Rosia Poieni copper deposit,Apuseni Mountains,Romania: advanced argillic overprint of a porphyry system

The Rosia Poieni deposit is the largest porphyry copper deposit in the Apuseni Mountains, Romania. Hydrothermal alteration and mineralization are related to the Middle Miocene emplacement of a subvolcanic body, the Fundoaia microdiorite. Zonation of the alteration associated with the porphyry copper deposit is recognized from the deep and central part of the porphyritic intrusion towards shallower and outer portions. Four alteration types have been distinguished: potassic, phyllic, advanced argillic, and propylitic. Potassic alteration affects mainly the Fundoaia subvolcanic body. The andesitic host rocks are altered only in the immediate contact zone with the Fundoaia intrusion. Mg-biotite and K-feldspar are the main alteration minerals of the potassic assemblage, accompanied by ubiquitous quartz; chlorite, and anhydrite are also present. Magnetite, pyrite, chalcopyrite and minor bornite, are associated with this alteration. Phyllic alteration has overprinted the margin of the potassic zone, and formed peripheral to it. It is characterized by the replacement of almost all early minerals by abundant quartz, phengite, illite, variable amounts of illite-smectite mixed-layer minerals, minor smectite, and kaolinite. Pyrite is abundant and represents the main sulfide in this alteration zone. Advanced argillic alteration affects the upper part of the volcanic structure. The mineral assemblage comprises alunite, kaolinite, dickite, pyrophyllite, diaspore, aluminium-phosphate-sulphate minerals (woodhouseite-svanbergite series), zunyite, minamyite, pyrite, and enargite (luzonite). Alunite forms well-developed crystals. Veins with enargite (luzonite) and pyrite in a gangue of quartz, pyrophyllite and diaspore, are present within and around the subvolcanic intrusion. This alteration type is partially controlled by fractures. A zonal distribution of alteration minerals is observed from the centre of fractures outwards with: (1) vuggy quartz; (2) quartz + alunite; (3) quartz + kaolinite ± alunite and, in the deeper part of the argillic zone, quartz + pyrophyllite + diaspore; (4) illite + illite-smectite mixed-layer minerals ± kaolinite ± alunite, and e) chlorite + albite + epidote. Propylitic alteration is present distal to all other alteration types and consists of chlorite, epidote, albite, and carbonates. Mineral parageneses, mineral stability fields, and alteration mineral geothermometers indicate that the different alteration assemblages are the result of changes in both fluid composition and temperature of the system. The alteration minerals reflect cooling of the hydrothermal system from >400 °C (biotite), to 300–200 °C (chlorite and illite in veinlets) and to lower temperatures of kaolinite, illite-smectite mixed layers, and smectite crystallization. Hydrothermal alteration started with an extensive potassic zone in the central part of the system that passed laterally to the propylitic zone. It was followed by phyllic overprint of the early-altered rocks. Nearly barren advanced argillic alteration subsequently superimposed the upper levels of the porphyry copper alteration zones. The close spatial association between porphyry mineralization and advanced argillic alteration suggests that they are genetically part of the same magmatic-hydrothermal system that includes a porphyry intrusion at depth and an epithermal environment of the advanced argillic type near the surface.Editorial handling: B. Lehmann     

Petrology and alteration geochemistry of the epithermal Balya Pb-Zn-Ag deposit,NW Turkey

The 1.5 km-large hydrothermal system of Balya is characterized by three alteration styles which from the outer halo towards the center are: (i) propylitic alteration with the hydrothermal mineral assemblage of calcite-daphnite-albite-epidote-quartz-pyrite; (ii) argillic/phyllic alteration with the hydrothermal mineral assemblage of sericite/muscovite-kaolinite-rutile-quartz ± pyrite; (iii) advanced argillic alteration with the hydrothermal mineral assemblage of alunite-jarosite-kaolinite-quartz-sericite ± pyrite. Hornblende andesite is the protolith of the hydrothermal alteration system. Enrichment in Si, Sb and Rb, and depletion in Na, Ca, Mg, Fe, Mn, P, Ba, Sr, and Zn distinguishes the argillic/phyllic and advanced alteration types from propylitic alteration and the unaltered hornblende andesite protolith. REE distribution patterns indicate an essentially immobile behaviour of REEs during the alteration cycle. K-Ar age data for unaltered and hydrothermally altered rocks define a synchronous age of 25.3 ± 1.2 Ma for both igneous and hydrothermal activity.     

Fluid evolution,wallrock alteration,and ore mineralization associated with the Rodalquilar epithermal gold-deposit in southeast Spain

At Rodalquilar gold mineralization is found in Late Tertiary volcanic rocks of the Sierra del Cabo de Gata and is related to a caldera collapse. Radial and concentric faults were preferred sites for gold deposition. Hydrothermal activity produced a specific alteration zoning around gold-bearing vein structures, grading from an innermost advanced argillic via an argillic into a more regionally developed propylitic zone. Advanced argillic alteration with silica, pyrophyllite, alunite, and kaolinite extends down to several hundred m indicating a hypogene origin. High-grade gold mineralization in vein structures is confined to the near-surface part of the advanced argillic alteration. Fine-grained gold is associated with hematite, jarosite, limonite, or silica. At a depth of about 120 m, the oxidic ore assemblage grades into sulfide mineralization with pyrite and minor chalcopyrite, covellite, bornite, enargite, and tennantite. Two types of fluids from different sources were involved in the hydrothermal system. Overpressured and hypersaline fluids of presumably magmatic origin initiated the hydrothermal system. Subsequent hydrothermal processes were characterized by the influx of low-salinity solutions of probable marine origin and by interactions between both fluids. Deep-reaching, advanced argillic alteration formed from high-salinity fluids with 20–30 equiv. wt% NaCl at about 225°C. Near-surface gold precipitation and silification are related to fluids with temperatures of about 175°C and 3–4 equiv. wt% NaCl. Gold was transported as Au(HS) ₂ ^– , and precipitation resulted from boiling with a concomitant decrease in temperature, pressure, and pH and an increase in fO₂. All features of the Rodalquilar gold deposit reveal a close relationship to acid-sulfate-type epithermal gold mineralization.     

Hydrothermal Alteration and Cu-Au Mineralization at Nena High Sulfidation-type Deposit, Frieda River, Papua New Guinea

Abstract. The Nena Cu‐Au deposit, located in the Frieda River mineral district of northwestern mainland Papua New Guinea, is a composite structurally‐lithologically controlled high sulfidation (HS) system. Its hydrothermal alteration and Cu‐Au mineralization are presented in this paper. Initially propylitized andesitic volcanics veined by epithermal quartz were pervasively superimposed by zoned HS alteration. The zonation grades from vuggy silica core to sulfur‐rich, pyritic silica‐alunite halo followed by pyrophyllite‐dickite‐kaolinite interval and finally to thin illite‐smectite margin, suggesting progressive decrease in temperature and increase in pH. This zonation is enveloped by chlorite‐epidote‐calcite‐gypsum alteration. The acid altered rocks were then invaded by multiple phases of pyrite, subsequently crosscut by quartz, vein alunite and barite. Then sequential deposition of bladed covellite, enargite, luzonite and stibioluzonite occurred from the NW to the SE portions of the deposit, forming a zonation suggestive of progressive decrease in temperature, sulfur fugacity and sulfidation stage. Most ore mineralization occurs in the vuggy silica core. Gold mineralization commenced from the transition of enargite to luzonite and continued throughout the stibioluzonite stage. Associated with gold deposition are Au‐rich pyrite, tennantite‐tetrahedrite, chalcopyrite‐bornite, native tellurium, electrum, calaverite, bismuthinite and galena. Native sulfur occupied the remaining cavities and represents the waning stage of the hydrothermal system. Fluid inclusions studies distinguished magmatic (>300–350d?C, 9–15 wt% NaCl equiv.) and meteoric (<150–200d?C, 1–2 wt% NaCl equiv.) fluids (Holzberger et al., 1996). Temperatures and salinities of fluid inclusions from barite associated with Cu sulfides show a general decrease from NW (330d?C, 9–15 wt% NaCl equiv.) to SE (172d?C, 10 wt% NaCl equiv.) parts of the deposit, indicating gradual entrainment of ground water (Hitchman and Espi, 1997). Interaction of magmatic fluids with meteoric water accompanied by changes in temperature, salinity, acidity and oxidation state of the resultant fluids is interpreted to have been the main cause of metal precipitation. Finally, supergene processes generated Au zone with an underlying chalcocite‐covellite‐digenite blanket over the primary sulfides at depth. Gold occurs as lattice constituent in scorodite, limonite‐goethite and jarosite. Chalcocite is more abundant and widespread than other Cu sulfides. Acidic fluids deposited powdery alunite and kaolinite, vein alunite and amorphous silica. Weakly secondary biotite‐quartz altered porphyry located below the known HS Cu‐Au deposit contains chalcopyrite‐bornite and is overprinted by quartz‐alunite‐pyro‐phyllite‐pyrite assemblage. This feature indicates close temporal, spatial and genetic relation between the two deposit types.     

Telescoped porphyry Cu-Mo-Au mineralisation, advanced argillic alteration and quartz-sulphide-gold-anhydrite veins in the Thames District, New Zealand

Porphyry Cu-Mo-Au mineralisation with associated potassic and phyllic alteration, an advanced argillic alteration cap and epithermal quartz-sulphide-gold-anhydrite veins, are telescoped within a vertical interval of 400-800 m on the northeastern margin of the Thames district, New Zealand. The geological setting is Jurassic greywacke basement overlain by Late Miocene andesitic-dacitic rocks that are extensively altered to propylitic and argillic assemblages. The porphyry Cu-Mo-Au mineralisation is hosted in a dacite porphyry stock and surrounding intrusion breccia. Relicts of a core zone of potassic K-feldspar-magnetite-biotite alteration are overprinted by phyllic quartz-sericite-pyrite or intermediate argillic chlorite-sericite alteration assemblages. Some copper occurs in quartz-magnetite-chlorite-pyrite-chalcopyrite veinlets in the core zone, but the bulk of the copper and the molybdenum are associated with the phyllic alteration as disseminated chalcopyrite and as molybdenite-sericite-carbonate veinlets. The advanced argillic cap has a quartz-alunite-dickite core, which is enveloped by an extensive pyrophyllite-diaspore-dickite-kaolinite assemblage that overlaps with the upper part of the phyllic alteration zone. Later quartz-sphalerite-galena-pyrite-chalcopyrite-gold-anhydrite-carbonate veins occur within and around the margins of the porphyry intrusion, and are associated with widespread illite-carbonate (argillic) alteration. Multiphase fluid inclusions in quartz stockwork veins associated with the potassic alteration trapped a highly saline (50-84 wt% NaCl equiv.) magmatic fluid at high temperatures (450 to >600 °C). These hypersaline brines were probably trapped at a pressure of about 300 bar, corresponding to a depth of 1.2 km under lithostatic conditions. This shallow depth is consistent with textures of the host dacite porphyry and reconstruction of the volcanic stratigraphy. Liquid-rich fluid inclusions in the quartz stockwork veins and quartz phenocrysts trapped a lower salinity (3-20 wt% NaCl equiv.), moderate temperature (300-400 °C) fluid that may have caused the phyllic alteration. Fluid inclusions in the quartz-sphalerite-galena-pyrite-chalcopyrite-gold-anhydrite-carbonate veins trapped dilute (1-3 wt% NaCl equiv.) fluids at 250 to 320 °C, at a minimum depth of 1.0 km under hydrostatic conditions. Oxygen isotopic compositions of the fluids that deposited the quartz stockwork veins fall within the 6 to 10‰ range of magmatic waters, whereas the quartz-sulphide-gold-anhydrite veins have lower '¹⁸O_water values (-0.6 to 0.5‰), reflecting a local meteoric water (-6‰) influence. A '¹⁸O versus 'D plot shows a trend from magmatic water in the quartz stockwork veins to a near meteoric water composition in kaolinite from the advanced argillic alteration. Data points for pyrophyllite and the quartz-sulphide-gold-anhydrite veins lie about midway between the magmatic and meteoric water end-member compositions. The spatial association between porphyry Cu-Mo-Au mineralisation, advanced argillic alteration and quartz-sulphide-gold-anhydrite veins suggests that they are all genetically part of the same hydrothermal system. This is consistent with K-Ar dates of 11.6-10.7 Ma for the intrusive porphyry, for alunite in the advanced argillic alteration, and for sericite selvages from quartz-gold veins in the Thames district.     

Hydrothermal Alteration of the Saplica Volcanic Rocks,Sebinkarahisar, Turkey

A widespread, intense hydrothermal alteration zone has developed in the Cretaceous Saplica volcanics as a result of the intrusion of Late Cretaceous-Paleocene granitoids. The propylitic, phyllitic (sericitic), and argillic alteration along with hematite, silica polymorphs, and two types of tourmaline mineralization developed under a wide range of Eh and pH conditions.

Alunite, kaolinite, and silica are abundant in the argillic alteration, whereas sericite dominates in the phyllic alteration. Most of the major alunite deposits are located along the periphery of the Saplica volcanic rocks and in addition contain alunite, kaolinite + quartz ± opal ± cristobalite. Illite and pyrite, barite, and gypsum also occur in small amounts.

Major and trace elements are concentrated in, or were leached from, the volcanic rocks, depending upon the alteration types. In general, Al + K and Mg + Ca + Fe were enriched in the alunitic + sericitic and propylitic alteration types, respectively. On the other hand, Ca, Mg, and Fe were leached during argillic alteration, and Fe was concentrated in hematite formation. Strong leaching of Na was determined for alteration types. Silica generally decreased in argillitic (kaolinitic and alunitic) alteration zones. Most trace elements were mobile during hydrothermal alteration. Y, Sc, Mo, Cr, Co, Ni, and Zn tend to be mobile in acid aqueous systems, and thus are nearly absent in these alunitic alteration zones. In the surrounding kaolinitic envelope, these elements are present at background (average) or slightly higher concentrations. Rb and Sr contents are high in the alunitic and kaolinitic zones. Barium is highest near the alunite zone because of the relative insolubility of barite in acidic solutions. Pb and Cu contents increase in the propylitic zone. Such hydrothermal alteration zones can be used effectively in the exploration and evaluation of mineral resources of the eastern Black Sea region.     

Mineral Paragenesis, Fluid Inclusions and Sulfur Isotope Systematics of the Lepanto Far Southeast Porphyry Cu-Au Deposit, Mankayan, Philippines

Abstract: The Lepanto Far Southeast porphyry Cu‐Au deposit is located beneath and to the southeast of the Lepanto enargite‐luzonite Cu–Au deposit in Mankayan, Benguet Province, Philippines. The principal orebody consists of potassic alteration subjected to partial retrograde chlorite alteration that rims stock‐work of quartz‐anhydrite veinlets. Fluid inclusions found in stockwork quartz and anhydrite in the biotitized orebody center are dominated by polyphase inclusions that homogenize at temperatures of >500C. Sulfur isotopic thermometry applied to the sulfides‐anhydrite pairs suggests around 500C. The principal ore minerals associated with quartz‐anhydrite stockworks are chalcopyrite and pyrite with minor bornite and Bi–Te–bearing tennantite, with trace of native gold. Rounded pyrite grains appear fractured and corroded and are interpreted as remnants of primary intermediate solid solution + pyrite assemblage. A breccia pipe truncates the deposit. Mineralization in the breccia pipe is brought by quartz‐anhydrite veinlets and infilling in the interstices between clasts. Chalcopyrite‐Au mineralization associated with molybdenite is recognized in the deeper zone in the breccia pipe. Fluid inclusion microthermometry on polyphase inclusions in veinlet quartz as well as sulfur isotope thermometry applied for the pair of anhydrite and sulfides suggests >450C. Fluid inclusions in veinlet quartz and anhydrite in the fringe advanced argillic alteration are chiefly composed of coexisting liquid‐rich inclusions and gas‐rich inclusions, in addition to coexisting polyphase inclusions and gas‐rich inclusions. These inclusions exhibit a wide range of homogenization temperatures, suggesting heterogeneous entrapping in the two‐fluid unmixing region. Sulfur isotopes of aqueous sulfide and sulfate exhibit a general trend from the smallest fractionation pairs (about 11%) in the biotitized orebody center to the largest fractionation (about 25%) pairs in the fringe advanced argillic alteration, suggesting a simple evolution of hydrothermal system. The slopes of arbitrary regression lines in δ³⁴S versus ³⁴S[SO₄ = –H₂S] diagram suggest that the abundance ratio of aqueous sulfate to sulfide in the hydrothermal fluid has been broadly constant at about 1:3 through temperature decrease. The intersection of these two regression lines at the δ³⁴S axis indicates that the bulk δ³⁴S is about +6%. Thus, the Lepanto FSE deposit is a further example which confirms enrichment in ³⁴S in the hydrous intermediate to silicic magmas and associated magmatic hydrothermal deposits in the western Luzon arc.     

Evolution of Hydrothermal System at the Dizon Porphyry Cu-Au Deposit, Zambales, Philippines

Abstract. Evolution of hydrothermal system from initial porphyry Cu mineralization to overlapping epithermal system at the Dizon porphyry Cu‐Au deposit in western central Luzon, Zambales, Philippines, is documented in terms of mineral paragen‐esis, fluid inclusion petrography and microthermometry, and sulfur isotope systematics. The paragenetic stages throughout the deposit are summarized as follows; 1) stockwork amethystic quartz veinlets associated with chalcopyrite, bornite, magnetite and Au enveloped by chlorite alteration overprinting biotite alteration, 2) stockwork quartz veinlets with chalcopyrite and pyrite associated with Au and chalcopyrite and pyrite stringers in sericite alteration, 3) stringer quartz veinlets associated with molybdenite in sericite alteration, and 4) WNW‐trending quartz veins associated with sphalerite and galena at deeper part, while enargite and stibnite at shallower levels associated with advanced argillic alteration. Chalcopyrite and bornite associated with magnetite in quartz veinlet stockwork (stage 1) have precipitated initially as intermediate solid solution (iss) and bornite solid solution (bnss), respectively. Fluid inclusions in the stockwork veinlet quartz consist of gas‐rich inclusions and polyphase inclusions. Halite in polyphase inclusions dissolves at temperatures ranging from 360d?C to >500d?C but liquid (brine) and gas (vapor) do not homogenize at <500d?C. The maximum pressure and minimum temperature during the deposition of iss and bnss with stockwork quartz veinlets are estimated to be 460 bars and 500d?C. Fluid inclusions in veinlet stockwork quartz enveloped in sericite alteration (stage 2) consist mainly of gas‐rich inclusions and polyphase inclusions. In addition to the possible presence of saturated NaCl crystals at the time of entrapment of fluid inclusions that exhibit the liquid‐vapor homogenization temperatures lower than the halite dissolution temperatures in some samples, wide range of temperatures of halite dissolution and liquid‐vapor homogenization of polyphase inclusions from 230d?C to >500d?C and from 270d?C to >500d?C, respectively, suggests heterogeneous entrapment of gaseous vapor and hypersaline brine. The minimum pressure and temperature are estimated to be about 25 bars and 245d?C. Fluid inclusions in veinlet quartz associated with molybdenite (stage 3) are dominated by gas‐rich inclusions accompanied with minor liquid‐rich inclusions that homogenize at temperatures between 350d?C and 490d?C. Fluid inclusions in vuggy veinlet quartz associated with stibnite (stage 4) consist mainly of gas‐rich inclusions with subordinate polyphase inclusions that do not homogenize below 500d?C. Fluid inclusions in veinlet quartz associated with galena and sphalerite (stage 4) are composed of liquid‐rich two‐phase inclusions, and they homogenize into liquid phase at temperatures ranging widely from 190d?C to 300d?C (suggesting boiling) and the salinity ranges from 1.0 wt% to 3.4 wt% NaCl equivalent. A pressure of about 15 bars is estimated for the dilute aqueous solution of 190d?C from which veinlet quartz associated with galena and sphalerite precipitated. In addition to a change in temperature‐pressure regime from lithostatic pressure during the deposition of iss and bnss with stockwork quartz veinlets to hydrostatic pressure during fracture‐controlled quartz veinlet associated with galena and sphalerite, a decrease in pressure is supposed to have occurred due to unroofing or removal of the overlying piles during the temperature decrease in the evolution of hydrothermal system. The majority of the sulfur isotopic composition of sulfides ranges from ±0 % to +5 %. Sulfur originated from an iso‐topically uniform and homogeneous source, and the mineralization occurred in a single hydrothermal system.     

The Mantos Blancos copper deposit: an upper Jurassic breccia-style hydrothermal system in the Coastal Range of Northern Chile

The Upper Jurassic Mantos Blancos copper deposit (500 Mt at 1.0% Cu), located in the Coastal Range of northern Chile, displays two superimposed hydrothermal events. An older phyllic alteration probably related to felsic magmatic–hydrothermal brecciation at ∼155 Ma, and younger (141–142 Ma) potassic, propylitic, and sodic alterations, coeval with dioritic and granodioritic stocks and sills, and dioritic dikes. Main ore formation is genetically related to the second hydrothermal event, and consists of hydrothermal breccias, disseminations and stockwork-style mineralization, associated with sodic alteration. Hypogene sulfide assemblages show distinctive vertical and lateral zoning, centered on magmatic and hydrothermal breccia bodies, which constitute the feeders to mineralization. A barren pyrite root zone is overlain by pyrite-chalcopyrite, and followed upwards and laterally by chalcopyrite-digenite or chalcopyrite-bornite. The assemblage digenite–supergene chalcocite characterizes the central portions of high-grade mineralization in the breccia bodies. Fluid inclusions show evidence of boiling during the potassic and sodic alteration events, which occurred at temperatures around 450–460°C and 350–410°C, and salinities between 3–53 and 13–45 wt% NaCl eq., respectively. The hydrothermal events occurred during episodic decompression due to fluid overpressuring, hydrofracturing, and sharp changes from lithostatic to hydrostatic conditions. Sulfur isotope results of hypogene sulfide minerals fall in a narrow range around 0 per mil, suggesting a dominance of magmatic sulfur. Carbon and oxygen isotopic data of calcites from propylitic alteration suggest a mantle-derived carbon and oxygen isotope fractionation due to low-temperature alteration.     

Constraints of stable isotopes on the origin of alunite from advanced argillic alteration systems in Bulgaria

Voluminous areas of advanced argillic alteration (AAA) constitute major exploration targets for surficial Cu–Au epithermal and potentially underlying porphyry-type deposits. In Bulgaria, more than 30 alunite occurrences are recognised, few of them being associated with a mineralised system. A mineralogical study combined with a stable isotopic (O, H, S) study has been carried out on nine alunite occurrences of advanced argillic zones hosted by volcanic rocks of Late Cretaceous age in the Srednogorie belt and of Oligocene age in the Rhodopes belt. This work was realised in order to constrain the origin of alunite and to define criteria to discriminate alunite from ore deposits and alunite from large barren alteration systems.Mineralogy of the nine occurrences consists of alunite + quartz + minor alumino-phospho-sulphates, associated with more or less kaolinite, dickite, pyrophyllite, diaspore and zunyite, depending on formation temperature. Alunite generally occurs as tabular crystals but is also present as fine-crystalline pseudocubic phases at Boukovo and Sarnitsa, in Eastern Rhodopes. In the advanced argillic alterations associated with economic ore, the presence of zunyite in the deeper parts indicates acid–fluorine–sulphate hydrothermal systems, whereas it is absent in uneconomic and barren advanced argillic alteration. All occurrences are formed at temperatures between 200 and 300 °C.(H, O, S) isotopic signatures of alunite combined with mineralogical features from all the studied occurrences, whatever their type, show characteristics of magmatic-hydrothermal systems. Sulphur data indicate essentially a magmatic origin for sulphur. Oxygen and hydrogen data suggest that hydrothermal fluids result from a mixing between magmatic fluids and an external component, which is identified as seawater-derived fluids or meteoric water in the vicinity of a sea. In most of the alunite occurrences, magmatic fluids are dominant and H₂S/SO₄ ratios are estimated to be higher than 2. Two exceptions exist in the Rhodopes. At Boukovo and Sarnitsa, where the estimated formation temperatures of alunite are the lowest, the external fluids are dominant and H₂S/SO₄ratios are estimated to be lower than or close to 1.At this stage of the work, the mineralogical and isotopic criteria do not enable a clear distinction between economic and uneconomic systems. However, some features are common in the economic ore deposits: the presence of zunyite in the deeper part of the system, the relatively high temperatures suggested by the zunyite + pyrophyllite + alunite + diaspore assemblages, the (O, H, S) signature of alunite, which is characteristic of dominant magmatic–hydrothermal acid–sulphate–fluorine systems.     

Zonation of Sulfate and Sulfide Minerals and Isotopic Composition in the Far Southeast Porphyry and Lepanto Epithermal Cu–Au Deposits,Philippines

The world‐class Far Southeast (FSE) porphyry system, Philippines, includes the FSE Cu–Au porphyry deposit, the Lepanto Cu–Au high‐sulfidation deposit and the Victoria–Teresa Au–Ag intermediate‐sulfidation veins, centered on the intrusive complex of dioritic composition. The Lepanto and FSE deposits are genetically related and both share an evolution characterized by early stage 1 alteration (deep FSE potassic, shallow Lepanto advanced argillic‐silicic, both at ~1.4 Ma), followed by stage 2 phyllic alteration (at ~1.3 Ma); the dominant ore mineral deposition within the FSE porphyry and the Lepanto epithermal deposits occurred during stage 2. We determined the chemical and S isotopic composition of sulfate and sulfide minerals from Lepanto, including stage 1 alunite (12 to 28 permil), aluminum–phosphate–sulfate (APS) minerals (14 to 21 permil) and pyrite (?4 to 2 permil), stage 2 sulfides (mainly enargite–luzonite and some pyrite, ?10 to ?1 permil), and late stage 2 sulfates (barite and anhydrite, 21 to 27 permil). The minerals from FSE include stage 2 chalcopyrite (1.6 to 2.6 permil), pyrite (1.1 to 3.4 permil) and anhydrite (13 to 25 permil). The whole‐rock S isotopic composition of weakly altered syn‐mineral intrusions is 2.0 permil. Stage 1 quartz–alunite–pyrite of the Lepanto lithocap, above about 650 m elevation, formed from acidic condensates of magmatic vapor at the same time as hypersaline liquid formed potassic alteration (biotite) near sea level. The S isotopic composition of stage 1 alunite–pyrite record temperatures of approximately 300–400°C for the vapor condensate directly over the porphyry deposit; this cooled to <250°C as the acidic condensate flowed to the NW along the Lepanto fault where it cut the unconformity at the top of the basement. Stage 1 alunite at the base of the advanced argillic lithocap over FSE contains cores of APS minerals with Sr, Ba and Ca; based on back‐scattered electron images and ion microprobe data, these APS minerals show a large degree of chemical and S‐isotopic heterogeneity within and between samples. The variation in S isotopic values in these finely banded stage 1 alunite and APS minerals (16 permil range), as well as that of pyrite (6 permil range) was due largely to changes in temperature, and perhaps variation in redox conditions (average ~ 2:1 H₂S:SO₄). Such fluctuations could have been related to fluid pulses caused by injection of mafic melt into the diorite magma chamber, supported by mafic xenoliths hosted in diorite of an earlier intrusion. The S isotopic values of stage 2 minerals indicate temperatures as high as 400°C near sea level in the porphyry deposit, associated with a relatively reduced fluid (~10:1 H₂S:SO₄) responsible for deposition of chalcopyrite. Stage 2 fluids were relatively oxidized in the Lepanto lithocap, with an H₂S:SO₄ ratio of about 4. The oxidation resulted from cooling, which was caused by boiling during ascent and then dilution with steam‐heated meteoric water in the lithocap. This cooling also resulted in the sulfidation state of minerals increasing from chalcopyrite stability in the porphyry deposit to that of enargite in the lithocap‐hosted high‐sulfidation deposit. The temperature at the base of the lithocap during stage 2 was ≥300°C, cooling to <250°C within the main lithocap, and about 200°C towards the limit of the Lepanto orebody, approximately 2 km NW of the porphyry deposit. Approximate 300°C and 200°C isotherms, estimated from S isotopic and fluid inclusion temperatures during stage 1 and stage 2, shifted towards the core of the FSE porphyry deposit with time. This general retreat in isotherms was more than 500 m laterally within Lepanto and 500 m vertically within FSE as the magmatic–hydrothermal system evolved and collapsed over the magmatic center. During this evolution, there is also evidence recorded by large S isotopic variations in individual crystals for sharp pulses of higher temperature, relatively reduced fluid injected into the porphyry deposit.     

Geothermometry, geochronology, and mass transfer associated with hydrothermal alteration of a rhyolitic hyaloclastite from Ponza Island, Italy

A rhyolitic hyaloclastite from Ponza Island, Italy, was hydrothermally altered, producing four distinct alteration zones based on X-ray diffraction mineralogy and field textures: (1) nonpervasive argillic zone; (2) propylitic zone; (3) silicic zone; and (4) sericitic zone. The unaltered hyaloclastite is volcanic breccia with clasts of vesiculated obsidian in a matrix of predominantly pumice lapilli. Incomplete alteration of the hyaloclastite resulted in the nonpervasive argillic zone, characterized by smectite and disordered opal-CT. The other three zones exhibit more complete alteration of the hyaloclastite. The propylitic zone is characterized by mixed-layer illite-smectite (I-S) with 10 to 85% I, mordenite, opal-C, and authigenic K-feldspar (akspar). The silicic zone is characterized by I-S with ≥90% I, pure illite, quartz, akspar, and occasional albite. The sericitic zone consists primarily of I-S with ≥66% I, pure illite, quartz, and minor akspar and pyrite. K/Ar dates of I-S indicate hydrothermal alteration occurred at 3.38 ± 0.08 Ma.Oxygen isotope compositions of I-S systematically decrease from zones 1 to 4. In the argillic zone, smectite has δ¹⁸O values of 21.7 to 22.0‰ and I-S from the propylitic, silicic, and sericitic zones ranges from 14.5 to 16.3‰, 12.5 to 14.0‰, and 8.6 to 11.9‰, respectively. δ¹⁸O values for quartz from the silicic and sericitic zones range from 12.6 to 15.9‰. By use of isotope fractionation equations and data from authigenic quartz-hosted primary fluid inclusions, alteration temperatures ranged from 50 to 65°C for the argillic zone, 85 to 125°C for the propylitic zone, 110 to 210°C for the silicic zone, and 145 to 225°C for the sericitic zone. Fluid inclusion data and calculated δ¹⁸O_water values indicate that hydrothermal fluids were seawater dominated.Mass-transfer calculations indicate that hydrothermal alteration proceeded in a relatively open chemical system and alteration in the sericitic zone involved the most extensive loss of chemical species, especially Si. Systematic gains in Mg occur in all alteration zones as a result of I-S clay mineral formation, and systematic losses of Na, Ca, and K occur in most zones. With the exception of Ca, calculations of mass transfer associated with hydrothermal alteration on Ponza agree with chemical fluxes observed in laboratory experiments involving hydrothermal reactions of rhyolite and seawater. The anomalous Ca loss at Ponza may be due to hydrothermal formation of anhydrite and later low-temperature dissolution. On the basis of Mg enrichments derived from circulating seawater, we estimate the following minimum water/rock ratios: 9, 3, 6, and 9 for the argillic, propylitic, silicic, and sericitic zones, respectively. Hydrothermal fluid pH for the propylitic and silicic zones was neutral to slightly basic and relatively acidic for the sericitic zone as a result of condensation of carbonic and perhaps other acids.     

Gold Abundance and Stable Isotopes (H, O, S) in Hydrothermal Alteration Zones of Gasa Island (Gasado), Korea

Geology of the Gasa Island (Gasado), Korea, consists mainly of tuffaceous rocks, rhyolite and andesitic rocks related to Cretaceous volcanic activity. These rocks are hydrothermally altered, and are classified into the following four alteration zones based on the alteration mineral assemblages: advanced argillic alteration (alunite‐pyrophyllite‐kaolinite‐pyrite); sericitic alteration (sericite‐kaolinite‐quartz); propylitic alteration (quartz‐chlorite‐carbonate‐pyrite); and silicified zones. Alunite in the advanced argillic zone occurred in two types; a massive or disseminated type and a vein type. Most of the massive or disseminated alunites are ≥50 μm in size, whereas the size of vein alunites is <20–30 μm. Alunite grain size is greater in the central part of disseminated or massive alunite, while it is smaller toward the margins. The gold content of each alteration zone is 21–2900 ppb, 15–88 ppb, 57–1730 ppb, and 2–231 ppb, respectively. The gold content of quartz veins developed in the alteration zones is 39–715 ppb. Gold is enriched in the minerals and rocks around faults and fissures, and is strongly concentrated in the advanced argillic alteration zone around faults. Hydrothermal solutions traveling along the fracture systems might be responsible for the comparatively high gold content in the study area. δ³⁴S of alunites occurring in the advanced argillic alteration zone range from +16.5 to +3.9‰, although most are in a comparatively narrow range from +8.6 to +5.2‰. There is no difference between disseminated or massive and vein alunites. The δ³⁴S of pyrites in the advanced argillic alteration zone are from +4.8 to ?2.9‰. Oxygen and hydrogen isotope values of alunites are from +8.5 to 0‰ and from ?59.6 to ?97.3‰, respectively. With an assumed temperature of 200°C, δD and δ¹⁸O of hydrothermal solutions calculated for alunites are from ?53.6 to ?91.3‰, and from ?2.4 to ?8.1 for massive or disseminated alunites and from ?6.6 to ?10.9‰ for vein alunites, respectively. These data suggest that meteoric water dominated during the alunite formation. Isotopic data, geological setting, mineralogy, size of alunite and pure alunite composition (K end member) indicate that alunites of the study area were formed in the steam‐heated environment of acid sulfate alteration.     

Comparison between the fluid characteristics of the Rodalquilar and two neighbouring epithermal gold deposits in Spain

The operating Rodalquilar gold deposit and the abandoned Triunfo and Maria Josefa gold mines are located within the Sierra del Cabo de Gata volcanic field some 40 km east of Almeria in SE Spain. While the gold mineralization at Rodalquilar is mainly controlled by caldera-tectonics, vein structures at Triunfo and Maria Josefa are not. Wall-rock alteration at Triunfo and Maria Josefa is characterized by argillic alteration (illite/sericite, kaolinite). The alteration zonation around the gold-mineralized vein structures at Rodalquilar ranges from advanced argillic alteration (porous quartz, alunite, pyrophyllite, dickite) over argillic alteration into a regionally developed propylitization. Fluid inclusion studies from all three mines indicate that gold was deposited from low-salinity fluids (2–5 wt.% NaCl equivalent) between 170° and 250 °C. However, the hydrothermal system at Rodalquilar was fed by a second fluid source. High-salinity, halite and/or sylvite-bearing, liquid-rich, and vapour-dominated, CO₂-bearing fluid inclusions are assumed to be of magmatic origin. High sulfidation ore mineral assemblages at depth (covellite, enargite, tennantite) and part of the advanced argillic alteration can be related to these fluids. Thus, part of those features which attribute the Rodalquilar gold deposit to the acid-sulfate or high sulfidation type of epithermal gold deposits, stem from magmatically derived fluids which are typical for a porphyry environment, whereas gold mineralization at all three localities is associated with low-salinity fluids, probably of marine origin.     

The Miduk porphyry Cu deposit,Kerman, Iran: A geochemical analysis of the potassic zone including halogen element systematics related to Cu mineralization processes

Miduk hypogene and supergene porphyry Cu–Mo mineralization occurs within the Miocene porphyritic quartz–diorite and host Eocene plagioclase–hornblende phyric andesitic pyroclastic and flow sequence. Both the host rocks were extensively altered by hydrothermal fluids to dominantly potassic, phyllic, and argillic with interstitial to distal propylitic types.     

Characteristics of Mineralizing Fluids of the Darreh‐Zerreshk and Ali‐Abad Porphyry Copper Deposits,Central Iran,Determined by Fluid Inclusion Microthermometry

The Darreh‐Zereshk (DZ) and Ali‐Abad (AB) porphyry copper deposits are located in southwest of the Yazd city, central Iran. These deposits occur in granitoid intrusions, ranging in composition from quartz monzodiorite through granodiorite to granite. The ore‐hosting intrusions exhibit intense hydrofracturing that lead to the formation of quartz‐sulfide veinlets. Fluid inclusions in hydrothermal quartz in these deposits are classified as a mono‐phase vapor type (Type I), liquid‐rich two phase (liquid + vapor) type (Type IIA), vapor‐rich two phase (vapor + liquid) type (Type IIB), and multi‐phase (liquid + vapor + halite + sylvite + hematite + chalcopyrite and pyrite) type (Types III). Homogenization temperatures (Th) and salinity data are presented for fluid inclusions from hydrothermal quartz veinlets associated with potassic alteration and other varieties of hypogene mineralization. Ore precipitation occurred between 150° to >600°C from low to very high salinity (1.1–73.9 wt% NaCl equivalent) aqueous fluids. Two stages of hydrothermal activity characterized are recognized; one which shows relatively high Th and lower salinity fluid (Type IIIa; Th_(L‐V) > Tm_(NaCl)); and one which shows lower Th and higher salinity (Type IIIb; Th_(L‐V) < Tm_(NaCl)). The high Th_(L‐V) and salinities of Type IIIa inclusions are interpreted to represent the initial existence of a dense fluid of magmatic origin. The coexistence of Type IIIb, Type I and Type IIB fluid inclusions suggest that these inclusions resulted either from trapping of boiling fluids and/or represent two immiscible fluids. These processes probably occurred as the result of pressure fluctuations from lithostatic to hydrostatic conditions under a pressure of 200 to 300 bar. Dilution of these early fluids by meteoritic water resulted in lower temperatures and low to moderate salinity (<20 wt% NaCl equiv.) fluids (Type IIA). Fluid inclusion analysis reveals that the hydrothermal fluid, which formed mineralized quartz veinlets in the rocks with potassic alteration, had temperatures of ～500°C and salinity ～50 wt% NaCl equiv. Cryogenic SEM‐EDS analyses of frozen and decrepitated ore‐bearing fluids trapped in the inclusions indicate the fluids were dominated with NaCl, and KCl with minor CaCl₂.     

Geochemical Aspects of Hypogene Hydrothermal Alteration Zones in the Chol-qeshlaghi Area, NW Iran: Constrains on REEs

Chol-qeshlaghi altered area lies in the northwestern part of the post-collisional Urumieh-Dokhtar magmatic arc, NW Iran. Pervasive silicic, argillic, phyllic and propylitic altered zones appears to be intimately affiliated to the fluids derivative of upper Oligocene Khankandi granodiorite. This paper is dedicated to the identification of geochemical characteristics of hydrothermal alterations, focusing on the determination of the mass gains and losses of REEs, to gain significant insights regarding the chemical exchanges prevailed between the host rocks and hydrothermal fluids. The low pH and high activity of SO_4~(-2) ligands in silicic alteration fluids, resulting in depletion of entire REEs. Decreasing of LREEs appeared in argillic zone may attributed to reduce in adsorption ability of clay minerals in low pH; whereas HREEs enrichment in phyllic zone was inclined to put it down to the abundance of sericite(± Fe oxides). A significant reduction of Eu/Eu* ratio in silicic zone can be attributed to negligible sulfides and clay minerals as some effective agents in adsorption of released Eu~(+2). Factors such as changes in pH, the abundance of absorptive neomorph mineral phases, activity of ligands play an important role in controlling the distribution and concentration of REEs in Chol-qeshlaghi alteration system.     

Hydrothermal fluid geochemistry at the Chah-Firuzeh porphyry copper deposit,Iran: Evidence from fluid inclusions

The Chah-Firuzeh porphyry copper deposit is located in 35 km north of Shahre Babak (Kerman province). It is associated with granodioriteic intrusive of Miocene age which intruded Eocene volcanosedimentary rocks. Copper mineralization was accompanied by both potassic and phyllic alteration. Field observations and petrographic studies demonstrate that the emplacement of Chah-Firuzeh pluton took place in several intrusive pulses, each with associated hydrothermal ore fluid formation that was also associated with hydrostatic pressure increasing respect to that of lithostatic pressure (and fracturing development-relative boiling) by circulated fluid. Copper is concentrated as a very early hydrothermal mineralized phase in the evolution of the hydrothermal system. Early hydrothermal alteration produced a potassic assemblage (orthoclase–biotite) in the central deep part of the stock. Alteration ore fluids could be classify into two groups of liquid-reach, containing solid phases, high temperature (390 to 500 °C) high salinity (more than 60 wt.% NaCl equiv.) and gas-rich, high temperature (311 to 570 °C), no solid phase and with low salinities. These magmatic source fluids illustrate sever boiling process and also are the responsible for the both potassic alteration, quartz group I and II veins and chalcopyrite deposition. Propylitic alteration occurred by the liquid-rich, low temperature (241 to 390 °C) and Ca-rich fluid with meteoric origin. Continuous decreasing temperature let the meteoric water diffusion into the system, mixed with magmatic fluids and descending the salinities down to the 1 wt.% NaCl equiv. and leaching the Cu from vein groups II and III by sever thermodynamic anarchies from potassic to the phyllic alteration zones. Phyllic alteration and copper leaching resulted from the inflow of oxidized and acidic meteoric waters with decreasing temperature of the system followed by the incursion of this fluid into and its convection in upper part of the system. A late episode of boiling occurred in the apical the phyllic zone, and was associated with significant copper deposition. Based on the field observation on sharp alteration and related mineralization, it is possible to conclude that all these procedures have been controlled by local faults that could be active even before the pluton injection. These faults and the new form ones (which have been formed after injection), could crash the hosted rocks, and act as physical dams to restrict and limit the mineralization in special strikes and zones within the Cah-Firuzeh ore deposit.     

Hydrothermal evolution of Daraloo porphyry copper deposit, Iran: evidence from fluid inclusions

The Daraloo field is located in the southeast of Iran (Kerman province). It is associated with Oligomiocene diorite/granodiorite to quartz monzonite stocks. Copper mineralization is basically relevant to potassic and phyllic alteration zones. Petrographic and geologic studies imply that mineralization is restricted to two major parts locating in the center and east of district. The larger central mineralization has a northwest–southeast trend perpendicular to the smaller one. Hydrothermal ore fluid formation occurred in relatively deep levels thereafter faulting and fracturing provided appropriate conduits to ascend fluids through shallower depths. Early hydrothermal alteration produced a confined potassic assemblage in the central and eastern parts of the stock. Two main fluid inclusion groups in relationship with alteration ore fluids have been identified. They are liquid-rich inclusions containing solid phases, with high temperatures (257°C to 554°C) and high salinities (31 to 67 wt.% NaCl equiv.), and vapor-rich inclusions with high temperatures and low salinities without any solid phases. These magmatic source fluids are responsible for boiling and also potassic and phyllic alteration zone. They also resulted in the formation of quartz groups I and II veins and chalcopyrite deposition. Propylitic alteration is attributed to a Ca-rich meteoric fluid. Inclusions originated from this fluid are liquid-rich having low temperatures (161°C to 269°C) and low salinities (1 to 13 wt.% NaCl). Mixing descending meteoric water with magmatic fluids reduces considerably the salinity of magmatic fluid. Mixing is also the impetus of leaching copper from potassic to the phyllic zone. It is possible to conclude that all these procedures are controlled by the main faults of district having NW–SE trend. Two fundamental events affecting the mineralization are cooling ore-bearing fluids and magnetite (±pyrite) emplacement. The latter one is formed in potassic and phyllic alteration zone in which copper-bearing fluids have interaction with magnetite minerals and so chalcopyrite minerals have been formed nearby magnetites. Temperature and pressure of hydrothermal fluid differentiation could be applied as a predictive tool to discriminate between barren and productive copper porphyry deposits. A simple comparison of temperature and pressure variations between Daraloo deposit and other copper porphyry deposits located in the same belt of Iran (Sahand-Bazman belt) illuminates that Daraloo system has high range of pressure implying deeper exsolution of hydrothermal fluid. On the other hand, economic mineralization has direct relationship with temperature range of orthomagmatic fluids so that if a deposit has a wide range of high temperature fluids, it could be inferred as a barren deposit. In conclusion, it could be inferred that Daraloo district can be categorized as a sub-economic porphyry deposit. On the other hand, restricted formation of chalcopyrite and the other copper-bearing minerals besides large amounts of magnetite and pyrite can approve obviously the low grade of mineralization in Daraloo district.     

Gold mineralisation and advanced argillic alteration at the Dobroyde prospect,central New South Wales

Gold mineralisation at the Dobroyde prospect in central New South Wales is hosted by a zoned alteration system characterised by peripheral propylitic alteration, grading inwards through argillic and advanced argillic alteration to a siliceous altered core. Overprinting textures indicate that propylitic, argillic, advanced argillic and siliceous assemblages were successively superimposed on each other. Au grades between 0.3–0.8 ppm are associated with siliceous alteration and cross‐cutting pyrite veinlets. Higher Au grades are associated with barite veins that cut the pyrite veinlets. Native Au, native Te, Au, Pb and Hg tellurides, Pb selenide, chalcopyrite, Zn‐sphalerite and tennantite‐tetrahedrite occur in the barite veins. Microscopic pyrophyllite shears cut the barite veins. The location of the Dobroyde prospect, the orientation of its internal alteration zonation and the orientation of auriferous barite veins in the core of the prospect are controlled by a 330°‐striking fault. Movement on this fault, synchronous with hydrothermal activity, at some time between the Late Ordovician and mid‐Devonian controlled the development of successive phases of brecciation, siliceous alteration, pyrite and later barite‐Au veining in the prospect core. The restricted distribution of auriferous barite veins within the siliceous altered core of the prospect is inferred to be controlled by the relatively brittle rheology of this assemblage during deformation, and its location on the fault that formed the main hydrothermal fluid conduit. Alteration zones distal from this fault remain unmineralised. The Dobroyde prospect may be a product of the same Early Devonian metallogenic epoch as the paragenetically similar Temora and Peak Hill deposits. All three deposits/prospects appear to be localised in splays of either the Gilmore Fault Zone or the Parkes Thrust.