CO2-bearing Fluids Research Articles

Fluid inclusion evidence for the physicochemical conditions of sulfide deposition in the Olympias carbonate-hosted Pb-Zn(Au, Ag) sulfide ore deposit, E. Chalkidiki peninsula, N. Greece

The Olympias Pb-Zn(Au, Ag) sulfide ore deposit, E. Chalkidiki, N. Greece, is hosted by marbles of the polymetamorphic Kerdilia Formation of Paleozoic or older age. The geologic environment of the ore also comprises biotite-hornblende gneisses and amphibolites intruded by Tertiary pegmatite-aplite dikes, lamprophyre dikes, the 30-Ma Stratoni granodiorite, and porphyritic stocks. Only limited parts of the deposit display shear folding and brecciation; most of it is undeformed. Microthermometry of fluid inclusions in gangue syn-ore quartz indicates three types of primary and pseudosecondary inclusions: (1) H2O-rich, 1–18 wt.% NaCl equivalent, <3.6 mol% CO2; (2) H2O-CO2 inclusions, <4wt.% NaCl equivalent, with variable CO2 contents, coexisting in both undeformed and deformed ore; (3) aqueous, highsalinity (28–32 wt,% NaCl equivalent) inclusions found only in undeformed ore. Type 2 inclusions are differentiated into two sub-types: (2a) relatively constant CO2 content in the narrow range of 8–15 mol% and homogenization to the liquid phase; (2b) variable CO2 content between 18 and 50 mol% and homogenization to the vapor phase. Type 1 and 2b inclusions are consistent with trapping of two fluids by unmixing of a high-temperature, saline, aqueous, CO2-bearing fluid of possible magmatic origin, probably trapped in type 2a inclusions. Fluid unmixing and concomitant ore mineralization took place at temperatures of 350 ± 30 °C and fluctuating pressures of less than 500 bar, for both undeformed and deformed ores. The wide salinity range of type 1 inclusions probably represents a complex effect of salinity increase, due to fluid unmixing and volatile loss, and dilution, due to mixing with low-salinity meteoric waters. High solute enrichment of the residual liquid, due to extreme volatile loss during unmixing, may account for high salinity type 3 inclusions. The Olympias fluid inclusion salinity-temperature gradients bear similarities to analogous gradients related to Pb-Zn ores formed in “granite”-hosted, low-T distalskarn, skarn-free carbonate-replacement and epithermal environments.

The genesis of emeralds and their host rocks from Swat, northwestern Pakistan: a stable-isotope investigation

Emerald deposits in Swat, northwestern Pakistan, occurring in talc-magnesite and quartz-magnesite assemblages, have been investigated through stable isotope studies. Isotopic analyses were performed on a total of seven emeralds, associated quartz (seven samples), fuchsite (three samples) and tourmaline (two samples) from the Mingora emerald mines. The oxygen isotopic composition (δ18O SMOW) of emeralds shows a strong enrichment in18O and is remarkably uniform at + 15.6 ± 0.4‰ (1σ,n = 7). Each of the two components of water in emerald (channel and inclusion) has a different range of hydrogen isotopic composition: the channel waters being distinctly isotopically heavier (δD = −51 to −32‰ SMOW) than the other inclusion waters (δD = −96 to −70‰ SMOW). Similarly the oxygen isotopic compositions of tourmaline and fuchsite are relatively constant (δ18O = + 13 to + 14‰ SMOW) and show enrichment in18O. Theδ18O values of quartz, ranging from + 15.1 to + 19.1‰ SMOW, are also high (+ 16.9 ± 1.4‰ 1σ, n = 7). The meanδD of channel waters measured from emerald (−42 ± 6.6‰ SMOW) and that of fluid calculated from hydrous mineralsδDcalculated (−47 ± 7.1‰ SMOW) are consistent with both metamorphic and magmatic origin. However, the close similarity between the measuredδD values of the hydroxyl hydrogen in fuchsite (−74 to −6‰ SMOW) and tourmaline (−84 and −69‰ SMOW) with pegmatitic muscovite and tourmaline suggests that the mineralization was probably caused by modified (18O-enriched) hydrothermal solutions derived from an S-type granitic magma. The variation in the carbon and oxygen isotopic composition of magnesite, locally associated with emerald mineralization, is also very restricted (δ13 ∼ −3.2 ± 0.7%, PDB;δ18O ∼ + 17.9 ± 1.27‰ SMOW). On the basis of the isotopic composition of fluid (δ13C ≈ −1.8 ± 0.7‰ PDB;δ18O ≈ + 13.6 ± 1.2‰ SMOW calculated for the 250-550 °C temperature), it is proposed that the Swat magnesites formed due to the carbonation of previously serpentinized ultramafic rocks by a CO2-bearing fluid of metamorphic origin.

Experimental constraints on the compositional evolution of crustal magmas

ABSTRACT:Recent water-undersaturated phase equilibrium data on the subsystems of the granite-H2O system have provided important new constraints on the topology of the cotectic surfaces and hence on the compositional evolution of felsic magmas. The effect of water on phase relations can be deduced from a comparison of anhydrous and H2O-saturated data or from data obtained in the presence of a CO2-bearing fluid. However, although new experimental evidence indicates that the silica enrichment of evolving H2O-undersaturated, H2O-unbuffered melts during the co-precipitation of quartz and feldspar is as previously thought for orthoclase-rich compositions, it suggests that such a trend is considerably less for Ab-rich compositions. For water-poor trachytic melts, the newly recognised strong destabilisation of the sanidine melt component relative to the anorthite melt component with increasing water content indicates that the co-precipitation of two feldspars will result in saturation of the melt with ternary alkali feldspar at an earlier stage (i.e. higher melt anorthite content) than previously thought. This, in turn, implies that the melt differentiation path will have a greater component of anorthite depletion during the equilibrium co-precipitation of ternary feldspars and that the melt will remain in the peritectic region of the two feldspar plus liquid surface over a greater interval of crystallisation, thereby enhancing the possibility that the resoption of plagioclase during the early stages of equilibrium with alkali feldspar may go to completion. Comparison of CO2-free and CO2-bearing haplogranitic phase equilibrium data suggests that CO2 may be playing an independent part in the modification of phase equilibria and may induce a significant destabilisation of the orthoclase melt component.

Volatiles associated with the alkaline - carbonatite magmatism at Alnö, Sweden: a study of fluid and solid inclusions in minerals from the Laångarsholmen ring complex

The Alno alkaline-carbonatite complex consists in its northernmost part at Laangarsholmen of a ring-type intrusion composed of pyroxenite, sovite and ijolite, emplaced in that order. The intrusion is surrounded by a breccia zone. The petrography, mineral chemistry and fluid/solid inclusion studies suggest that the ring complex and the main intrusion at Alno have had a somewhat different magmatic evolution, implying different evolution of fluid phases also. At Laangarsholmen, a mafic silicate magma started to crystallize Al-diopside of 0.11 CaTs (Tschermak’s) content during a mid-crustal stage of evolution (ca. 5–6 kbar and 1175° C). At that stage, the mafic magma was coexisting with a Mg-bearing calcitic melt, recorded in the abundant inclusions, trapped by the crystallizing Al-diopside. The two immiscible melts appear to have separated at ca. 5 kbar and 1150° C, in good agreement with recent experimental studies. The silicate magma crystallized di+ap+magnetite during its ascent, and was in contact with a saline hydro-carbonic fluid trapped as inclusions in diopside (di) and apatite (ap) (type B2 inclusions reluctant to dissolution up to 550° C). As PH2O started to increase, Fe-pargasite began to replace the pyroxene. It appears that the fluid present at that stage was aqueous and contained ca. 40% NaCl. With decreasing PT, the fluid separated into two immiscible phases of high- and low-salinity (type B1 of 65% NaCl and Cl of 7% NaCl), respectively. At the shallow depths of the final emplacement, the composition of the fluid phase was most probably controlled by supply of meteoric water as indicated by the dilution trend of some B1 type inclusions. After separation, the carbonatite magma fractionated calcite+ap+dol (as shown by dolomite inclusions in early crystallizing apatite). Around 4 kbar, a CO2-bearing aqueous fluid of low salinity (d=0.85) was coexisting with the melt, and became trapped in the apatite formed during the mid-crustal stage (type A1 fluid inclusions). The residual melt was emplaced into the shallow crust and gave rise to phlogopite-bearing sovite. Fluid inclusions (type A2) trapped in calcite and in recrystallized apatite indicate that the fluid phase evolved towards a late (Na+K) hydro-carbonic fluid during cooling at the shallow depths of the final emplacement. The ijolite does not show signs of liquid immiscibility with the sovite at Laangarsholmen, and exhibits mostly post-magmatic activity of fluid phases.

Comparison of decrepitation, microthermometric and compositional characteristics of fluid inclusions in barren and auriferous mesothermal quartz veins of the Cowra Creek Gold District, New South Wales, Australia

Fluid inclusions in quartz from barren and Au-sulfide-bearing veins from the Cowra Creek Gold District, New South Wales, Australia, have been characterized based on their decrepitation behavior and gas geochemistry. Inclusions in Au-sulfide veins, and some regional sulfide-bearing veins, show distinctly higher CO 2 CH 4 ratios compared to barren quartz-only and quartz-sulfid veins from the deposit environment. Additionally, the occurrence of low-temperature peaks in acoustic decrepigrams from Au-sulfide veins that had previously been attributed to the presence of CO 2-bearing fluid inclusions has been confirmed using optical techniques. This characteristic peak is absent from quartz-sulfide and quartz-only veins. These results suggest that the gas content of fluid inclusions can distinguish Au-bearing from barren quartz veins, and that the acoustic decrepitation technique may provide a rapid and simple means of identifying different generations of quartz, and potentially productive veins in mesothermal environments.

95/03258 European coal geology

The Lincang Neogene high-Ge coal deposit in Yunnan, southwestern China, is one of the major coal-hosted Ge deposits in the world. This study reports new data on the petrological, mineralogical, and geochemical compositions of 57 samples (including coal bench samples, roofs, floors, partings, and batholith granite) of three high-Ge coal seams (S3, Z2, and X1) from the Dazhai Mine, Lincang Ge ore deposit, and provides new insights into the origin and modes of occurrence of the minerals and elements present.The coals have huminite random reflectances in the 0.33–0.48% range. On a mineral-free basis, the coal samples are dominated by huminite-group macerals, all having more than 88.5% total huminite. Ulminite and attrinite generally dominate the huminite macerals. Structured inertinite is rare, with funginite being the most abundant inertinite form. The minerals in the coals are mainly composed of quartz, and, to a lesser extent, kaolinite, illite, and mica. A hydrous beryllium sulfate phase (BeSO4·4H2O) is present in the low temperature ashes of several coal samples.Compared to average values for world low-rank coals, beryllium (up to 2000 μg/g and 343 μg/g on average), Ge (up to 2176 μg/g and 1590 μg/g on average), and W (up to 339 μg/g and 170 μg/g on average) are unusually enriched in the Lincang coals, with a concentration coefficient > 100 (CC = ratio of element concentration in investigated coals vs. world low-rank coals); elements As (156 μg/g on average), Sb (38 μg/g), Cs (25.2 μg/g), and U (52.5 μg/g) are significantly enriched (10 < CC < 100); niobium (28.2 μg/g) is enriched (CC = 8.55); zinc, Rb, Y, Cd, Sn, Er, Yb, Lu, Hg, Tl, and Pb are slightly enriched (2 < CC < 5).The biotite- and two-mica granites, which served as both the basement for the coal-bearing sequence and as a source of sediment input, were also either hydrothermally-altered or -argillized. The alteration appears to have taken place during or shortly after deposition of the coal-bearing sequence. Two types of metasomatites of hydrothermal origin, including quartz–carbonate and carbonate, were identified, which occur as partings and as roof and floor strata. These metasomatites were formed at the syngenetic or early diagenetic stages of coal deposition. The rare earth elements in these hydrothermal rocks are characterized by a heavy REE enrichment type and by distinct positive Eu anomalies, compared to the upper continental crust.Hydrothermal solutions have played a significant role in producing the elemental and mineralogical anomalies in the Lincang Ge ore deposit. The hydrothermal solutions leaching the batholith granite were a mixture of alkaline N2-bearing and volcanogenic CO2-bearing fluids, which led to the enrichment of trace elements, not only including assemblages of Ge–W and Be–Nb–U (both leached from granite and the deposited in the peat), but also As–Sb (from volcanogenic solution), as well as the alteration and argillization of the batholith granites, and the formation of carbonate and quartz–carbonate metasomatites.

Evidence of temperature increase of CO2-bearing fluids from Aluto-Langano geothermal field (Ethiopia): a fluid inclusions study of deep wells LA-3 and LA-6

The Aluto-Langano geothermal field is located within one of the lost active volcanic areas of the Main Ethiopian Rift system. At Aluto, exploratory drilling has revealed the existence of high temperature (ca. 335 o C) two-phase fluids. This study is focused on wells LA-3 and LA-6, which are located on the main upflow zone of the geothermal system. Evidence for the occurrence of high intensity water-rock interaction is given by the presence of minerals such as calcite, chlorite, hematite, illite, quartz, sphene, epidote, garnet, prehnite, biotite and actinolite. Seven samples have been selected from drillcores recovered at different depths for petrographic observation, microthermometry and crushing experiments. Primary and essentially secondary fluid inclusions are recognized in authigenic calcite and quartz crystals as well as in igneous quartz crystals of the reservoir rock. Most of the inclusions are two-phase liquid-rich (liquid fraction: 0.8-0.9), but single-phase vapour inclusions are also present, especially in the upper part of the system. A total of 333 temperatures on cooling and 392 temperatures on heating were measuring for liquid-rich (P and S) inclusions. The recognition of first melting indicates a fluid dominated by Na(K)Cl. Melting ice temperatures (T mi ) range from 0.0 to −1.9 o C. Clathrate was never observed. Homogenization temperatures (T h ) range from 240 to 350 o C and are generally lower than the measured inhole temperatures at each depth. Both T mi and T h values show bimodal frequency distributions suggesting that several generations of fluids have circulated early in the system. Crushing experiments and cooling demonstrate that important chemical changes have occurred from early hydrothermal fluid circulation to the present day, especially as regards P CO2 . The T mi -T h distribution defines a dilution trend between low salinity heated ground waters and a saline (about 3% NaCl eq.) high temperature fluid (350 oC ) rising from a deep source. The mineral association calcite, epidote, garnet and/or prehnite is consistent with the initial very low CO 2 content. The fluid inclusions study demonstrates heating up of the system from about 250 o C to the present-day temperatures of 320-335 o C. This heating could be explained by an intake of high enthalpy fluid in the upflow of the system

Fluid inclusion evidence for basement decompression during Permo-Triassic extension, SE New England, USA

CO2-bearing fluid inclusions in strongly lineated but weakly foliated late Precambrian gneisses within the Hope Valley Shear zone of Connecticut and Rhode Island are of mixed composition (Xco2± 0.1; 7 wt% NaCl equivalent) and variable density (0.59–0.86 g/ml) and occur mainly as isolated inclusions. Also present are dilute (3 wt% NaCl equivalent) aqueous inclusions which occur on healed fractures related to greenschist facies retrograde metamorphism. Isochores for dense isolated CO2-bearing inclusions indicate pressures of 7.5–9 kbar at 500–600° C, the estimated temperature conditions of peak metamorphism. Published 40Ar/39Ar hornblende plateau age spectra indicate cooling through about 500° C at 265 ± 5 Ma. Isochores for low-density CO2-bearing inclusions and aqueous inclusions intersect at the conditions of retrograde metamorphism (325–400° C) and indicate pressures of 3–4 kbar. Published 40Ar/39Ar biotite plateau ages indicate cooling through about 300° C at 250 ± 5 Ma. These data define a P–T uplift curve for the region which is convex towards the temperature axis and indicate uplift rates between 0.4 and 3.3 mm/year in Permian time. Exhumation of basement gneisses was coeval with normal (west-down) motion along the regional basement–cover contact (Honey Hill–Lake Char–Willimantic fault system), and is interpreted as due to post-orogenic extensional collapse of the Alleghanian orogeny.

The geochemistry and fluid history of the Proterozoic Laurel Lake Au–Ag deposit, Flin Flon greenstone belt

The Laurel Lake Au–Ag deposit is situated 25 km southwest of Flin Flon in the Proterozoic Flin Flon Domain and consists of branching quartz–muscovite–pyrite–tennantite–chalcopyrite–sphalerite–galena–electrum–carbonate veins (stage 1) surrounded by a widespread zone of sericitized and pyritized Amisk Group felsic volcanic rocks. The deposit has been deformed and metamorphosed during the Hudsonian orogeny and is crosscut by nonauriferous quartz–dolomite–tourmaline–pyrite veins (stage 2). The timing of mineralization, the lack of obvious relation to a major shear zone, and high base metal sulphide and Ag/Au ratio (5:1) distinguish this deposit from epigenetic mesothermal gold deposits in the Flin Flon Domain. Fluid inclusion and stable-isotope data indicate that the mineralizing fluids had a high temperature (&gt;300 °C), were saline (&gt;10.3 wt.% NaCl equivalent) and CO2 bearing and had an isotopic composition similar to modified seawater. This fluid leached sulphur, base metals, and precious metals as it interacted with Amisk Group volcanic rocks. The hydrogen isotopic compositions of fine-grained muscovites in the surrounding altered felsic volcanic rocks have been reset during later metamorphism, whereas the coarse stage 1 vein muscovites have partially preserved their primary hydrogen isotopic compositions and fluorine contents. Stage 2 veins were deposited from low-salinity (&lt;6.4 wt.% NaCl equivalent), CO2-bearing fluids, which also have the hydrogen and oxygen isotopic compositions of modified seawater. The Laurel Lake deposit has fluid, vein, and alteration characteristics that distinguish it from both epithermal and mesothermal deposits, and they can be explained by the involvement of modified seawater.

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

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

Evaluation of the fluid-inclusion crushing-stage as an aid in exploration for mesothermal gold-quartz deposits

Case studies in the Wabigoon and Uchi Archaean greenstone belts of Canada demonstrate that the liquid CO 2-bearing fluid inclusions, which are diagnostic of mesothermal gold-quartz-carbonate-sulphide deposits, may be reliably and reproducibly detected in the field by crushing-stage analysis. The technique alone cannot distinguish veins of different ore grade in a given exploration terrain, but after preliminary crushing tests to assess the composition of local metamorphic fluids, samples from potentially auriferous mesothermal deposits may be inexpensively and unequivocally identified in the field. The most powerful application of the crushing-stage is in geochemical surveys of sediments in which diagnostic fluid inclusions in quartz may offer a much wider exploration target than the related gold anomaly. Unmistakable haloes of liquid CO 2-bearing fluid inclusions are rapidly detectable in the wall rocks surrounding mesothermal veins. The haloes are spatially as extensive as the alteration mineral assemblages, and thus in field situations where outcrop is sparse or highly weathered, crushing analysis may aid in targeting areas for more detailed exploration.

Fluid inclusion studies of the Felbertal scheelite deposit

Fluid inclusion measurements on quartz, scheelite, beryl, fluorite and calcite in the metamorphosed Felbertal scheelite deposit display two main types of fluid inclusions: 1. H2O-CO2 fluid inclusions are characterized by variable amounts of CO2 up to 18 wt.%. They show two or three phases at room temperature. The bulk homogenization temperatures for the inclusions range between +269 °C and +357 °C. The calculated salinities are between 2.2 and 7.8 wt.% NaCl equivalent. For the late CO2-bearing fluid inclusions a methane component is evident from microthermometrical data (Tmclath >10.0 °C combined with TmCO2<−56.6 °C) and from Raman microprobe analyses. 2. Aqueous, two-phase fluid inclusions with salinities in the range between 0 and 11 wt.% NaCl equivalent. Their homogenization temperatures are scattered between 100 °C and 360 °C.

H 2OCH 4NaClCO 2 inclusions from the footwall contact of the Tanco granitic pegmatite: Estimates of internal pressure and composition from microthermometry, laser Raman spectroscopy, and gas chromatography

Fluid inclusions in tourmaline and quartz from the footwall contact of the Tanco granitic pegmatite, S.E. Manitoba were studied using microthermometry (MT), laser Raman spectroscopy (LRS) and gas chromatography (GC). CH 4-bearing, aqueous inclusions occur in metasomatic tourmaline of the footwall amphibolite contact. The internal pressures estimated from MT are lower than those obtained from LRS (mean difference = 54 ± 19 bars). The difference is probably due to errors in the measurement of Th CH 4 (V) and to the presence of clathrate at Th CH 4 (V) into which CO 2 had been preferentially partitioned. LRS estimates of pressure (125–184 bars) are believed to be more accurate. Aqueous phase salinities based on LRS estimates of pressure are higher than those derived using the data from MT: 10–20 eq. wt% NaCl. The composition of the inclusions determined by GC bulk analysis is 97.3 mol% H 2O, 2.2 mol% CH 4, 0.4 mol% CO 2, 250 ppm C 2H 6, 130 ppm N 2, 33 ppm C 3H 8, 11 ppm C 2H 4, and 3 ppm C 3H 6, plus trace amounts of C 4 hydrocarbons. The composition is broadly similar to that calculated from MT (92% H 2O and 8% CH 4, with 7 eq. wt% NaCl dissolved in the aqueous phase and 2 mol% CO 2 dissolved in the CH 4 phase), as expected due to the dominance of a single generation of inclusions in the tourmaline. However, two important differences in composition are: 1. (i) the CH 4 to CO 2 ratio of this fluid determined by GC is 5.33, which is significantly lower than that indicated by MT (49.0); and 2. (ii) the H 2O content estimated from MT is 92 mol% compared to 98 mol% from GC. GC analyses may have been contaminated by the presence of secondary inclusions in the tourmaline. However, the rarity of the latter suggests that they cannot be completely responsible for the discrepancy. The differences may be accounted for by the presence of clathrate during measurement of Th CH 4 (critical), which would reduce CO 2 relative to CH 4 in the residual fluid, and by errors in visually estimating vol% H 2O. The compositions of the primary inclusions in tourmaline are unlike any of those found within the pegmatite and indicate that the fluid was externally derived, probably of metamorphic origin. Inclusions in quartz of the border unit of the pegmatite are secondary and are either aqueous (18 to 30 eq. wt% CaCl 2; Th total = 184 ± 14° C) or carbonic. Tm CO 2 for the carbonic inclusions ranges from −57.5 to −65.4°C and is positively correlated with Th CO 2. Analyses of X CH 4 based on LRS agree within 5 mol% of those derived from MT and together indicate a range of compositions from 5 to 50 mol% CH 4 in the CO 2 phase. Bulk analysis by GC gives 99.0 mol% H 2O, 0.6 mol% CO 2, 0.4 mol% CH 4, 160 ppm N 2, 7 ppm C 2H 6, 4 ppm C 3H 8, and 2 ppm C 2H 4, with trace amounts of COS (carbonyl sulphide) and C 3H 6. The level of H 2O in the analysis is consistent with the dominance of the aqueous inclusions in these samples, and the CH 4: CO 2 ratios are consistent with estimates from MT and LRS. The preservation of variable ratios of CH 4:CO 2 in inclusions < 50 μm apart indicates that neither H 2 diffusion out of the inclusions nor reduction of fluids leaving the pegmatite were responsible for the more oxidized chemistries of the border unit inclusions relative to those in the tourmaline of the metasomatised amphibolite. The compositions of the inclusions in the quartz lie between those of the fluid trapped by the tourmaline (externally derived) and the measured composition of a CO 2-bearing pegmatitic fluid, which indicates that the secondary fluids trapped in the border unit quartz were produced by late mixing.

Partitioning of F between H2O and CO2 fluids and topaz rhyolite melt

Fluid/melt distribution coefficients for F have been determined in experiments conducted with peraluminous topaz rhyolite melts and fluids consisting of H2O and H2O+CO2 at pressures of 0.5 to 5 kbar, temperatures of 775°–1000°C, and concentrations of F in the melt ranging from 0.5 to 6.9 wt%. The major element, F, and Cl concentrations of the starting material and run product glasses were determined by electron microprobe, and the concentration of F in the fluid was calculated by mass balance. The H2O concentrations of some run product glasses were determined by ion microprobe (SIMS). The solubility of melt in the fluid phase increases with increasing F in the system; the solubility of H2O in the melt is independent of the F concentration of the system with up to 6.3 wt% F in the melt. No evidence of immiscible silica- and fluoriderich liquids was detected in the hydrous but water-undersaturated starting material glasses (≦8.5 wt% F in melt) or in the water-saturated run product glasses. F concentrates in topaz rhyolite melts relative to coexisting fluids at most conditions studied; however, DF (wt% F in fluid/wt% F in melt) increases strongly with increasing F in the system. Maximum values of DF in this study are significantly larger than those previously reported in the literature. Linear extrapolation of the data suggests that DF is greater than one for water-saturated, peraluminous granitic melts containing ≧8 wt% F at 800° C and 2 kbar. DF increases as temperature and as (H2O/H2O+CO2) of the fluid increase. For topaz rhyolite melts containing ≦1 wt% F and with H2O-rich fluids, DF is independent of changes in pressure from 2 to 5 kbar at 800° C; for melts containing ≦1 wt% F and in equilibrium with CO2-bearing fluids the concentrations of F in fluid increases with increasing pressure. F-and lithophile element-enriched granites may evolve to compositions containing extreme concentrations of F during the final stages of crystallization. If F in the melt exceeds 8 wt%, DF is greater than one and the associated magmatic-hydrothermal fluid contains >4 molal F. Such F-enriched fluids may be important in the mass transport of ore constituents, i.e., F, Mo, W, Sn, Li, Be, Rb, Cs, U, Th, Nb, Ta, and B, from the magma.

Evidence for CO 2 infiltration in granulite facies marbles from Lofoten-Vesteralen, Norway

Lofoten-Vesteralen comprises an amphibolite to granulite facies terrain, metamorphosed in the granulite facies at 1.8 Ga. Amphibolite facies marbles retain close to premetamorphic carbon and oxygen isotopic signatures ( δ 13C ∼ +10‰ (PDB), δ 18O ∼ +26‰ (SMOW)). The margins of marbles near the amphibolite-granulite transition and granulite facies marbles show large shifts to much lighter carbon and oxygen (to δ 13C ∼ −7‰ (PDB) and δ 18O ∼ +10‰ (SMOW)). These shifts imply exchange with a CO 2-bearing fluid. Large CO 2/rock weight ratios were achieved in granulite facies marbles and this could reflect large-scale infiltration of CO 2 into the granulite facies crust. The occurrence of carbonic metamorphism in at least some granulite terrains could be a reflection of high mantle CO 2 degassing rates in the Precambrian or the recycling of carbon in a subduction related environment.

Genesis, mineralogy and geochemistry of uranium in the Gortdrum stratiform copper deposit, Ireland

The Gortdrum Cu-Ag-As-Sb-Hg-U orebody occurs in Lower Carboniferous strata on the downthrown side of an ENE transcurrent fault system in Southern County Tipperary, Republic of Ireland. The deposit comprises a linear discordant zone of brecciated carbonates and country rocks that are altered and mineralised. Research has indicated anomalous radioelement concentrations associated with the main copper orebody and in particular with the altered breccias within this zone. The metal association (Cu-Ag-As-Sb-Hg-U) is considered unique for Irish Carboniferous carbonate-hosted copper deposits. However, the low temperature mineral assemblage of early uranium-bearing minerals with later sulphide stages is reminiscent of many vein-type hydrothermal ore deposits. The geochemistry of uranium-enriched rocks indicates that the alteration of the basic dykes was a most significant event in the trapping of uranium within the limestones. Propylitization of the early basic dykes by CO2-bearing fluids produced the alteration which led to the development of hematite, leucoxene and clay minerals. The reducing environments attendant with such mineralogy created a favourable environment for uranium precipitation. The reduction of U+6 to U+4 by oxidation of reduced Fe in dolomitized brecciated limestone occurred prior to the main sulphide mineral sequences. The genesis of uranium in the deposit is linked to radioelement remobilization from uranium-bearing heavy minerals in sediments of upper Devonian-Lower Carboniferous age. The uranium became available to low temperature hydrothermal fluids which carried then deposited the uranium along a transcurrent fault system. The source of the heavy minerals is considered to be the Leinster Granite to the east, by which time in the Carboniferous, unroofing of the main pluton had commenced.

Fluid activity in the lower crust and upper mantle: mineralogical evidence bearing on the origin of amphibole and scapolite in ultramafic and mafic granulite xenoliths

AbstractXenoliths in an olivine nephelinite from the McBride Province, North Queensland, include Cr-diopside lherzolites, spinel and garnet websterites, felsic, 2-pyroxene and garnet granulites, and hornblendites. The spinel and garnet websterites are interpreted as crystal segregations from olivine basalt or alkali olivine basalt magma at ∼ 12 kbar followed by isobaric cooling (to approximately 900–1000°C) and subsolidus reequilibration. Garnet and 2-pyroxene granulites are mineralogically and texturally distinct and are considered to represent relatively large degrees of crystallization of basaltic magmas at comparable or slightly lower pressures (8–12 kbar). Mafic and ultramafic xenoliths have been modified to varying degrees following the relatively recent influx of a H2O- and CO2-bearing fluid. Variable amounts of amphibole and mica developed in response to the introduced fluid and it is argued that some hornblendites are the end-products of this process acting on spinel websterites. Felsic and 2-pyroxene granulite xenoliths display only minor evidence of increasedPH2O. Mineralogical and textural evidence indicates high-sulphur Ca-rich scapolite in several garnet granulites did not form in response to the increased fluid activities. It is proposed the scapolite was a primary cumulate phase precipitated from alkali basaltic magma under elevatedfo2andfso2conditions.

Fluid inclusion from drill hole DW-5, Hohi geothermal area, Japan: Evidence of boiling and procedure for estimating CO 2 content

Fluid inclusion studies have been used to derive a model for fluid evolution in the Hohi geothermal area, Japan. Six types of fluid inclusions are found in quartz obtained from the drill core of DW-5 hole. They are: (I) primary liquid-rich with evidence of boiling; (II) primary liquid-rich without evidence of boiling; (III) primary vapor-rich (assumed to have been formed by boiling); (IV) secondary liquid-rich with evidence of boiling; (V) secondary liquid-rich without evidence of boiling; (VI) secondary vapor-rich (assumed to have been formed by boiling). Homogenization temperatures ( T h) range between 196 and 347°C and the final melting point of ice ( T m) between −0.2 and −4.3°C. The CO 2 content was estimated semiquantitatively to be between 0 and 0.39 wt. % based on the bubble behavior on crushing. NaCl equivalent solid solute salinity of fluid inclusions was determined as being between 0 and 6.8 wt. % after minor correction for CO 2 content. Fluid inclusions in quartz provide a record of geothermal activity of early boiling and later cooling. The CO 2 contents and homogenization temperatures of fluid inclusions with evidence of boiling generally increase with depth; these changes, and NaCl equivalent solid solute salinity of the fluid can be explained by an adiabatic boiling model for a CO 2-bearing low-salinity fluid. Some high-salinity inclusions without CO 2 are presumed to have formed by a local boiling process due to a temperature increase or a pressure decrease. The liquid-rich primary and secondary inclusions without evidence of boiling formed during the cooling process. The salinity and CO 2 content of these inclusions are lower than those in the boiling fluid at the early stage, probably as a result of admixture with groundwater.

Magnesite abundance as a guide to gold mineralization associated with ultramafic flows, Timmins area

Altered komatiitic flows of the Tisdale Group locally contain secondary calcite, dolomite or magnesite, where alteration intensity and bulk-rock composition are favourable. Talc is present only in the least carbonatized samples and does not coexist with quartz and magnesite. Magnesite is present only in carbonatized ultramafic komatiitic flows (> 20 wt.% MgO) containing at least 18 wt.% loss on ignition (> 14 wt.% CO 2). Magnesite abundance increases with increasing loss on ignition and MgO (MgO + CaO) ) whole-rock ratio. Altered flows having magnesite to dolomite weight precent ratios exceeding 70 occur in proximity to mineable concentrations of gold and define surface-exploration targets 500 m in diameter. The spatial association of gold with the more magnesian ultramafic komatiitic flows arises in part because of the reactive nature of olivine-rich rocks in the presence of CO 2-bearing aqueous hydrothermal fluids, and possibly because the most magnesian ultramafic flows occur in proximity to an eruptive vent area where the likelihood of rock-fluid interaction is greatest because of the local structural regime. Talc-magnesite—quartz assemblages are present in some ultramafic dykes which cut the older Deloro Group volcanic rocks; the apparent absence of gold in these rocks may be attributed to the higher formation temperature of the talc-bearing, relative to the talc-free, magnesite-quartz assemblages.

Synthesis and stability relations of wairakite, CaAl2 Si4 O12�2H2O

Hydrothermal investigation of the bulk composition CaO·Al2O3·4SiO2 + excess H2O has been conducted using conventional techniques over the temperature range 200–500° C and 500–5,000 bars P fluid. The fully ordered wairakite was synthesized unequivocally in the laboratory, probably for the first time. The gradual, sluggish and continuous transformation from disordered to ordered wairakite evidently accounts for failure by previous investigators to synthesize ordered wairakite in runs of week-long duration. The dehydration of metastable disordered wairakite to metastable hexagonal anorthite, quartz and H2O has been determined; this reaction takes place at temperatures exceeding 400° C, even at fluid pressures of 500 bars or less. The upper P fluid-T boundary of the disordered phase is equivalent to the maximum temperature curve of synthetic wairakite presented by previous investigators. The hydrothermal breakdown of natural wairakite above its stability limit appears to be a very slow process. The equilibrium dehydration of wairakite to anorthite, quartz and H2O occurs at 330±5° C at 500 bars, 348±5° C at 1,000 bars, 372±5° C at 2,000 bars and 385±5° C at 3,000 bars. Where fluid pressure equals total pressure, the thermal stability range of wairakite is about 100° C wide. At lower temperatures wairakite reacts with H2O to form laumontite. Reconnaissance experiments dealing with the effect of CO2 on stabilities of calcium zeolites suggest that wairakite or laumontite may be replaced by the assemblage calcite + montmorillonite in the presence of a CO2-bearing fluid phase. The determined P fluid -T field of wairakite is compatible with field observations in some metamorphic terrains where it is related to the shallow emplacement of granitic magma and with direct pressure-temperature measurements in certain active geothermal areas. Under inferred conditions of higher μCO2/μH2O ratios, essentially unmetamorphosed rocks grade directly into those characteristic of the greenschist facies; moderately high values of μCO2 in carbonate-bearing rocks result in the downgrade extension of the greenschist facies at the expense of zeolite-bearing assemblages.