Abstract
Tin and tungsten are important metals for the industrializing society. Deciphering the origin and evolution of hydrothermal fluids responsible for their formation is critical to underpin genetic models of ore formation. Traditional approaches obtain isotopic information mainly from bulk analysis of both ore and gangue minerals, or less frequently from in situ analysis of gangue minerals, which either bear inherited complexities and uncertainties or are indirect constraints. Hence, directly obtaining isotopic information from ore minerals such as cassiterite by in situ techniques is warranted. However, this has been hampered by challenges from both analytical and applicational aspects. In this study, we first demonstrate a lack of crystallographic orientation effects during cassiterite ion microprobe oxygen isotope analysis. Along with our newly developed matrix-matched reference material, the Yongde-Cst, which has a recommended δ18O value of 1.36 ± 0.16‰ (VSMOW) as defined by gas source isotope ratio mass spectrometry, in situ oxygen isotope analysis of cassiterite now is possible. We further refine the oxygen isotope fractionation (1000 ln α) for quartz-cassiterite by first-principles calculations, which is given by the equation of 1.259 × 106/T2 + 8.15 × 103/T − 4.72 (T is temperature in Kelvin). The 1000 ln α for quartz-cassiterite has a sensitive response to temperature, and makes cassiterite-quartz an excellent mineral pair in oxygen isotope thermometry, as described by the equation of T (℃) = 2427 × (δ18Oqtz − δ18Ocst)−0.4326 − 492.4. Using the well-established 1000 ln α of quartz-water, 1000 ln α of cassiterite-water is derived as 2.941 × 106/T2 − 11.45 × 103/T + 4.72 (T in Kelvin), which shows a weak response to temperature. This makes cassiterite an ideal mineral from which to derive δ18O of fluids as robust temperature estimates are no longer a prerequisite. We have applied oxygen isotope analysis to cassiterite samples from six Sn(-W) deposits in China. The results show considerable variability in δ18O values both within a single deposit and among studied deposits. Combining the δ18O of cassiterite samples and the equilibrium oxygen isotope fractionation, we find that the δ18O values of ore-forming fluids show a strong magmatic affinity with variable but mostly no to low degree involvements (~0-10%) of meteoric water, hence our results invite a reassessment on the extent and role of meteoric water in Sn-W mineralization. This study demonstrates that in situ oxygen isotope analysis of cassiterite is a promising tool to refine sources of ore-forming fluids, and to decode hydrothermal dynamics controlling tin and tungsten mineralization.
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source isotope ratio mass spectrometry
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References
Bigeleisen J, Mayer MG (1947) Calculation of equilibrium constants for isotopic exchange reactions. J Chem Phys 15:261–267. https://doi.org/10.1063/1.1746492
Blevin PL, Chappell BW (1995) Chemistry, origin, and evolution of mineralized granites in the Lachlan fold belt, Australia: the metallogeny of I- and S-type granites. Econ Geol Bull Soc 90:1604–1619. https://doi.org/10.2113/gsecongeo.90.6.1604
Bodnar RJ, Lecumberri-Sanchez P, Moncada D, Steele-MacInnis M (2014) 13.5 - Fluid inclusions in hydrothermal ore deposits. In: Turekian HDHK (ed) Treatise on geochemistry (Second Edition). Elsevier, Oxford, pp 119–142
Breiter K, Skoda R, Uher P (2007) Nb-Ta-Ti-W-Sn-oxide minerals as indicators of a peraluminous P- and F-rich granitic system evolution: Podlesi, Czech Republic. Mineral Petrol 91:225–248. https://doi.org/10.1007/s00710-007-0197-1
Cai MH, Mao JW, Ting L, Pirajno F, Huang HL (2007) The origin of the Tongkeng-Changpo tin deposit, Dachang metal district, Guangxi, China: clues from fluid inclusions and He isotope systematics. Miner Deposita 42:613–626. https://doi.org/10.1007/s00126-007-0127-5
Cao HW, Zou H, Zhang YH, Zhang ST, Zheng L, Zhang LK, Tang L, Pei QM (2016) Late Cretaceous magmatism and related metallogeny in the Tengchong area: evidence from geochronological, isotopic and geochemical data from the Xiaolonghe Sn deposit, western Yunnan, China. Ore Geol Rev 78:196–212. https://doi.org/10.1016/j.oregeorev.2016.04.002
Carr P, Norman MD, Bennett VC, Blevin PL (2020) Tin enrichment in magmatic-hydrothermal environments associated with cassiterite mineralization at Ardlethan Eastern Australia: insights from Rb-Sr and Sm-Nd Isotope Compositions in Tourmaline. Econ Geol. https://doi.org/10.5382/econgeo.4774
Carr PA, Norman MD, Bennett VC (2017) Assessment of crystallographic orientation effects on secondary ion mass spectrometry (SIMS) analysis of cassiterite. Chem Geol 467:122–133. https://doi.org/10.1016/j.chemgeo.2017.08.003
Chen XC, Hu RZ, Bi XW, Li HM, Lan JB, Zhao CH, Zhu JJ (2014) Cassiterite LA-MC-ICP-MS U/Pb and muscovite Ar-40/Ar-39 dating of tin deposits in the Tengchong-Lianghe tin district, NW Yunnan, China. Miner Deposita 49:843–860. https://doi.org/10.1007/s00126-014-0513-8
Chen XC, Hu RZ, Bi XW, Zhong H, Lan JB, Zhao CH, Zhu JJ (2015) Petrogenesis of metaluminous A-type granitoids in the Tengchong-Lianghe tin belt of southwestern China: evidences from zircon U-Pb ages and Hf-O isotopes, and whole-rock Sr-Nd isotopes. Lithos 212:93–110. https://doi.org/10.1016/j.lithos.2014.11.010
Cheng YB, Mao JW, Rusk B, Yang ZX (2012) Geology and genesis of Kafang Cu-Sn deposit, Gejiu district, SW China. Ore Geol Rev 48:180–196. https://doi.org/10.1016/j.oregeorev.2012.03.004
Chi G, Diamond LW, Lu H, Lai J, Chu H (2021) Common problems and pitfalls in fluid inclusion study: a review and discussion. Minerals 11:7
Clayton RN, Mayeda TK, Oneil JR (1972) Oxygen isotope-exchange between quartz and water. J Geophys Res 77:3057–4000. https://doi.org/10.1029/JB077i017p03057
Cooke DR, Hollings P, Wilkinson JJ, Tosdal RM (2014) 13.14 - Geochemistry of porphyry deposits. In: Turekian HDHK (ed) Treatise on geochemistry (Second Edition). Elsevier, Oxford, pp 357–381
Cui XL, Wang QF, Deng J, Wu HY, Shu QH (2019) Genesis of the Xiaolonghe quartz vein type Sn deposit, SW China: insights from cathodoluminescence textures and trace elements of quartz, fluid inclusions, and oxygen isotopes. Ore Geol Rev 111. UNSP 10292910.1016/j.oregeorev.2019.05.015
D’Errico ME, Lackey JS, Surpless BE, Loewy SL, Wooden JL, Barnes JD, Strickland A, Valley JW (2012) A detailed record of shallow hydrothermal fluid flow in the Sierra Nevada magmatic arc from low-δ18O skarn garnets. Geology 40:763–766. https://doi.org/10.1130/g33008.1
Fekete S, Weis P, Driesner T, Bouvier AS, Baumgartner L, Heinrich CA (2016) Contrasting hydrological processes of meteoric water incursion during magmatic-hydrothermal ore deposition: an oxygen isotope study by ion microprobe. Earth Planet Sci Lett 451:263–271. https://doi.org/10.1016/j.epsl.2016.07.009
Feng L, Li H, Li T (2020) Potential reference materials for hematite oxygen isotope analysis. Minerals 10:987
Fu M, Changkakoti A, Krouse HR, Gray J, Kwak TAP (1991) An oxygen, hydrogen, sulfur, and carbon isotope study of carbonate-replacement (skarn) tin deposits of the Dachang tin field, China. Econ Geol Bull Soc 86:1683–1703. https://doi.org/10.2113/gsecongeo.86.8.1683
Giannozzi P, Baroni S, Bonini N, Calandra M, Car R, Cavazzoni C, Ceresoli D, Chiarotti GL, Cococcioni M, Dabo I, Dal Corso A, de Gironcoli S, Fabris S, Fratesi G, Gebauer R, Gerstmann U, Gougoussis C, Kokalj A, Lazzeri M, Martin-Samos L, Marzari N, Mauri F, Mazzarello R, Paolini S, Pasquarello A, Paulatto L, Sbraccia C, Scandolo S, Sclauzero G, Seitsonen AP, Smogunov A, Umari P, Wentzcovitch RM (2009) QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J Phys Condens Matter 21:395502. https://doi.org/10.1088/0953-8984/21/39/395502
Guo J, Zhang RQ, Li CY, Sun WD, Hu YB, Kang DM, Wu JD (2018a) Genesis of the Gaosong Sn-Cu deposit, Gejiu district, SW China: constraints from in situ LA-ICP-MS cassiterite U-Pb dating and trace element fingerprinting. Ore Geol Rev 92:627–642. https://doi.org/10.1016/j.oregeorev.2017.11.033
Guo J, Zhang RQ, Sun WD, Ling MX, Hu YB, Wu K, Luo M, Zhang LC (2018b) Genesis of tin-dominant polymetallic deposits in the Dachang district, South China: insights from cassiterite U-Pb ages and trace element compositions. Ore Geol Rev 95:863–879. https://doi.org/10.1016/j.oregeorev.2018.03.023
Harlaux M, Kouzmanov K, Gialli S, Marger K, Bouvier A-S, Baumgartner LP, Rielli A, Dini A, Chauvet A, Kalinaj M, Fontboté L (2021) Fluid mixing as primary trigger for cassiterite deposition: evidence from in situ δ18O-δ11B analysis of tourmaline from the world-class San Rafael tin (-copper) deposit, Peru. Earth Planet Sci Lett 563. https://doi.org/10.1016/j.epsl.2021.116889
Hu GX, Clayton RN, Polyakov VB, Mineev SD (2005) Oxygen isotope fractionation factors involving cassiterite (SnO2): II. Determination by direct isotope exchange between cassiterite and calcite. Geochim Cosmochim Acta 69:1301–1305. https://doi.org/10.1016/j.gca.2004.09.002
Huang F, Chen LJ, Wu ZQ, Wang W (2013) First-principles calculations of equilibrium Mg isotope fractionations between garnet, clinopyroxene, orthopyroxene, and olivine: implications for Mg isotope thermometry. Earth Planet Sci Lett 367:61–70. https://doi.org/10.1016/j.epsl.2013.02.025
Huberty JM, Kita NT, Kozdon R, Heck PR, Fournelle JH, Spicuzza MJ, Xu H, Valley JW (2010) Crystal orientation effects in δ18O for magnetite and hematite by SIMS. Chem Geol 276:269–283. https://doi.org/10.1016/j.chemgeo.2010.06.012
Isa J, Kohl IE, Liu MC, Wasson JT, Young ED, McKeegan KD (2017) Quantification of oxygen isotope SIMS matrix effects in olivine samples: correlation with sputter rate. Chem Geol 458:14–21. https://doi.org/10.1016/j.chemgeo.2017.03.020
Kita NT, Ushikubo T, Fu B, Valley JW (2009) High precision SIMS oxygen isotope analysis and the effect of sample topography. Chem Geol 264:43–57. https://doi.org/10.1016/j.chemgeo.2009.02.012
Legros H, Richard A, Tarantola A, Kouzmanov K, Mercadier J, Vennemann T, Marignac C, Cuney M, Wang RC, Charles N, Bailly L, Lespinasse MY (2019) Multiple fluids involved in granite-related W-Sn deposits from the world-class Jiangxi province (China). Chem Geol 508:92–115. https://doi.org/10.1016/j.chemgeo.2018.11.021
Lehmann B (1982) Metallogeny of tin: magmatic differentiation versus geochemical heritage. Econ Geol 77:50–59
Li XH, Li WX, Wang XC, Li QL, Liu Y, Tang GQ (2009) Role of mantle-derived magma in genesis of early Yanshanian granites in the Nanling Range, South China: in situ zircon Hf-O isotopic constraints. Sci China Ser D 52:1262–1278. https://doi.org/10.1007/s11430-009-0117-9
Li Y, Li XH, Selby D, Li JW (2018) Pulsed magmatic fluid release for the formation of porphyry deposits: tracing fluid evolution in absolute time from the Tibetan Qulong Cu-Mo deposit. Geology 46:7–10. https://doi.org/10.1130/G39504.1
Li Y, Zhang S, Hobbs R, Caiado C, Sproson AD, Selby D, Rooney AD (2019) Monte Carlo sampling for error propagation in linear regression and applications in isochron geochronology. Sci Bull 64:189–197. https://doi.org/10.1016/j.scib.2018.12.019
Li Y, Tang G-Q, Liu Y, He S, Chen B, Li Q-L, Li X-H (2021) Revisiting apatite SIMS oxygen isotope analysis and Qinghu-AP reference material. Chem Geol 582:120445. https://doi.org/10.1016/j.chemgeo.2021.120445
Liang T, Wang DH, Hou KJ, Li HQ, Huang HM, Cai MH, Wang DM (2011) LA-MC-ICP-MS zircon U-Pb dating of Longxianggai pluton in Dachang of Guangxi and its geological significance. Acta Petrol Sin 27:1624–1636
Liu P, Mao JW, Jian W, Mathur R (2020) Fluid mixing leads to main-stage cassiterite precipitation at the Xiling Sn polymetallic deposit, SE China: evidence from fluid inclusions and multiple stable isotopes (H-O-S). Miner Deposita 55:1233–1246. https://doi.org/10.1007/s00126-019-00933-0
Perdew JP, Zunger A (1981) Self-interaction correction to density-functional approximations for many-electron systems. Phys Rev B 23:5048–5079. https://doi.org/10.1103/PhysRevB.23.5048
Peres P, Kita NT, Valley JW, Fernandes F, Schuhmacher M (2013) New sample holder geometry for high precision isotope analyses. Surf Interface Anal 45:553–556. https://doi.org/10.1002/sia.5061
Polyakov VB, Mineev SD, Clayton RN, Hu G, Gurevich VM, Khramov DA, Gavrichev KS, Gorbunov VE, Golushina LN (2005) Oxygen isotope fractionation factors involving cassiterite (SnO2): I. Calculation of reduced partition function ratios from heat capacity and X-ray resonant studies. Geochim Cosmochim Acta 69:1287–1300. https://doi.org/10.1016/j.gca.2004.08.034
Richet P, Bottinga Y, Javoy M (1977) A review of hydrogen, carbon, nitrogen, oxygen, sulphur, and chlorine stable isotope fractionation among gaseous molecules. Annu Rev Earth Planet Sci 5:65–110. https://doi.org/10.1146/annurev.ea.05.050177.000433
Schmitt AK, Zack T (2012) High-sensitivity U-Pb rutile dating by secondary ion mass spectrometry (SIMS) with an O2+ primary beam. Chem Geol 332–333:65–73. https://doi.org/10.1016/j.chemgeo.2012.09.023
Scicchitano MR, Rubatto D, Hermann J, Majumdar AS, Putnis A (2018) Oxygen isotope analysis of olivine by ion microprobe: matrix effects and applications to a serpentinised dunite. Chem Geol 499:126–137. https://doi.org/10.1016/j.chemgeo.2018.09.020
Sharp ZD, Gibbons JA, Maltsev O, Atudorei V, Pack A, Sengupta S, Shock EL, Knauth LP (2016) A calibration of the triple oxygen isotope fractionation in the SiO2-H2O system and applications to natural samples. Geochim Cosmochim Acta 186:105–119. https://doi.org/10.1016/j.gca.2016.04.047
Shulaker DZ, Schmitt AK, Zack T, Bindeman I (2015) In-situ oxygen isotope and trace element geothermometry of rutilated quartz from Alpine fissures. Am Miner 100:915–925. https://doi.org/10.2138/am-2015-4961
Tang GQ, Li XH, Li QL, Liu Y, Ling XX, Yin QZ (2015) Deciphering the physical mechanism of the topography effect for oxygen isotope measurements using a Cameca IMS-1280 SIMS. J Anal at Spectrom 30:950–956. https://doi.org/10.1039/c4ja00458b
Tang GQ, Liu Y, Li QL, Feng LJ, Wei GJ, Su W, Li Y, Ren GH, Li XH (2020) New natural and fused quartz reference materials for oxygen isotope microanalysis. Atomic Spectrosc 41:188–193. https://doi.org/10.46770/As.2020.05.002
Taylor R, Clark C, Reddy SM (2012) The effect of grain orientation on secondary ion mass spectrometry (SIMS) analysis of rutile. Chem Geol 300:81–87. https://doi.org/10.1016/j.chemgeo.2012.01.013
Trail D, Bindeman IN, Watson EB, Schmitt AK (2009) Experimental calibration of oxygen isotope fractionation between quartz and zircon. Geochim Cosmochim Acta 73:7110–7126. https://doi.org/10.1016/j.gca.2009.08.024
Troullier N, Martins JL (1991) Efficient pseudopotentials for plane-wave calculations. Phys Rev B Condens Matter 43:1993–2006. https://doi.org/10.1103/physrevb.43.1993
Urey HC (1947) The thermodynamic properties of isotopic substances. J Chem Soc 562–581. https://doi.org/10.1039/jr9470000562
Valley JW (2003) Oxygen isotopes in zircon. Rev Mineral Geochem 53:343–385. https://doi.org/10.2113/0530343
Vanderbilt D (1990) Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys Rev B Condens Matter 41:7892–7895. https://doi.org/10.1103/physrevb.41.7892
Wang W, Dong G, Sun Z, Dong P, Pan Y, Ketchaya YB, Lemdjou YB, Geng J (2020) The genesis of Eocene granite-related Lailishan tin deposit in western Yunnan, China: Constraints from geochronology, geochemistry, and S-Pb–H–O isotopes. Geol J 56:508–524. https://doi.org/10.1002/gj.3928
Wang WZ, Zhou C, Qin T, Kang JT, Huang SC, Wu ZQ, Huang F (2017) Effect of Ca content on equilibrium Ca isotope fractionation between orthopyroxene and clinopyroxene. Geochim Cosmochim Acta 219:44–56. https://doi.org/10.1016/j.gca.2017.09.022
Wentzcovitch RM (1991) Invariant molecular-dynamics approach to structural phase transitions. Phys Rev B Condens Matter 44:2358–2361. https://doi.org/10.1103/physrevb.44.2358
Wilkinson JJ (2001) Fluid inclusions in hydrothermal ore deposits. Lithos 55:229–272. https://doi.org/10.1016/S0024-4937(00)00047-5
Wood SA, Samson IM (2000) The hydrothermal geochemistry of tungsten in granitoid environments: I. Relative solubilities of ferberite and scheelite as a function of T, P, pH, and mNaCl. Econ Geol 95:143–182. https://doi.org/10.2113/gsecongeo.95.1.143
Xiong YQ, Shao YJ, Mao JW, Wu SC, Zhou HD, Zheng MH (2019) The polymetallic magmatic-hydrothermal Xiangdong and Dalong systems in the W-Sn-Cu-Pb-Zn-Ag Dengfuxian orefield, SE China: constraints from geology, fluid inclusions, H-O-S-Pb isotopes, and sphalerite Rb-Sr geochronology. Miner Deposita 54:1101–1124. https://doi.org/10.1007/s00126-019-00863-x
Yao Y, Chen J, Lu JJ, Wang RC, Zhang RQ (2014) Geology and genesis of the Hehuaping magnesian skarn-type cassiterite-sulfide deposit, Hunan Province, Southern China. Ore Geol Rev 58:163–184. https://doi.org/10.1016/j.oregeorev.2013.10.012
Zhang J, Mao JW, Cheng YB, Li XL (2012) Mineralization process of the Kafang tin-copper deposit in the Gejiu district, Yunnan Province: constraints from fluid inclusion. Acta Petrol Sin 28:166–182
Zhang L-G, Liu J, Chen Z, Zhou H (1994) Experimental investigations of oxygen isotope fractionation in cassiterite and wolframite. Econ Geol 89:150–157. https://doi.org/10.2113/gsecongeo.89.1.150
Zhang LP, Zhang RQ, Hu YB, Liang JL, Ouyang ZX, He JJ, Chen YX, Guo J, Sun WD (2017) The formation of the Late Cretaceous Xishan Sn-W deposit, South China: geochronological and geochemical perspectives. Lithos 290:253–268. https://doi.org/10.1016/j.lithos.2017.08.013
Zhang R-Q, Lu J-J, Wang R-C, Yang P, Zhu J-C, Yao Y, Gao J-F, Li C, Lei Z-H, Zhang W-L, Guo W-M (2015) Constraints of in situ zircon and cassiterite U-Pb, molybdenite Re–Os and muscovite 40Ar–39Ar ages on multiple generations of granitic magmatism and related W–Sn mineralization in the Wangxianling area, Nanling Range, South China. Ore Geol Rev 65:1021–1042. https://doi.org/10.1016/j.oregeorev.2014.09.021
Zheng Y-F (1991) Calculation of oxygen isotope fractionation in metal oxides. Geochim Cosmochim Acta 55:2299–2307
Acknowledgements
We thank Shun Wang for providing the Yongde-Cst. We thank Prof Ian Williams and Dr Patrick Carr for their constructive comments and suggestions that significantly improved the presentation and clarity of this manuscript. We extend our gratitude to Prof David Dolejs and Prof Bernd Lehmann for their informative suggestions and professional editorial handling.
Funding
This research is supported by National Key Research and Development Program of China (2018YFA0702600), National Natural Science Foundation of China (42022022), and Pioneer Hundred Talents Program of Chinese Academy of Sciences and CNNC Science Fund for Talented Young Scholars (QNYC2019-2).
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Table S1, SIMS cassiterite oxygen isotope composition of the Yongde-Cst;Table S2, SIMS cassiterite oxygen isotope composition from six Chinese Sn(-W) deposits.
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Li, Y., He, S., Zhang, RQ. et al. Cassiterite oxygen isotopes in magmatic-hydrothermal systems: in situ microanalysis, fractionation factor, and applications. Miner Deposita 57, 643–661 (2022). https://doi.org/10.1007/s00126-021-01068-x
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DOI: https://doi.org/10.1007/s00126-021-01068-x