The Proterozoic,albitite-hosted,Valhalla uranium deposit,Queensland, Australia: a description of the alteration assemblage associated with uranium mineralisation in diamond drill hole V39

The Valhalla uranium deposit, located 40 km north of Mount Isa, Queensland, Australia, is an albitite-hosted, Mesoproterozoic U deposit similar to albitite-hosted uranium deposits in the Ukraine, Sweden, Brazil and Guyana. Uranium mineralisation is hosted by a thick package of interbedded fine-grained sandstones, arkoses and gritty siltstones that are bound by metabasalts belonging to the ca. 1,780 Ma Eastern Creek Volcanics in the Western Succession of the Mount Isa basin. Alteration associated with U mineralisation can be divided into an early, main and late stage. The early stage is dominated by laminated and intensely altered rock comprising albite, reibeckite, calcite, (titano)magnetite ± brannerite. The main stage of mineralisation is dominated by brecciated and intensely altered rocks that comprise laminated and intensely altered rock cemented by brannerite, apatite, (uranoan)-zircon, uraninite, anatase, albite, reibeckite, calcite and hematite. The late stage of mineralisation comprises uraninite, red hematite, dolomite, calcite, chlorite, quartz and Pb-, Fe-, Cu-sulfides. Brannerite has U–Pb and Pb–Pb ages that indicate formation between 1,555 and 1,510 Ma, with significant Pb loss evident at ca. 1,200 Ma, coincident with the assemblage of Rodinia. The oldest ages of the brannerite overlap with ⁴⁰Ar/³⁹Ar ages of 1,533 ± 9 Ma and 1,551 ± 7 Ma from early and main-stage reibeckite and are interpreted to represent the timing of formation of the deposit. These ages coincide with the timing of peak metamorphism in the Mount Isa area during the Isan Orogeny. Lithogeochemical assessment of whole rock data that includes mineralised and unmineralised samples from the greater Mount Isa district reveals that mineralisation involved the removal of K, Ba and Si and the addition of Na, Ca, U, V, Zr, P, Sr, F and Y. U/Th ratios indicate that the ore-forming fluid was oxidised, whereas the crystal chemistry of apatite and reibeckite within the ore zone suggests that F⁻ and were important ore-transporting complexes. δ¹⁸O values of co-existing calcite and reibeckite indicate that mineralisation occurred between 340 and 380°C and involved a fluid having δ¹⁸O_fluid values between 6.5 and 8.6‰. Reibeckite δD values reveal that the ore fluid had a δD_fluid value between −98 and −54‰. The mineral assemblages associated with early and main stages of alteration, plus δ¹⁸O_fluid and δD_fluid values, and timing of the U mineralisation are all very similar to those associated with Na–Ca alteration in the Eastern Succession of the Mount Isa basin, where a magmatic fluid is favoured for this style of alteration. However, isotopic data from Valhalla is also consistent with that from the nearby Mount Isa Cu deposit where a basinal brine is proposed for the transport of metals to the deposit. Based on the evidence to hand, the source fluids could have been derived from either or both the metasediments that underlie the Eastern Creek Volcanics or magmatism that is manifest in the Mount Isa area as small pegmatite dykes that intruded during the Isan Orogeny.     

Carbonate alteration associated with talc-chlorite mineralization in the eastern Pyrenees, with emphasis on the St. Barthelemy Massif

Summary The eastern Pyrenees host a large number of talc-chlorite mineralizations of Albian age (112–97 Ma), the largest of which occur in the St. Barthelemy massif. There talc develops by hydrothermal replacement of dolostones, which were formed by alteration of calcite marbles. This alteration is progressive. Unaltered calcite marbles have oxygen isotope composition of about 25‰ (V-SMOW). The δ¹⁸O values decrease down to values of 12‰ towards the contact with dolostones. This ¹⁸O depletion is accompanied by Mg enrichment, LREE fractionation and systematic shifts in the Sr isotope compositions, which vary from ⁸⁷Sr/⁸⁶Sr = 0.7087–0.7092 in unaltered calcite marbles to slightly more radiogenic compositions with ⁸⁷Sr/⁸⁶Sr = 0.7094 near dolomitization fronts. Dolostones have δ¹⁸O values (about 9‰) lower than calcitic marbles, higher REE content and more radiogenic Sr isotope composition (⁸⁷Sr/⁸⁶Sr = 0.7109 to 0.7130). Hydrothermal calcites have δ¹⁸O values close to dolostones but substantially lower δ¹³C values, down to −6.5‰, which is indicative of the contribution of organic matter. The REE content of hydrothermal calcite is one order of magnitude higher than that of calcitic marbles. Its highly radiogenic Sr composition with ⁸⁷Sr/⁸⁶Sr = 0.7091 to 0.7132 suggests that these elements were derived from silicate rocks, which experienced intense chlorite alteration during mineralization. The chemical and isotopic compositions of the calcite marbles, the dolostones and the hydrothermal calcites are interpreted as products of successive stages of fluid-rock interaction with increasing fluid-rock ratios. The hydrothermal quartz, calcite, talc and chlorite are in global mutual isotopic equilibrium. This allows the calculation of the O isotope composition of the infiltrating water at 300 °C, which is in the δ¹⁸O = 2–4.5‰ range. Hydrogen isotope compositions of talc and chlorite indicate a δD = 0 to −20‰. This water probably derived from seawater, with minor contribution of evolved continental water.     

Stable isotopes and amphibole chemistry on hydrothermally altered granitoids in the North Chilean Precordillera: a limited role for meteoric water?

Whole rock and mineral stable isotope and microprobe analyses are presented from granitoids of the North Chilean Precordillera. The Cretaceous to Tertiary plutonic rocks contain important ore deposits and frequently display compositional and textural evidence of hydrothermal alteration even in barren rocks. Deuteric alteration includes replacement of biotite and amphibole by chlorite and epidote, sericitization and saussuritization of feldspars, and uralitization of clinopyroxene and/or amphibole. While whole rock compositions are not significantly affected, compositional variations in amphiboles suggest two types of hydrothermal alteration. Hornblende with actinolitic patches and rims and tight compositional trends from hornblende to Mg-rich actinolite indicate increasing oxygen fugacity from magmatic to hydrothermal conditions. Uralitic amphiboles exhibiting irregular Mg-Fe distribution and variable Al content are interpreted as reflecting subsolidus hydration reactions at low temperatures. The δD values of hydrous silicates vary from −63 to −105‰. Most δ¹⁸O values of whole rocks are in the range of 5.7 to 7.7‰ and are considered normal for igneous rocks in the Andes. These δ¹⁸O values also coincide well with the oxygen isotope composition of geochemically similar recent volcanics from the Central Andean Volcanic Zone (δ¹⁸O = 7.0–7.4‰). Only one sample in this study (δ¹⁸O = 3.0‰) appears to be depleted by isotope exchange with light meteoric water at high temperatures. The formation of secondary minerals in all other intrusions is mainly the product of deuteric alteration. This also holds true for the sample from El Abra, the only pluton associated with mineralization. This indicates the dominant role of a magmatic rather than a meteoric fluid in the alteration of the Cretaceous and Tertiary granitoids in northern Chile. Received: 8 July 1998 / Accepted: 15 April 1999     

The origin of high δ<Superscript>18</Superscript>O zircons: marbles,megacrysts, and metamorphism

The oxygen isotope ratios (δ¹⁸O) of most igneous zircons range from 5 to 8‰, with 99% of published values from 1345 rocks below 10‰. Metamorphic zircons from quartzite, metapelite, metabasite, and eclogite record δ¹⁸O values from 5 to 17‰, with 99% below 15‰. However, zircons with anomalously high δ¹⁸O, up to 23‰, have been reported in detrital suites; source rocks for these unusual zircons have not been identified. We report data for zircons from Sri Lanka and Myanmar that constrain a metamorphic petrogenesis for anomalously high δ¹⁸O in zircon. A suite of 28 large detrital zircon megacrysts from Mogok (Myanmar) analyzed by laser fluorination yields δ¹⁸O from 9.4 to 25.5‰. The U–Pb standard, CZ3, a large detrital zircon megacryst from Sri Lanka, yields δ¹⁸O = 15.4 ± 0.1‰ (2 SE) by ion microprobe. A euhedral unzoned zircon in a thin section of Sri Lanka granulite facies calcite marble yields δ¹⁸O = 19.4‰ by ion microprobe and confirms a metamorphic petrogenesis of zircon in marble. Small oxygen isotope fractionations between zircon and most minerals require a high δ¹⁸O source for the high δ¹⁸O zircons. Predicted equilibrium values of Δ¹⁸O(calcite-zircon) = 2–3‰ from 800 to 600°C show that metamorphic zircon crystallizing in a high δ¹⁸O marble will have high δ¹⁸O. The high δ¹⁸O zircons (>15‰) from both Sri Lanka and Mogok overlap the values of primary marine carbonates, and marbles are known detrital gemstone sources in both localities. The high δ¹⁸O zircons are thus metamorphic; the 15–25‰ zircon values are consistent with a marble origin in a rock-dominated system (i.e., low fluid_(external)/rock); the lower δ¹⁸O zircon values (9–15‰) are consistent with an origin in an external fluid-dominated system, such as skarn derived from marble, although many non-metasomatized marbles also fall in this range of δ¹⁸O. High δ¹⁸O (>15‰) and the absence of zoning can thus be used as a tracer to identify a marble source for high δ¹⁸O detrital zircons; this recognition can aid provenance studies in complex metamorphic terranes where age determinations alone may not allow discrimination of coeval source rocks. Metamorphic zircon megacrysts have not been reported previously and appear to be associated with high-grade marble. Identification of high δ¹⁸O zircons can also aid geochronology studies that seek to date high-grade metamorphic events due to the ability to distinguish metamorphic from detrital zircons in marble.     

电子探针测年方法应用于晶质铀矿的成因类型探讨

电子探针Th-U-Pb测年因其高分辨率与高精度的优势,在独居石、锆石等定年矿物中得到了推广,但在Th、U、Pb含量高的晶质铀矿、沥青铀矿等矿物中则应用较少。本文在铁矿床变质岩绿泥石、阳起石黑云母蚀变岩首次发现U含量高的晶质铀矿,基于此,结合该铁矿床地区的地质背景,利用偏光显微镜与电子探针等分析测试手段,将镜下蚀变现象、年龄计算与其他相关元素分析相结合,重点对晶质铀矿的成矿年龄及成矿规律进行探讨。研究发现:通过镜下观察判断,晶质铀矿的成因类型与澳大利亚著名的变质型铀矿相似,均为古老的变质型,且周围的脉石矿物均为绿泥石,绿泥石皆由黑云母退变质而成,铀矿的赋存位置显示其与黑云母、绿泥石之间有紧密联系,其成矿年龄与黑云母、绿泥石形成年龄息息相关。继而根据电子探针数据计算成矿年龄,判断成矿期次,得出主要成矿期在(1654±17)Ma~(1805±17)Ma,为中元古代中期,且主要成矿期与热液蚀变作用黑云母化有关,后期活化富集时期在(657±17)Ma~(807±17)Ma,为新元古代南华纪时期,此阶段是热液侵入、绿泥石化广泛发育的时期;选取较大颗粒对晶质铀矿的环带年龄进行计算,从年龄分布上证实后期有强烈的流体活动的发生,且主要与绿泥石化相关。另外,对比变质型与沉积型铀矿中Y2O3与UO2含量发现,两者之间存在负相关关系,此关系对判断铀矿成因即是否为变质型或沉积型可能有指示意义,但缺乏大量的数据佐证,需进一步研究。     

Stable isotope geochemistry and diagenetic mineralization associated with the Tono sandstone-type uranium deposit in Japan

The Tono sandstone-type uranium mine area, middle Honsyu, Japan is composed of Miocene lacustrine sedimentary rocks in the lower part (18–22 Ma) and marine facies in the upper part (15–16 Ma). Calcite and pyrite occur as dominant diagenetic alteration products in these Neogene sedimentary rocks. The characteristics of calcite and pyrite differ significantly between lacustrine and marine facies. Abundant pyrite, calcite, organic matter, and small amounts of marcasite or pyrrhotite occur in the lacustrine facies, whereas small amounts of calcite and framboidal pyrite, organic matter and no marcasite or pyrrhotite are found within the marine units. The δ¹³C values of calcite in the lacustrine deposits are low (−19 to −6‰ PDB) but those in marine formation are high (−11 to +3‰). This implies that the contribution of marine carbonate is larger in upper marine sedimentary rocks, and carbon in calcite in the lower lacustrine formation was derived both from oxidation of organic matter and from dissolved marine inorganic carbon. The δ³⁴S values of framboidal pyrite in the upper marine formation are low (−14 to −8‰ CDT), indicating a small extent of bacterial seawater sulfate reduction, whereas those of euhedral-subhedral pyrite in the lower lignite-bearing arkose sandstone are high (+10 to +43‰), implying a large extent of closed-system bacterial seawater sulfate reduction. The δ³⁴S and δ¹³C data which deviate from a negative correlation line toward higher δ¹³C values suggest methanogenic CO₂ production. During diagenesis of the lacustrine unit, large amounts of euhedral-subhedral pyrite were formed, facilitated by extensive bacterial reduction of seawater sulfate with concomitant oxidation of organic matter, and by hydrolysis reactions of organic matter, producing CH₄ and CO₂. Uranium minerals (coffinite and uraninite) were also formed at this stage by the reduction of U⁶⁺ to U⁴⁺. The conditions of diagenetic alteration within the lacustrine deposits and uranium mineralization is characterized by low Eh in which nearly equal concentrations of CH₄ and HCO₃ ⁻ existed and reduced sulfur species (H₂S, HS⁻) are predominant among aqueous sulfur species, whereas diagenetic alteration of the marine formations was characterized by a predominance of SO₄ ²⁻ among dissolved sulfur species. Modern groundwater in the lacustrine formation has a low Eh value (−335 mV). Estimated and measured low Eh values of modern and ancient interstitial waters in lacustrine environments indicate that a reducing environment in which U⁴⁺ is stable has been maintained since precipitation of uranium minerals. Received: 9 February 1996 / Accepted: 11 April 1997     

Phase equilibrium and stable isotope constraints on the formation of metasomatic garnet-vesuvianite veins (SW Adamello,N Italy)

 Metasomatic garnet-vesuvianite veins occur within the contact metamorphic marble sequence of the Lower Triassic Prezzo formation in a narrow, 1–5 m wide zone along an intrusive marble-granodiorite contact at the southwestern border of the Tertiary Adamello batholith. The metasomatic mineral assemblage is comprised of garnet, vesuvianite, clinopyroxene, wollastonite, and pyrrhotite, which were precipitated from the vein-forming fluid in a preexisting calcite matrix at conditions of about 2800 bars and 630° C. The veins are enriched in silicon, aluminum, iron, magnesium, titanium and depleted in calcium with respect to the unaltered contact metamorphic marble. Graphite, which is present in the unaltered Prezzo Marble is absent in the veins. Irregularly shaped mineralogically distinct zones with different degrees of silicification can be distinguished within the veins. The isotopic compositions of calcite (cc) in the unaltered marble are about δ¹⁸O (SMOW; Standard mean Ocean Water)=21.0‰ and δ¹³C(PDB; Peedee belemnite)=0.0‰. They are reset to significantly lower values within the veins, where δ¹⁸O_cc is 15.0 to 16.0‰ and δ¹³C_cc is −4.5 to −3.5‰. The isotopic front coincides with an abrupt change in the microscopic texture of matrix carbonate which occurs at the sharp boundary between graphite-bearing and graphite-free material. Within the veins the oxygen isotope fractionation between calcite and garnet (gar) varies systematically with distance from highly silicified zones. The variations in Δ¹⁸O_cc-gar are as large as 2‰, on a millimeter scale, indicating garnet-calcite isotopic disequilibrium. Vein formation was due to the infiltration of a water rich fluid of magmatic provenance into the carbonate country rock along fractures. Removal of graphite from the wall rock by dissolution through the metasomatic fluid induced recrystallization of matrix calcite. Permeability was enhanced during calcite recrystallization facilitating material transport into the wall rock and metasomatic alteration. Vein garnet was precipitated in isotopic equilibrium with the metasomatic fluid. The isotopic composition of preexisting calcite was initially out of equilibrium with the vein-forming fluid and it was shifted towards equilibrium by surface-reaction controlled calcite-fluid isotopic exchange during calcite recrystallization. Due to the short lifetime of the metasomatic system, calcite-fluid isotopic equilibrium was generally not attained. Within the veins, oxygen and carbon transport was fast relative to mineral-fluid exchange of their isotopes and the geometry of the isotopic pattern is largely controlled by the kinetics of mineral-fluid exchange. Received: 16 June 1994/Accepted: 20 May 1995     

Mineralogical, fluid inclusion, and stable isotope constraints on mechanisms of ore deposition at the Samgwang mine (Republic of Korea)—a mesothermal, vein-hosted gold–silver deposit

The Samgwang mine is located in the Cheongyang gold district (Cheonan Metallogenic Province) of the Republic of Korea. It consists of eight massive, gold-bearing quartz veins that filled NE- and NW-striking fractures along fault zones in Precambrian granitic gneiss of the Gyeonggi massif. Their mineralogy and paragenesis allow two separate vein-forming episodes to be recognized, temporally separated by a major faulting event. The ore minerals occur in quartz and calcite of stage I, associated with fracturing and healing of veins. Hydrothermal wall-rock alteration minerals of stage I include Fe-rich chlorite (Fe/(Fe+Mg) ratios 0.74-0.81), muscovite, illite, K-feldspar, and minor arsenopyrite, pyrite, and carbonates. Sulfide minerals deposited along with electrum during this stage include arsenopyrite, pyrite, pyrrhotite, sphalerite, marcasite, chalcopyrite, galena, argentite, pyrargyrite, and argentian tetrahedrite. Only calcite was deposited during stage II. Fluid inclusions in quartz contain three main types of C–O–H fluids: CO₂-rich, CO₂–H₂O, and aqueous inclusions. Quartz veins related to early sulfides in stage I were deposited from H₂O–NaCl–CO₂ fluids (1,500–5,000 bar, average 3,200) with T _htotal values of 200°C to 383°C and salinities less than about 7 wt.% NaCl equiv. Late sulfide deposition was related to H₂O–NaCl fluids (140–1,300 bar, average 700) with T _htotal values of 110°C to 385°C and salinities less than about 11 wt.% NaCl equiv. These fluids either evolved through immiscibility of H₂O–NaCl–CO₂ fluids as a result of a decrease in fluid pressure, or through mixing with deeply circulated meteoric waters as a result of uplift or unloading during mineralization, or both. Measured and calculated sulfur isotope compositions (δ³⁴S_H2S = 1.5 to 4.8‰) of hydrothermal fluids from the stage I quartz veins indicate that ore sulfur was derived mainly from a magmatic source. The calculated and measured oxygen and hydrogen isotope compositions (δ¹⁸O_H2O = −5.9‰ to 10.9‰, δD = −102‰ to −87‰) of the ore-forming fluids indicate that the fluids were derived from magmatic sources and evolved by mixing with local meteoric water by limited water–rock exchange and by partly degassing in uplift zones during mineralization. While most features of the Samgwang mine are consistent with classification as an orogenic gold deposit, isotopic and fluid chemistry indicate that the veins were genetically related to intrusions emplaced during the Jurassic to Cretaceous Daebo orogeny.     

Hydrothermal alteration,fluid inclusions and stable isotope systematics of the Alvo 118 iron oxide–copper–gold deposit,Carajás Mineral Province (Brazil): Implications for ore genesis

The Alvo 118 iron oxide–copper–gold (IOCG) deposit (170 Mt at 1.0 wt.% Cu, 0.3 g/t Au) lies in the southern sector of the Itacaúnas Shear Belt, Carajás Mineral Province, along a WNW–ESE-striking, 60-km-long shear zone, close to the contact of the ~2.76-Ga metavolcano-sedimentary Itacaiúnas Supergroup and the basement (~3.0 Ga Xingu Complex). The Alvo 118 deposit is hosted by mafic and felsic metavolcanic rocks and crosscutting granitoid and gabbro intrusions that have been subjected to the following hydrothermal alteration sequence towards the ore zones: (1) poorly developed sodic alteration (albite and scapolite); (2) potassic alteration (biotite or K-feldspar) accompanied by magnetite formation and silicification; (3) widespread, pervasive chlorite alteration spatially associated with quartz–carbonate–sulphide infill ore breccia and vein stockworks; and (4) local post-ore quartz–sericite alteration. The ore assemblage is dominated by chalcopyrite (~60%), bornite (~10%), hematite (~20%), magnetite (10%) and subordinate chalcocite, native gold, Au–Ag tellurides, galena, cassiterite, F-rich apatite, xenotime, monazite, britholite-(Y) and a gadolinite-group mineral. Fluid inclusion studies in quartz point to a fluid regime composed of two distinct fluid types that may have probably coexisted within the timeframe of the Cu–Au mineralizing episode: a hot (>200°C) saline (32.8‰ to 40.6 wt.% NaCl eq.) solution, represented by salt-bearing aqueous inclusions, and a lower temperature (<200°C), low to intermediate salinity (<15 wt.% NaCl eq.) aqueous fluid defined by two-phase (L_H2O + V_H2O) fluid inclusions. This trend is very similar to those defined for other IOCG systems of the Carajás Mineral Province. δ ¹⁸O_H2O values in equilibrium with calcite (−1.0‰ to 7.5‰ at 277°C to 344°C) overlap the lower range for primary magmatic waters, but the more ¹⁸O-depleted values also point to the involvement of externally derived fluids, possibly of meteoric origin. Furthermore, sulphide δ ³⁴S values (5.1‰ to 6.3‰), together with available boron isotope and Cl/Br–Na/Cl data provide evidence for a significant component of residual evaporative fluids (e.g., bittern fluids generated by seawater evaporation) in this scenario that, together with magma-derived brines, would be the main sources of the highly saline fluids involved in the formation Alvo 118 IOCG deposit. The restricted high temperature sodic alteration, the pervasive overprinting of the potassic alteration minerals by chlorite proximal to the ore zones, ore breccias with open-space filling textures in brittle structures, microthermometric and stable isotope data indicate, collectively, that the Alvo 118 IOCG system developed at structurally high levels and may be considered the shallower representative of the IOCG systems of the CMP.     

Magmatic-dominated fluid evolution in the Jurassic Nambija gold skarn deposits (southeastern Ecuador)

The Jurassic (approximately 145 Ma) Nambija oxidized gold skarns are hosted by the Triassic volcanosedimentary Piuntza unit in the sub-Andean zone of southeastern Ecuador. The skarns consist dominantly of granditic garnet (Ad_20–98) with subordinate pyroxene (Di_46–92Hd_17–42Jo_0–19) and epidote and are spatially associated with porphyritic quartz-diorite to granodiorite intrusions. Endoskarn is developed at the intrusion margins and grades inwards into a potassic alteration zone. Exoskarn has an outer K- and Na-enriched zone in the volcanosedimentary unit. Gold mineralization is associated with the weakly developed retrograde alteration of the exoskarn and occurs mainly in sulfide-poor vugs and milky quartz veins and veinlets in association with hematite. Fluid inclusion data for the main part of the prograde stage indicate the coexistence of high-temperature (500°C to >600°C), high-salinity (up to 65 wt.% eq. NaCl), and moderate- to low-salinity aqueous-carbonic fluids interpreted to have been trapped at pressures around 100–120 MPa, corresponding to about 4-km depth. Lower-temperature (510–300°C) and moderate- to low-salinity (23–2 wt.% eq. NaCl) aqueous fluids are recorded in garnet and epidote of the end of the prograde stage. The microthermometric data (Th from 513°C to 318°C and salinity from 1.0 to 23 wt.% eq. NaCl) and δ¹⁸O values between 6.2‰ and 11.5‰ for gold-bearing milky quartz from the retrograde stage suggest that the ore-forming fluid was dominantly magmatic. Pressures during the early retrograde stage were in the range of 50–100 MPa, in line with the evidence for CO₂ effervescence and probable local boiling. The dominance of magmatic low-saline to moderately saline oxidizing fluids during the retrograde stage is consistent with the depth of the skarn system, which could have delayed the ingression of external fluids until relatively low temperatures were reached. The resulting low water-to-rock ratios explain the weak retrograde alteration and the compositional variability of chlorite, essentially controlled by host rock compositions. Gold was precipitated at this stage as a result of cooling and pH increase related to CO₂ effervescence, which both result in destabilization of gold-bearing chloride complexes. Significant ingression of external fluids took place after gold deposition only, as recorded by δ¹⁸O values of 0.4‰ to 6.2‰ for fluids depositing quartz (below 350°C) in sulfide-rich barren veins. Low-temperature (<300°C) meteoric fluids (δ¹⁸O_water between −10.0‰ and −2.0‰) are responsible for the precipitation of late comb quartz and calcite in cavities and veins and indicate mixing with cooler fluids of higher salinities (about 100°C and 25 wt.% eq. NaCl). The latter are similar to low-temperature fluids (202–74.5°C) with δ¹⁸O values of −0.5‰ to 3.1‰ and salinities in the range of 21.1 to 17.3 wt.% eq. CaCl₂, trapped in calcite of late veins and interpreted as basinal brines. Nambija represents a deep equivalent of the oxidized gold skarn class, the presence of CO₂ in the fluids being partly a consequence of the relatively deep setting at about 4-km depth. As in other Au-bearing skarn deposits, not only the prograde stage but also the gold-precipitating retrograde stage is dominated by fluids of magmatic origin.     

Hypogene Zn carbonate ores in the Angouran deposit,NW Iran

The world-class Angouran nonsulfide Zn–Pb deposit is one of the major Zn producers in Iran, with resources estimated at about 18 Mt at 28% Zn, mainly in the form of the Zn carbonate smithsonite. This study aims to characterize these carbonate ores by means of their mineralogy and geochemistry, which has also been extended to the host rocks of mineralization and other local carbonate rock types, including the prominent travertines in the Angouran district, as well as to the local spring waters. Petrographical, chemical, and stable isotope (O, H, C, Sr) data indicate that the genesis of the Zn carbonate ores at Angouran is fairly distinct from that of other “classical” nonsulfide Zn deposits that formed entirely by supergene processes. Mineralization occurred during two successive stages, with the zinc being derived from a preexisting sulfide ore body. A first, main stage of Zn carbonates (stage I carbonate ore) is associated with both preexisting and subordinate newly formed sulfides, whereas a second stage is characterized by supergene carbonates (Zn and minor Pb) coexisting with oxides and hydroxides (stage II carbonate ore). The coprecipitation of smithsonite with galena, pyrite and arsenopyrite, as well as the absence of Fe- and Mn-oxides/hydroxides and of any discernible oxidation or dissolution of the sphalerite-rich primary sulfide ore, shows that the fluids responsible for the main, stage I carbonate ores were relatively reduced and close to neutral to slightly basic pH with high fCO₂. Smithsonite δ¹⁸O_VSMOW values from stage I carbonate ore range from 18.3 to 23.6‰, while those of stage II carbonate ore show a much smaller range between 24.3 and 24.9‰. The δ¹³C values are fairly constant in smithsonite of stage I carbonate ore (3.2–6.0‰) but show a considerable spread towards lower δ¹³C_VPDB values (4.6 to −11.2‰) in stage II carbonate ore. This suggests a hypogene formation of stage I carbonate ore at Angouran from low-temperature hydrothermal fluids, probably mobilized during the waning stages of Tertiary–Quaternary volcanic activity in an environment characterized by abundant travertine systems throughout the whole region. Conversely, stage II carbonate ore is unambiguously related to supergene weathering, as evidenced by the absence of sulfides, the presence of Fe-Mn-oxides and arsenates, and by high δ¹⁸O values found in smithsonite II. The variable, but still relatively heavy carbon isotope values of supergene smithsonite II, suggests only a very minor contribution by organic soil carbon, as is generally the case in supergene nonsulfide deposits.     

Carbon and oxygen isotope constraints on fluid sources and fluid–wallrock interaction in regional alteration and iron-oxide–copper–gold mineralisation, eastern Mt Isa Block, Australia

The source of metasomatic fluids in iron-oxide–copper–gold districts is contentious with models for magmatic and other fluid sources having been proposed. For this study, δ ¹⁸O and δ ¹³C ratios were measured from carbonate mineral separates in the Proterozoic eastern Mt Isa Block of Northwest Queensland, Australia. Isotopic analyses are supported by petrography, mineral chemistry and cathodoluminescence imagery. Marine meta-carbonate rocks (ca. 20.5‰ δ ¹⁸O and 0.5‰ δ ¹³C calcite) and graphitic meta-sedimentary rocks (ca. 14‰ δ ¹⁸O and −18‰ δ ¹³C calcite) are the main supracrustal reservoirs of carbon and oxygen in the district. The isotopic ratios for calcite from the cores of Na–(Ca) alteration systems strongly cluster around 11‰ δ ¹⁸O and −7‰ δ ¹³C, with shifts towards higher δ ¹⁸O values and higher and lower δ ¹³C values, reflecting interaction with different hostrocks. Na–(Ca)-rich assemblages are out of isotopic equilibrium with their metamorphic hostrocks, and isotopic values are consistent with fluids derived from or equilibrated with igneous rocks. However, igneous rocks in the eastern Mt Isa Block contain negligible carbon and are incapable of buffering the δ ¹³C signatures of CO₂-rich metasomatic fluids associated with Na–(Ca) alteration. In contrast, plutons in the eastern Mt Isa Block have been documented as having exsolved saline CO₂-rich fluids and represent the most probable fluid source for Na–(Ca) alteration. Intrusion-proximal, skarn-like Cu–Au orebodies that lack significant K and Fe enrichment (e.g. Mt Elliott) display isotopic ratios that cluster around values of 11‰ δ ¹⁸O and −7‰ δ ¹³C (calcite), indicating an isotopically similar fluid source as for Na–(Ca) alteration and that significant fluid–wallrock interaction was not required in the genesis of these deposits. In contrast, K- and Fe-rich, intrusion-distal deposits (e.g. Ernest Henry) record significant shifts in δ ¹⁸O and δ ¹³C towards values characteristic of the broader hostrocks to the deposits, reflecting fluid–wallrock equilibration before mineralisation. Low temperature, low salinity, low δ ¹⁸O (<10‰ calcite) and CO₂-poor fluids are documented in retrograde metasomatic assemblages, but these fluids are paragenetically late and have not contributed significantly to the mass budgets of Cu–Au mineralisation.     

Contrasting fluids and reservoirs in the contiguous Marcona and Mina Justa iron oxide–Cu (–Ag–Au) deposits,south-central Perú

The Marcona–Mina Justa deposit cluster, hosted by Lower Paleozoic metaclastic rocks and Middle Jurassic shallow marine andesites, incorporates the most important known magnetite mineralization in the Andes at Marcona (1.9 Gt at 55.4% Fe and 0.12% Cu) and one of the few major iron oxide–copper–gold (IOCG) deposits with economic Cu grades (346.6 Mt at 0.71% Cu, 3.8 g/t Ag and 0.03 g/t Au) at Mina Justa. The Middle Jurassic Marcona deposit is centred in Ica Department, Perú, and the Lower Cretaceous Mina Justa Cu (Ag, Au) prospect is located 3–4 km to the northeast. New fluid inclusion studies, including laser ablation time-of-flight inductively coupled plasma mass spectrometry (LA-TOF-ICPMS) analysis, integrated with sulphur, oxygen, hydrogen and carbon isotope analyses of minerals with well-defined paragenetic relationships, clarify the nature and origin of the hydrothermal fluid responsible for these contiguous but genetically contrasted deposits. At Marcona, early, sulphide-free stage M-III magnetite–biotite–calcic amphibole assemblages are inferred to have crystallized from a 700–800°C Fe oxide melt with a δ¹⁸O value from +5.2‰ to +7.7‰. Stage M-IV magnetite–phlogopite–calcic amphibole–sulphide assemblages were subsequently precipitated from 430–600°C aqueous fluids with dominantly magmatic isotopic compositions (δ³⁴S = +0.8‰ to +5.9‰; δ¹⁸O = +9.6‰ to +12.2‰; δD = −73‰ to −43‰; and δ¹³C = −3.3‰). Stages M-III and M-IV account for over 95% of the magnetite mineralization at Marcona. Subsequent non-economic, lower temperature sulphide–calcite–amphibole assemblages (stage M-V) were deposited from fluids with similar δ³⁴S (+1.8‰ to +5.0‰), δ¹⁸O (+10.1‰ to +12.5‰) and δ¹³C (−3.4‰), but higher δD values (average −8‰). Several groups of lower (<200°C, with a mode at 120°C) and higher temperature (>200°C) fluids can be recognized in the main polymetallic (Cu, Zn, Pb) sulphide stage M-V and may record the involvement of modified seawater. At Mina Justa, early magnetite–pyrite assemblages precipitated from a magmatic fluid (δ³⁴S = +0.8‰ to +3.9‰; δ¹⁸O = +9.5‰ to +11.5‰) at 540–600°C, whereas ensuing chalcopyrite–bornite–digenite–chalcocite–hematite–calcite mineralization was the product of non-magmatic, probably evaporite-sourced, brines with δ³⁴S ≥ +29‰, δ¹⁸O = 0.1‰ and δ¹³C = −8.3‰. Two groups of fluids were involved in the Cu mineralization stage: (1) Ca-rich, low-temperature (approx. 140°C) and high-salinity, plausibly a basinal brine and (2) Na (–K)-dominant with a low-temperature (approx. 140°C) and low-salinity probably meteoric water. LA-TOF-ICPMS analyses show that fluids at the magnetite–pyrite stage were Cu-barren, but that those associated with external fluids in later stages were enriched in Cu and Zn, suggesting such fluids could have been critical for the economic Cu mineralization in Andean IOCG deposits.     

Contrasting stable isotope behavior between calcite and dolomite marbles,Lone Mountain,Nevada

 Late Proterozoic to Cambrian carbonate rocks from Lone Mountain, west central Nevada, record multiple post-depositional events including: (1) diagenesis, (2) Mesozoic regional metamorphism, (3) Late Cretaceous contact metamorphism, related to the emplacement of the Lone Mountain granitic pluton and (4) Tertiary hydrothermal alteration associated with extension, uplift and intrusion of silicic porphyry and lamprophyre dikes. Essentially pure calcite and dolomite marbles have stable isotopic compositions that can be divided into two groups, one with positive δ¹³C values from+3.1 to +1.4 ‰ (PDB) and high δ¹⁸O values from +21.5 to +15.8 ‰ (SMOW), and the other with negative δ¹³C values from –3.3 to –3.6‰ and low δ¹⁸O values from +16.9 to +11.1‰. Marbles also contain minor amounts of quartz, muscovite and phlogopite. Brown and blue luminescent, clear, smooth textured quartz grains from orange luminescent calcite marbles have high δ¹⁸O values from +23.9 to +18.1‰, while brown luminescent, opaque, rough textured quartz grains from red luminescent dolomite marbles typically have low δ¹⁸O values from +2.0 to +9.3‰. The δ¹⁸O values of muscovite and phlogopite from marbles are typical of micas in metamorphic rocks, with values between +10.4 and +14.4‰, whereas mica δD values are very depleted, varying from −102 to −156‰. No significant lowering of the δ¹⁸O values of Lone Mountain carbonates is inferred to have occurred during metamorphism as a result of devolatilization reactions because of the essentially pure nature of the marbles. Bright luminescence along the edges of fractures, quartz cements and quartz overgrowths in dolomite marbles, low δD values of micas, negative δ¹³C values and low δ¹⁸O values of calcite and dolomite, and depleted δ¹⁸O values of quartz from dolomite marbles all indicate that meteoric fluids interacted with Lone Mountain marbles during the Tertiary. Partial oxygen isotopic exchange between calcite and low ¹⁸O meteoric fluids lowered the δ¹⁸O values of calcite, resulting in uniform quartz-calcite fractionations that define an apparent pseudoisotherm. These quartz-calcite fractionations significantly underestimate both the temperature of metamorphism and the temperature of post-metamorphic alteration. Partial oxygen isotopic exchange between quartz and meteoric fluids also resulted in ¹⁸O depletion of quartz from dolomite marbles. This partial exchange was facilitated by an increase in the surface area of the quartz as a result of its dissolution by meteoric fluids. The negative δ¹³C values in carbonates result from the oxidation of organic material by meteoric fluids following metamorphism. Stable isotopic data from Lone Mountain marbles are consistent with the extensive circulation of meteoric hydrothermal fluids throughout western Nevada in Tertiary time. Received: 1 February 1994/Accepted: 12 September 1995     

μ-XRF技术在黄龙铺钼(铀)矿床铀矿物学研究中的应用

东秦岭碳酸岩型钼成矿带是全球最大的钼成矿带。该带内的黄龙铺矿床是中国最早发现的碳酸岩型钼矿床之一。最近的野外地质调查发现,部分钼矿石具有较高的放射性异常,但其放射性元素的赋存形式和矿物学特征尚不明确。本文借助聚毛细管微束X射线荧光光谱分析（μ-XRF）分析速度快、原位无损、高灵敏度的分析优势,快速查明铀矿物的空间位置,再结合扫描电镜分析（SEM）和X射线能谱分析（EDS）,确定铀矿物的种类及其次生变化。研究表明：黄龙铺矿床高放射性矿石中主要的铀矿物为钛铀矿、铌钛铀矿和晶质铀矿,它们与方解石、长石、黄铁矿、辉钼矿和黄铜矿呈共生关系。矿石中铀矿物后期均遭受氧化性流体改造,发生了明显的蚀变,钛铀矿蚀变之后转变为含Nb的钛铁氧化物,铌钛铀矿和晶质铀矿蚀变后矿物内部形成大量空洞,流体来源可能为大气降水。背散射电子（BSE）图像上灰度差异明显,暗示着矿物中元素分布的不均一性。     

Formation and alteration of plagiogranites in an ultramafic-hosted detachment fault at the Mid-Atlantic Ridge (ODP Leg 209)

We examined small-scale shear zones in drillcore samples of abyssal peridotites from the Mid-Atlantic Ridge. These shear zones are associated with veins consisting of chlorite + actinolite/tremolite assemblages, with accessory phases zircon and apatite, and they are interpreted as altered plagiogranite melt impregnations, which originate from hydrous partial melting of gabbroic intrusion in an oceanic detachment fault. Ti-in-zircon thermometry yields temperatures around 820°C for the crystallization of the evolved melt. Reaction path modeling indicates that the alteration assemblage includes serpentine of the adjacent altered peridotites. Based on the model results, we propose that formation of chlorite occurred at higher temperatures than serpentinization, thus leading to strain localization around former plagiogranites during alteration. The detachment fault represents a major pathway for fluids through the oceanic crust, as evidenced by extremely low δ¹⁸O of altered plagiogranite veins (+3.0–4.2‰) and adjacent serpentinites (+ 2.6–3.7‰). The uniform oxygen isotope data indicate that fluid flow in the detachment fault system affected veins and adjacent host serpentinites likewise. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Oxygen isotope mapping in the Panorama VMS district, Pilbara Craton, Western Australia: applications to estimating temperatures of alteration and to exploration

Whole rock oxygen isotope data are presented for the Panorama district, in the Archean Pilbara Craton of Western Australia, where near-perfect exposure reveals a cross section through a complete volcanogenic massive sulfide (VMS) hydrothermal alteration system. The δ¹⁸O values decrease with depth in the volcanic pile, across semi-conformable alteration zones, to values below 6‰ immediately above a large (180 km²) subvolcanic intrusion. Altered rocks in the upper parts of the subvolcanic intrusion have lower δ¹⁸O values (6–8‰) than least altered granite (8‰), apart from sericite–quartz altered zones, which are slightly higher (8–10‰). Corridors of low δ¹⁸O values crosscut this regional zonation, and are coincident with transgressive feldspar-destructive alteration zones, which underlie VMS mineralization. The whole rock oxygen isotope distribution patterns are interpreted to represent alteration temperature, where high δ¹⁸O values correspond to low temperature alteration and low δ¹⁸O values correspond to high temperature alteration. Alteration temperatures, which were calculated using modal alteration mineral abundances and an assumed fluid δ¹⁸O, are consistent with this interpretation. Increasing temperatures with depth in the volcanic pile and high temperatures in transgressive corridors leading up to VMS deposits, are consistent with a convective hydrothermal model, in which heat from the subvolcanic intrusion drove seawater through the volcanic pile. Granite-hosted sericite–quartz alteration zones are ¹⁸O-enriched, and are tentatively interpreted to have formed from a mixed magmatic-evolved seawater fluid. Received: 12 April 1999 / Accepted: 6 April 2000     

The Darasun gold deposit,Eastern Transbaikal region: Chemical composition,REE patterns,and stable carbon and oxygen isotopes of carbonates from ore veins

The chemistry, REE patterns, and carbon and oxygen isotopic compositions of carbonates from ore veins of the Darasun deposit are discussed. In addition to the earlier described siderite, calcite, and carbonates of the dolomite-ankerite series, kutnahorite is identified. The total REE content in Fe-Mg carbonates of the dolomite-ankerite series (2.8–73 ppm) is much lower than in later calcite (18–390 ppm). δ¹³C of Fe-Mg carbonates and calcite varies from +1.1 to −6.7‰ and from −0.9 to −4.9‰, respectively. δ¹⁸O of Fe-Mg carbonates and calcite varies from +17.6 to 3.6‰ and from +15.7 to −0.5‰, respectively. The REE sum and carbon and oxygen isotopic compositions reveal zonal distribution relative to the central granodiorite porphyry stock. The correlation between the carbon and oxygen isotopic compositions and REE sum reflects variations in the physicochemical formation conditions and composition of ore-forming fluid. The isotopic composition of fluid is calculated, and possible sources of its components are considered. Earlier established evidence for a magmatic source of ore-forming fluid and participation of meteoric water in ore formation is confirmed. Geochemical evidence for interaction of ore-forming fluid with host rocks is furnished. The relationships between the REE sum, on the one hand, and carbon and oxygen isotopic compositions of hydrothermal ore-forming fluid, on the other, are established.     

Sulfur isotope characteristics of the Archean Cu–Zn Gossan Hill VHMS deposit, Western Australia

Gossan Hill is an Archean (∼3.0 Ga) Cu–Zn–magnetite-rich volcanic-hosted massive sulfide (VHMS) deposit in the Yilgarn Craton of Western Australia. Massive sulfide and magnetite occur within a layered succession of tuffaceous, felsic volcaniclastic rocks of the Golden Grove Formation. The Gossan Hill deposit consists of two stratigraphically separate ore zones that are stratabound and interconnected by sulfide veins. Thickly developed massive sulfide and stockwork zones in the north of the deposit are interpreted to represent a feeder zone. The deposit is broadly zoned from a Cu–Fe-rich lower ore zone, upwards through Cu–Zn to Zn–Ag–Au–Pb enrichment in the upper ore zone. New sulfur isotope studies at the Gossan Hill deposit indicate that the variation is wider than previously reported, with sulfide δ³⁴S values varying between −1.6 and 7.8‰ with an average of 2.1 ± 1.4‰ (1σ error). Sulfur isotope values have a broad systematic stratigraphic increase of approximately 1.2‰ from the base to the top of the deposit. This variation in sulfur isotope values is significant in view of typical narrow ranges for Archean VHMS deposits. Copper-rich sulfides in the lower ore zone have a narrower range (δ³⁴S values of −1.6 to 3.4‰, average ∼1.6 ± 0.9‰) than sulfides in the upper ore zone. The lower ore zone is interpreted to have formed from a relatively uniform reduced sulfur source dominated by leached igneous rock sulfur and minor magmatic sulfur. Towards the upper Zn-rich ore zone, an overall increase in δ³⁴S values is accompanied by a wider range of δ³⁴S values, with the greatest variation occurring in massive pyrite at the southern margin of the upper ore zone (−1.0 to 7.8‰). The higher average δ³⁴S values (2.8 ± 2.1‰) and their wider range are explained by mixing of hydrothermal fluids containing leached igneous rock sulfur with Archean seawater (δ³⁴S values of 2 to 3‰) near the paleoseafloor. The widest range of δ³⁴S values at the southern margin of the deposit occurs away from the feeder zone and is attributed to greater seawater mixing away from the central upflow zone. Received: 10 June 1999 / Accepted: 28 December 1999     

Magmatic zircon oxygen isotopes of 1.88–1.87 Ga orogenic and 1.65–1.54 Ga anorogenic magmatism in Finland

Summary Oxygen isotope ratios of igneous zircon from magmatic rocks in Finland provide insights into the evolution and growth of the Precambrian crust during the Svecofennian orogeny. These data preserve magmatic δ¹⁸O values and correlate with major discontinuities in the lower crust. Oxygen isotope ratios of zircon across the 1.88–1.87 Ga Central Finland granitoid complex (CFGC) range from 5.50‰ to 6.84‰, except for three plutons in contact with the adjacent greenstone and metasedimentary belts (δ¹⁸O(Zrc) = 7.60‰–7.78‰). There is a systematic variation in δ¹⁸O(Zrc) with respect to geographic location in the CFGC, ranging from 6.60±0.23‰ (σ) in the northeast to 5.90±0.40‰ in the west-southwest. These values correlate with a change in crustal thickness and shift in geochemical composition. The oxygen isotope composition of the 1.65–1.54 Ga rapakivi granites and related rocks in southern Finland show a decreasing trend from north to south, independent of their emplacement age. The southern anorogenic granite group has an average δ¹⁸O in zircon of 6.14±0.07‰ and the northern anorogenic group has an average δ¹⁸O in zircon of 8.14±0.59‰. This difference reflects the boundary between island arc terrains accreted during the Paleoproterozoic. Deceased