微量磷灰石中磷酸根氧同位素分析方法
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摘要
生物磷灰石壳体的磷酸根氧同位素组成是重建古温度理想指标之一,在古环境研究中具有重要意义.针对牙形石等磷灰石量极少的情况,稳定可靠的前处理方法是分析其δ~(18)O_(PO4)的重要保障,目前仅有少数国外实验室已建立了相关提取分析方法.结合这些方法的优缺点对分析步骤进行改进优化,建立了微量磷灰石的磷酸根氧同位素分析方法,通过硝酸消解磷灰石并除去非磷酸根氧,利用KF溶液沉淀法分离Ca~(2+),采用氨缓冲溶液形式调节pH,并加入AgNO_3溶液以氨挥发法将PO43-转化成Ag_3PO_4结晶分离,气体稳定同位素质谱仪在线测定Ag_3PO_4氧同位素组成.结果表明,方法全流程未产生明显的氧同位素分馏,样品最低仅需0.2mg,标准偏差小于0.2‰(1σ),与目前国际报道的分析精度一致.
The oxygen isotope composition of phosphate( δ~(18)O_(PO4))in bioapatite plays a significant role in paleo-environmental research as one of the ideal proxies for paleo-temperature reconstruction.However,for trace bioapatite(e.g.,conodonts),a reliable pre-treatment technology is quite important and difficult for its δ~(18)O_(PO4) analysis,resulting in analytical technique established only in several overseas laboratories.Here we combine the advantages of those methods and present a protocol on the analysis of δ~(18)O_(PO4) as Ag_3PO_4 for bioapatite of total sample size as small as 0.2 mg using a thermal conversion elemental analyzer(TC/EA)coupled to a continuous flow isotope ratio mass spectrometer(CF-IRMS)via a helium stream.Ag_3PO_4 is precipitated by NH3 buffer method after apatite being dissolved with nitric acid,Ca~(2+)being removed with KF solution and the solution being neutralized with ammonia buffer solution.The results indicate that analysis of δ~(18)O_(PO4) maintains an external precision of±0.2‰(1σ),meeting the international analytical standards.This method for analyzing δ~(18)O_(PO4) of phosphate extracted from bioapatite is robust to be used to reconstruct paleo-temperature.
The oxygen isotope composition of phosphate( δ~(18)O_(PO4))in bioapatite plays a significant role in paleo-environmental research as one of the ideal proxies for paleo-temperature reconstruction.However,for trace bioapatite(e.g.,conodonts),a reliable pre-treatment technology is quite important and difficult for its δ~(18)O_(PO4) analysis,resulting in analytical technique established only in several overseas laboratories.Here we combine the advantages of those methods and present a protocol on the analysis of δ~(18)O_(PO4) as Ag_3PO_4 for bioapatite of total sample size as small as 0.2 mg using a thermal conversion elemental analyzer(TC/EA)coupled to a continuous flow isotope ratio mass spectrometer(CF-IRMS)via a helium stream.Ag_3PO_4 is precipitated by NH3 buffer method after apatite being dissolved with nitric acid,Ca~(2+)being removed with KF solution and the solution being neutralized with ammonia buffer solution.The results indicate that analysis of δ~(18)O_(PO4) maintains an external precision of±0.2‰(1σ),meeting the international analytical standards.This method for analyzing δ~(18)O_(PO4) of phosphate extracted from bioapatite is robust to be used to reconstruct paleo-temperature.
引文
Amiot,R.,Wang,X.,Zhou,Z.,et al.,2015.Environment and Ecology of East Asian Dinosaurs during the Early Cretaceous Inferred from Stable Oxygen and Carbon Isotopes in Apatite.Journal of Asian Earth Sciences,98:358-370.https://doi.org/10.1016/j.jseaes.2014.11.032
Chen,J.,Shen,S.Z.,Li,X.H.,et al.,2016.High-Resolution SIMS Oxygen Isotope Analysis on Conodont Apatite from South China and Implications for the End-Permian Mass Extinction.Palaeogeography,Palaeoclimatology,Palaeoecology,448(448):26-38.https://doi.org/10.1016/j.palaeo.2015.11.025
Elrick,M.,Witzke,B.,2016.Orbital-Scale Glacio-Eustasy in the Middle Devonian Detected Using Oxygen Isotopes of Conodont Apatite:Implications for Long-Term Greenhouse-Icehouse Climatic Transitions.Palaeogeography,Palaeoclimatology,Palaeoecology,445:50-59.https://doi.org/10.1016/j.palaeo.2015.12.019
Gehler,A.,Gingerich,P.D.,Pack,A.,2016.Temperature and Atmospheric CO2 Concentration Estimates through the PETM Using Triple Oxygen Isotope Analysis of Mammalian Bioapatite.Proceedings of the National Academy of Sciences,113(28):7739-7744.https://doi.org/10.1073/pnas.1518116113
Griffin,J.M.,Montanez,I.P.,Matthews,J.A.,2015.A Refined Protocol forδ18 OPO4 Analysis of Conodont Bioapatite.Chemical Geology,417:11-20.https://doi.org/10.1016/j.chemgeo.2015.08.025
Halas,S.,Skrzypek,G.,Meier-Augenstein,W.,et al.,2011.Inter-Laboratory Calibration of New Silver Orthophosphate Comparison Materials for the Stable Oxygen Isotope Analysis of Phosphates.Rapid Communications in Mass Spectrometry Rcm.,25(5):579-584.https://doi.org/10.1002/rcm.4892
Joachimski,M.M.,Breisig,S.,Buggisch,W.,et al.,2009.Devonian Climate and Reef Evolution:Insights from Oxygen Isotopes in Apatite.Earth&Planetary Science Letters,284(3-4):599-609.https://doi.org/10.1016/j.epsl.2009.05.028
LaPorte,D.F.,Holmden,C.,Patterson,W.P.,2009.Oxygen Isotope Analysis of Phosphate:Improved Precision Using TC/EA CF-IRMS+.Journal of Mass Spectrometry,44(6):879-890.https://doi.org/10.1002/jms.1549
ONeil,J.R.,Vennemann,T.W.,Mckenzie,W.F.,2003.Effects of Speciation on Equilibrium Fractionations and Rates of Oxygen Isotope Exchange between(PO4)aq,and H2O.Geochimica et Cosmochimica Acta,67(17):3135-3144.oi:10.1016/s0016-7037(02)00970-5
Pucéat,E.,Joachimski,M.M.,Bouilloux,A.,et al.,2010.Revised Phosphate-Water Fractionation Equation Reassessing Paleotemperatures Derived from Biogenic Apatite.Earth&Planetary Science Letters,298(1-2):135-142.https://doi.org/10.1016/j.epsl.2010.07.034
Qiao,P.J.,Zhu,W.L.,Shao,L.,et al.,2015.Carbonate Stable Isotope Stratigraphy of Well Xike-1,Xisha Islands.Earth Science,40(4):725-732(in Chinese with English abstract).
Quinton,P.C.,Macleod,K.G.,2014.Oxygen Isotopes from Conodont Apatite of the Midcontinent,US:Implications for Late Ordovician Climate Evolution.Palaeogeography,Palaeoclimatology,Palaeoecology,404(3):57-66.https://doi.org/10.1016/j.palaeo.2014.03.036
Rosenau,N.A.,Tabor,N.J.,Herrmann,A.D.,2014.Assessing the Paleoenvironmental Significance of Middle-Late Pennsylvanian Conodont Apatiteδ18 O Values in the Illinois Basin.Palaios,29(6):250-265.https://doi.org/10.2110/palo.2013.112
Sun,Y.,Joachimski,M.M.,Wignall,P.B.,et al.,2012.Lethally Hot Temperatures during the Early Triassic Greenhouse.Science,338(6105):366-370.https://doi.org/10.1126/science.1224126
Sun,Y.D.,Wignall,P.B.,Joachimski,M.M.,et al.,2016a.Climate Warming,Euxinia and Carbon Isotope Perturbations during the Carnian(Triassic)Crisis in South China.Earth&Planetary Science Letters,444:88-100.https://doi.org/10.1016/j.epsl.2016.03.037
Sun,Y.D.,Wiedenbeck,M.,Joachimski,M.M.,2016b.Chemical and Oxygen Isotope Composition of Gem-Quality Apatites:Implications for Oxygen Isotope Reference Materials for Secondary Ion Mass Spectrometry(SIMS).Chemical Geology,440:164-178.https://doi.org/10.1016/j.chemgeo.2016.07.013
Vennemann,T.W.,Fricke,H.C.,Blake,R.E.,2002.Oxygen Isotope Analysis of Phosphates:A Comparison of Techniques for Analysis of Ag3PO4.Chemical Geology,185(3-4):321-336.https://doi.org/10.1016/s0009-2541(01)00413-2
Wang,R.,Chen,J.B.,Zhao,L.S.,et al.,2013.In Situ Oxygen Isotope Analysis of Conodonts by SIMS and Its Application for Paleo-Sea Surface Temperature.Global Geology,32(4):652-658(in Chinese with English abstract).
Yang,K.H.,Yu,X.G.,Chu,F.Y.,et al.,2016.Environmental Changes in Methane Seeps Recorded by Carbon and Oxygen Isotopes in the Northern South China Sea.Earth Science,41(9):1206-1215(in Chinese with English abstract).
Zhang,H.,Wang,J.N.,Zhu,Y.G.,et al.,2015.Research and Application of Analytical Technique onδ18 Op of Inorganic Phosphate in Soil.Chinese Journal of Analytical Chemistry,43(2):187-192(in Chinese with English abstract).
Zhou,L.Q.,Ian,S.,Liu,J.H.,et al.,2012.Methodology of SHRIMP In-Situ O Isotope Analysis on Conodont.Acta Geologica Sinica,86(4):611-618(in Chinese with English abstract).
乔培军,朱伟林,邵磊,等,2015.西沙群岛西科I井碳酸盐岩稳定同位素地层学.地球科学,40(4):725-732.
王润,陈剑波,赵来时,等,2013.二次离子质谱微区原位牙形石氧同位素分析及其在古海表水温记录中的应用.世界地质,32(4):652-658.
杨克红,于晓果,初凤友,等,2016.南海北部甲烷渗漏系统环境变化的碳、氧同位素记录.地球科学,41(7):1206-1215.
张晗,王佳妮,朱永官,等,2015.土壤无机磷酸盐中氧同位素分析方法的研究及应用.分析化学,43(2):187-192.
周丽芹,Ian,S.,刘建辉,等,2012.牙形石SHRIMP微区原位氧同位素分析方法.地质学报,86(4):611-618.
Chen,J.,Shen,S.Z.,Li,X.H.,et al.,2016.High-Resolution SIMS Oxygen Isotope Analysis on Conodont Apatite from South China and Implications for the End-Permian Mass Extinction.Palaeogeography,Palaeoclimatology,Palaeoecology,448(448):26-38.https://doi.org/10.1016/j.palaeo.2015.11.025
Elrick,M.,Witzke,B.,2016.Orbital-Scale Glacio-Eustasy in the Middle Devonian Detected Using Oxygen Isotopes of Conodont Apatite:Implications for Long-Term Greenhouse-Icehouse Climatic Transitions.Palaeogeography,Palaeoclimatology,Palaeoecology,445:50-59.https://doi.org/10.1016/j.palaeo.2015.12.019
Gehler,A.,Gingerich,P.D.,Pack,A.,2016.Temperature and Atmospheric CO2 Concentration Estimates through the PETM Using Triple Oxygen Isotope Analysis of Mammalian Bioapatite.Proceedings of the National Academy of Sciences,113(28):7739-7744.https://doi.org/10.1073/pnas.1518116113
Griffin,J.M.,Montanez,I.P.,Matthews,J.A.,2015.A Refined Protocol forδ18 OPO4 Analysis of Conodont Bioapatite.Chemical Geology,417:11-20.https://doi.org/10.1016/j.chemgeo.2015.08.025
Halas,S.,Skrzypek,G.,Meier-Augenstein,W.,et al.,2011.Inter-Laboratory Calibration of New Silver Orthophosphate Comparison Materials for the Stable Oxygen Isotope Analysis of Phosphates.Rapid Communications in Mass Spectrometry Rcm.,25(5):579-584.https://doi.org/10.1002/rcm.4892
Joachimski,M.M.,Breisig,S.,Buggisch,W.,et al.,2009.Devonian Climate and Reef Evolution:Insights from Oxygen Isotopes in Apatite.Earth&Planetary Science Letters,284(3-4):599-609.https://doi.org/10.1016/j.epsl.2009.05.028
LaPorte,D.F.,Holmden,C.,Patterson,W.P.,2009.Oxygen Isotope Analysis of Phosphate:Improved Precision Using TC/EA CF-IRMS+.Journal of Mass Spectrometry,44(6):879-890.https://doi.org/10.1002/jms.1549
ONeil,J.R.,Vennemann,T.W.,Mckenzie,W.F.,2003.Effects of Speciation on Equilibrium Fractionations and Rates of Oxygen Isotope Exchange between(PO4)aq,and H2O.Geochimica et Cosmochimica Acta,67(17):3135-3144.oi:10.1016/s0016-7037(02)00970-5
Pucéat,E.,Joachimski,M.M.,Bouilloux,A.,et al.,2010.Revised Phosphate-Water Fractionation Equation Reassessing Paleotemperatures Derived from Biogenic Apatite.Earth&Planetary Science Letters,298(1-2):135-142.https://doi.org/10.1016/j.epsl.2010.07.034
Qiao,P.J.,Zhu,W.L.,Shao,L.,et al.,2015.Carbonate Stable Isotope Stratigraphy of Well Xike-1,Xisha Islands.Earth Science,40(4):725-732(in Chinese with English abstract).
Quinton,P.C.,Macleod,K.G.,2014.Oxygen Isotopes from Conodont Apatite of the Midcontinent,US:Implications for Late Ordovician Climate Evolution.Palaeogeography,Palaeoclimatology,Palaeoecology,404(3):57-66.https://doi.org/10.1016/j.palaeo.2014.03.036
Rosenau,N.A.,Tabor,N.J.,Herrmann,A.D.,2014.Assessing the Paleoenvironmental Significance of Middle-Late Pennsylvanian Conodont Apatiteδ18 O Values in the Illinois Basin.Palaios,29(6):250-265.https://doi.org/10.2110/palo.2013.112
Sun,Y.,Joachimski,M.M.,Wignall,P.B.,et al.,2012.Lethally Hot Temperatures during the Early Triassic Greenhouse.Science,338(6105):366-370.https://doi.org/10.1126/science.1224126
Sun,Y.D.,Wignall,P.B.,Joachimski,M.M.,et al.,2016a.Climate Warming,Euxinia and Carbon Isotope Perturbations during the Carnian(Triassic)Crisis in South China.Earth&Planetary Science Letters,444:88-100.https://doi.org/10.1016/j.epsl.2016.03.037
Sun,Y.D.,Wiedenbeck,M.,Joachimski,M.M.,2016b.Chemical and Oxygen Isotope Composition of Gem-Quality Apatites:Implications for Oxygen Isotope Reference Materials for Secondary Ion Mass Spectrometry(SIMS).Chemical Geology,440:164-178.https://doi.org/10.1016/j.chemgeo.2016.07.013
Vennemann,T.W.,Fricke,H.C.,Blake,R.E.,2002.Oxygen Isotope Analysis of Phosphates:A Comparison of Techniques for Analysis of Ag3PO4.Chemical Geology,185(3-4):321-336.https://doi.org/10.1016/s0009-2541(01)00413-2
Wang,R.,Chen,J.B.,Zhao,L.S.,et al.,2013.In Situ Oxygen Isotope Analysis of Conodonts by SIMS and Its Application for Paleo-Sea Surface Temperature.Global Geology,32(4):652-658(in Chinese with English abstract).
Yang,K.H.,Yu,X.G.,Chu,F.Y.,et al.,2016.Environmental Changes in Methane Seeps Recorded by Carbon and Oxygen Isotopes in the Northern South China Sea.Earth Science,41(9):1206-1215(in Chinese with English abstract).
Zhang,H.,Wang,J.N.,Zhu,Y.G.,et al.,2015.Research and Application of Analytical Technique onδ18 Op of Inorganic Phosphate in Soil.Chinese Journal of Analytical Chemistry,43(2):187-192(in Chinese with English abstract).
Zhou,L.Q.,Ian,S.,Liu,J.H.,et al.,2012.Methodology of SHRIMP In-Situ O Isotope Analysis on Conodont.Acta Geologica Sinica,86(4):611-618(in Chinese with English abstract).
乔培军,朱伟林,邵磊,等,2015.西沙群岛西科I井碳酸盐岩稳定同位素地层学.地球科学,40(4):725-732.
王润,陈剑波,赵来时,等,2013.二次离子质谱微区原位牙形石氧同位素分析及其在古海表水温记录中的应用.世界地质,32(4):652-658.
杨克红,于晓果,初凤友,等,2016.南海北部甲烷渗漏系统环境变化的碳、氧同位素记录.地球科学,41(7):1206-1215.
张晗,王佳妮,朱永官,等,2015.土壤无机磷酸盐中氧同位素分析方法的研究及应用.分析化学,43(2):187-192.
周丽芹,Ian,S.,刘建辉,等,2012.牙形石SHRIMP微区原位氧同位素分析方法.地质学报,86(4):611-618.
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