Multiple generations of titanites and their geochemical characteristics record the magmatic-hydrothermal processes and timing of the Dongguashan porphyry-skarn Cu-Au system, Tongling district, Eastern China

Abstract

Dongguashan is one of the largest porphyry-skarn Cu-Au deposits in eastern China and titanite is found in the ore system. Five types of both magmatic and hydrothermal titanites are distinguished, based on their textural and chemical characteristics. Types 1 and 2 titanites are magmatic in origin whereas types 3, 4, and 5 are hydrothermal. Magmatic titanites are wedge-shaped and display concentric and sector zoning, whereas hydrothermal titanites show a wide range of textures that vary with different alteration stages. REE, Sn, Mo, and Cu are enriched in magmatic titanites (types 1 and 2). In contrast, vanadium and HFSE are enriched in hydrothermal titanites, especially in type 4 titanite from the propylitic alteration zone. Magmatic titanite (type 1) coexists with magnetite and K-feldspar and crystallized in oxidized and H2O-rich magma at 730–760 °C. Type 2 titanite contains ilmenite inclusions reflecting changes in the fO2 of the magma chamber, possibly caused by input of mafic magma. The mobility and enrichment of HFSE and association with fluorapatite reflect the F-rich composition of the magmatic-hydrothermal fluid at Dongguashan. The relationship between titanite textures and chemistry indicates that titanite can serve as a recorder of magmatic-hydrothermal processes in porphyry copper systems. U-Pb dating of type 4 titanite from the propylitic alteration zone and type 5 titanite from skarn yielded ages of 139.0 ± 2.6 Ma and 137.0 ± 2.0 Ma, respectively, indicating that it formed synchronously with the associated quartz monzodiorite.

This is a preview of subscription content, access via your institution.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

References

  1. Aja SU, Wood SA, Williams-Jones AE (1997) The solubility of some alkali-bearing Zr minerals in hydrothermal solutions. Aqueous Chem Geochem Oxides, Oxyhydroxides, Relat Mater 432:69–74

    Google Scholar 

  2. Aleinikoff JN, Wintsch RP, Fanning CM, Dorais MJ (2002) U-Pb geochronology of zircon and polygenetic titanite from the Glastonbury Complex, Connecticut, USA: an integrated SEM, EMPA, TIMS, and SHRIMP study. Chem Geol 188(1):125–147

    Google Scholar 

  3. Aleksandrov SM, Troneva MA (2007) Composition, mineral assemblages, and genesis of titanite and malayaite in skarns. Geochem Int 45:1012–1024

  4. Angiboust S, Harlov D (2017) Ilmenite breakdown and rutile-titanite stability in metagranitoids: natural observations and experimental results. Am Mineral 102(8):1696–1708

    Google Scholar 

  5. Baker J, Peate D, Waight T, Meyzen C (2004) Pb isotopic analysis of standards and samples using a 207Pb-Pb204 double spike and thallium to correct for mass bias with a double-focusing MC-ICP-MS. Chem Geol 211:275–303

    Google Scholar 

  6. Broska I, Harlov D, Tropper P, Siman P (2007) Formation of magmatic titanite and titanite–ilmenite phase relations during granite alteration in the Tribeč Mountains, Western Carpathians, Slovakia. Lithos 95:58–71

  7. Cao MJ, Qin KZ, Li GM, Evans NJ, Jin LY (2015) In situ LA-(MC)-ICP-MS trace element and Nd isotopic compositions and genesis of polygenetic titanite from the Baogutu reduced porphyry Cu deposit, Western Junggar, NW China. Ore Geol Rev 65:940–954

    Google Scholar 

  8. Celis A (2015) Titanite as an indicator mineral for alkalic Cu-Au porphyry deposits in south Central British Columbia. Doctoral dissertation, University of British Columbia

  9. Chang YF, Liu XP, Wu YC (1991) The copper-iron belt of the lower and middle reaches of the Changjiang River (in Chinese). Geological Publishing House, Beijing (in Chinese with English abstract)

    Google Scholar 

  10. Che XD, Linnen RL, Wang RC, Groat LA, Brand AA (2013) Distribution of trace and rare earth elements in titanite from tungsten and molybdenum deposits in Yukon and British Columbia. Canada Can Miner 51:415–438

    Google Scholar 

  11. Chew DM, Petrus JA, Kamber BS (2014) U-Pb LA-ICPMS dating using accessory mineral standards with variable common Pb. Chem Geol 363:185–199

    Google Scholar 

  12. Chiaradia M, Vallance J, Fontbote L, Stein H, Schaltegger U, Coder J, Richards J, Villeneve M, Gendall I (2009) U-Pb, Re–Os, and 40Ar/39Ar geochronology of the Nambija Au-skarn and Pangui porphyry Cu deposits, Ecuador: implications for the Jurassic metallogenic belt of the northern Andes. Mineral Deposita 44(4):371–387

    Google Scholar 

  13. Chu GZ (2003) Metallogenic system of Shizishan Cu–Au ore–field in Tongling area and its prospecting significances. Dissertation, China University of Geosciences, Beijing (in Chinese with English abstract)

  14. Cooke DR, Baker M, Hollings P, Sweet G, Chang Z, Danyushevsky L, Gilbert S, Zhou T, White N, Gemmell JB, Inglis S (2014) New advances in detecting the distal geochemical footprints of porphyry systems-epidote mineral chemistry as a tool for vectoring and fertility assessments. Soc Econ Geol Special Publ 18:127–152

    Google Scholar 

  15. Deer WA, Howie RA, Zussman J (1982) Rock-forming minerals. Orthosilicates, Geological Society of London

    Google Scholar 

  16. Deng XD, Li JW, Zhou MF, Zhao XF, Yan DR (2015) In-situ LA-ICPMS trace elements and U-Pb analysis of titanite from the Mesozoic Ruanjiawan W–Cu–Mo skarn deposit, Daye district, China. Ore Geol Rev 65:990–1004

    Google Scholar 

  17. Einaudi MT, Meinert LD, Newberry RJ (1981) Skarn deposits. Econ. Geol. 75th Anniversary Volume: 317–391

  18. Fan Y, Zhou TF, Yuan F, Qian CC, Lu SM, Cooke D (2008) LA-ICP-MS zircon U-Pb ages of the A-type granites in the Lu-Zong (Lujiang-Zongyang) area and their geological significances. Acta Petrol Sin 24(8):1715–1724 (in Chinese with English abstract)

    Google Scholar 

  19. Frost BR, Lindsley DH (1992) Equilibria among Fe-Ti oxides, pyroxenes, olivine, and quartz: part II. Application. Am Mineral 77:1004–1020

    Google Scholar 

  20. Frost BR, Chamberlain KR, Schumacher JC (2001) Sphene (titanite): phase relations and role as a geochronometer. Chem Geol 172:131–148

    Google Scholar 

  21. Fu Y, Sun XM, Zhou HY, Lin H, Yang YJ (2016) In-situ LA-ICP-MS U-Pb geochronology and trace elements analysis of polygenetic titanite from the giant Beiya gold-polymetallic deposit in Yunnan Province Southwest China. Ore Geol Rev 77:43–56

    Google Scholar 

  22. Gieré R (1996) Formation of rare earth minerals in hydrothermal systems. In: Jones AP, Wall F, Williams TC (eds) Rare earth minerals: chemistry, Origin and Ore Deposits. Chapman & Hall, London, pp 105–150

    Google Scholar 

  23. Groat LA, Carter RT, Hawthorne FC, Ercitt TS (1985) Tantalian niobian titanite from the Irgon claim, southeastern Manitoba. Can Mineral 23:569–571

    Google Scholar 

  24. Harlov D, Tropper P, Seifert W, Nijland T, Förster HJ (2006) Formation of Al-rich titanite (CaTiSiO4O–CaAlSiO4OH) reaction rims on ilmenite in metamorphic rocks as a function of fH2O and fO2. Lithos 88:72–84

    Google Scholar 

  25. Hayden LA, Watson EB, Wark DA (2008) A thermobarometer for sphene (titanite). Contrib Mineral Petrol 155:529–540

    Google Scholar 

  26. Horie K, Hidaka H, Gauthier-Lafaye F (2008) Elemental distribution in apatite, titanite and zircon during hydrothermal alteration: durability of immobilization mineral phases for actinides. Phys Chem Earth 33:962–968

    Google Scholar 

  27. Ismail R, Ciobanu CL, Cook NJ, Teale GS, Giles D, Schmidt A, Wade B (2014) Rare earths and other trace elements in minerals from skarn assemblages, hillside iron oxide-copper-gold deposit, Yorke Peninsula, South Australia. Lithos 187:456–477

    Google Scholar 

  28. Jiang SY, Wang RC, Xu XS, Zhao KD (2005) Mobility of high field strength elements (HFSE) in magmatic-, metamorphic-, and submarine-hydrothermal systems. Phys Chem Earth 30:1020–1029

    Google Scholar 

  29. Kontonikas-Charos A, Ehrig K, Cook NJ, Ciobanu CL (2019) Crystal chemistry of titanite from the Roxby Downs Granite, South Australia: insights into petrogenesis, subsolidus evolution and hydrothermal alteration. Contrib Mineral Petrol 174(7):59

    Google Scholar 

  30. Li JW, Deng XD, Zhou MF, Liu YS, Zhao XF, Guo JL (2010) Laser ablation ICP–MS titanite U–Th–Pb dating of hydrothermal ore deposits: a case study of the Tonglushan Cu–Fe–Au skarn deposit, SE Hubei Province, China. Chem Geol 270:56–67

    Google Scholar 

  31. Liou JG, Zhang RY, Ernst WG, Liu J, McLimans R (1998) Mineral parageneses in the Piampaludo eclogitic body, Gruppo di Voltri, western Ligurian Alps. Schweiz Mineral Petrogr Mitt 78(2):317–335

    Google Scholar 

  32. Liu YN, Fan Y, Zhou TF, Zhang LJ, White NC, Hl H (2018) LA-ICP-MS titanite U-Pb dating and mineral chemistry of the Luohe magnetite-apatite (MA)-type deposit in the Lu-Zong volcanic basin, Eastern China. Ore Geol Rev 92:284–296

    Google Scholar 

  33. Lu SM (2007) The magmatism and fluid mineralization in Shizishan copper-gold ore-field of Tongling, Anhui province. Dissertation, Hefei University of Technology (in Chinese with English abstract)

  34. Lucassen F, Franz G, Dulski P, Romer RL, Rhede D (2011) Element and Sr isotope signatures of titanite as indicator of variable fluid composition in hydrated eclogite. Lithos 121:12–24

    Google Scholar 

  35. Mao JW, Wang YT, Lehmann B, Yu JJ, Du AD, Mei YX, Li YF, Zang WS, Stein H, Zhou TF (2006) Molybdenite Re–Os and albite 40Ar/39Ar dating of Cu–Au–Mo and magnetite porphyry systems in the Yangtze River Valley and metallogenic implications. Ore Geol Rev 29:307–324

    Google Scholar 

  36. Mao JW, Xie GQ, Duan C, Pirajno F, Ishiyama D, Chen YC (2011) A tectono-genetic model for porphyry–skarn–stratabound Cu–Au–Mo–Fe and magnetite–apatite deposits along the Middle–Lower Yangtze River Valley, Eastern China. Ore Geol Rev 43:294–314

    Google Scholar 

  37. McLeod GW, Dempster TJ, Faithfull JW (2011) Deciphering magma-mixing processes using zoned titanite from the Ross of Mull Granite, Scotland. J Petrol 52:55–82

    Google Scholar 

  38. Meinert L, Dipple G, Nicolescu S (2005) World skarn deposits. Econ Geol 100:299–336

    Google Scholar 

  39. Meyer C, Hemley JJ (1967) Wall rock alteration. In: Barnes HL (ed) Geochemistry of hydrothermal ore deposits, First Edition. Holt Rinehart & Winston, New York, pp 166–235

  40. Middleton AW, Förster HJ, Uysal IT, Golding SD, Rhede D (2013) Accessory phases from the Soultz monzogranite, Soultz-sous-Forêts, France: implications for titanite destabilisation and differential REE, Y and Th mobility in hydrothermal systems. Chem Geol 335:105–117

    Google Scholar 

  41. Oberti R, Smith DC, Rossi G, Caucia F (1991) The crystal-chemistry of high-aluminium titanites. Eur J Mineral 3:777–792

    Google Scholar 

  42. Pan YM, Dong P (1999) The Lower Changjiang (Yangzi/Yangtze River) metallogenic belt, east Central China: intrusion- and wall rock hosted Cu-Fe-Au, Mo, Zn, Pb, Ag deposits. Ore Geol Rev 15:177–242

    Google Scholar 

  43. Pan LC, Hu RZ, Bi XW, Li CS, Wang XS, Zhu JJ (2018) Titanite major and trace element compositions as petrogenetic and metallogenic indicators of Mo ore deposits: examples from four granite plutons in the southern Yidun arc, SW China. Am Mineral 103:1417–1434

    Google Scholar 

  44. Piccoli P, Candela P, Rivers M (2000) Interpreting magmatic processes from accessory phases: titanite–a small-scale recorder of large-scale processes. Trans R Soc Edinb Earth Sci 91:257–267

    Google Scholar 

  45. Rene M (2011) Titanite-ilmenite assemblage in microgranodiorites from the northeastern margin of the Klenov granite body (Bohemian Massif, Czech Republic). Acta Geodynamica Geomat 8(4):479–487

    Google Scholar 

  46. Salvi S, Fontan F, Monchoux P, Williams-Jones AE, Moine B (2000) Hydrothermal mobilization of high field strength elements in alkaline igneous systems: evidence from the Tamazeght complex (Morocco). Econ Geol 95:559–576

    Google Scholar 

  47. Samson IM, Wood SA (2005) The rare earth elements in hydrothermal fluids and concentration in hydrothermal mineral deposits, exclusive of alkaline settings. In: Linnen RL, Samson IM (eds) Rare element geochemistry and mineral deposits, Geol Assoc Can Short Course Notes, vol 17, pp 269–298

    Google Scholar 

  48. Sillitoe RH (2010) Porphyry copper systems. Econ Geol 105:3–41

    Google Scholar 

  49. Smith DC (1981) The pressure and temperature dependence of Al solubility in sphene in the system Ti–Al–Ca–Si–O–H. Prog Exp Petrol 18:193–197

    Google Scholar 

  50. Smith MP, Storey CD, Jeffries TE, Ryan C (2009) In situ U-Pb and trace element analysis of accessory minerals in the Kiruna district, Norrbotten, Sweden: new constraints on the timing and origin of mineralization. J Petrol 50:2063–2094

    Google Scholar 

  51. Song SW, Mao JW, Xie GQ, Chen L, Santosh M, Chen GH, Rao JF, Ouyang YP (2019) In situ LA-ICP-MS U–Pb geochronology and trace element analysis of hydrothermal titanite from the giant Zhuxi W (Cu) skarn deposit, South China. Mineral Deposita 54(4):569–590

    Google Scholar 

  52. Stern RA (1997) The GSC sensitive high resolution ion microprobe (SHRIMP): analytical techniques of zircon U-Th-Pb age determinations and performance evaluation. Radiogenic age and isotopic studies: report 10. Geol Surv Can Curr Res: 1–31

  53. Storey CD, Jeffries TE, Smith M (2006) Common lead-corrected laser ablation ICP–MS U–Pb systematics and geochronology of titanite. Chem Geol 227:37–52

    Google Scholar 

  54. Storey CD, Smith MP, Jeffries TE (2007) In situ LA-ICP-MS U-Pb dating of metavolcanics of Norrbotten, Sweden: records of extended geological histories in complex titanite grains. Chem Geol 240:163–181

    Google Scholar 

  55. Tang YC, Wu YC, Chu GZ (1998) Geology of copper-gold polymetallic deposits along the Yangtze River, Anhui province. Geological Publishing House, Beijing (in Chinese)

    Google Scholar 

  56. Tiepolo M, Oberti R, Vannucci R (2002) Trace-element incorporation in titanite: constraints from experimentally determined solid/liquid partition coefficients. Chem Geol 191:105–119

    Google Scholar 

  57. Tulloch AJ (1979) Secondary Ca–Al silicates as low-grade alteration products of granitoid biotite. Contrib Mineral Petrol 69:105–117

    Google Scholar 

  58. Wang SW, Zhou TF, Yuan F, Fan Y, Zhang LJ, Song YL (2015) Petrogenesis of Dongguashan skarn–porphyry Cu–Au deposit related intrusion in the Tongling district, eastern China: geochronological, mineralogical, geochemical and Hf isotopic evidence. Ore Geol Rev 64:53–70

    Google Scholar 

  59. Wones DR (1989) Significance of the assemblage titanite + magnetite + quartz in granitic rocks. Am Mineral 74:744–749

    Google Scholar 

  60. Wu CL, Dong SW, Guo HP, Guo XY, Gao QM, Liu LG, Chen QL, Lei M, Wooden JL, Mazadab FK, Mattinson C (2008) Zircon SHRIMP U–Pb dating of intermediate–acid intrusive rocks from Shizishan, Tongling and the deep processes of magmatism. Acta Petrol Sin 24:1801–1812 (in Chinese with English abstract)

    Google Scholar 

  61. Xie L, Wang RC, Chen J, Zhu JC (2010) Mineralogical evidence for magmatic and hydrothermal processes in the Qitianling oxidized tin bearing granite (Hunan, South China): EMP and (MC)-LA-ICPMS investigations of three types of titanite. Chem Geol 276:53–68

    Google Scholar 

  62. Xirouchakis D, Lindsley DH (1998) Equilibria among titanite, hedenbergite, fayalite, quartz, ilmenite, and magnetite: experiments and internally consistent thermodynamic data for titanite. Am Mineral 83:712–725

    Google Scholar 

  63. Xirouchakis D, Lindsley DH, Frost BR (2001) Assemblages with titanite (CaTiOSiO4), Ca-Mg-Fe olivine and pyroxenes, Fe-Mg-Ti oxides, and quartz: part II. Application. Am Mineral 86:254–264

    Google Scholar 

  64. Zhou TF, Fan Y, Yuan F (2008) Advances on petrogenesis and metallogenic study of the mineralization belt of the Middle and Lower Reaches of the Yangtze River area. Acta Petrol Sin 24:1665–1678

    Google Scholar 

  65. Zhou TF, Wu MA, Fan Y, Duan C, Yuan F, Zhang LJ, Liu J, Qian B, Franco P, Cooke D (2011) Geological, geochemical characteristics and isotope systematics of the Longqiao iron deposit in the Lu-Zong volcano-sedimentary basin, Middle-Lower Yangtze (Changjiang) River Valley, Eastern China. Ore Geol Rev 43:154–169

    Google Scholar 

  66. Zhu QQ, Xie GQ, Jiang ZS, Sun JF, Li W (2014) Characteristics and in situ U-Pb dating of hydrothermal titanite by LA-ICPMS of the Jingshandian iron skarn deposit, Hubei Province. Acta Petrol Sin 30(5):1322–1338 (in Chinese with English abstract)

    Google Scholar 

Download references

Acknowledgments

We especially thank Bernd Lehmann, Shaoyong Jiang, Mingjian Cao, and an anonymous reviewer for their careful reviews and critical and thorough comments, which significantly improved an earlier draft of this manuscript, and Pete Hollings for help with polishing the English. We thank Yutao Shu at the Dongguashan Cu mine for help with samples and logistics as well as all the staff and samplers who provided help onsite, particularly with safety. We would also like to thank Jay Thompson, Sebastien Meffre, Paul Olin, Sandrin Feig, and Karsten Goemann at CODES and the Central Science Laboratory (CSL), University of Tasmania, for their help with samples and analytical work.

Funding

This work was financially supported by the National Natural Science Foundation of China (grants 41320104003) and the National Key Research and Development Program of China (2016YFC0600206).

Author information

Affiliations

Authors

Corresponding author

Correspondence to Taofa Zhou.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Editorial handling: S.-Y. Jiang

Electronic supplementary material

ESM 1

(XLSX 105 kb)

ESM 2

(XLSX 130 kb)

ESM 3

(XLSX 161 kb)

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Xiao, X., Zhou, T., White, N.C. et al. Multiple generations of titanites and their geochemical characteristics record the magmatic-hydrothermal processes and timing of the Dongguashan porphyry-skarn Cu-Au system, Tongling district, Eastern China. Miner Deposita 56, 363–380 (2021). https://doi.org/10.1007/s00126-020-00962-0

Download citation

Keywords

  • Dongguashan porphyry-skarn Cu-Au deposit
  • Magmatic and hydrothermal titanites
  • U-Pb geochronology
  • Trace elements
  • Magmatism and ore-forming processes