Skip to main content

Advertisement

Log in

Fluid-mediated partial alteration in monazite: the role of coupled dissolution–reprecipitation in element redistribution and mass transfer

  • Original Paper
  • Published:
Contributions to Mineralogy and Petrology Aims and scope Submit manuscript

Abstract

Monazite [(Ce,LREE,Th,U,Ca)(P,Si)O4], with complex zoning in Th and other elements, is commonly observed in metamorphic and igneous rocks. The hypothesis that this alteration is a product of fluid-mediated element mass transfer has been tested in the piston-cylinder press (CaF2 assembly, cylindrical graphite oven) at 1,000 MPa and 900°C and in cold seal autoclaves on a hydrothermal line at 500 MPa and 600°C. Experiments included a relatively homogeneous monazite-(Ce) (7–8 wt% ThO2) from a heavy mineral sand plus a series of alkali-bearing fluids including 2N NaOH, 2N KOH, and Na2Si2O5 + H2O. Experiments were conducted using BSE imaging, EMP analysis, and both TEM and HRTEM. A subset of monazite grains from each experiment show evidence of partial alteration in the form of areas enriched in Th + Si with sharp curvilinear compositional boundaries extending from the grain rim into the monazite interior. These ThSiO4-enriched textures are similar to those commonly seen in natural examples of metasomatised monazite in both magmatic and metamorphic rocks. In the Na2Si2O5 + H2O experiments, scarce inclusions of britholite formed in the altered monazite. The altered monazite is also characterised by strong depletion in Pb, Ca, and Y. Thorium and Si mobility, coupled with the formation of britholite inclusions, during partial alteration in the monazite grain is considered to be the product of fluid-aided coupled dissolution–reprecipitation as opposed to solid-state diffusion. Since other fluids, including NaCl and KCl brines, do not result in the formation of these textures, the experimental replication of ThSiO4-enriched areas in the monazite strongly suggests that similar textures in monazite observed in nature are fluid induced, specifically by alkali-bearing fluids. If true, complex metasomatically induced textures in monazite could yield information concerning the nature of the fluid responsible for their formation as well as allow for the dating of the metasomatic event, presuming that all the original radiogenic Pb has been removed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

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

Similar content being viewed by others

References

  • Andersen JG, Doraiswamy LK, Larson MA (1998a) Microphase-assisted ‘autocatalysis’ in a solid-liquid reaction with a precipitating product—I. Theory. Chem Eng Sci 53:2451–2458

    Article  Google Scholar 

  • Andersen JG, Larson MA, Doraiswamy LK (1998b) Microphase-assisted ‘autocatalysis’ in a solid-liquid reaction with a precipitating product—II. Experimental. Chem Eng Sci 53:2459–2468

    Article  Google Scholar 

  • Ayers JC, Miller C, Gorisch B, Milleman J (1999) Textural development of monazite during high-grade metamorphism: Hydrothermal growth kinetics, with implications for U, Th-Pb geochronology. Am Miner 84:1766–1780

    Google Scholar 

  • Ayers JC, Loflin M, Miller CF, Barton MD, Coath C (2004) Dating fluid infiltration using monazite. In: Wanty, Seal II (eds) Eleventh international symposium in water-rock interaction, proceedings 1. Balkema Publishers, Roterdam, pp 247–251

  • Ayres M, Harris N (1997) REE fractionation and Nd-isotope disequilibrium during crustal anatexis: Constraints from Himalayan leucogranites. Chem Geol 139:249–269

    Article  Google Scholar 

  • Bea F (1996) Residence of REE, Y, Th and U in granites and crustal protoliths; Implications for the chemistry of crustal melts. J Petrol 37:521–552

    Article  Google Scholar 

  • Bingen B, van Breemen O (1998) U-Pb monazite ages in amphibolite- to granulite-facies orthogneiss reflect hydrous mineral breakdown reactions: Sveconorwegian Province of SW Norway. Contrib Miner Petrol 132:336–353

    Article  Google Scholar 

  • Bingen B, Demaiffe D, Hertogen J (1996) Redistribution of rare earth elements, thorium, and uranium over accessory minerals in the course of amphibolite to granulite-facies metamorphism: the role of apatite and monazite in orthogneisses from southwestern Norway. Geochem Cosmochim Acta 60:1341–1354

    Article  Google Scholar 

  • Bosse V, Boulvais P, Gautier P, Tiepolo M, Ruffet G, Devidal JL, Cherneva Z, Gerdjikov I, Paquette JL (2009) Fluid-induced disturbance of the monazite Th-Pb chronometer: In situ dating and element mapping in pegmatites from the Rhodope (Greece, Bulgaria). Chem Geol 261:286–302

    Article  Google Scholar 

  • Cherniak DJ, Pyle JM (2008) Th diffusion in monazite. Chem Geol 256:52–61

    Article  Google Scholar 

  • Cherniak DJ, Watson EB, Grove M, Harrison TM (2004) Pb diffusion in monazite: a combined RBS/SIMS study. Geochim Cosmochim Acta 68:829–840

    Article  Google Scholar 

  • Cocherie A, Be Mezeme E, Legendre O, Fanning CM, Faure M, Rossi P (2005) Electron-microprobe dating as a tool for determining the closure of Th-U-Pb systems in migmatitic monazites. Am Miner 90:607–618

    Article  Google Scholar 

  • Corrie SL, Kohn MJ (2008) Trace-element distributions in silicates during prograde metamorphic reactions: implications for monazite formation. J Met Geol 26:451–464

    Article  Google Scholar 

  • Demoux A, Schärer U, Corsini M (2008) Variscan evolution of the Tanneron massif, SE France, examined through U-Pb monazite ages. J Geol Soc Lond 165:467–478

    Article  Google Scholar 

  • Dumond G, McLean N, Williams ML, Jercinovic MJ, Bowring SA (2008) High-resolution dating of granite petrogenesis and deformation in a lower crustal shear zone: Athabasca granulite terrane, western Canadian Shield. Chem Geol 254:175–196

    Article  Google Scholar 

  • Finger F, Krenn E (2007) Three metamorphic monazite generations in a high-pressure rock from the Bohemian Massif and the potentially important role of apatite in stimulating polyphase monazite growth along a PT loop. Lithos 95:103–115

    Article  Google Scholar 

  • Fitzsimons ICW, Kinny PD, Harley SL (1997) Two stages of zircon and monazite growth in anatectic leucogneiss: SHRIMP constraints on the duration and intensity of Pan-African metamorphism in Prydz Bay, East Antarctica. Terra Nova 9:47–51

    Article  Google Scholar 

  • Förster H-J (1998) The chemical composition of REE-Y-Th-U-rich accessory minerals from peraluminous granites of the Erzgebirge-Fichtelgebirge region, Germany. Part I: the monazite-(Ce)—brabantite solid solution series. Am Miner 83:259–272

    Google Scholar 

  • Förster H-J, Harlov DE (1999) Monazite-(Ce)—huttonite solid solutions in granulite-facies metabasites from the Ivrea-Verbano Zone, Italy. Miner Mag 63:587–594

    Google Scholar 

  • Gagné S, Jamieson RA, MacKay R, Wodicka N, Corrigan D (2009) Texture, composition, and age variations in monazite from the lower amphibolite to the granulte facies Longstaff Bluff Formation, Baffin Island, Canada. Can Miner 47:847–869

    Article  Google Scholar 

  • Gardés E, Montel J-M, Seydoux-Guillaume A-M, Wirth R (2007) Pb diffusion in monazite: new constraints from the experimental study of Pb2+ ↔ Ca2+ interdiffusion. Geochim Cosmochim Acta 71:4036–4043

    Article  Google Scholar 

  • Goncalves P, Williams ML, Jercinovic MJ (2005) Electron-microprobe age mapping of monazite. Am Miner 90:578–585

    Article  Google Scholar 

  • Grew ES, Yates MG, Wilson CJL (2008) Aureoles of Pb(II)-enriched feldspar around monazite in paragenesis and anatectic pods of the Napier Complex, Enderby Land, East Antarctica: the roles of dissolution-reprecipitation and diffusion. Contrib Miner Petrol 155:363–378

    Article  Google Scholar 

  • Hansen EC, Harlov DE (2007) Whole-rock, phosphate, and silicate compositional trends across an amphibolite- to granulite-facies transition, Tamil Nadu, India. J Petrol 48:1641–1680

    Article  Google Scholar 

  • Harlov DE, Förster H-J (2002) High grade fluid metasomatism on both a local and regional scale: the Seward Peninsula, Alaska and the Val Strona di Omegna, Ivrea-Verbano Zone, Northern Italy Part II: Phosphate mineral chemistry. J Petrol 43:801–824

    Article  Google Scholar 

  • Harlov DE, Förster H-J (2003) Fluid-induced nucleation of (Y + REE)-phosphate minerals in apatite: Nature and experiment. Part II. Fluorapatite. Am Miner 88:1209–1229

    Google Scholar 

  • Harlov DE, Hetherington CJ (2010) Partial high-grade alteration of monazite using alkali-bearing fluids: experiment and nature. Am Miner 95:1105–1108

    Article  Google Scholar 

  • Harlov DE, Förster H-J, Nijland TG (2002) Fluid-induced nucleation of (Y + REE)-phosphate minerals in apatite: Nature and experiment. Part I. Chlorapatite. Am Miner 87:245–261

    Google Scholar 

  • Harlov DE, Wirth R, Förster H-J (2005) An experimental study of dissolution-reprecipitation in fluorapatite: fluid infiltration and the formation of monazite. Contrib Miner Petrol 150:268–286

    Article  Google Scholar 

  • Harlov DE, Wirth R, Hetherington CJ (2007) The relative stability of monazite and huttonite at 300–900°C and 200–1000 MPa: metasomatism and the propagation of metastable mineral phases. Am Miner 92:1652–1664

    Article  Google Scholar 

  • Hawkins DP, Bowring SA (1997) U-Pb systematics of monazite and xenotime: case studies from the Paleoproterozoic of the Grand Canyon, Arizona. Contrib Miner Petrol 127:87–103

    Article  Google Scholar 

  • Hawkins DP, Bowring SA (1999) U-Pb monazite, xenotime and titanite geochronological onstraints on the prograde to post-peak metamorphic thermal history of Paleoproterozoic migmatites from the Grand Canyon, Arizona. Contrib Miner Petrol 134:150–169

    Article  Google Scholar 

  • Hetherington CJ, Harlov DE (2008) Metasomatic thorite and uraninite inclusions in xenotime and monazite from granitic pegmatites, Hidra anorthosite massif, southwestern Norway: mechanics and fluid chemistry. Am Miner 93:806–820

    Article  Google Scholar 

  • Hetherington CJ, Harlov DE, Budzyn B (2010) Experimental metasomatism of monazite and xenotime: mineral stability, REE mobility and fluid composition. Miner Petrol 99:165–184

    Article  Google Scholar 

  • Hinchey AM, Carr SD, Rayner N (2007) Bulk compositional controls on the preservation of age domains within metamorphic monazite: a case study from quartzite and garnet cordierite-gedrite gneiss of Thor-Odin dome, Monashee complex, Canadian Cordillera. Chem Geol 240:85–102

    Article  Google Scholar 

  • Hövelmann J, Putnis A, Geisler T, Schmidt BC, Golla-Schindler U (2010) The replacement of plagioclase feldspars by albite: observations from hydrothermal experiments. Contrib Miner Petrol 159:43–59

    Article  Google Scholar 

  • Janots E, Brunet F, Goffé B, Poinssot C, Burchard M, Cemic L (2007) Thermochemistry of monazite-(La) and dissakisite-(La): implications for monazite and allanite stability in metapelites. Contrib Miner Petrol 154:1–14

    Article  Google Scholar 

  • Johannes W (1973) Eine vereinfachte Piston-Zylinder-Apparatur hoher Genauigkeit. N Jb Miner 1973:337–351

    Google Scholar 

  • Johannes W, Bell PM, Mao HK, Boettcher AL, Chipman DW, Hays JF, Newton RC, Seifert F (1971) An interlaboratory comparison of piston-cylinder pressure calibration using the albite-breakdown reaction. Contrib Miner Petrol 32:24–38

    Article  Google Scholar 

  • Kelly NM, Clarke GL, Harley SL (2006) Monazite behaviour and age significance in poly-metamorphic high-grade terrains: a case study from the western Musgrave Block, central Australia. Lithos 88:100–134

    Article  Google Scholar 

  • Krenn E, Finger F (2007) Formation of monazite and rhabdophane at the expense of allanite during Alpine low temperature retrogression of metapelitic basement rocks from Crete, Greece: microprobe data and geochronological implications. Lithos 95:130–147

    Article  Google Scholar 

  • Krenn E, Janak M, Finger F, Broska I, Konecny P (2009) Two types of metamorphic monazite with contrasting La/Nd, Th, and Y signatures in an ultrahigh-pressure metapelite from the Pohorje Mountains, Slovenia: indications for pressure-dependent REE exchange between apatite and monazite? Am Miner 94:801–815

    Article  Google Scholar 

  • Labotka TC, Cole DR, Fayek M, Riciputi LR, Stadermann FJ (2004) Coupled cation and oxygen-isotope exchange between alkali feldspar and aqueous chloride solution. Am Miner 89:1822–1825

    Google Scholar 

  • Mahan KH, Goncalves P, Williams ML, Jercinovic MJ (2006) Dating metamorphic reactions and fluid flow: application to exhumation of high-P granulites in a crustal-scale shear zone, western Canadian Shield. J Met Geol 24:193–217

    Article  Google Scholar 

  • Martins L, Farias Vlach SR, de Assis Janasi V (2009) Reaction microtextures of monazite: correlation between chemical and age domains in the Nazaré Paulista migmatite, SE Brazil. Chem Geol 261:271–285

    Article  Google Scholar 

  • Mezeme EBe, Cocherie A, Faure M, Legendre O, Rossi Ph (2006) Electron microprobe monazite geochronology of magmatic events: examples from Variscan migmatites and granitoids, Massif Central, France. Lithos 87:276–288

    Article  Google Scholar 

  • Möller A, Hensen BJ, Armstrong RA, Mezger K, Ballèvre M (2003) U-Pb zircon and monazite age constraints on granulite-facies metamorphism and deformation in the Strangways Metamorphic Complex (central Australia). Contrib Miner Petrol 145:406–423

    Article  Google Scholar 

  • Montel J-M (1986) Experimental determination of the solubility of Ce-monazite in SiO2-Al2O3–K2O–Na2O melts at 800°C, 2 kbar, under H2O-saturated conditions. Geology 14:659–662

    Article  Google Scholar 

  • Niedermeier DRD, Putnis A, Geisler T, Golla-Schindler U, Putnis CV (2009) The mechanism of cation and oxygen isotope exchange in alkali feldspars under hydrothermal conditions. Contrib Miner Petrol 157:65–76

    Article  Google Scholar 

  • Norberg N, Neusser G, Wirth R, Rhede D, Harlov D (2011) Microstructural evolution and element mobility during experimental albitisation of K-feldspar: implications for the regional albitisation of granitoids and ore deposition. Contrib Miner Petrol (in press)

  • Oelkers EH, Poitrasson F (2002) An experimental study of the dissolution stoichiometry and rates of a natural monazite as a function of temperature from 50 to 230°C and pH from 1.5 to 10. Chem Geol 191:73–87

    Article  Google Scholar 

  • Orville PM (1963) Alkali ion exchange between vapor and feldspar phases. Am J Sci 261:201–237

    Article  Google Scholar 

  • Orville PM (1972) Plagioclase cation exchange equilibria with aqueous chloride solution: results at 700°C and 2000 bars in the presence of quartz. Am J Sci 272:234–272

    Article  Google Scholar 

  • Perchuk LL, Safanov OG, Gerya TV, Fu B, Harlov DE (2000) Mobility of components in metasomatic transformation and partial melting of gneisses: an example from Sri Lanka. Contrib Miner Petrol 140:212–232

    Article  Google Scholar 

  • Petrík I, Koneczny P (2009) Metasomatic replacement of inherited metamorphic monazite in a biotite-garnet granite from the Nízke Tatry Mountains, Western Carpathians, Slovakia: chemical dating and evidence for disequilibrium melting. Am Miner 94:957–974

    Article  Google Scholar 

  • Plümper O, Putnis A (2009) The complex hydrothermal history of granitic rocks: Multiple feldspar replacement reactions under subsolidus conditions. J Petrol 50:967–987

    Article  Google Scholar 

  • Putnis A (2002) Mineral replacement reactions: from macroscopic observations to microscopic mechanisms. Miner Mag 66:689–708

    Article  Google Scholar 

  • Putnis A (2009) Mineral replacement reactions. Thermodynamics and kinetics of water-rock interaction. In: Oelkers EH, Schott J (eds) Reviews in mineralogy and geochemistry, vol 70, pp 87–124

  • Putnis A, Austrheim H (2010) Fluid induced processes: metasomatism and metamorphism. Geofluids 10:254–269

    Google Scholar 

  • Putnis CV, Tsukamoto K, Nishimura Y (2005) Direct observations of pseudomorphism: compositional and textural evolution at a fluid-solid interface. Am Miner 90:1909–1912

    Article  Google Scholar 

  • Pyle JM, Spear FS, Wark DA, Daniel CG, Storm LC (2005) Contributions to precision and accuracy of monazite microprobe ages. Am Miner 90:547–577

    Article  Google Scholar 

  • Rapp RP, Ryerson FJ, Miller CF (1987) Experimental evidence bearing on the stability of monazite during crustal anatexis. Geophys Res Lett 14:307–310

    Article  Google Scholar 

  • Rasmussen B, Muhling JR (2007) Monazite begets monazite: evidence for dissolution of detrital monazite and reprecipitation of syntectonic monazite during low-grade regional metamorphism. Contrib Miner Petrol 154:675–689

    Article  Google Scholar 

  • Roedder E (1984) Fluid inclusions. Reviews in mineralogy, vol 12, 644 pp

  • Schmidt C, Rickers K, Bilderback DH, Huang R (2007) In situ synchrotron-radiation XRF study of REE phosphate dissolution in aqueous fluids to 800°C. Lithos 95:87–102

    Article  Google Scholar 

  • Seydoux-Guillaume A-M, Paquette JL, Wiedenbeck M, Montel JM, Heinrich W (2002) Experimental resetting of the U-Th-Pb systems in monazite. Chem Geol 191:165–181

    Article  Google Scholar 

  • Simmat R, Raith MM (2008) U-Th-Pb monazite geochronometry of the Eastern Ghats Belt, India: timing and spatial disposition of poly-metamorphism. Precamb Res 162:16–39

    Article  Google Scholar 

  • St-Onge MR, Wodicka N, Ijewliw O (2007) Polymetamorphic evolution of the Trans-Hudson orogen, Baffin Island, Canada: Integration of petrological, structural and geochronological data. J Petrol 48:271–302

    Article  Google Scholar 

  • Suzuki K, Adachi M (1991) Precambrian provenance and Silurian metamorphism of the Tsubonosawa paragneiss in the South Kitakami terrance, Northeast Japan, revealed by the chemical Th-U-total Pb isochron ages of monazite, zircon and xenotime. Geochem J 25:357–376

    Google Scholar 

  • Suzuki K, Kato T (2008) CHIME dating of monazite, xenotime, zircon and polycrase: Protocol, pitfalls and chemical criterion of possibly discordant age data. Gond Res 14:569–586

    Article  Google Scholar 

  • Suzuki K, Adachi M, Tanaka T (1991) Middle Precambrian provenance of Jurassic sandstone in the Mino Terrane, central Japan: Th-U-total Pb evidence from an electron microprobe monazite study. Sed Geol 75:141–147

    Article  Google Scholar 

  • Vavra G, Schaltegger U (1999) Post-granulite facies monazite growth and rejuvenation during Permian to Lower Jurassic thermal and fluid events in the Ivrea Zone (Southern Alps). Contrib Miner Petrol 134:405–414

    Article  Google Scholar 

  • Villaseca C, Martín Romera C, De la Rosa J, Barbero L (2003) Residence and redistribution of REE, Y, Zr, Th, and U during granulite-facies metamorphism: Behaviour of accessory and major phases in peraluminous granulites of central Spain. Chem Geol 200:293–323

    Article  Google Scholar 

  • Watt GR (1995) High-thorium monazite-(Ce) formed during disequilibrium melting of metapelites under granulite-facies conditions. Miner Mag 59:735–743

    Article  Google Scholar 

  • Watt GR, Harley SL (1993) Accessory phase controls on the geochemistry of crustal melts and restites produced during water-undersaturated partial melting. Contrib Miner Petrol 114:550–566

    Article  Google Scholar 

  • Williams ML, Jercinovic MJ (2002) Microprobe monazite geochronology: putting absolute time into microstructural analysis. J Struct Geol 24:1013–1028

    Article  Google Scholar 

  • Williams ML, Jercinovic MJ, Gonclaves P, Mahan K (2006) Format and philosophy for collecting, compiling, and reporting microprobe ages. Chem Geol 225:1–15

    Article  Google Scholar 

  • Williams ML, Jercinovic MJ, Hetherington CJ (2007) Microprobe monazite geochronology: understanding geologic processes by integrating composition and chronology. Ann Rev Earth Planet Sci 35:137–175

    Article  Google Scholar 

  • Williams ML, Jercinovic MJ, Harlov DE, Budzyn B, Hetherington CJ (2011) Resetting monazite ages during fluid-related alteration. Chem Geol (in press)

  • Wing BA, Ferry JM, Harrison TM (2003) Prograde destruction and formation of monazite and allanite during contact and regional metamorphism of pelites: petrology and geochronology. Contrib Miner Petrol 145:228–250

    Article  Google Scholar 

  • Wirth R (2004) Focused ion beam (FIB): A novel technology for advanced application of micro- and nanoanlysis in geosciences and applied mineralogy. Eur J Miner 15:863–875

    Article  Google Scholar 

  • Wolf MB, London D (1995) Incongruent dissolution of REE- and Sr-rich apatite in peraluminous granitic liquids: differential apatite, monazite, and xenotime solubilities during anatexis. Am Miner 80:765–775

    Google Scholar 

  • Xia F, Brugger J, Chen G, Ngothai Y, O’Neill B, Putnis A, Pring A (2009) Mechanism and kinetics of pseudomorphic mineral replacement reactions: a case study of the replacement of pentlandite by violarite. Geochim Cosmochim Acta 73:1945–1969

    Article  Google Scholar 

  • Zhu XK, O’Nions RK (1999) Zonation of monazite in metamorphic rocks and its implications for high temperature thermochronology: a case study from the Lewisian terrain. Earth Planet Sci Lett 171:209–220

    Article  Google Scholar 

Download references

Acknowledgments

We thank Mike Williams, Mike Jercinovic, Dieter Rhede, and Onna Appelt for support with the electron microprobe. Anja Schreiber is thanked for FIB preparation of the TEM foils. Helga Kemnitz is acknowledged for assistance with the SEM. Ilya Veksler is thanked for useful discussions during an early phase of the project. Daniel Dunkley is thanked for reviewing an earlier version of this paper. Jacques Touret, Andrew Putnis, Kazuhiro Suzuki, and Timo Nijland are thanked for their constructive reviews of the paper.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Daniel E. Harlov.

Additional information

Communicated by J. L. R. Touret.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Harlov, D.E., Wirth, R. & Hetherington, C.J. Fluid-mediated partial alteration in monazite: the role of coupled dissolution–reprecipitation in element redistribution and mass transfer. Contrib Mineral Petrol 162, 329–348 (2011). https://doi.org/10.1007/s00410-010-0599-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00410-010-0599-7

Keywords

Navigation