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.     

Gold and copper mineralization at the El Indio deposit, Chile

A Middle Tertiary volcanic belt in the High Andes of north-central Chile hosts numerous precious- and base-metal epithermal deposits over its 150 km north-south trend. The El Indio district, believed to be associated with a hydrothermal system in the late stages of development of a volcanic caldera, consists of a series of separate vein systems located in an area of 30 km² which has undergone intense argillic-sericitic-solfataric alteration. The majority of the known gold-copper-silver mineralization occurs within a structural block only 150 by 500 m in surface area, with a recognized vertical extent exceeding 300 m. This block is bounded by two high-angle northeast-trending faults oriented subparallel to the mineralized veins.Hypogene mineralization at El Indio is grouped into two main ore-forming stages: Copper and Gold. The Copper stage is composed chiefly of enargite and pyrite forming massive veins up to 20 m wide, and is accompanied by alteration of the wall rocks to alunite, kaolinite, sericite, pyrite and quartz. The Gold stage consists of vein-filling quartz, pyrite, native gold, tennantite and subordinate amounts of a wide variety of telluride minerals. Associated with this stage is pervasive alteration of the wall rocks to sericite, kaolinite, quartz and minor pyrophyllite. The transition from copper to gold mineralization is marked by the alteration of enargite to tennantite and by minor deposition of sphalerite, galena, huebnerite, chalcopyrite and gold. Mineral stability relations indicate that there was a general decrease in the activity of S₂ accompanied by variations in the activity of Te₂ during the Gold stage.Fluid-inclusion data show homogenization temperatures ranging from about 220 to 280°C, with salinities on the order of 3–4 eq. wt. % NaCl for the Copper stage. The Gold-stage inclusions indicate a similar range in homogenization temperatures, but significantly lower salinities (0.1–1.4 eq. wt. % NaCl). Fluid inclusions of transition minerals show a weak inverse relationship between homogenization temperatures (190–250°C) and salinities (3.4–1.4 eq. wt. % NaCl), which may represent mixing of hotter Gold-stage fluids with cooler late-Copper-stage fluids. No evidence of boiling was found in fluid inclusions, but CO₂ vapor-rich inclusions were identified in wall-rock quartz phenocrysts which pre-date copper and gold mineralization.Mineral stability calculations indicate that given a fairly restricted range of solution compositions, the Copper-, Transition- and Gold-stage minerals at El Indio could have been deposited from a single solution, with constant total dissolved sulfur which underwent reduction through time. Limited sulfur-isotope data indicates that pyrite from the Copper stage was not in isotopic equilibrium with Copper-stage alunite or Transition-stage sphalerite. The sulfur-isotope and fluid-inclusion data indicate that two fluids with comparable temperatures but different compositions flowed through the El Indio system. The earlier fluid deposited copper attended by sericite-alunite-kaolinite alteration, and later epithermal fluids deposited gold with quartz-sericite-kaolinite-pyrite alteration.     

Lithologic controls on mineralization at the Lagunas Norte high-sulfidation epithermal gold deposit, northern Peru

The 13.1-Moz high-sulfidation epithermal gold deposit of Lagunas Norte, Alto Chicama District, northern Peru, is hosted in weakly metamorphosed quartzites of the Upper Jurassic to Lower Cretaceous Chimú Formation and in overlying Miocene volcanic rocks of dacitic to rhyolitic composition. The Dafne and Josefa diatremes crosscut the quartzites and are interpreted to be sources of the pyroclastic volcanic rocks. Hydrothermal activity was centered on the diatremes and four hydrothermal stages have been defined, three of which introduced Au ± Ag mineralization. The first hydrothermal stage is restricted to the quartzites of the Chimú Formation and is characterized by silice parda, a tan-colored aggregate of quartz-auriferous pyrite–rutile ± digenite infilling fractures and faults, partially replacing silty beds and forming cement of small hydraulic breccia bodies. The δ³⁴S values for pyrite (1.7–2.2?‰) and digenite (2.1?‰) indicate a magmatic source for the sulfur. The second hydrothermal stage resulted in the emplacement of diatremes and the related volcanic rocks. The Dafne diatreme features a relatively impermeable core dominated by milled slate from the Chicama Formation, whereas the Josefa diatreme only contains Chimú Formation quartzite clasts. The third hydrothermal stage introduced the bulk of the mineralization and affected the volcanic rocks, the diatremes, and the Chimú Formation. In the volcanic rocks, classic high-sulfidation epithermal alteration zonation exhibiting vuggy quartz surrounded by a quartz–alunite and a quartz–alunite–kaolinite zone is observed. Company data suggest that gold is present in solid solution or micro inclusions in pyrite. In the quartzite, the alteration is subtle and is manifested by the presence of pyrophyllite or kaolinite in the silty beds, the former resulting from relatively high silica activities in the fluid. In the quartzite, gold mineralization is hosted in a fracture network filled with coarse alunite, auriferous pyrite, and enargite. Alteration and mineralization in the breccias were controlled by permeability, which depends on the type and composition of the matrix, cement, and clast abundance. Coarse alunite from the main mineralization stage in textural equilibrium with pyrite and enargite has δ³⁴S values of 24.8–29.4?‰ and $ {\delta^{18 }}{{\mathrm{O}}_{{\mathrm{S}{{\mathrm{O}}_4}}}} $ values of 6.8–13.9?‰, consistent with H₂S as the dominant sulfur species in the mostly magmatic fluid and constraining the fluid composition to low pH (0–2) and logfO₂ of ?28 to ?30. Alunite–pyrite sulfur isotope thermometry records temperatures of 190–260 °C; the highest temperatures corresponding to samples from near the diatremes. Alunite of the third hydrothermal stage has been dated by ⁴⁰Ar/³⁹Ar at 17.0?±?0.22 Ma. The fourth hydrothermal stage introduced only modest amounts of gold and is characterized by the presence of massive alunite–pyrite in fractures, whereas barite, drusy quartz, and native sulfur were deposited in the volcanic rocks. The $ {\delta^{18 }}{{\mathrm{O}}_{{\mathrm{S}{{\mathrm{O}}_4}}}} $ values of stage IV alunite vary between 11.5 and 11.7?‰ and indicate that the fluid was magmatic, an interpretation also supported by the isotopic composition of barite (δ³⁴S?=?27.1 to 33.8?‰ and $ {\delta^{18 }}{{\mathrm{O}}_{{\mathrm{S}{{\mathrm{O}}_4}}}} $ ?=?8.1 to 12.7?‰). The Δ³⁴S_py–alu isotope thermometry records temperatures of 210 to 280 °C with the highest values concentrated around the Josefa diatreme. The Lagunas Norte deposit was oxidized to a depth of about 80 m below the current surface making exploitation by heap leach methods viable.     

安徽青阳峙门口层状硫铁矿矿床地质特征及成因研究

青阳峙门口层状硫铁矿矿床赋存于石炭纪地层中,矿体主要呈似层状、透镜状;尽管经历了热变质与接触变质作用,但矿体中仍残留胶黄铁矿和菱铁矿,矿石中不仅可以见到交代残余结构,还可见到草莓结构和微层理构造.黄铁矿中砷的质量分数和S/Se,Co/Ni比值显示火山热水沉积特征.同位素分析显示,矿石中硫化物的硫同位素组成表现出火山热水沉积和热液改造特征;矿石中铅同位素组成则显示,黄铁矿中铅以上地壳铅为主,混有少量地幔铅.上述研究表明峙门口层状硫铁矿矿床是由石炭纪喷流沉积形成的层状矿床或矿胚层,经燕山期岩浆热液和构造作用改造所形成.     

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     

Sulfur isotopic composition of hydrothermal precipitates from the Lau back-arc: implications for magmatic contributions to seafloor hydrothermal systems

The sulfur isotopic composition of sulfides and barite from hydrothermal deposits at the Valu Fa Ridge back-arc spreading center in the southern Lau Basin has been investigated. Sulfide samples from the White Church area at the northern Valu Fa Ridge have δ³⁴S values averaging +3.8‰ (n= 10) for bulk sphalerite-chalcopyrite mineralization and +4.8‰ for pyrite (n= 10). Barite associated with the massive sulfides exhibits an average of +20.7‰ (n= 10). Massive sulfides from the active Vai Lili hydrothermal field at the central Valu Fa Ridge have much higher δ³⁴S ratios averaging +8.0‰ for bulk sphalerite-chalcopyrite mineralization (n= 5), +9.3‰ for pyrite samples (n= 5), and +8.0‰ and +10.9‰ for a chalcopyrite and a sphalerite separate, respectively. The isotopic composition of barite from the Vai Lili field is similar to that of barite from the White Church area and averages +21.0‰ (n= 8). Sulfide and barite samples from the Hine Hina area at the southern Valu Fa Ridge have δ³⁴S values that are considerably lighter than those observed for samples from the other areas and average −4.9‰ for pyrite (n= 9), −4.0 and −5.7‰ for two samples of sphalerite-chalcopyrite intergrowth, and −3.4‰ for a single chalcopyrite separate. The total spread in the isotopic composition of sulfides from Vai Lili and Hine Hina is more than 20‰ over a distance of less than 30 km. The δ³⁴S values of sulfides at Hine Hina are the lowest values so far reported for volcanic-hosted polymetallic massive sulfides from the modern seafloor. Barite from the Hine Hina field also has unusually light sulfur with δ³⁴S values of +16.1 to +16.7‰ (n= 5). Isotopic compositions of the sulfides at Hine Hina indicate a dramatic decrease in δ³⁴S from ordinary magmatic values and, in the absence of biogenic sulfur and/or boiling, imply a unique ³⁴S-depleted source of probable magmatic origin. Sulfide-barite mineralization in the Hine Hina area is associated with a distinctive alteration assemblage consisting of cristobalite, pyrophyllite, kaolinite, opal-CT, talc, pyrite, native sulfur, and alunite. Similar styles of alteration are typically known from high-sulfidation epithermal systems on land. Alunite-bearing, advanced argillic alteration in the Hine Hina field confirms the role of acidic, volatile-rich fluids, and a δ³⁴S value of +10.4‰ for the sulfur in the alunite is consistent with established kinetic isotope effects which accompany the disproportionation of magmatic SO₂ into H₂S and H₂SO₄. The Hine Hina field occurs near the propagating tip of the Valu Fa back-arc spreading center (i.e., dominated by dike injections and seafloor eruptions) and therefore may have experienced the largest contribution of magmatic volatiles of the three fields. The sulfur isotopic ratios of the hydrothermal precipitates and the presence of a distinctive epithermal-like argillic alteration in the Hine Hina field suggest a direct contribution of magmatic vapor to the hydrothermal system and support the concept that magmatic volatiles may be an important component of some volcanogenic massive sulfide-forming hydrothermal systems. Received: 16 January 1997 / Accepted: 28 October 1997     

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.     

REE and HFS element behaviour in the alteration facies of the Erenler Dağı Volcanics (Konya,Turkey) and kaolinite occurrence

Mainly high-K, calc-alkaline, Late Miocene to Pliocene volcanic rocks cropped out of the Konya area in Central Anatolia, Turkey. The volcanic rocks are predominantly andesitic to dacitic in composition and rarely basalt, basaltic andesite, basaltic trachyandesite and pyroclastics. Kaolinite, illite, Ca-montmorillonite, alunite, jarosite, minamiite and silica polymorphs were formed by widespread and intense hydrothermal alteration in or around the volcanic products. To investigate the effects of hydrothermal alteration on the chemistry of volcanic rocks, the whole rock chemical composition (major and trace elements, including rare-earth elements (REE) was analysed. The results of the study demonstrate notable differences in the REE behaviour in the different sample groups. REE trends of fresh parent rocks to weakly-, moderately-altered, kaolinitic and alunitic rocks are characterised by strong LREE enrichment ((La/Lu)_cn = 14.57, 11,8 to 15.20, 4.54 to 13.30, 12.5 to 24.2 and 34.6 to 47.26, respectively). Most of the samples have pronounced negative and/or weakly-negative Eu anomalies ranging from 0.75 to 0.98 while three samples have weakly-positive Eu anomalies. LRE element contents are higher than those of HREE in the samples. The LRE elements were strongly enriched in the kaolinitic and alunitic alteration; in weakly- and moderately-altered rocks. LREE are nearly immobile whereas HRE elements show different behaviour in different rock groups. The HFS and TRT elements are slightly mobilised in weakly-altered rocks, but enriched in other alteration types. Elements commonly assumed to be immobile (e.g. Y, Zr, Nb, Hf, TiO₂, Al₂O₃, REE) show variation in mass calculation. LIL elements showed enrichment over LREE and MREE, and similar behaviour, in contrast with HFSE. A clear increment of trans-transition elements (TRTE) was found mainly in alunitic and partly in kaolinitic samples.     

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.     

安徽伏川蛇绿岩套的Nd-Sr-O同位素研究

安徽歙县伏川的蛇绿岩套形成于中-晚元古宙,其Nd、Sr和O同位素组成是:ε_Nd(T)=+0.7-+3.8,ε_Sr(T)=+30.7-+53.9,δ¹⁸O=3.2-11.0‰。据地质学和同位素地球化学特征,该岩套位于杨子板块南缘、江南古岛弧的弧后小洋盆地轴部。ε_Nd(T)值的变化是由于蛇绿岩形成过程中受到下伏不成熟硅铝质基底地壳的混染引起的;ε_Sr(T)和δ¹⁸O的变化,是在蛇绿岩形成时或形成后不久遭受海水热液蚀变的结果。     

Oxygen and hydrogen isotope study of high-pressure metagabbros and metabasalts (Cyclades, Greece): implications for the subduction of oceanic crust

Oxygen and hydrogen stable isotope ratios of eclogite-facies metagabbros and metabasalts from the Cycladic archipelago (Greece) document the scale and timing of fluid–rock interaction in subducted oceanic crust. Close similarities are found between the isotopic compositions of the high-pressure rocks and their ocean-floor equivalents. High-pressure minerals in metagabbros have low δ¹⁸O values: garnet 2.6 to 5.9‰, glaucophane 4.3 to 7.1‰; omphacite 3.5 to 6.2‰. Precursor actinolite that was formed during the hydrothermal alteration of the oceanic crust by seawater analyses at 3.7 to 6.3‰. These compositions are in the range of the δ¹⁸O values of unaltered igneous oceanic crust and high-temperature hydrothermally altered oceanic crust. In contrast, high-pressure metabasalts are characterised by ¹⁸O-enriched isotopic compositions (garnet 9.2 to 11.5‰, glaucophane 10.6 to 12.5‰, omphacite 10.2 to 12.8‰), which are consistent with the precursor basalts having undergone low-temperature alteration by seawater. D/H ratios of glaucophane and actinolite are also consistent with alteration by seawater. Remarkably constant oxygen isotope fractionations, compatible with isotopic equilibrium, are observed among high-pressure minerals, with Δ_{glaucophane−garnet} = 1.37 ± 0.24‰ and Δ_{omphacite−garnet} = 0.72 ± 0.24‰. For the estimated metamorphic temperature of 500 °C, these fractionations yield coefficients in the equation Δ = A * 10⁶/T ² (in Kelvin) of A_{glaucophane−garnet} = 0.87 ± 0.15 and A_{omphacite−garnet} = 0.72 ± 0.24. A fractionation of Δ_{glaucophane–actinolite} = 0.94 ± 0.21‰ is measured in metagabbros, and indicates that isotopic equilibrium was established during the metamorphic reaction in which glaucophane formed at the expense of actinolite. The preservation of the isotopic compositions of gabbroic and basaltic oceanic crust and the equilibrium fractionations among minerals shows that high-pressure metamorphism occurred at low water/rock ratios. The isotopic equilibrium is only observed at hand-specimen scale, at an outcrop scale isotopic compositional differences occur among adjacent rocks. This heterogeneity reflects metre-scale compositional variations that developed during hydrothermal alteration by seawater and were subsequently inherited by the high-pressure metamorphic rocks. Received: 4 January 1999 / Accepted: 7 July 1999     

The geology and geochronology of the Annandagstoppane granite,Western Dronning Maud Land,Antarctica

The Annandagstoppane Granite is exposed at three nunataks in Western Dronning Maud Land, Antarctica. It comprises medium- to coarse-grained granite crosscut by veins of pegmatite and graphic granite and has many S-type characteristics such as containing normative corundum greater than 1.1%, molecular Al₂O₃/(CaO+K₂O+Na₂O) greater than 1.1 and very little zircon. Hydrothermal alteration in the Granite is variably developed and has affected only certain minerals in any phase. R-Sr and Pb whole rock and mineral isotopic data suggest: 1) that Sr isotopes within it were nearly homogenized on a whole rock scale about 2823 Ma ago by this hydrothermal alteration; 2) that the Pb isotopic system was also disturbed at that time, and 3) that the Granite may have been was emplaced sometime during the interval 3115 Ma to 2945 Ma ago. The Granite was probably intruded by the Annandagstoppane Gabbro about 1200 Ma ago, resetting the Rb-Sr system in biotite. The Annandagstoppane Granite may form part of a basement complex to the Proterozoic sedimentary, volcanic and mafic igneous rocks exposed to the east in the Ahlmannryggen and the Borgmassivet. Its chemical composition and geologic history appears to be unique in Antarctica and in the Kaapvaal Craton of Southern Africa, consistent with the possibility that the Annandagstoppane Granite is part of a crustal fragment that joined Antarctica relatively late in the history of that continent.     

Another sea area separated from the Panthalassic Ocean in the Norian,the Late Triassic: The lowest Sr isotopic composition of the Ishimaki limestone in central Japan

Mt. Ishimaki is the Jurassic accretionary complex of the Chichibu Belt in Toyohashi City, near Nagoya in central Japan. The Ishimaki limestone is thought to be seamount-type limestone. The P₁ elements of the conodonts Norigondolella navicula and Ancyrogondolella quadrata found in the limestone indicate it is of Norian age. The Sr isotopic compositions of 45 Ishimaki limestone samples ranged from 0.7055 to 0.7077. Eighteen of these samples had lower Sr isotopic compositions than the lowest Sr isotopic composition (0.7068) of seawater throughout the Phanerozoic. The Sr isotopic compositions in the limestone block are generally lower at the base of the block and higher at the top. The present Sr isotopic compositions of the Ishimaki limestone are unlikely to have been reduced by post-depositional alteration because most of the limestone samples had a low amount of Mn (<300 ppm) or high Sr/Mn ratios (>2) and the conodont elements had low (1–2) CAI (conodont alteration index) values. Additionally, there was little acid-insoluble residue. Thus, the low Sr isotopic compositions are thought to represent the strontium of the past ambient seawater. The low Sr isotopic compositions are in complete disagreement with the generally recognised range of seawater Sr isotopic compositions in the Norian stage of the Late Triassic (0.7075–0.7078) because the depositional environment of the Ishimaki limestone was closed or semi-closed from the Panthalassic Ocean. Therefore, the Sr isotopic composition of the limestone differs from that of the Panthalassic seawater. The low Sr isotopic compositions were probably affected by Sr inflows from mafic oceanic crust by hydrothermal fluid circulation or from hinterlands surrounded by mafic rocks by river water circulation.     

Geochemical and H-O-Sr-Nd isotope evidence for magmatic processes and meteoric-water interactions in the basal complex of La Gomera, Canary Islands

The plutonic rocks of the Basal Complex of La Gomera, Canary Islands, Spain, were studied by means of major and trace element contents and by H-O-Sr-Nd isotope compositions in order to distinguish primary magmatic characteristics and late-stage alteration products. Deciphering the effects of alteration allowed us to determine primary, plume-related compositions that indicated D- and ¹⁸O-depletion relative to normal upper mantle, supporting the conclusions of earlier studies on the plutonic rocks of Fuerteventura and La Palma. Late-stage alteration took place during the formation of the intrusive series induced by interaction with meteoric water. Inferred isotopic compositions of the meteoric water indicate that the water infiltrated into the rock edifice at a height of about 1500 m above sea level, suggesting the existence of a subaerial volcano which was active during the intrusive activity and that it has been either distroyed or remain buried by later volcanic and landslide events.     

Stable Carbon Isotopic Compositions of Methylated-MTTC in Crude Oils from Saline Lacustrine Depositional Environment: Source Implications

Significantly high abundant methyl-MethylTrimethylTridecylChromans (MTTCs) have been detected in aromatic hydrocarbon fractions in crude oils from the Jizhong Depression and Jianghan Basin. The distribution of these compounds is dominated by methyl-MTTC and dimethyl-MTTC series, which indicate diagenetic products of a hypersaline depositional environment in the early stage and show a low degree of methylation. The occurrence of significantly high abundant methyl-MTTC depends mainly on good preservation conditions with a strongly reductive, hypersaline and water-columned depositional environment and subsequent non-intensive diagenetic transformations. The stable carbon isotopic compositions of the methyl-MTTCs and dimethyl-MTTCs in two samples are far different from the stable carbon isotopic composition of C30 hopane of apparent bacteria biogenesis (up to 4.11‰ and 5.75‰, respectively). This obviously demonstrates that the methyl-MTTC and dimethyl-MTTCs cannot be of bacteria origin, which is different from the previous point of view about non-photosynthetic bacteria products or possible bacteria-reworked products. On the contrary, the stable carbon isotopic compositions of methyl-MTTC and dimethyl-MTTCs in the two samples were similar to that of the same carbon-numbered n-alkanes (nC27-nC28-nC29), which indicates that they share the same source origin. Especially in the crude oil from the Zhao61 well, stable carbon isotopic compositions are also similar to that of the same carbon-numbered steranes with ααα-20R isomer (mostly less than 0.4‰). In consideration of the results of previous studies on saline lake ecological sedimentation, the authors hold that the methyl-MTTC and dimethyl-MTTCs in the saline lake sediments should be of algal biogenesis origin.     

Kaolin Occurrences in the Erenler Dagi Volcanics,Southwest Konya Province,Turkey

Mainly calc-alkaline, andesitic, and dacitic volcanics from different late Miocene-Pliocene eruption centers crop out WSW of Konya, and locally are interbedded with lacustrine sediments. Hydrothermal alteration within these rocks is widespread. In addition to kaolinite, other major alteration products include halloysite, alunite, cristobalite, quartz, illite, montmorillonite, and zeolitegroup minerals. Based on the cristobalite-quartz relationship, the kaolinization temperature is estimated as ～100°C.

The samples were mineralogically and chemically examined using XRD, SEM-EDS, IR, DTA-TG, and XRF. The crystallinity of the kaolinite is moderate, and shows structural disorder. Both the kaolinite and halloysite are almost stoichometric. Kaolinization generally led to Al₂O₃ increases and release of alkalies, alkaline earths, most of the Fe₂O₃, and SiO₂. SiO₂ and Al₂O₃ contents are low, and LOI is very high for halloysite deposits relative to kaolin occurrences. The kaolinite-alunite assemblages indicate that pH of the altering solutions initially was ～4. SEM investigation demonstrates that kaolinite has booklet texture, whereas halloysite is acicular to needleshaped. The chemical, mineralogic, and firing properties of the kaolin deposits are appropriate for use as refractory raw material. The Erenler Dagi kaolin deposits are excellent examples of the acid-sulfate type of hydrothermal alteration. The findings of the study may be useful in exploration for similar hydrothermal mineral occurrences worldwide.     

Geological and Geochemical Characteristics of the Hydrothermal Clay Alteration in South Korea

Abstract: Hydrothermally altered areas forming pyrophyllite‐kaolin‐sericite‐alunite deposits are distributed in Chonnam and Kyongsang areas, Cretaceous volcanic field of the Yuchon Group. The Chonnam alteration area is located within depression zone which is composed of volcanic and granitic rocks of late Cretaceous age. The clay deposits of this area show the genetic relationship with silicic lava domes. The Kyongsang alteration area is mainly distributed within Kyongsang Basin comprising volcanic, sedimentary and granitic rocks of Cretaceous and Tertiary age. Most of the clay deposits of this area are closely related to cauldrons. Paleozoic clay deposit occurs in the contact zone between Precambrian Hongjesa granite gneiss and Paleozoic Jangsan quartzite of Choson Supergroup. Cretaceous igneous rocks of the both alteration areas belong to high K calc‐alkaline series formed in the volcanic arc of continental margin by subduction‐related magmatism. Chonnam igneous rocks show more enrichment of crustal components such as K, La, Ce, Sm, Nd and Ba, higher (La/Yb)cn ratio, and higher initial ⁸⁷Sr/⁸⁶Sr ratio (0. 708 to 0. 712) than those of Kyongsang igneous rocks. This might be due to the difference of degree of crustal contamination during Cretaceous magmatism. The most characteristic alteration minerals of Chonnam clay deposits are alunite, kaolin, quartz, pyrophyllite and diaspore which were formed by acidic solution. Those of Kyongsang clay deposits are sericite, quartz and pyrophyllite which were formed by weak acid and neutral solution. The formation ages of the clay deposits of two alteration areas range from 70. 1 to 81. 4 Ma and 39. 7 to 79. 4 Ma, respectively. The Daehyun clay deposit in Ponghwa area of Kyongsang province shows the alteration age range from 290 to 336 Ma. This result shows the different alteration episode from the hydrothermal alteration of Cretaceous to early Tertiary in the Kyongsang and Chonnam alteration areas. These data indicate, at least, three hydrothermal activities of Tertiary (middle to late Eocene), late Cretaceous (Santonian to Maastrichtian) and Paleozoic Carboniferous Periods in South Korea.     

Microbial alteration of natural gas in Xinglongtai field of the Bohai Bay Basin, China

Xinglongtai field has been an important petroleum-producing area of Liaohe Depression for 30 years. Oil exploration and production were the focus of this field, but the gas was ignored. This study examined twenty five gas samples with the purpose of determining the gas genetic types and their geochemical characteristics. Molecular components, stable carbon isotopic compositions and light hydrocarbons were also measured, and they proved that microbial activity has attacked some of the gas components which resulted in unusual carbon isotopic distributions. Propane seems to be selectively attacked during the initial stage of microbial alteration, with abnormally lower con-tent compared to that of butane as well as anomalously heavy carbon isotope. As a consequence, the carbon isotopic distribution among the gas components is partially reverse, as δ13C1<δ13C2<δ13C3>δ13C4. Besides, n-alkanes of C3+ gas components are preferentially attacked during the process of microbial alteration. This is manifested that n-alkanes are more enriched in 13C than corresponding iso-alkanes. As a result, the concentrations of n-alkanes be-come very low, which may be misleading in indentifying the gas genetic types. As to four gas samples, light hydro-carbon compositions display evidence for microbial alteration. The sequence of hexane isomers varies obviously with high content of 2,3-DMC4, which indicates that they have been in the fourth level of extensively bacterial al-teration. So the geochemical characteristics can be affected by microbial alteration, and recognition of microbial alteration in gas accumulations is very important for interpreting the natural gas genetic types.     

Stable isotope evidence for magmatic fluid input during large-scale Na–Ca alteration in the Cloncurry Fe oxide Cu–Au district, NW Queensland, Australia

Sodic–calcic alteration is common in mineralized hydrothermal systems, yet the relative importance of igneous vs. basinal fluid sources remains controversial. One of the most extensive volumes of sodic–calcic rocks occurs near Cloncurry, NW Queensland, and was formed by overlapping hydrothermal systems that were active synchronously with emplacement of mid‐crustal batholithic granitoids (c. 1.55–1.50 Ga). Altered rocks contain albite–oligoclase, actinolite, diopside, titanite and magnetite. Alteration was localized by: (A) composite veins and breccias containing crystallized magma intimately intergrown with hydrothermal precipitates; (B) intrusions that host setting A veins and breccias; and (C) extensive breccia and vein systems linked to regional fault systems. Isotope analyses of actinolites in settings A and B indicate calculated δ¹⁸O_H2O (+8.2 to +10.6‰) and variably depleted δD_H2O (?130 to ?54‰) compared with typical magmatic fluids, whereas those from setting C typically indicate calculated δ¹⁸O_H2O (+8.0 to +12.8‰) and δD_H2O (?29 to ?99‰). The lowest δD_H2O values are interpreted as representing residual fluids after significant (> 90%) open‐system magmatic degassing. Overall the stable isotope, field, geochronological and geobarometric data suggest that these sodic–calcic alteration systems were formed by the episodic incursion of magmatic fluids that underwent minor isotopic modification as a result of varying degrees of interaction with country rocks.