POST-MIOCENE AND BRONZE-AGE SUPERGENE ...

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The Canadian Mineralogist Vol. 48, pp. 163-181 (2010) DOI : 10.3749/canmin.48.1.163

POST-MIOCENE AND BRONZE-AGE SUPERGENE Cu–Pb ARSENATE – HUMATE– OXALATE – CARBONATE MINERALIZATION AT MEGA LIVADI, SERIFOS, GREECE Harald G. DILL§, Frank MELCHER and Stephan KAUFHOLD Federal Institute for Geosciences and Natural Resources, P.O. Box 510163, D–30631 Hannover, Germany

Astrid TECHMER Leibnitz Institute for Applied Geosciences, P.O. Box 510163, D–30631 Hannover, Germany

Berthold WEBER Bürgermeister-Knorr Str. 8, D–92637 Weiden i.d.OPf., Germany

Wolfgang BÄUMLER Hesslach 24, D–95466 Weidenberg, Germany

Abstract As a result of the Late Miocene skarn-type Fe mineralization at Mega Livadi on the Isle of Serifos, Greece, arsenical copper mineralization of hydrothermal origin formed in calcareous roof-rocks of a granodioritic intrusion. The hypogene mineralization, with pyrite, As-rich tennantite-group minerals and arsenopyrite, underwent strong alteration during the Pliocene and Quaternary by descending meteoric waters. We subdivide the geogenic and anthropogenic processes responsible for this alteration into five mineralizing stages, differing from each other by their element budget, Eh and pH. The supergene stages I to III comprise a variegated assemblage of oxides, hydroxides and arsenates: stage I (goethite, mixture of fine-grained Fe–As–Sb–Cu minerals, pharmacosiderite), stage II (Sb-bearing beudantite, REE-bearing beudantite), stage III (arseniosiderite). The anthropogenic stages IV and V are characterized by a set of hitherto unknown K–Cu humates and oxalates (stage IV) and the common Cu carbonates malachite and azurite (stage V). Chemical weathering induced by the (sub)tropical climatic conditions during the Late Miocene and Pliocene was responsible for the supergene associations of stages I through III at Mega Livadi. In the course of this alteration, the content of Fe decreased and As increased. Anomalously high contents of LREE in beudantite are used as a “minerostratigraphic” tracer to correlate the mineralization of stage II with a phase of pervasive formation of laterite in the Aegean region during the Pliocene. After a hiatus, an anthropogenic episode of mineralization was triggered by ancient mining activities during the early Bronze Age, around 3325 to 2890 BC, when miners began exploiting the soft arsenical Fe and Cu ore at shallow depth. This mineralization evolved under more temperate climatic conditions as a result of ventilation during mining. Bronze-age K–Cu humate–oxalate aggregates and Cu carbonates precipitated from pedogenetic fluids as a function of variable redox conditions and a pH value fluctuating around neutral. This sequence of per descensum mineralization with arsenates, humates and carbonates at Serifos, Greece, is of importance in three ways. It offers an insight into the most recent weathering processes of base-metal mineralization in the Aegean Sea region. It gives an overview of mining activities across Europe from Cyprus, the “Cradle of Cu mining”, to Great Britain during the Bronze Age. Also, the physicochemical results obtained from the study of this multistage alteration may be employed to explain the compositional variation under (sub)tropical through temperate climatic conditions in tailings derived from beneficiation of As–Cu ores elsewhere. Keywords: arsenate of Cu–Pb, humate–oxalate, carbonate, Neogene, Bronze Age, supergene, anthropogenic, Serifos, Greece.

Sommaire Suite à la minéralization en fer de type skarn d’âge tardi-miocène à Mega Livadi sur l’île de Serifos, en Grèce, il y eut un épisode de minéralisation hydrothermale en Cu et As dans les calcaires au contact supérieur d’un pluton granodioritique. La minéralisation hypogène, avec pyrite, minéraux du groupe de la tennantite arsenifères et l’arsénopyrite, ont subi une forte altération au cours du Pliocène et du Quaternaire, attribuable aux eaux météoriques descendantes. Nous subdivisons les processus géogéniques

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E-mail address: [email protected]

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et anthropogéniques responsables de cette altération en cinq stades, avec distinctions dans leurs bilans d’éléments, leur Eh et leur pH. Les stades supergènes I à III contiennent un assemblage varié d’oxydes, d’hydroxydes et d’arsenates: stade I (goethite, mélange de minéraux Fe–As–Sb–Cu à grains fins, pharmacosidérite), stade II (beudantite riche en Sb, beudantite riche en terres rares), et stade III (arséniosidérite). Les stades anthropogéniques IV et V se distinguent par la présence de humates et oxalates de K–Cu méconnus (stade IV) et les carbonates de Cu connus malachite et azurite (stage V). On attribue au lessivage chimique causé par les conditions climatiques (sub)tropicales au cours du Miocène tardif et du Pliocène les associations supergènes des stades I à III à Mega Livadi. Au cours de cette altération supergène, la teneur en Fe a diminué, et la teneur en As a augmenté. Des teneurs anormalement élevées en terres rares légères dans la beudantite ont été utilisées comme traceurs “minérostratigraphiques” pour établir une corrélation entre la minéralisation du stade II avec un épisode de formation répandue de latérite dans la région aégéenne au Pliocène. Après une lacune, une nouvelle minéralisation, anthropogénique, a été déclenchée au cours des anciennes activités au début de l’âge de Bronze, dans l’intervalle 3325 à 2890 BC, quand les mineurs se sont mis à exploiter le minerai mou de fer et de cuivre arsenifère à faible profondeur. Cette phase anthropogénique aurait évolué à des conditions climatiques tempérées suite à la ventilation des galleries exploitées. Des agrégats de humates et oxalates de K–Cu et des carbonates de Cu ont précipité à partir de fluides pédogéniques en fonction des conditions redox variables et d’un pH fluctuant autour de la neutralité. Cette séquence de minéralisation per descensum impliquant arsenates, humates et carbonates à Serifos, est importante de trois façons. Elle aide à mieux comprendre les processus les plus récents de lessivage de la minéralisation impliquant des métaux de base dans la région de la mer Égée. Elle fournit une vue d’ensemble des activités d’exploitation minière en Europe, de Chypre, le “berceau des mines de Cu”, jusqu’en Grande-Bretagne à l’âge de Bronze. De plus, les résultats physicochimiques obtenus peuvent servir pour expliquer les variations compositionnelles en passant de conditions (sub)tropicales à tempérées dans les haldes dérivées de l’enrichissement des minerais As–Cu ailleurs.

(Traduit par la Rédaction)

Mots-clés: arsenate de Cu–Pb, humate–oxalate, carbonate, néogène, âge de Bronze, supergène, anthropogénique, Serifos, Grèce.

Introduction Supergene minerals or compounds form in many different settings, for example, natural weathering in a gossan formed at the expense of pre-existing mineralization, and as a coating on artifacts (Llorca & Monchoux 1991, Ettler et al. 2001, Bouzari & Clark 2002, Dill 2008, 2009a, Belogub et al. 2008). Not all of them are generally agreed and accepted as minerals sensu stricto (Nickel 1995). Collectors are anxious to find well-preserved crystals of the Cu carbonates azurite and malachite, but the earthy or massive aggregates of these minerals have rarely attracted the interest of scientists, with the exception of some studies of their stable isotopes by Melchiorre et al. (1999, 2000) or their thermal behavior during manufacturing (Frost et al. 2002). Supergene mineralization has mainly been studied in porphyry copper deposits by Brimhall et al. (1985), Lichtner & Biino (1992), Sillitoe et al. (1996) and Sillitoe (2002), who attempted to use it as a guide to ore. In the Aegean region, Skarpelis & Argyraki (2008) investigated the renowned carbonate-hosted Pb–Zn–Ag deposit at Lavrion, Greece. Ferricretes of this type and base-metal slags have been the object of many investigations, dealing with the metallurgical processes as well as the weathering of these mining artifacts (Hauptmann et al. 1992, Mascaro et al. 1995, Manasse et al. 1991, Manasse & Mellini 2002, Ettler et al. 2001, Dill et al. 2002, Dill 2009a). The present study bridges the gap between mineralogical studies of anthropogenic mining residues (post-mining mineral assemblage) and minerals resulting from descending meteoric waters. The mineralization under study pertains to the large group of

mineral-forming processes triggered by ventilation in underground mines exploiting coal and metals (Dill & Pöllmann 2002, Zodrow 2005, Dill et al. 2008). In the present study, we deal with supergene mineralization (gossan) grading into a post-mining mineralization (this mineralization may be considered “tertiary” because it is found in mining sites and mine waste). In ancient adits of the Mega Livadi mine at Serifos, Greece, a hitherto unknown mineralization composed of Cu–Pb arsenates, Cu humate–oxalates and Cu carbonates was found. Carbonates and humate–oxalates, the latter discovered for the first time in such a context, allow for a precise dating of the mineralizing processes. These geochronological data have wide implications for the archeology and mining history of the Mediterranean region and, in context with a physicochemical study of these oxidized minerals at Mega Livadi, Greece, also provide an insight into the paleoclimate throughout the Neogene and Quaternary in this part of the Mediterranean region.

Archeometallurgical and Geological Setting The Mediterranean region is known as the cradle of copper mining. “Aes cyprium” or “aes cuprum” originated from the Isle of Cyprus which, in antiquity, was among the largest producers of copper. Its mining industry may be traced back to 2760 BC (Greensmith 1994). Cyprus-type VMS deposits have intensively been mined and studied by Robertson & Xenophontos (1993), Little et al. (1999) and Robertson (2002), among others. Little attention has, however, been paid to the

supergene cu–pb mineralization at mega livadi, serifos, greece

minerals that developed from these primary ores during supergene alteration, and to the chemical compounds, in this text also called minerals, left behind after mining and smelting of these base metal ores had come to a halt (Greensmith 1994). This type of supergene alteration is

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also named post-mining mineralization. Other islands in the Mediterranean with deposits exploited for Cu and Fe during ancient times have totally been eclipsed by the archeometallurgical and mineralogical studies focused on Cyprus (Fig. 1). The Mega Livadi deposit on the

Fig. 1. Overview of the study area in the Mediterranean area. a) Sketch map to show the Isle of Serifos in relation to the cradle of Cu mining on the Isle of Cyprus in the Mediterranean area. The numbers in boxes refer to the early periods of Cu–(Fe) mining in Cyprus and Serifos. Other carbonate-hosted base-metal deposits in the Cyclades Archipelago near Lavrion and Thera have been mentioned in the text for their extensive supergene mineralization. They belong to the Attic–Cycladic metallogenic belt sensu Skarpelis (2002). b) Geology of the Isle of Serifos, Greece (modified after Salemink 1985). The framed area denotes the study area in plan view. c) Cross section (for position, see Fig. 1b).The framed area denotes the study area projected onto a W–E transect with altitude expressed in meters. This part of the cross section is exaggerated as to height for the sake of presentation and measures roughly 30 to 40 m in vertical extent.

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Isle of Serifos, Greece, part of the Cyclades archipelago in the Aegean Sea, is a Cu–Fe skarn deposit that was mined for its “soft iron ores” on top of a skarn body (Marinos 1982). Soft iron ore contains much hydrated oxidized iron, and consequently is easy to process. Seven million tonnes of Fe ore were exploited until the shutdown of the mine in 1964. The island of Serifos has a domal architecture dominated by a pluton of hornblende–biotite granodiorite intruded in the late Miocene (Marinos 1951, Altherr & Seidel 1977, Brichau et al. 2008). This pluton was emplaced into a sequence of orthogneisses, schists, amphibolites, quartzites and marbles of the Cycladic blueschist unit, and cross-cuts the regional tectonometamorphic structure (Grasemann et al. 2002). At the northwestern contact of the granodiorite, Ca–Fe–Mg skarns display four contact-metamorphic zones marked by garnet, scapolite, hornblende and actinolite (Salemink 1985) (Fig. 1). Salemink (1985) calculated temperatures of formation on the basis of phase relations and d18O measurements in coexisting minerals. In the country rock surrounding the pluton, skarn formation took place under oxidizing conditions at temperatures as high as 550°C. Hematite–magnetite developed at a temperature around 400°C. According to thermodynamic analyses, the ilvaite-bearing skarns formed under reducing conditions down to a temperature of 300°C. The outermost parts of the intrusive contacts indicate a temperature of formation of 125°C based on d18O determinations on coexisting quartz + calcite. Thermodynamic analyses, based upon the observed mineral parageneses, showed that at Serifos, metasomatism took place under gradually decreasing temperatures and under maintenance of local equilibrium between an Fe-bearing hydrothermal fluid and solids present along the transport channels. The primary mineralization associated with the Ca–Fe–Mg skarn consists of magnetite, hematite, some sphalerite, galena, pyrite, chalcopyrite, fluorite, barite, ankerite and siderite (Marinos 1951). The granodiorite-related mineralization forms part of the Miocene Attic–Cycladic Metallogenic Belt that is terminated in the northwest by the famous

Lavrion carbonate-replacement skarn-type Pb–Ag– Zn deposits and in the southeast by the Thera skarn deposit (Fig. 1) (Skarpelis 2002). Among the supergene minerals, malachite, cuprite and native copper have been documented. Neither the primary ore nor products of its supergene alteration have been investigated in detail. In his overview of ore deposits in Greece, Marinos (1982) reported that 7 million tonnes of iron ore have been mined since ancient times and about 2 million tonnes are still left in place. The ore consists of goethite-rich “limonite” grading between 35 and 48% iron and 1 and 2% manganese. The chemical composition of a soft iron ore typical of the gossan at Mega Livadi is given in Table 1.

Methodology The sampling was performed in galleries located about 60 m above sea level; these galleries tunnel through the gossan of this skarn deposit. Samples were taken from the altered primary ore located in the outermost part of the skarn aureole within the schist and marble units (Fig. 1). No mining records are available on these underground workings. Therefore, only the sampling area can be given in Figure 1. Sampling was carried out along a transect of roughly 30 m along the walls and the roofs, which are unsupported in the galleries. Of the 12 samples taken, those showing conspicuous encrustations were selected for further analyses. Minerals were identified by examination of polished sections, and with standard SEM–EDX and X-ray-diffraction analysis using powder and singlecrystal methods. The description of the newly discovered K–Cu humates is mainly based on results of electron-microprobe analyses (EMPA), energy-dispersive scanning electron microscopy (ESEM) and infrared spectroscopy. Electron-microprobe analyses were carried out using a CAMECA SX100 equipped with five wavelengthdispersive spectrometers and a Princeton Gamma Tech energy-dispersive system. Oxide, phosphate and silicate phases were analyzed at an acceleration voltage of 20 kV and a sample current (on brass) of 20 nA. Natural albite, chromite, kaersutite, almandine, apatite, magnetite, pentlandite, biotite, rutile, rhodonite, galena, as well as synthetic gallium arsenide and pure metals were used as standards. Hand samples were analyzed by X-ray fluorescence spectrometry (XRF) for their major and trace elements. The XRF was run in the conventional mode using beads prepared with borate as flux material. Monitor samples and more than 50 certified reference materials (CRM) were used for the correction procedures. The mean values of the elements under study were listed in Table 1. The minerals can be characterized by the intensity and position of IR absorption bands. Infrared spectroscopy is not suitable for a complete mineralogical assessment, because of the similarity of spectra of the


silicates (overlapping bands). However, some minerals show characteristic mid-IR absorption bands that can be used for mineral identification (e.g., kaolinite, halloysite, carbonates, sulfates, quartz). Infrared spectroscopy thus represents a suitable method complementary to XRD analyses. This is especially true for a precise discrimination of organic compounds that could well “escape” routine analytical methods. To measure the mid-infrared (MIR) range of the spectra, the KBr pellet technique (1 mg sample in 200 mg KBr) was applied. Spectra were collected on a Thermo Nicolet Nexus FTIR spectrometer (beam splitter: KBr, detector DTGS TEC). The resolution was adjusted to 2 cm–1. The XRD patterns were recorded using a Philips X´Pert PW3710 u–2u diffractometer (CuKa radiation, 40 kV and 40 mA), equipped with a 1° divergence slit, a secondary monochromator, a point detector and a sample changer (sample diameter 28 mm). The samples were investigated from 2° to 80° 2u with a step size of 0.02° 2u and a measuring time of 3 s per step. The toploading technique of specimen preparation was used. For the SEM investigation, a FEI Quanta 600 F operated in low-vacuum mode (0.6 mbar) was used. Therefore, sputtering of the samples with gold or carbon is not necessary. The microscope is equipped with the EDX system Genesis 4000 of EDAX. Radiocarbon dating was carried out on Cu carbonate – humate – oxalate samples in the conventional way described by Geyh & Schleicher (1990) at the Leibniz Institute for Applied Geophysics in Hannover. The sample was dissolved with phosphoric acid for CO2 extraction. The 14C age was calibrated using the calibration program CALIB REV. 4.4 (Stuiver & Reimer 1993).

Results Textural and chemical overview of the secondary mineral assemblage Based on visual examination, the mineral encrustations may be subdivided into two principal parts. The top part consists of aggregates of well-crystallized lathand needle-shaped minerals. The basal part, in contact with the wallrock of the stopes, occurs as aggregates of massive to earthy rust-brown minerals. Carbonate and humate–oxalate minerals Specimen taken from the roof and from the walls of the adit at Mega Livadi show lavender-blue aggregates made-up of sprays of acicular minerals developed on rust-brown encrustations (Fig. 2a). Green lath-shaped crystals are scattered between these blue aggregates. The blue mineral aggregates are a mixture of the Cu carbonates azurite and malachite and probable (or poorly defined?) K–Cu humate–oxalates. The carbonate

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and humate–oxalate minerals make up more than half of the assemblage. Azurite: Copper carbonates need to be described in context with these complex humate–oxalate compounds as in places, they are intimately intergrown with the common Cu carbonates. In light of a small peak in the XRD spectrum, the aggregates of the blue mineral were identified as azurite. However, their external morphology is very different from azurite sensu lato (Fig. 2b), and the crystallinity as determined by XRD is poor. For comparison, well-crystallized azurite from the carbonate-hosted Cu deposit at Schwaz–Brixlegg, Austria, is shown (Fig. 2c). These azurite aggregates, dominated by the {001} faces, originated by breakdown of the tennantite–tetrahedrite solid-solution series in the Devonian Schwaz Dolomite (Krismer et al. 2007, 2008). Clear indications for the poorly crystallized carbonate minerals at Mega Livadi can be obtained from IR spectroscopy. Results of electron-mcroprobe analyses (Table 2) of azurite reveal quite constant compositions at 70 wt% CuO, as well as 1.7 wt% ZnO, 0.5 wt% As2O5, with traces of NiO ( oxalate). The relative amounts of humate and oxalate are estimated from IR spectra. Results of electron-microprobe analyses are consistent with K– Cu humate–oxalates composed of 25 wt% CuO and 27 wt% K2O. Zinc, Ca, Fe and Cl may be present in

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Fig. 3. Diagram to show the temporal and spatial relation of the mineral assemblages in the oxidized part of the Mega Livadi Cu–Fe skarn deposit, Greece. Minerals given in small characters have been proven by micro-analytical, SEM–EDX and XRD, minerals in capital letters refer to the primary sulfide–arsenide mineralization whose minerals, excluding pyrite, can only be deduced from the morphology of solution cavities. Chemical compounds given in italics record unknown minerals and mineral aggregates of uncertain composition. The horizontal line denotes the boundary between the early Bronze Age anthropogenic mineralization and the post-late Miocene supergene alteration of the Mega Livadi late-stage skarn mineralization.

small amounts (Table 2). On the basis of morphology and chemical composition, two different types of K– Cu humate–oxalate may be identified (Figs.2e, 5a). Humate I displays parquet-like textures in the BSE image (Fig. 5a), which can be made visible in a threedimensional way under the SEM, where sprays of azurite grew onto these humate aggregates (Fig. 5b). The second type of K–Cu humate (hu II) is intimately intergrown with azurite (Fig. 2e). Both modifications differ significantly from each other in their Cu contents, which is twice as high in humate II intergrown with azurite as in K–Cu humate I. The chemical analyses suggest that part of the humate is converted into some oxalato-cuprates, and the resultant mineral phase may perhaps be the K-dominant analogue of wheatleyite [Na2Cu(C2O4)2•2H2O] (Frost et al. 2008). Arsenate minerals Ca–Fe arsenate: A Ca–Fe arsenate yielding analytical totals ranging from 88 to 90 wt% is the most common

arsenate in the rusty-brown encrustations underneath the Cu humate–carbonate coating. Together with beudantite-group minerals, it forms colloform aggregates (Fig. 5c). At Mega Livadi, these phases may also contain Sb ( Cu oxalate) >> Cu carbonate. The oxalate state is poorly represented in the Mediterranean area, probably because of a limited supply of organic material, which


is prevalent under temperate humid conditions or in case of a constant supply with faunal remains. Both conditions are not fulfilled in the abandoned galleries at Mega Livadi. These sequences of supergene mineralization caused by descending meteoric waters and anthropogenic mineralization composed of arsenates, humates and carbonates at Serifos, Greece, may also be representative of the physicochemical variation in impoundments and tailings derived from beneficiation of As–Cu ores under (sub)tropical (through temperate) climatic conditions (Dill et al. 2002).

Acknowledgements We are indebted to J. Lodziak, who conducted the electron-microprobe analyses, and M. Hein, who carried out the IR spectroscopic analyses. Chemical analyses were carried out in the laboratory of BGR by F. Korte. The preparation of samples and SEM analyses were performed by I. Bitz and D. Klosa. D. Weck carried out the XRD analyses. Single-crystal XRD analysis was done by T. Gesing (Hannover University), and studies of the organometallic compounds were performed by R. Ellerbrock (Institut für Bodenlandschaftsforschung, Muencheberg). We express our gratitude to two anonymous referees. We extend our gratitude also to Associate Editor Gemma R. Olivo and to Robert F. Martin for their comments and for their editorial handling.

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Received April 20, 2009, revised manuscript accepted December 26, 2009.