UNIVERSIDAD DE CONCEPCION DEPARTAMENTO DE CIENCIAS DE LA TIERRA 7" CONGRESO GEOL6GICO CHILENO 1994 ACTAS VOLUMEN li pg. 1491-1495 AGE AND SULPHUR ISOTOPE SIGNATURES OF BRAZILIAN AND COLOMBIAN EMERALDS

G. Giuliki 1-2, A. Cheilktz 1-3, G. Firaud 4, J-L. Zh"mrman l, V. Caril10 5, F. Rueda 5, J. Baker 6 and R. Montigny

Introduction tion on sulphides coeval to emerald precipitation with the aim to identify the possible sources of In south America, emeralds are found only in sulphur. and Colombia (Fig.1) which are amongst the firsts in the world in emerald quality and production. This last proceeds from two contrasted emerald vein type deposits, currently quoted 192 in the classification for emerald S, Emerald Belt '~'"''"" deposits. In Brazil, emeralds are hosted by greenstone terranes mostly in highly ,' Manaus metamorphosed cratonic area&. The mine- BRA Z 1.L .-'! ralization belongs to the biotite-schist beryl type t. Santa where the sources of beryllium, chromium and -.- Terezinha.e Goias Salvador . vanadium necessary to form the green variety of Bqasíiia I beryl are likely found in juxtaposed Pegmatites ! ltabira PA C I F I C and metamorphic-mafic rocks516. However, Rio de neither Pegmatites nor ultramafic rocks are o c E ..I .v ..I " Janeiro found in the vicinities of Colombian deposits: 4 emerald is hosted by carbonate veins located within black sha1e.s of the Cretaceous-Eocene basin of the Eastern Cordillera798. Today, an hydrothermal model is proposed for the genesis of Brazilian and Colombian.emeralds 499710. However, the age of formation, of these deposits is unknown and controversies still exist concerning the origin of the, mineralizing fluids: O- lOOOkm a magmatic versus metamorphic versus u sedimentary source is always debated. Figure 1 : Map of South America showing the location In this paper, we present the first ages of two of the eastern and western emerald zones of Colombia and major Brazilian and Colombian emerald depo- the main emerald deposits of Brazil (solid circle). sits, and the results of sulphur isotopic investiga Geological setting I - Centre de Recherches Pétrographiques et Géochimiques, UPRA CNRS 6821, BP. 20, 54501 The Carnaíba and Socotó emerald deposits Vandoeuvre-lb-Nancy Cedex, France. (Brazil) 2 - ORSTOM, Département TOA URlH, 213 rue La Fayette, 75480 Paris cedex 10, France. These two deposits are located in the Stare 3 - Ecole Nationale Sup6rieure de Géologie, ßP. 452, at the proximity of the Transamazonian (2.0 Ga) 54001 Nancy cedex, France. Carnaíba and Campo Formoso granites] 1, 4 - Institut de Géodynamique, URA CNRS 1279, respectively. The niineralization is developed at Université de Nice, Parc Valrose, 06034 Nice cedex, France. the expense of Early Proterozoic 5 - MINERALCO S.A., calle 32, no 1307, Bogotl, metamorphosed utramafic rocks and juxtaposed Colombia. pegmatite intrusives. Both pegmatite and 6 - Geologisch Institut, Nieuve Prinsengracht 130, 1018 serpentinite were pervaded by metasomatic VZ, Amsterdam, the Nederlands. fluids496, inducing the formation of plagioclasite 7 - E.O.G.P.S., 5 rue Descartes, 67084 Strasbourg, (rock derived from the metasomatism of France. pegmatite and composed mainly by plagioclase)

1491 Giuliani, G. et al. and phlogopitite (rock derived from the and chlorite - free phlogopites give similar K-Ar. serpentinite and composed mainly of ages, 1979 f 28 Ma and 1973 k 20 Ma (20) phlogopite), respectively. These metasomatic respectively, we conclude that emerald minera- rocks display a clear zoning from the central lization is contemporaneous with the pervasive pegmatite intrusive to the enclosing serpentinite, muscovitization of the granite. Bulk samples and forming a metasomatic column (see Fig.3). individual grains from, the phlogopitites of Emerald is found either within plagioclasite or within phlogopitite in which spinel (chromite) Carnaíba were dated16 by 4oAr/39A1 as well as has disappeared during the metasomatic leaching syngenetic solid inclusions trapped along of the rocks . growing zones of the emerald host crystal. In Two stages of mineralization are evidenced in spite of the huge amount of excess 4oAr detected the deposits12: the first corresponds to the in adjacent emerald, ages of 1951 C 8 Ma and formation of the emerald-bearing phlogopitite 1934 C 8 Ma (lo) were determined for the with the precipitation of emerald, molybdenite, Trecho Velho and Braúlia emerald pits. A scheelite and apatite; the second, is charac- muscovite from the second stage of minera- terized by the formation of molybdenite- lization gave a plateau age of 1976 * 8 Ma (lo), muscovite-bearing quartz veins which crosscut which may correspond to a higher closure the first stage. temperature of the K-Ar system during the cooling of the whole pluton and associated The Colombian emerald deposits- hydrothermal halo. They define two emerald-bearing zones situated Age of Colombian emerald deposits. along two major polyphased thrust limits of the Eastern Cordillera which correspond to the Two emerald deposits from the westem emerald original borders of the Cretaceous-Eocene zone (Fig.l), the Coscuez and Quipama-Muzo basin13. The deposits are located within the mines, have been dated by 40ArI3YAr induction Lower Cretaceous black shales series. The and laser microprobe methods on contem- mineralization is hosted within breccias. poraneous greenish Cr-V-bearing K-mica aggre- networks of extension fractures and pockets gatesl7.18. It consists of muscovite 3s a Gomi- related to hydrofacturingg. The hydrothermal nnnt phase C kaolinite, C paragonite, k quartz, f circulations induced albitization, carbonatization albite, and k chlorite, pyrite and calcite. and pyritization halos developed around the Contamination of the K-mica aggregates by mineralized structuresI4. Emerald occurs within wall-rock impurities was eliminated by in situ calcite-dolomite-pyrite veins. JOArP9Ar laser spot analysis. Two distinct plateaus and spot fusion ages of 35 K-Ar 40Ar/39Ar and dating to 38 Ma and 31.5 to 32.6 Ma (Fig.2) were obtained for the Coscuez and Quipama samples, Age of Camaíía and Socotó emerald deposits

K-Ar and 4oAr/39Ar measurements were performed on biotites and deuteric muscovites from the Carnaíba and Campo Formoso granites's. For the Camaiba granite, biotites and muscovites provide isochrons with age of 1888 k 32 and 1979 C 28 Ma (20)~respectively. For the campo Formoso granite, the biotites yield ages between 1875 k 45 Ma and 1908 C 47 Ma (20) and the muscovites yield ages of 1897 f 34 Ma and 2040 k 24 Ma (20). In contrast, phlogopites from emerald-bearing phlogopitites display K-Ar ages that spread between 1900 and %"Ar Re1eaS;ed 2000 Ma with an isochron of 1973 f 20 Ma Figure 2: Induction (bulk sample) and continuous laser (20) for Carnaiba. Generally, the youngest microprobe step heating (single grain aggregate) ages for biotite and phlogopite ages occur for chloritized the Quipamn-Muzo muscovite. samples. Since in Carnaíba, deuteric muscovites

1492 .Giuliani, G. et al.

respectively. These results give anmambiguous Sulphur isotope data late Eocene to lower Oligocene age for the muscovite synchronous with emerald deposi- Carnaíía and Socotó molybdenites tion. Concordant conventional K-Ar ages show that in spite of the smallsize of micas (< 0.5 The 634S values of molybdenites related to mm), they did not suffer significant 39Ar loss quartz vein, .plagioclasite, phlogopitite and due to recoil during irradiation of the samples. metasomatized pegmatite are comprised between Internal 39Ar recoil may explain the slight 2.95 to 3.53%0(Fig.3). Molybdenites precipitate disturbances observed on the age spectra. during the percolation of hydrothermal fluids

4

o Molybdenite a Muscovite Phlogopite o Emerald 0 Tourmaline 4 Plagioclase h ..... Metasomatized Limit of emerald d 'cPegmatite precipitation Coarse-grained Fine-grained plagioclasite plagioclasite m Phlogopitite a Quartz vein

Figure 3 : Spatial relationship between emerald-molybdcnitc-bcaringphlogopitites (metasomatic column of the first stage of mineralization) and molybdenite-bearing quartz veins (second stage of mineralization), and the corresponding 63JS values (a,) of molybdenites from the Carnafia and Socotó emerald deposits. The metasomatic column is composed by six zqnes which are from the central pegmatite vein to the hosting serpentinite rock zone 1: pegmatite transformed into plagioclasite (albite, andesine in composition) with disseminated phlogopitc and sometimes emerald and quartz; zone 2, corresponding to a coarse-grained phlogopitite with phlogopite, apatite, emerald and quartz; zone 3, composed by a fine-grained phlogopitite with an inner subzone where apatite and emerald precipitated. and an outer subzone with only spinel and phlogopite. In zone 3, the . disappearanceof emerald corresponds to the presence of spinel (chromite) within phlogopitite; zone 4, formed by an assemblage of phlogopite, spinel, and amphibole: zone 5, is composcd by phlogopite, spinel, amphibole and talc: zone 6, representing the serpentinite which is composed of spinel, amphibole, talc, serpcntinc and chlorite. Braúlia, Marota, Trecho Velho and Bode correspond to diffcrcnt prospecting pits of Camaiba.

1493 I t

Giuliani, G. et al. within both pegmatite and serpentinite. Sulphur emerald deposits of Coscuez and Quipama- , can (1) .result from leaching of previous Muzo. These ages correspond to a strong sulphides of the pegmatite or, (2) be carried by shortening episode starting during the Eocene i the hydrothermal fluid. 634s of the different which is related to an acceleration of the types of molybdenite are constant, indicating convergence rate between the Nazca and South that the oxidation of the hydrothermal solution American plates. Thrusting and uplift of the remained below the SO2/H2 boundary or Eastem Cordillera during late Eocene to Pliocene time appears younger than the emerald constant. 634s melt of uncontaminated granitic formation. An evaporite source for the NaCI- magmas19 are likely to be between - 3 and 3 %O, rich brines trapped within emerald crystals is and the resulting fluids with a 634s in the range constrained by the sulphur isotope data obtained on pyrites. Based on (I) oxygen, carbon and of -3 %O to 7 %O. The 634s values of sulfur isotopes data, (2) geochemical profiles molybdenites are within this suggested range, through the mineralized zones which show that and a magmatic origin can be proposed either leaching of major and trace elements following hypothesis (1) or .(2). The (particularly Al, Be, Cr, V. and REE) from the contamination of external wall-rock sulphur is enclosing black shales is accompanied by their avoided and the slight decrease in 634s for partial redistribution as infilling vein mobybdenites from phlogopitites to quartz-veins minerals18-25 and (3) the chemical composition (deviation of 0.7 %O) can be related to more of the primary fluid inclusions (NaC1-CaC12- acidic conditions (fluctuation of pH) prevailing rich brines), a hydrothermal sedimentary model during the precipitation of molybdenite in the is proposed for the Colombian emerald genesis. quartz veins. Carnaíba and Socotó emerald deposits yield Transamazonian ages (1980-1970 Ma) which Colombian pyrites are not separated in time with the granite and pe.gmatite emplacements. In Carnaíba, emerald The calculated 6343 values of H2S in solution in mineralization is contemporaneous with the equilibrium with hydrothermal pyrite for a pervasive muscovitization which affected the juxtaposed granite. The sulphur signature of temperature of formation of 300°C, from six molybdenites is magmatic. Thus, Brazilian and emerald deposits, range from 14.8 to 19.4 '%O Colombian emerald deposits differ considerably whereas sedimentary pyrite from the enclosing and the magmatic versus sedimentary origin for black shales yield a 834s of -2.4 %O. The narrow sulphur allows to propose a magmatic versus range in 634S H2S between the different sedimentary origin for beryllium for these two deposits suggests, (1) an uniform and probably contrasted type of deposits. unique source for the sulphide sulphur, (2) the non participation of magmatic or sedimentary sulphur. Evaporitic sulphates are a likely source REFERENCES for heavy sulphur and the calculated 634s H2S 1 - Schwarz, D., 1987. Esmeraldas-inclu~~esem gemas. overlap the expected 634s range of Jurassic and Imprensa Universitaria UFOP Ouro Preto, Brazil, 450 p. Lower Cretaceous sulphates20. i 2 - Kazmi, AH., and Snee, L.W., 1990. Emeralds of Fluid inclusionsl8J1, oxygen22, carbon22 .and Pakistan. Geology, gemmology and genesis: A.H. sulphur isotopes20 data give a typical evaporitic Kazmi and L.W. Snee (Editors), Geol. Survey Pakistan- sedimentary signature for the mineralizing fluid Van Nostrand Reinhold Co., 269 p. and in consequence, promote a hydrothermal sedimentary model for Colombian emerald 3 - Couto, P. and Almeida, J.T., 1982. Geologia e. - mineraIization18122.23,24. mineralizaçöes na aera do garimpo de Camaiba, Bahia. Anais XYXVI Congresso Brasileiro de Geologia, 3: 850- CONCLUSIONS 861.

Brazilian and Colombian emeralds define two 4 - Giuliani, G., Silva, L.J.H.D. and Couto. P.. 1990. contrasted type of deposits which differ by their Origin of emerald deposits of Brazil. Mineralium geological setting, tectonics, paragenesis and Deposita, 25: 57-64. geochemistry. Two distinct upper Eocene to lower Oligocene ages have been determined for the Colombian

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5 - Rudowski. L., Giuliani, G. and Sabaté, P.. 1987. Les 17 - Cheilletz, A., Féraud G., Giuliani, G. and phlogopitites a émeraude au voisinage des granites de Rodriguez, C.T., 1991. 40Ar/39Ar laser-probe dating of Campo Formoso et Carnaíba (Bahia, Brésil): un exemple the Colombian emerald deposits: metallogenic de minéralisation protérozoique Be, Mo et W dans des implications. In “Source, Transport and Deposition of ultrabasites métasomatisées. C.R. Acad. Sci., Paris, T. Metals”, SGA Meeting, 25 Years Anniversary, August 301, II. 18: 1129-1134. 30-September 3, Nancy, Pagel, M. & Leroy, J., eds., Rotterdam, Balkema, 373-376. 6 - Rudowski, L., 1989. Pétrologie et géochimie des granites uansamazoniens de Campo Formoso et Carnaíba 18 - Cheilletz, A., Féraud. G., Giuliani, G. and (Bahia, Brésil), et des phlogopitites h émeraudes asociées. Rodriguez, C.T., 1994. Time-pressure-temperature Unpubl. Thesis University Paris VI, 292 p. constraints on the formation of Colombian emeralds: a laser-probe and fluid inclusion study. Economic 7 - Forero, H.O., 1987. Esmeraldas. Publ. geol. Ingeo- Geology, 89, 2: 362-380. min., Recursos’ minerales de Colombia, T.11 : 557-605. 19 - Ohmoto, H. and Rye, R.O., 1979. Isotopes of 8 - Baker, P.J., 1975. Projecto de esmeraldas, Informe sulfur and carbon. In: H.L. Barnes (Editors), final Naciones-Unidas-Ingeominas,COL-72/004,7 Ip. Geochemistry of hydrothermal ore deposits, Wiley, New York, 509-567. 9 - Giuliani, G., Rodriguez, C.T. ana Rueda, F., 1990. Les gisements d’émeraude de la Cordillere orientale de la 20 - Giuliani, G., Cheilletz, A., Baker, J. and Arhan, T., i Colombie: nouvelles données métallogéniques. 1993. Evaporitic origin of the parent brines of Mineralium Deposita, 25: 105-111. Colombian emeralds: fluid inclusions and sulphur isotopic evidences. In “European Current Research On 10 - Kozlowski. A., Metz, P. and Jaramillo, H.A.E., Fluid Inclusions”, ECROFI XII, Varsovia, June 13-18, 1988. Emeralds from Somondoco, Colombia: chemical Kozlowski, A., ed., Archiwum Mineralogiczne, t. composition, fluid inclusions and origin. Neues Jarhbuch XLLX, 1: 82-84. Miner. Abh., 159: 23-49. 21 - Giuliani, G., Cheilletz A, Dubessy, J. and Il - Sabaté, P., Marinho, M.M.’, Vidal, Ph. and Caen- Rodriguez, C.T.. 1993. Chemical composition of fluid Vachette, M., 1990. The 2 Ga peraluminous magmatism inclusions in Colombian emerald deposits. Proceedings of the -Contendas belts (Bahia. Brazil): Eighth Quadriennal IAGOD Symposium. Ottawa. geologic and isotopic constraints on the sources. Chem. August 12-18, 1990, E. schweizerbart’sche Verlagsb- Ceol., 83: 325-338. uchandlung eds., Stuttgart, 159-168.

12 - Giuliani, G. and Fernandés; P.C.A., 1988. The 22 - Giuliani, G., Sheppard, S.M.F., Cheilletz, A. and Archaean and Proterozoic molybdenum mineralizations of Rodriguez, C.T., 1992. Fluid inclusions and I8O/I6O, the Bahia State: metallogenetic implications. Anais VI1 13C/12C isotopes geochemistry contribution to the Congresso Latino-Americano de Geologia, Belém, 1: genesis of emerald deposits from the Eastern Cordillera. 230-242. C. R. Acad. Sci., Paris, 314: 269-274. 13 - Mégard, F., 1987. Cordilleran Andes and Marginal 23 - Cheilletz, A., Giuliani, G., and Arhan, T., 1993. Andes: A Review of Andean Geology North of the Arica Late Eocene-Oligocene shortening episode in the Eastern Elbow (18 deg. S), In: Monger, J.W.H., and Cordillera of Colombia viewed by emerald dating. In: Francheteau, J., eds., Circum -Pacific Orogenic Belts and Deuxibme Symposium International de Géodynamique Evolution of the Pacific Ocean Basin. American Andine, ISAG 93, Oxford, 21-23 septembre 1993, Geophysical Union, Geodynamics Series, 18: 71-95. Editions de I’ORSTOM, Paris, 473-476.

14 - Beus, A.A., 1979.‘Sodium: a geochemical indicator 24 - Giuliani, G., Cheilletz, A., Carrillo, V. and Rueda, of emerald mineralization in the Cordillera Oriental of F., 1994. The formation of. the emerald deposits of Colombia. J. Geochem. Explor., II: 195-208. Colombia: an example of basinal fluids migration within the Eastern Cordillera of Colombia. Abstracts 15 - Giuliani, G., Zimmermann, J.L. and Montigny R., PACROFI V Conference, Cuernavaca, Mexico, May 19- 1994. K-Ar and 40Ar/39Ar evidence for a Transamazo- 21, 26-27. . nian age-for the granites and emerald-bearing K-meta- somatites from Campo Formoso and Carnaíba (Bahia, 25 - Giuliani, G.. Cheilletz, A., Sheppard, S.M.F. and Brazil). Journ. South Amer. Earth Sci., in press. Arboleda, C., 1993. Geochemistry and origin of the emerald deposits of Colombia. In: Current Research in 16 - Cheilletz, A., Féraud, G., Giuliani. G. and Ruffet, Geology Applied to Ore Deposits, 2nd SGA Meeting, Granada. September 9-1 I, Fenoll Hach:Ali, P.,.Torres- G., 1993. Emerald dating through 40Ar/39Ar step- Ruiz, J. & Gervilla, F., eds., 105-108. heating and laser spot analysis of syngenetic phlogopite. EPSL, 120, 473-485.

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