Fluid fluxes during low-temperature alteration: implications of multi-style alteration assemblages from the Welsh Borderland,UK

Localized (domainal) low-temperature alteration may indicate variations in the chemistry of alteration fluids and/or discrete fluid flow paths during metamorphism. Occurrences of epidote- and pumpellyite-dominated domains are often used as evidence for large fluxes of Ca-rich fluids. However, comparative studies of two domainal alteration styles from basaltic to andesitic lavas and volcaniclastic rocks at Builth Wells, Wales, UK suggest that such interpretations cannot be applied universally. Here, only one set of domains can be attributed to large fluxes of Ca-rich fluids. In contrast, the second set of domains formed where the host rock supplied the necessary Ca, and fluid/rock ratios were relatively low. These domains are hosted by rocks which show a Caledonian regional metamorphic imprint, characterized by the alteration assemblage albite+chlorite+titanite±prehnite±pumpellyite±calcite±muscovite±quartz (considered to have formed at c. 200°C and ≤2.5 kbar). Type 1 domains lie along fluid channelways, such as veins. Pumpellyite is the dominant secondary mineral, but the alteration assemblage is variable with pumpellyite±prehnite±calcite±titanite±chlorite (±quartz). The domains formed at temperatures of 130–230°C during Ordovician hydrothermal activity, before the peak of regional metamorphism. In contrast, Type 2 domains are not associated with obvious fluid channelways. A central prehnite-dominated zone typically has a rim with the assemblage pumpellyite+calcite±prehnite±chlorite±titanite±K-rich phyllosilicate. These domains probably formed from pelitic xenoliths which contained a volcaniclastic component at temperatures of 130–230°C and at relatively low fluid/rock ratios. However, the timing of domain formation is uncertain. Pyrobitumen, in veins and disseminated throughout the rock, may have influenced the formation of both types of domain by stabilizing pumpellyite in preference to epidote and causing metamorphic calcite formation through the release of CO₂ to the alteration fluids. © 1996 John Wiley & Sons, Ltd.     

德兴铜厂斑岩铜矿脉体类型、分布规律及其对成矿的指示意义

德兴铜矿是中国东部重要的大型斑岩铜矿,由朱砂红、铜厂和富家坞等3个矿床组成。在详细的野外脉体填图基础上,文章把德兴铜厂斑岩铜矿的成矿脉体划分为A脉、B脉、D脉和H脉等4种类型。研究发现,A脉的形成与钾化蚀变有关,脉体不规则且不连续,以粒状石英±钾长石±黑云母±磁铁矿±少量黄铁矿±少量黄铜矿的矿物组合为特征;B脉的形成与钾质硅酸盐水解有关,脉体较规则且连续,以石英±辉钼矿±黄铜矿±黄铁矿的矿物组合为特征,石英颗粒呈典型的梳状或长柱状对称于脉壁生长;D脉的形成与石英-绢云母化蚀变有关,以黄铁矿±石英±黄铜矿的矿物组合为特征,脉壁发育绢云母晕;H脉的形成与碳酸盐化有关,以方解石±赤铁矿±黄铁矿±黄铜矿的矿物组合为特征。这4种脉体分别记录了成矿流体演化至不同阶段,热液蚀变作用的特点及其与Cu-Mo硫化物沉淀的关系。脉体的宽度-间距定量统计分析表明,脉体宽度(T)服从于幂次分布定律;脉体间距(S)服从于负指数分布或介于对数正态分布与负指数分布之间。脉体宽度分维值D值(0.91~1.35)普遍>1,反映脉体系统的连通性较差,矿化程度较弱。脉体间距变差系数Cν值(0.49~0.92)均<1,说明脉体簇生聚集程度较低,矿化程度较弱;处于脉体聚集中心的脉体,代表着热液流体运移的通道,制约着其他脉体的展布。     

Characterisation of the Sarcheshmeh copper mine tailings,Kerman province,southeast of Iran

Mineral processing operation at the Sarcheshmeh porphyry copper mine has produced huge quantities of tailings materials containing sulphide minerals in particular pyrite. These tailings materials were geochemically and mineralogically characterised to assess pyrite and chalcopyrite oxidation, acid mine drainage generation, and trace element mobility to lead development of a proper remediation plan. Five vertical trenches up to 4.2 m deep were excavated from the tailings surface, and 70 solid samples were taken in 0.3 m intervals. The samples were first mineralogically analysed. Pyrite was the main sulphide mineral found in the tailings. The gangue minerals include quartz ± muscovite–illite ± chlorite ± albite ± orthoclase ± halite. The samples were geochemically analysed for total concentrations of 62 elements, paste pH, SO₄ ^2?, CO₃ ^2?, and HCO₃ ^?. The maximum concentrations of SO₄ ^2? (1,300, 1,170, 1,852, 1,960 and 837 mg/L) were observed at a depth of 0.9 m in profiles A, B, C, D and E, respectively. The tailings have a high acid-producing potential and low acid-neutralising potential (pyrite 4–6 wt %, calcite 1 wt %). Fe₂(SO₄)₃, CuSO₄, MgSO₄ and MnSO₄ were the dominant secondary sulphate minerals in the tailings. The lowest pH values (2.9, 3 and 3) were measured at a depth of 0.3 m in the profiles A, B and C, 3.9 at a depth of 0.6 m in the profile D and 3 at a depth of 0.9 m in the profile E. The upper portions of the profiles C (1.8 m) and D (2.1 m) were moderately oxidised, while oxidation in the profiles A, B and E did not extend more than 1.2, 1.2 and 1.5 m beneath the tailings surface. Zn, Pb, Rb, U, Hf, Nd, Zr and Ga show almost a constant trend with depth. Cd, Sr, Th, La and Ce increased with increasing depth of the tailings materials while, Co, V, Ti, Cr, Cu, As, Mn, Ag, Mo and Ni exhibit initially a decreasing trend from tailings surface to the depths that vary between 0.9 and 1.2. They then remained constant with the depth. The results show pyrite and chalcopyrite oxidation at surface layers of the tailings and subsequent leaching of the oxidation products and trace elements by infiltrated atmospheric precipitation.     

Hydrothermal evolution of the Sar-Cheshmeh porphyry Cu–Mo deposit,Iran: Evidence from fluid inclusions

The Sar-Cheshmeh porphyry Cu–Mo deposit is located in Southwestern Iran (∼65 km southwest of Kerman City) and is associated with a composite Miocene stock, ranging in composition from diorite through granodiorite to quartz-monzonite. Field observations and petrographic studies demonstrate that the emplacement of the Sar-Cheshmeh stock took place in several pulses, each with associated hydrothermal activity. Molybdenum was concentrated at a very early stage in the evolution of the hydrothermal system and copper was concentrated later. Four main vein Groups have been identified: (I) quartz+molybdenite+anhydrite±K-feldspar with minor pyrite, chalcopyrite and bornite; (II) quartz+chalcopyrite+pyrite±molybdenite±calcite; (III) quartz+pyrite+calcite±chalcopyrite±anhydrite (gypsum)±molybdenite; (IV) quartz±calcite±gypsum±pyrite±dolomite. Early hydrothermal alteration produced a potassic assemblage (orthoclase-biotite) in the central part of the stock, propylitic alteration occurred in the peripheral parts of the stock, contemporaneously with potassic alteration, and phyllic alteration occurred later, overprinting earlier alteration. The early hydrothermal fluids are represented by high temperature (350–520 °C), high salinity (up to 61 wt% NaCl equivalent) liquid-rich fluid inclusions, and high temperature (340–570 °C), low-salinity, vapor-rich inclusions. These fluids are interpreted to represent an orthomagmatic fluid, which cooled episodically; the brines are interpreted to have caused potassic alteration and deposition of Group I and II quartz veins containing molybdenite and chalcopyrite. Propylitic alteration is attributed to a liquid-rich, lower temperature (220–310 °C), Ca-rich, evolved meteoric fluid. Influx of meteoric water into the central part of the system and mixing with magmatic fluid produced albitization at depth and shallow phyllic alteration. This influx also caused the dissolution of early-formed copper sulphides and the remobilization of Cu into the sericitic zone, the main zone of the copper deposition in Sar-Cheshmeh, where it was redeposited in response to a decrease in temperature.     

Experimental modeling of Au and Pt coupled transport by chloride hydrothermal fluids at 350–450°C and 500–1000 bar

The coupled solubility of Au_(cr) and Pt_(cr) has been measured in acidic chloride solutions at 350–450°С and 0.5 and 1 kb using the autoclave technique with determination of dissolved metal contents after quenching. The constants of the reaction combining the dominant species of Au and Pt in high-temperature hydrothermal fluids (K_(Au–Pt)) have been determined: 2 Au_(cr) + PtCl₄^2- = Pt_(cr) + 2AuCl₂^-; log K_(Au–Pt) =–1.02 ± 0.25 (450°С, 1 kb), 0.09 ± 0.15 (450°С, 0.5 kb), and –1.31 ± 0.20 (350°С, 1 kb). It has been established that the factors affecting the Au/Pt concentration ratio in hydrothermal fluids and precipitated ores are temperature, pressure, redox potential, and sulfur fugacity. An increase in temperature results in an increase in the Au/Pt concentration ratio (up to ~550°С at P = 1 kb). A decrease in pressure and redox potential leads to enrichment of fluid in Au. An increase in sulfur fugacity in the stability field of Pt sulfides results in increase in the Au/Pt concentration ratio. Native platinum is replaced by sulfide mineral in low-temperature systems enriched in Pt (relative to Au).     

Genesis of coffinite and the U-Ti association in lower old red sandstone sediments,Ousdale, Caithness,Scotland

The mineralogy of a fault-related uranium occurrence, in clastic rocks overlying granite, is described from borehole material. Coffinite is the only important uranium mineral. Other notable minerals are sulphides, fluorite, calcite and hydrocarbon. Coffinite is epigenetic and paragenetically late, rimming sulphides and hycrocarbon. It occurs partly in spatial association with a TiO₂ mineral (probably anatase). This U-Ti association is attributed to adsorption of U by altered Ti-minerals prior to growth of the U mineral. Thus is has similarities with many diagenetic occurrences, though their mineralogy is usually different (the U-Ti association being represented by uranotitanates). The latter are attributed to local supersaturation of TiO₂, which did not occur at Ousdale because Ti was relatively mobile in the fluids. Coffinite + TiO₂ + quartz is interpreted as a stable low-temperature assemblage. The mineralogy thus indicates a hydrothermal uranium mineralization of an unusual type (without prominent uraninte), formed from relatively low-temperature fluids containing complexing agents which mobilized Ti.     

Genesis of wollastonite- and grandite-rich skarns in a suite of marble-calc-silicate rocks from Sittampundi, Tamil Nadu: constraints on the P–T–fluid regime in parts of the Pan-African mobile belt of South India

The Pan-African tectonothermal activities in areas near Sittampundi, south India, are characterized by metamorphic changes in an interlayered sequence of migmatitic metapelites, marble and calc-silicate rocks. This rock sequence underwent multiple episodes of folding, and was intruded by granite batholiths during and subsequent to these folding events. The marble and the calc-silicate rocks develop a variety of skarns, which on the basis of mineralogy; can be divided into the following types: Type I: wollastonite?+?clinopyroxene (mg#?=?71–73)?+?grandite (16–21 mol% Adr)?+?quartz?±?calcite, Type II: grandite (25–29 mol% Adr )?+?clinopyroxene (mg#?=?70)?+?calcite?+?quartz, and Type III: grandite (36–38 mol% Adr)?+?clinopyroxene (mg#?=?55–65)?+?epidote?+?scapolite?+?calcite?+?quartz. Type I skarn is 2–10 cm thick, and is dominated by wollastonite (>70 vol%) and commonly occurs as boudinaged layers parallel to the regional foliation Sn₁ related to the Fn₁ folds. Locally, thin discontinuous lenses and stringers of this skarn develop along the axial planes of Fn₂ folds. The Type II skarn, on the other hand, is devoid of wollastonite, rich in grandite garnet (40–70 vol%) and developed preferentially at the interface of clinopyroxene-rich calc-silicates layers and host marble during the later folding event. Reaction textures and the phase compositional data suggest the following reactions in the skarns: 1. calcite?+?SiO₂?→?wollastonite?+?V, 2. calcite?+?clinopyroxene?+?O₂?→?grandite?+?SiO₂?+?V, 3. scapolite?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V and 4. epidote?+?calcite?+?quartz?+?clinopyroxene?+?O₂?→?grandite?+?V Textural relations and composition of phases demonstrate that (a) silica metasomatism of the host marble by infiltration of aqueous fluids (X_CO2?<?0.15) led to production of large volumes of wollastonite in the wollastonite-rich skarn whereas mobility of FeO, SiO₂ and CaO across the interface of marble and calc-silicate and infiltration of aqueous fluids (X_CO2?<?0.35) were instrumental for the formation of grandite skarns. Composition of minerals in type II skarn indicates that Al₂O₃ was introduced in the host marble by the infiltrating fluid. Interpretation of mineral assemblages observed in the interlayered metapelites and the calcareous rocks in pseudosections, isothermal P-X_CO2 and isobaric T-X_CO2 diagrams tightly bracket the “peak” metamorphic conditions at c.9?±?1 kbar and 750°?±?30°C. Subsequent to ‘peak’ metamorphic conditions, the rocks were exhumed on a steeply decompressive P–T path. The estimated ‘peak’ P–T estimates are inconsistent with the “extreme” metamorphic conditions (>11 kbar and >950°C) inferred for the Pan-African tectonothermal events from the neighboring areas. Field and petrological attributes of these skarn rocks are consistent with the infiltration of aqueous fluid predominantly during the Fn₁ folding event at or close to the ‘peak’ metamorphic conditions. Petrological features indicate that the buffering capacity of the rocks was lost during the formation of type I and II skarns. However, the host rock could buffer the composition of the permeated fluids during the formation of type III skarn. Aqueous fluids derived from prograde metamorphism of the metapelites seem to be the likely source for the metasomatic fluids that led to the formation of the skarn rocks.     

Volcanic Activity, Hydrothermal Alteration and Epithermal Gold-Silver Mineralization in the Ryuo Mine Area in the Kitami Metallogenic Province, Hokkaido, Japan

Abstract: Characterization of Neogene magmatism in the Ryuo mine area in the Kitami metallogenic province was carried out on the basis of K-Ar data for felsic–to–mafic terrestrial extrusive and intrusive volcanism from Late Miocene to Early Pliocene. The Ryuo epithermal gold-silver deposit occurs primarily in the felsic volcaniclastic rocks of the Ikutahara Formation and in Ryuo Rhyolite. The Ryuo mineralization age of 7. 7 – 8. 1 Ma coincides well with the hydrothermal alteration age (7. 7 Ma) of Ryuo Rhyolite hosting ore veins. It is concluded that the Ryuo mineralization was essentially accompanied by felsic volcanic activity during the sedimentation of the Ikutahara Formation, and was closely related both temporally and spatially to the intrusive activity of Ryuo Rhyolite. Hydrothermal alteration related to the epithermal gold-silver mineralization of the Ryuo deposit is primarily characterized by early regional and vein-related alterations, and late steam-heated alteration. Early regional alteration consists of a smectite halo (smectite+pyrite±quartz±opal–CT±mordenite°Clinoptilolite–heulandite series mineral). Early vein-related alteration is primarily marked by potassic alteration. This alteration halo can be subdivided into a K-feldspar halo (quartz+adular–ia+pyrite±illite±interstratified illite/smectite±smectite), an illite halo (quartz+illite + chlorite + pyrite ± interstratified illite/smec–tite±smectite) and an interstratified illite/smectite halo (quartz + interstratified illite/smectite+pyrite±smectite). Late steam-heated alteration characterized by kaolinite or alunite locally overprints the early K-feldspar halo. The style of the Ryuo gold-silver deposit is a low-sulfidation epithermal type. The gold–silver–bearing quartz vein precipitates during boiling of ore fluid. The origin of the ore fluid might be meteoric water. The temperature and sulfur fugacity conditions during precipitation of electrum and acanthite are estimated to be 206°– 238°C and 10^-13.5 – 10^-11.6 atm, respectively.     

Gold mineralisation at the Lady Bountiful Mine,Western Australia: An example of a granitoid-hosted Archaean lode gold deposit

The Lady Bountiful granitoid-hosted lode gold deposit, located in the mid-greenschist facies metamorphosed Ora Banda greenstone sequence, is hosted predominantly by the late-tectonic Liberty Granodiorite. Gold mineralisation is localised along quartz-veined, sinistral, brittle fault-zone(s) that transect the boundary between the Liberty Granodiorite and Mt Pleasant sill. Quartz vein textures indicate two stages of a single gold-related vein-development event, with high-grade gold mineralisation restricted to the second stage. Ore minerals include pyrite, chalcopyrite, pyrrhotite, galena, sphalerite, Au−Ag−Bi−Pb-tellurides, and native gold. Fluid infitration has resulted in narrow (<1 m) bleached wallrock alteration envelopes to the fault zones comprising albite-K-mica ±chlorite±calcite±rutile assemblages. Temperature-pressure conditions varied from Stage I (300°±50°C, ≈2 kbar) to Stage II (250°±50°C, ≈0.5 to 2 kbar), with the hydrothermal fluid in both stages characterised by X(CO₂)≤0.15 and moderate salinity (≈1.28 m NaCl). Intermittent phase separation of Stage II mineralising fluids, initiated by pressure fluctuations in dilational sites, and/or fluid-dominated fluid: wallrock interaction, are invoked as the dominant depositional mechanisms. The granitoid-hosted Lady Bountiful lode gold deposit shares many features with other granitoid-hosted lode gold deposits in the Yilgarn Craton and the Superior Province. Granitoid-hosted lode gold deposits, such as the Lady Bountiful deposit, provide additional evidence that the dominant control on the localisation of gold mineralisation within a granitoid host is structure, with competency contrasts playing a significant role. Furthermore, the hydrothermal wallrock alteraction and orefluid chemistry characteristics of the granitoid-hosted lode gold deposits are comparable to those established for greenstone-hosted lode gold mineralisation.     

Gold deposits of the Bardoc Tectonic Zone: a distinct style of orogenic gold in the Archaean Eastern Goldfields Province,Yilgarn Craton,Western Australia

The Bardoc Tectonic Zone is an ～80 km-long and up to 12 km wide, intensely sheared corridor of Late Archaean supracrustal rocks that is bounded by pre- to syn-tectonic granites in the Eastern Goldfields Province, Yilgarn Craton. This zone has produced over 100 t of gold from a range of deposits, the largest being Paddington (～40 t Au). This shear system is connected along strike to the Boulder – Lefroy Shear Zone, which hosts considerably larger deposits including the giant Golden Mile Camp (>1500 t produced Au). In contrast to the diverse characteristics of gold deposits associated with the Boulder – Lefroy Shear Zone, mineralogical and geochemical data from five representative localities in the Bardoc Tectonic Zone have relatively uniform features. These are: (i) quartz – carbonate veins in competent mafic units with wall-rock alteration characterised by carbonate + quartz + muscovite + chlorite ± biotite + sulf-arsenide + sulfide + oxide + gold assemblages; (ii) arsenopyrite as the dominant sulfur-bearing mineral; (iii) a unique three-stage paragenetic history, commencing with pyrrhotite, and progressing to arsenopyrite and then to pyrite-dominated alteration; (iv) a lack of minerals indicative of oxidising conditions, such as hematite and sulfates; (v) δ³⁴ sulfur compositions of pre- to syn-gold iron sulfides ranging from 1 to 9 ‰; and (vi) a lack of tellurides. These features characterise a coherent group of moderately sized orogenic-gold deposits, and when compared with the larger gold deposits of the Boulder – Lefroy Shear Zone, potentially highlight the petrological and geochemical differences between high-tonnage and smaller deposits in the Eastern Goldfields Province.     

Fluid inclusion and H–O–C isotope geochemistry of the Yaochong porphyry Mo deposit in Dabie Shan,China: a case study of porphyry systems in continental collision orogens

The Yaochong porphyry Mo deposit in Xinxian County, Henan Province, China, is located in the Hong’an terrane, that is, the western part of the Dabie orogen. The Dabie orogen is part of a >1,500 km long, Triassic continental collision belt between the North China Block and the South China Block. Four types of vein are present. Paragenetically, from early to late, they are as follows: stage 1 quartz + K-feldspar ± pyrite ± magnetite vein; stage 2 quartz + K-feldspar + molybdenite ± pyrite vein; stage 3 quartz + polymetallic sulfides ± K-feldspar vein; and stage 4 quartz ± carbonate ± fluorite vein. Four compositional types of fluid inclusion, pure CO₂, CO₂ bearing, aqueous, and solid bearing, are present in quartz from the first three stages; only low-salinity aqueous fluid inclusions occur in quartz from the last stage. All the estimated salinities are ≤13.1 wt% NaCl eq., and no halite crystals were identified. Homogenization temperatures for the fluid inclusions from stages 1 to 4 are in the ranges of 262–501, 202–380, 168–345, and 128–286 °C, respectively, and estimated depths decrease from 6.9 to 8.9 km, through 6.2–7.2, to ~4.7 km. Quartz separates from the veins yielded a δ¹⁸O value of 7.7–11.2 ‰, corresponding to δ¹⁸O_H2O values of ?1.3 to 6.9 ‰ using temperature estimates from fluid inclusion data; δD_H2O values of fluid inclusion vary from ?80 to ?55 ‰, and δ¹³C_CO2 from ?2.3 to 2.7 ‰, suggesting that the ore-fluids evolved from magmatic to meteoric sources. We conclude that the ore-forming fluid system at Yaochong was initially high temperature, high salinity, and CO₂-rich and then progressively evolved to CO₂-poor, lower salinity, and lower temperature, by mixing with meteoric water, which results in ore precipitation.     

Ultrahigh‐pressure and high‐P lawsonite eclogites in Muzhaerte,Chinese western Tianshan

Lawsonite eclogites are crucial to decipher material recycling along a cold geotherm into the deep Earth and orogenic geodynamics at convergent margins. However, their tectono‐metamorphic role and record especially at ultrahigh‐pressure (UHP) conditions are poorly known due to rare exposure in orogenic belts. In a ~4 km long cross‐section in Muzhaerte, China, at the western termination of the HP‐UHP metamorphic belt of western Tianshan, metabasite blocks contain omphacite and lawsonite inclusions in porphyroblastic garnet, although matrix assemblages have been significantly affected by overprinting at shallower structural levels. Two types of lawsonite eclogites occur in different parts of the section and are distinguished based on inclusion assemblages in garnet: Type 1 (UHP) with the peak equilibrium assemblage garnet+omphacite±jadeite+lawsonite+rutile+coesite±chlorite±glaucophane and Type 2 (HP) with the assemblage garnet+omphacite±diopside+lawsonite+titanite+quartz±actinolite±chlorite+glaucophane. Pristine coesite and lawsonite and their pseudomorphs in Type 1 are present in the mantle domains of zoned garnet, indicative of a coesite‐lawsonite eclogite facies. Regardless of grain size and zoning profiles, garnet with Type 1 inclusions systematically shows higher Mg and lower Ca contents than Type 2 (prp_4–25grs_13–24 and prp_1–8grs_20–45 respectively). Phase equilibria modelling indicates that the low‐Ca garnet core and mantle of Type 1 formed at UHP conditions and that there was a major difference in peak pressures (i.e., maximum return depth) between the two types (2.8–3.2 GPa at 480–590°C and 1.3–1.85 GPa at 390–500°C respectively). Scattered exposures of Type 1 lawsonite eclogite is scatteredly exposed in the north of the Muzhaerte section with a structural thickness of ~1 km, whereas Type 2 occurs throughout the rest of the section. We conclude from this regular distribution that they were derived from two contrasting units that formed along two different geothermal systems (150–200°C/GPa for the northern UHP unit and 200–300°C/GPa for the southern HP unit), with subsequent stacking of UHP and HP slices at a kilometre scale.     

Relationships between Volcanism, Hydrothermal Alteration and Epithermal Gold-Silver Mineralization in the Muka Mine Area in the Kitami Metallogenic Province, Hokkaido, Japan

Abstract: Neogene magmatism in the Muka mine area in the Kitami metallogenic province was characterized on the basis of K-Ar age data by felsic–to–mafic terrestrial extrusive and intrusive volcanism from Late Miocene to Early Pliocene. The geology of the Muka mine area comprises the Upper Cretaceous-Paleocene Yubetsu Group, consisting primarily of sandstone and shale; Upper Miocene Ikutahara Formation, consisting of clastic and felsic volcaniclastic rocks and Kane-hana Lava (rhyolite) of 7. 5 Ma; Upper Miocene Yahagi Formation, consisting of clastics, felsic volcaniclastics and rhyolite lavas; Late Miocene andesite and rhyolite dikes (Chidanosawa Rhyolite of 7. 2 Ma and Hon-Mukagawa Andesite of 6. 6 Ma); Lower Pliocene Hakugindai Lava (basalt: 4. 0 Ma); and Quaternary System. The volcanism consists of earlier Late Miocene felsic extrusive activity during the sedimentation of the Ikutahara Formation, later Late Miocene felsic extrusive and intrusive activities during the sedimentation of the Yahagi Formation and intermediate intrusive activity after the sedimentation of the Yahagi Formation and Early Pliocene mafic extrusive activity. The Muka gold-silver ore deposit occurs primarily in the felsic volcaniclastic rocks and Kanehana Lava of the Ikutahara Formation and in Hon-Mukagawa Andesite. These wall–rocks, the clastic rocks of the Ikutahara Formation and the clastic and felsic volcaniclastic rocks of the Yahagi Formation were affected to various extents by hydrothermal alteration. The hydrother-mal alteration can be divided into two stages (early and late) based on the modes of occurrence and mineral assemblages. Early hydrothermal alteration is characterized by regional and vein-related alterations associated with epithermal gold-silver mineralization in a near-neutral hydrothermal system. Regional alteration can be subdivided into a zeolite zone (mordenite+adularia±heulandite–clinoptilolite series mineral±smectite±quartz°Cristobalite±opal–CT) and a smectite zone (smec–tite±quartz±opal–CT). Vein-related alteration can be subdivided into a K-feldspar zone (quartz+adularia±illite±interstratified illite/smectite±pyrite), an illite zone (quartz+illite°Chlorite±interstratified illite/smectite±smectite±pyrite) and an interstratified illite/smectite zone (quartz+interstratified illite/smectite±smectite±pyrite). The adularization age of 6. 8 Ma in the K-feldspar zone that developed in Kanehana Lava hosting ore veins coincides well with the epithermal gold-silver mineralization age of 6. 6 Ma. Late hydrothermal alteration is characterized by a kaolinite zone (kaolinite±dickite±alunite±quartz°Cristobalite± tridymite±pyrite) in an acid hydrothermal system, and cuts early alteration zones such as the K-feldspar zone. Other modes of occurrence of acid alteration are a 7Å halloysite-kaolinite vein in the hydrothermal explosion breccia dike and smectite–kaoli–nite veins along joint planes of Kanehana Lava. The style of the gold-silver deposit associated with early near-neutral hydrothermal alteration is a low-sulfidation epithermal type. The low-sulfidation epithermal gold-silver mineralization of 6. 6 Ma in the vicinity of the Muka ore deposit was essentially accompanied by felsic volcanic activity during the sedimentation of the Yahagi Formation, and was closely related both temporally and spatially to the felsic intrusive activity of Chidanosawa Rhyolite of 7. 2 Ma. The related hydrother-mal activity of the gold-silver mineralization took place at intervals of approximately 0. 4–0. 6 Ma after the volcanic activity related to the mineralization.     

Seeing through the magnetite:Reassessing Eoarchean atmosphere composition from Isua(Greenland) ≥3.7 Ga banded iron formations

Estimates of early atmosphere compositions from metamorphosed banded iron formations(BIFs)including the well-studied ≥3.7 BIFs of the Isua supracrustal belt(Greenland)are dependent on knowledge of primary versus secondary Fe-mineralogical assemblages.Using new observations from locally well preserved domains,we interpret that a previously assumed primary redox indicator mineral,magnetite,is secondary after sedimentary Fe-clays(probably greenalite)±carbonates.Within ~3.7 Ga Isua BIF,pre-tectonic nodules of quartz+Fe-rich amphibole±calcite reside in a finegrained(≤100 μm)quartz+magnetite matrix.We interpret the Isua nodule amphibole as the metamorphosed equivalent of primary Fe-rich clays,armoured from diagenetic oxidative reactions by early silica concretion.Additionally,in another low strain lacunae,~3.76 Ga BIF layering is not solid magnetite but instead fine-grained magnetite+quartz aggregates.These magnetite+quartz aggregates are interpreted as the metamorphosed equivalent of Fe-clay-rich layers that were oxidised during diagenesis,because they were not armoured by early silicification.In almost all Isua BIF exposures,this evidence has been destroyed by strong ductile deformation.The Fe-clays likely formed by abiotic reactions between aqueous Fe~(2+)and silica.These clays along with silica±carbonate were deposited below an oceanic Fe-chemocline as the sedimentary precursors of BIF.Breakdown of the clays on the sea floor may have been by anaerobic oxidation of Fe~(2+),a mechanism compatible with iron isotopic data previously published on these rocks.The new determinations of the primary redoxsensitive Fe-mineralogy of BIF significantly revise estimates of early Earth atmospheric oxygen and CO_2 content,with formation of protolith Fe-rich clays and carbonates compatible with an anoxic Eoarchean atmosphere with much higher CO_2 levels than previously estimated for Isua and in the present-day atmosphere.     

The mineral chemistry of new titanates from the jagersfontein kimberlite,South Africa: Implications for metasomatism in the upper mantle

New members of the crichtonite mineral series are described in which K, Ba, Ca and REE are in significant concentrations (5 wt% oxides) filling the A formula position in AM₂₁O₃₈. These phases are chromium (16 wt% Cr₂O₃) titanates (58 wt% TiO₂) enriched in ZrO₂ (5 wt%) and constitute a mineral repository for refractory and large ion lithophile elements in the upper mantle. The mineral senes coexists with Mg-Cr-ilmenite, Nb-Cr-rutile, and Ca-Cr (NbZr) armalcolite that have equally unusual chemistries. Kimberlitic crichtonites are depleted in the intermediate lanthanides but highly enriched in LREE and HREE with chondrite normalized abundances of 10³ to 10⁵. Crichtonite, armalcolite, and Nb-Cr-rutile occupy a compositional range in TiO₂ contents bridging the gap between ilmenite and rutile, two minerals having a widespread distribution in kimberlites and mantle-derived nodule suites.In common with other associations, and based on similarities in mineral chemistry, it is concluded that these minerals formed at P = 20–30 kb, 900–1100°C by reaction of peridotite with metasomatizing fluids. Kimberlitic crichtonite may be expressed as spinel + Cr-ferropseudobrookite, and armalcolite is equivalent to Cr-geikielite + rutile in the system (FeMg)-TiO₂-Cr₂O₃. This system contains a number of Cr-Ti compounds not found as minerals but it is proposed that the ubiquitous occurrence of ilmenite intergrowths in kimberlitic rutile results from decomposition of high pressure αPbO₂-type crystallographic shear structures. The new minerals have exotic chemistries and the high K-affinities broaden the scope for the origin of alkalic rocks, the generation of highly potassic magmas in the upper mantle, and suggest that alkali metasomatism may be pervasive.     

Calorimetric Study of Natural Basic Copper Phosphate—Pseudomalachite

The thermochemical study of a natural basic copper phosphate, pseudomalachite Cu₅(PO₄)₂(OH)₄ (Virneberg deposit, Germany), was carried out using high-temperature melt solution calorimetry method with a Tian–Calvet microcalorimeter. The enthalpy of formation of the mineral from elements was obtained to be Δ _f H_el(298.15 K) =–3214 ± 13 kJ/mol. The value of the Gibbs energy of pseudomalachite formation calculated using literature data on its standard entropy is Δ _f H_el^°(298.15 K) =–2812 ± 13 kJ/mol.     

Pressure-temperature Evolution of the Metapelites in the Motuo Area,the Eastern Himalayan Syntaxis

The Motuo area is located in the east of the Eastern Himalayan Syntaxis. There outcrops a sequence of high-grade metamorphic rocks, such as metapelites. Petrology and mineralogy data suggest that these rocks have experienced three stages of metamorphism. The prograde metamorphic mineral assemblages(M1) are mineral inclusions(biotite + plagioclase + quartz ± sillimanite ± Fe-Ti oxides) preserved in garnet porphyroblasts, and the peak metamorphic assemblages(M2) are represented by garnet with the lowest XSps values and the lowest XFe# ratios and the matrix minerals(plagioclase + quartz ± Kfeldspar + biotite + muscovite + kyanite ± sillimanite), whereas the retrograde assemblages(M3) are composed of biotite + plagioclase + quartz symplectites rimming the garnet porphyroblasts. Thermobarometric computation shows that the metamorphic conditions are 562–714°C at 7.3–7.4 kbar for the M1 stage, 661–800°C at 9.4–11.6 kbar for the M2 stage, and 579–713°C at 5.5–6.6 kbar for the M3 stage. These rocks are deciphered to have undergone metamorphism characterized by clockwise P-T paths involving nearly isothermal decompression(ITD) segments, which is inferred to be related to the collision of the India and Eurasia plates.     

An oxygen isotope study of two contrasting orogenic vein gold systems in the Meguma Terrane, Nova Scotia, Canada, with implications for fluid sources and genetic models

Sampling of quartz vein material from two gold deposits of similar geological setting but different ages (The Ovens, 408?Ma; Dufferin, 380?Ma) in the Meguma Terrane of Nova Scotia has been done to compare and contrast their ??¹⁸O_quartz signatures. Despite different ages of formation, quartz from all vein types in each of the deposits (i.e. saddle-reef, bedding-concordant leg reefs, en echelon, discordant) shows limited intra-deposit variation with similar average ??¹⁸O values of +15.2?±?0.9?? (n?=?16) for The Ovens and +15.7?±?0.6?? (n?=?12) for Dufferin. Using an average ??¹⁸O value of +15.4?? for the two deposits, the corresponding ??¹⁸O_H2O values, calculated for 400°C and 350°C based on constraints from mineral assemblages and fluid inclusion studies, indicate averages of 11.4?±?0.2?? and +10.2?±?0.2??, respectively. The isotopic data indicate that: (1) the vein-forming fluids have a metamorphic signature, (2) all vein types in the two deposits represent formation from a single, isotopically homogeneous fluid, and (3) a fluid of similar isotopic signature was generated by two contrasting tectono-thermal events in the Meguma Terrane that were separated by 30?Ma. Integration of these results with previously published data for 14 Meguma gold deposits indicate a general stratigaphic dependence in ??¹⁸O_H2O values for deposits when arranged in their relative stratigraphic position such that ??¹⁸O_H2O values increase upwards in the stratigraphy. This apparent trend cannot be explained by models involving either fluid mixing or cooling of the vein-forming fluids, but instead is modelled using fluid/rock interaction taking into account a change in the modal mineralogy of the metasedimentary rocks upwards in the stratigraphy.     

Calorimetric Study of Natural Anapaite

The thermochemical study of natural hydrous calcium and iron phosphate, anapaite Ca₂Fe(PO₄)₂ · 4H₂O (Kerch iron ore deposit, Crimea, Russia), was carried out using high-temperature melt solution calorimetry with a Tian-Kalvet microcalorimeter. The enthalpy of formation of the mineral from elements was obtained to be Δ _f H_el°(298.15 K) =–4812 ± 16 kJ/mol. The values of the standard entropy and the Gibbs energy of anapaite formation are S°(298.15 K) = 404.2 J/K mol and Δ _f G_el°(298.15 K) =–4352 ± 16 kJ/mol, respectively.