Hydrothermal alteration nature of Candelarias Auquartz deposits in the metamorphic terrane of northern Sierras Pampeanas de Crdoba, Argentina

Diana Mutti, Carolina Mndez & Alejandro Di Marco Department of Geology, Buenos Aires University, Intendente Giraldes 2160 - C1428EGA -Argentina

Abstract. An alteration envelope at least 1 m wide is centred on Au-quartz fissure veins hosted in retrograde metamorphic rocks of the Ordovician Guamanes shear zone. Geochemical traverses indicate that the hanging wall rock is enriched in Al2O3, K2O, MgO, P2O5, CaO, Au and Ba. Cs, As, Cd, Be and U are enriched in rocks of the hanging wall and footwall. Transference of P2O5, FeOt, CaO, Ba and Au from the footwall to the hanging wall, and MnO and Na2O migration toward the fissure vein is interpreted. The study confirms element mobilization from the metamorphic terrane and suggests a metasedimentary source for the vein quartz. Keywords: Sierras Pampeanas, shear zone, Au-quartz, alteration, rock sources

1 Introduction
This paper presents preliminary results of a study on the mobility of chemical elements during the development of Au-quartz vein deposits in Candelaria, Sierras Pampeanas de Crdoba, related to the reactivation of the Guamanes shear zone and a change of rheology conditions from ductile-brittle to brittle-ductile. The retrograde episode is attributed to greenschist facies metamorphism during the late Devonian-Carboniferous Achalian orogeny (404 to 360 Ma; Sims et al. 1997). Candelarias mineralization yields Devonian 40Ar-39Ar white mica step heating ages in the 378-351 Ma range (Skirrrow et al. 2000). The mobility of elements in superimposed shear zones on Precambrian-early Palaeozoic metamorphicgranite terrains has been little studied in Argentina, and its influence on mineralization episodes and ore deposits has not been analysed. However, this type of environment covers ~25% of the surface of central-north Argentina, and defines an extensive corridor which was built by the Pampean (late Precambrian-Cambrian), Famatinian (Ordovician-Silurian) and Achalian (Devonian - early Carboniferous) orogenies. This corridor of orogenic deposit type mineralization, crops out in Sierra de Rinconada, Sierra de Culampaj, Sierra de las Minas y Ulapes, Cumbre del Perchel and Sierra de Comechingones, and has been worked with small-scale mining operations of fissure-vein type-Au-quartz ore deposits, with minor sulphide and oxide minerals (Mutti et al. 2007).

mylonitic rocks are inferred to be related to W-NW shortening during the Famatinian orogeny and Precordillera accretion to the western protomargin of Gondwana (Sims et al. 1997). Textural, structural, petrographic and chemical features of Au-quartz veins with base metal deposits in the Candelaria area of the Cumbre del Perchel, show a complex alteration, deformation and mineral deposition history in the Palaeozoic. The Guamanes mesoscopic and microscopic ductilebrittle and brittle-ductile structures show folded quartzmica ribbons, delta and sigma-type porphyroclasts in protomylonites and mylonites, mica fish, S-C planes, grain boundary migration, polygonal grains, and stretching lineations. Features of Candelarias mineralization suggest that hydrothermal fluid flux was connected with the retrograde metamorphism on the shear belt, and the subjacent juvenile water derived from the Achalian magma chambers (Mutti et al. 2007). Our recent mapping, project UBACyT X156, suggests a main mineralized area at the eastern side of the Guamanes belt, reflecting a transitional behaviour of the rocks from intensely to less deformed toward the Cruz del Eje Metamorphic Complex. The deposits are emplaced along a 3 km wide belt striking N-S to NNWSSE, and are developed in a feldsparbiotitemuscovite gneiss. The gneiss crops out in contact with feldspar biotitemuscovite schist, which is exposed in tight chevron fold hinges. Locally, the Au-quartz veins are hosted in protomylonite belts (<5 m wide) interlayed with gneisses, schists and mylonites (<7 m wide). The veins have also been controlled by 1st and 2nd order moderately plunging chevron type folds, with N(NNW)-S(SSE) axes and hing line spacings of 1,000 m and 5 m respectively.

3 Achalian Vein Mineralization

Quartz vein systems (<1.5 m thick) in the Ordovician fold-thrust-belt of Guamanes have been related to the late (retrograde) stage of the Achalian orogenic evolution. The fissure veins display extensional features that crosscut the major structural elements of the compressive Famatinian - Achalian domains. The Guamanes Belt hosts widespread deposits (30) with an average grade of ~ 20 g/t Au. The mineralization occurs in a stepped and en echelon fissure system as open space filling, with laminated, ribbon and breccia textures. The mineralization typically contains gold, pyrite, arsenopyrite, sphalerite, chalcopyrite, galena, hematite, milky and grey quartz, red chalcedony, biotite, white mica, calcite and chlorite. Mutti et al. (2007)

2 Geological Setting
The Guamanes shear zone crops out in a belt 54 x 8 km with NW strike and moderate to steep NE dips, in the Sierras Pampeanas de Crdobas basement. The

recognized different gold-type occurrences. The P-T conditions during early growth of barren and ore-bearing sulphides milky quartz, and late goldsulphides-grey quartz (from fluid inclusion data), show average values of 310C at 2.5 Kbar and 280C at range of 0.8-1.9 Kbar respectively. The fluid inclusion data also suggest a fluid cooling history of the vein systems, ending with the deposition of red jasper or chalcedonic material at low temperatures (100-150C; Mutti et al. 2009).

zones of veins. Hematite and clays accompany this progressive change and suggest decreasing temperature. Desilicification (SiO2), partial destruction of feldspar (CaO, Na2O, K2O and FeOt) and garnet (FeOt and MnO) components, and white mica participation in the footwall are recognized by chemical and petrographic correlation. Figure 1b also shows that all components were mobile during regional hydrothermal alteration, in both the wall rock adjacent to the vein and the regional distal mylonitic rocks.

4 Hydrothermal Sources

Alteration

and

Rock

A total of 25 representative whole-rock samples have been analyzed for major oxides and trace elements by ICP - ICP/MS at Activation Laboratories of Canada. Nineteen are from hydrothermally altered wall rocks (protomylonite gneiss), weakly altered and/or unaltered gneisses near the veins (between 1.5 and 5 m from the quartz vein-protomylonite contact), and regional unaltered distal mylonites and protomylonites (>150 m); five are of quartz from laminated veins; and one is from an ophthalmic structure in gneiss near to one Au-quartz vein.

4.1 Wall rock alteration and mass change

A general trend of hydrothermal alteration in Candelarias gold deposits is presented using the single precursor system method of McLean and Barret (1993). The precursor rocks have been divided in two groups in order to facilitate the local and regional correlation: 1) non or weakly altered gneiss proximal to the vein (between 1.5 and 5 m from the quartz veinprotomylonite contact), and 2) the unaltered distal mylonite and protomylonite (>150 m from the vein contact). Mass changes for each element were determined against TiO2 that remained relatively immobile during alteration (range = 0.19-0.26 %; arithmetic mean = 0.22 %; standard deviation = 0.028 %; number of samples = 9). Figure 1a shows that all components were mobile during local hydrothermal alteration in Au-quartz deposits. Gains of P2O5, CaO, Al2O3, K2O, MgO, FeOt, As, Au, Be, Ba, Cd, Zn and U are recognized in the hanging wall, whereas SiO2, MnO and Cu are depleted. The footwall shows gains in Al2O3, K2O, As, Cd, Be and U, and loss in MnO, Na2O, FeOt, , P2O5, CaO, SiO2, Ba, Pb, Cu and Au. The hanging walls gain in Al2O3, K2O, MgO, FeOt, Ba, Be and U, can be related to potassic sericitization with biotite > muscovite sericite overgrown in layers on the protomylonite. In this way, the alteration molar ratio index 3K/Al 0.8 in Candelarias hanging wall rocks, represents the potassic alteration. Pyrite and sphalerite, with traces of As and Cd-Bi respectively, show a weak sulphidation and carbonatization through calcite deposition. The alteration model also shows a change in the MgO/(Fe2O3 + MgO) ratio, consistent with the chlorite volume increase from proximal to distal

Figure 1. Average gains and losses of oxides (expressed in wt %) and selected trace elements (in ppm) resulting from hydrothermal alteration of: a. hanging and footwall (wall rock) with respect to the proximal gneiss near to the vein (1.5 to 5 m); b. wall rock and proximal gneiss near to the vein (1.5 to 5 m) with respect to unaltered distal mylonite and protomylonite (> 150 m). Explanation in text.

Increasing content in FeOt, SiO2, Al2O3, K2O, MgO, Au, U, Cd, As, Be, Rb, Cs and Ba is registered in the weak and unaltered gneises near the veins with respect the unaltered distal regional mylonite and protomylonite, whereas Na2O, P2O5 and CaO decrease. P2O5, Al2O3, CaO, K2O, MgO, As, Cd and Be show an increase in wallrock in respect to unaltered distal regional mylonite and protomylonite, with decreasing in MnO, Na2O, SiO2 and FeOt. These changes can be related to weathering and/or possible variation in the sedimentary protolith.

4.2 Rock sources

The precursor rocks and altered wall rocks of the veins were analyzed for their rare earth elements (REE); Figure 2a-c shows a flat REE-normalized pattern with a value near to 1, using the average Post-Archean siliciclastic sedimentary rocks (PAAS, Nance and Taylor

1976). This feature suggests the presence of a sedimentary protolith for the metamorphic analyzed material, without fractionation during fluid-rock interaction or mineral deposition.

elements is frequently related to surface, underground and/or deep water circulation in ore-forming processes. In this way, Skirrow et al. (2000) suggest a Carboniferous origin related to uplift and a new magmatic episode.

5 Discussion and Conclusions

Deformation and lithogeochemistry studies indicate that Candelarias Au-quartz deposits are controlled by protomylonite belts with moderately foliated, altered wall rock. Mass change data suggest transference of P2O5, FeOt, CaO, Ba and Au from the footwall to the hanging wall. P2O5, Al2O3, K2O, MgO, CaO, As, Cd, Be, U and Au are enriched in the wall rock (especially the hanging wall); whereas MnO and Na2O possible migrated to the fissure vein. Although a local macroscopic alteration halo is not conspicuous, it is characterized by biotitization, sericitization (or muscovite), silicification, sulphidisation and carbonatisation, accompanied by hematite and minor chlorite and clays towards the distal zone. Silicification and quartz veins are considered to have been derived from metasedimentary sources, although the equilibrium quartz-sericite pair shows 18Ofluid values of 5.0 to 10.06 and Dfluid values of - 61.84 to - 126.43 (Skirrow et al. 2000; Mutti et al. 2009 and unpublished data), which predominantly lie in the superimposed fields of metamorphic and magmatic waters (see reference in Skirrow et al. 2000).

Figure 2. PASS-normalized rare-earth element patterns for: a. unaltered regional Guamaness rocks; b. weak and/or unaltered hydrothermal proximal gneiss near veins (1.5 to 5 m of quartz vein-protomylonite contact); c. hydrothermal altered wall rocks (hanging and footwalls); d. milky quartz-sulphides filling veins (white), quartz-Au filling veins (grey) and red chalcedony (black). References in text.

Acknowledgments
We thank reviewers David Skinner (GNS Science) and Mathijs Booden (University of Auckland), and UBACyT X156 project financial support.

The quartz samples (Fig. 2d) show REE patterns similar to those of metasedimentary rocks, suggesting a sedimentary inheritance. The REEs have normalized values between ~ 0.01 and 0.4, which is common in this type of material because REEs are incompatible in quartz. Thus, the quartz-Au veins and the milky quartzsulphide veins further indicate a common local source related to fluids derived from the basement. This assumption is not inconsistant with the relative immobility of the REEs during bulk alteration, because slivers of pervasive wallrock are present within the veins . The quartz REE pattern defines a small positive Eu anomaly, indicating relative oxidizing conditions during successive stages of silica deposition. However, the major expression of oxidizing conditions is the deposition of red chalcedony (<150C) during the late stage of brecciation and open space filling. This positive signature is in accordance with the Eu2+/Eu3+ redox potential, which depends strongly on temperature, and favors predominance of Eu3+ in low temperature fluids. The red chalcedony has higher Mn (4.360 ppm), Ba (177 ppm), Cu (48.5 ppm) and Be (1.4 ppm), with respect to the milky and grey quartz. The migration of these

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