanchard M,Balan E,Natarajan SK,Vuilleumier R,Mauri F(2015)Equilibrium magnesium isotope fractionation between aqueous Mg2?and carbonate minerals:insights from path integral molecular dynamics.Geochim Cosmochim Acta163:126-139
Pogge von Strandmann PAE(2008)Precise magnesium isotope measurements in core top planktic and benthic foraminifera.Geochem Geophys Geosyst 9:1-13
Pogge von Strandmann PAE,Burton KW,James RH,van Calsteren P,Gislason SR,Sigfu′sson B(2008)The influence of weathering processes on riverine magnesium isotopes in a basaltic terrain.Earth Planet Sci Lett 276:187-197
Pogge von Strandmann PAE,Elliott T,Marschall HR,Coath C,Lai Y-J,Jeffcoate AB,Ionov DA(2011)Variations of Li and Mg isotope ratios in bulk chondrites and mantle xenoliths.Geochim Cosmochim Acta 75:5247-5268
Prokoph A,Shields GA,Veizer J(2008)Compilation and time-series analysis of a marine carbonate d18O,d13C,87Sr/86Sr and d34Sdatabase through Earth history.Earth Sci Rev 87:113-133
Ra K,Kitagawa H,Shiraiwa Y(2010)Mg isotopes and Mg/Ca values of coccoliths from cultured specimens of the species Emiliania huxleyi and Gephyrocapsa oceanica.Mar Micropaleontol 77:119-124
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