Carbon,hydrogen, and oxygen isotope studies of the regional metamorphic complex at Naxos,Greece

At Naxos, Greece, a migmatite dome is surrounded by schists and marbles of decreasing metamorphic grade. Sillimanite, kyanite, biotite, chlorite, and glaucophane zones are recognized at successively greater distances from the migmatite dome. Quartz-muscovite and quartz-biotite oxygen isotope and mineralogie temperatures range from 350 to 700°C.The metamorphic complex can be divided into multiple schist-rich (including migmatites) and marblerich zones. The δ¹⁸O values of silicate minerals in migmatite and schist units and quartz segregations in the schist-rich zones decrease with increase in metamorphic grades. The calculated δ¹⁸O_H2O values of the metamorphic fluids in the schist-rich zones decrease from about 15‰ in the lower grades to an average of about 8.5‰ in the migmatite.The δD values of OH-minerals (muscovite, biotite, chlorite, and glaucophane) in the schist-rich zones also decrease with increase in grade. The calculated δD_H2O values for the metamorphic fluid decrease from ?5‰ in the glaucophane zone to an average of about ?70‰ in the migmatite. The δD values of water in fluid inclusions in quartz segregations in the higher grade rocks are consistent with this trend.Theδ¹⁸O values of silicate minerals and quartz segregations in marble-rich zones are usually very large and were controlled by exchange with the adjacent marbles. The δD values of the OH minerals in some marble-rich zones may reflect the value of water contained in the rocks prior to metamorphism.Detailed data on 20 marble units show systematic variations of δ¹⁸O values which depend upon metamorphic grade. Below the 540°C isograd very steep δ¹⁸O gradients at the margins and large δ¹⁸O values in the interior of the marbles indicate that oxygen isotope exchange with the adjacent schist units was usually limited to the margins of the marbles with more exchange occurring in the stratigraphic bottom than in the top margins. Above the 540°C isograd lower δ¹⁸O values occur in the interior of the marble units reflecting a greater degree of recrystallization and the occurrence of Ca-Mg-silicates.Almost all the δ¹³C values of the marbles are in the range of unaltered marine limestones. Nevertheless, the δ¹³C values of most marble units show a general correlation with δ¹⁸O values.The $\text{CO}{}_2\text{H}{}_2\text{O}$ mole ratio of fluid inclusions in quartz segregations range from 0.01 to 2. Theδ¹³C values of the CO₂ range from ?8.0 to 3.6‰ and indicate that at some localities CO₂ in the metamorphic fluid was not in carbon isotopic equilibrium with the marbles.     

Sulphur isotopes from the gruvåsen sulphide skarn deposit,Bergslagen, Sweden

Summary The Gruvåsen sulphide skarns in Western Bergslagen are hosted by a sequence of marbles and metacherts, intruded by a number of thin mafic sills and dykes of midProterozoic age. The sulphide skarns show a zonal distribution with Cu-Zn-Fesulphide-rich pyroxene skarns (± scheelite, molybdenite, cassiterite, bismuth) in the central, and Zn-Fe-Pb-As-sulphide-rich amphibole skarns in the peripheral zones of mineralization. The sulphide skarns in the central zone are closely related to a phase of local potassic alteration that affected the marbles, cherts and mafic intrusions. ³⁴S values of sulphides range between + 0.5 and + 1.3% for the central zone, and between-1.4 and + 1.5% for the peripheral zone. Sulphide-pair sulphur isotope geothermometry (Ohmoto and Rye, 1979) yields temperatures around 555°C corresponding with the temperature of 550–600°C estimated from silicate and sulphide parageneses. Although the Gruvâsen deposit is situated close to the Filipstad-type granitic intrusion, this granite is unlikely to have a genetic relationship with the sulphide mineralization, because the sulphide skarns were deformed at about 1,860 Ma, whereas the postkinematic Filipstad-type granite is dated at +- 1,640Ma (Oen, 1982). Hydrothermal fluids at estimated temperatures around 550°C, presumably heated by the coeval solidifying mafic sills and dykes, are considered responsible for the dissolution and transport of sulphur from the mafic rocks, and of metals from both mafic and felsic rocks underlying the Gruvåsen marbles, and for the redeposition of metals and sulphur in the Gruvåsen sulphide skarn deposit.

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Schwefelisotopen der Gruvåsen Sulfid-Skarnlagerstätte, Bergslagen, Schweden

Zusammenfassung Die sulfidischen Skarne von Gruvåsen, West-Bergslagen, sitzen in Mergeln and Metaquarziten auf, die von zahlreichen mitelproterozoischen, geringmächtigen mafischen Sills und Gängen durchdrungen werden. Die Sulfid-Skarne sind zoniert. Im zentralen Bereich der Mineralisation treten Cu-Zn-Fe-sulfidreiche Pyroxen-Skarne auf (+- Scheelit, Molybdenit, Cassiterit, Wismuth), während die Randzonen vorwiegend aus Zn-Fe-Pb-As-sulfidreichen Amphibol-Skarnen bestehen. Die zentralen Skarnanteile zeigen engen Zusammenhang mit einer lokalen K-Alteration der Mergel, Metaquarzite und mafischen Intrusionen. In der zentralen Zone liegen die ³⁴ S-Werte der Sulfide zwischen + 0.5 und + 1.3%, in der Randzone zwischen - 1.43 und + 1.5%. SchwefelisotopenGeothermometrie von Sulfidpaaren (Ohmoto & Rye, 1979) ergaben Temperaturen um 550°C. Diese stimmen mit den Temperaturen aus den Silikat- und Sulfidparagenesen von 550–600°C gut überein. Obwohl die Gruvåsen Lagerstätte nahe der FilipstadTyp Granitintrusion liegt, erscheint eine genetische Verbindung mit der Sulfidmineralisation unwahrscheinlich, da die Sulfid-Skarne ein Deformationsalter von 1860 Mio zeigen, während der postkinematische Filipstad-Typ Granit auf +- 1640 mio datiert ist (Oen, 19982). Es wird vermutet, daß hydrothermale Lösungen, die durch die erstarrenden mafischen Sills und Gänge auf etwa 550°C aufgeheizt worden sind, für die Vererzung verantwortlich sind. Der Schwefel kann aus den mafischen Gesteinen bezogen werden, die Metalle aus mafischen und felsischen Gesteinen, die die Gruvåsen Mergel unterlagern. Hydrothermale Aktivität verursachte Lösung, Transport und Umlagerung des Schwefels und der Metalle in die Gruväsen Sulfid-Skarn Lagerstätte.

     

Effects of annealing on deformation textures in galena

Experimental annealing of galena samples with known deformation histories shows that this mineral has the necessary properties to be a valuable source of information about low-grade deformational environments. Annealed galena displays recovery and/or recrystallization features dependent upon the type of texture inherited from the tectonic event, which in turn is closely linked to deformation temperatures.In samples deformed at temperatures less than 200 ° C in the laboratory, later annealing produced subgrains, mosaics of new grains, or rapid grain boundary migration as the annealing temperatures were varied from 200 ° C to 700 ° C. Kink bands maintained characteristic straight simple boundaries inherited from the deformation event. Samples deformed above 300 ° C developed syntectonically recrystallized textures. Kink bands had been converted to elongate grains with complex sutured grain boundaries during deformation, and mosaics of new grains were found in highly deformed regions. These textures were extremely stable through later annealing. Despite our changing annealing temperatures through 500 ° C, we did not produce similar textures from both low and high temperature deformation runs.Examination of polished and etched galena from low-grade tectonic settings may well be worth the effort since galena textures appear to display features indicative of deformational evironments, even after being subjected to considerable post-tectonic thermal perturbations.     

Petrology of chlorite-spinel marbles from NW Spitsbergen (Svalbard)

Small dolomite marble lenses and bands occur in the vast Caledonian migmatite and gneiss area of NW Spitsbergen (Svalbard archipelago). The fine-banded marbles contain numerous assemblages of minerals: calcite, dolomite, olivine, clinohumite, diopside, amphibole, chlorite, spiner and phologopite. The coexistence of calcite + dolomite + olivine + chlorite + spinel over the entire area indicates metamorphic temperatures of 600 to 680° at an estimated pressure of 4 kilobars. A temperature of near 600°C for the peak of metamorphism is suggested by mineral assemblages at the southernmost locality, Jäderinfjellet. Calcite-dolomite geothermometry indicated 595°C at the same locality. The spatial distribution of the marble assemblages suggests that metamorphism occurred under nearly isothermal conditions over an area of at least 25 by 30 kilometres.     

A cathodoluminescence and petrographical study of marbles from the Pohorje area in Slovenia

Marbles from the Pohorje area in Slovenia are investigated by mineralogical-petrographical analyses of thin sections as well as by cathodoluminescence in order to detect their local variability in texture and mineral assemblages. The CL colours observed in a cold cathode device are related to the manganese contents. An attempt is made to relate the textures seen under CL to mineral reactions during the process of metamorphism. The predominantly calcite marbles from Pohorje exhibit orange luminescence with some dolomite lenses with red luminescence. The typical mineral assemblages are calcite+tremolite+phlogopite or calcite+dolomite+tremolite+phlogopite. Therefore, the estimated temperature from the stability of mineral assemblage is assumed at approximately 500 °C.     

Grain growth in synthetic marbles with added mica and water

Evolution of grain size in synthetic marbles was traced from compaction of unconsolidated powder, through primary recrystallization and normal grain growth, to a size stabilized by second phases. To form the marbles, reagent grade CaCO₃ was mixed with 0, 1 and 5 volume% mica and heat-treated under pressure with added water. Densification with negligible recrystallization occurred within one hour at 500° C and 500 MPa confining pressure. Primary recrystallization occurred at 500–550° C, causing increases of grain size of factors of 2–5. Resulting samples had uniform grain size, gently curved grain boundaries, and near-equilibrium triple junctions; they were used subsequently for normal grain growth studies. Normal grain growth occurred above 550° C; at 800° C, grain size (D) increased from 7 m (D ₀) to 65 m in 24 hours. Growth rates fit the equation, D ⁿ -D ₀ ⁿ =Kt, where K is a constant and n2.6. Minor amounts of pores or mica particles inhibit normal grain growth and lead to a stabilized grain size, D _max, which depends on the size of the second phases and the inverse of their volume fraction raised to a power between 0.3 and 1. Once D _max is reached, normal growth continues only if second phases are mobile or coarsen, or if new driving forces are introduced that cause unpinning of boundaries. Normal grain growth in Solnhofen limestone was significantly slower than in pure synthetic marble, suggesting that migration is also inhibited by second phases in the limestone.     

Dating the events of metamorphism and granitic magmatism in the Alpine orogen of Naxos (Cyclades,Greece)

An isotopic dating investigation (66 K-Ar and 34 Rb-Sr analyses) provided the geochronological framework for the Alpine events of metamorphism and granitic magmatism on Naxos. The oldest phase of high-pressure/medium-temperature metamorphism, M1, was dated by Rb-Sr and K-Ar analyses of paragonites, phengitic muscovites and muscovites at 45±5 Ma (Middle Eocene). Most of the record of the M1 phase has been eraded by a second phase of medium-pressure/high-temperature metamorphism, M2, which induced a metamorphic zonation with anatectic melting in the highest-grade part, the migmatite dome. Most K-Ar dates of M2 hornblendes, muscovites, biotites and tourmalines range from about 21 Ma in the lower-grade part (biotite-chloritoid zone) to about 11 Ma in the migmatite dome. From the pattern of K-Ar mineral dates it is concluded that the M2 phase took place 25±5 Ma ago (Late Oligocene/Early Miocene) and was followed by a prolonged cooling history until about 11 Ma ago (Late Miocene), when the ambient temperature in the migmatite dome had decreased to below 400–360 °C. A Rb-Sr whole-rock isochron analysis of a granodioritic mass dated the intrusion (and the associated M3 phase of contact-metamorphism) at 11.1±0.7 Ma (Late Miocene), with an initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7112 ±0.0001. A local phase of low-grade retrograde metamorphism, M4, probably related to Late Alpine overthrusting, was dated at about 10 Ma (Late Miocene).     

The behavior of trace elements during the chemical evolution of the H2O-, B-, and F-rich granite–pegmatite–hydrothermal system at Ehrenfriedersdorf, Germany: a SXRF study of melt and fluid inclusions

Detailed melt and fluid inclusion studies in quartz hosts from the Variscan Ehrenfriedersdorf complex revealed that ongoing fractional crystallization of the highly evolved H₂O-, B-, and F-rich granite magma produced a pegmatite melt, which started to separate into two immiscible phases at about 720°C, 100 MPa. With cooling and further chemical evolution, the immiscibilty field expanded. Two conjugate melts, a peraluminous one and a peralkaline one, coexisted down to temperatures of about 490°C. Additionally, high-salinity brine exsolved throughout the pegmatitic stage, along with low-density vapor. Towards lower temperatures, a hydrothermal system gradually developed. Boiling processes occurred between 450 and 400°C, increasing the salinities of hydrothermal fluids at this stage. Below, the late hydrothermal stage is dominated by low-salinity fluids. Using a combination of synchrotron radiation-induced X-ray fluorescence analysis and Raman spectroscopy, the concentration of trace elements (Mn, Fe, Zn, As, Sb, Rb, Cs, Sr, Zr, Nb, Ta, Ag, Sn, Ta, W, rare earth elements (REE), and Cu) was determined in 52 melt and 8 fluid inclusions that are representative of distinct stages from 720°C down to 380°C. Homogenization temperatures and water contents of both melt and fluid inclusions are used to estimate trapping temperatures, thus revealing the evolutionary stage during the process. Trace elements are partitioned in different proportions between the two pegmatite melts, high-salinity brines and exsolving vapors. Concentrations are strongly shifted by co ncomitant crystallization and precipitation of ore-forming minerals. For example, pegmatite melts at the initial stage (700°C) have about 1,600 ppm of Sn. Concentrations in both melts decrease towards lower temperatures due to the crystallization of cassiterite between 650 and 550°C. Tin is preferentially fractionated into the peralkaline melt by a factor of 2–3. While the last pegmatite melts are low in Sn (64 ppm at 500°C), early hydrothermal fluids become again enriched with about 800 ppm of Sn at the boiling stage. A sudden drop in late hydrothermal fluids (23 ppm of Sn at 370°C) results from precipitation of another cassiterite generation between 400 and 370°C. Zinc concentrations in peraluminous melts are low (some tens of parts per million) and are not correlated with temperature. In coexisting peralkaline melts and high-T brines, they are higher by a factor of 2–3. Zinc continuously increases in hydrothermal fluids (3,000 ppm at 400°C), where the precipitation of sphalerite starts. The main removal of Zn from the fluid system occurs at lower temperatures. Similarly, melt and fluid inclusion concentrations of many other trace elements directly reflect the crystallization and precipitation history of minerals at distinctive temperatures or temperature windows.     

The metamorphic evolution of migmatites from the Ötztal Complex (Tyrol,Austria) and constraints on the timing of the pre-Variscan high-T event in the Eastern Alps

Within the Ötztal Complex (ÖC), migmatites are the only geological evidence of the pre-Variscan metamorphic evolution, which led to the occurrence of partial anatexis in different areas of the complex. We investigated migmatites from three localities in the ÖC, the Winnebach migmatite in the central part and the Verpeil- and Nauderer Gaisloch migmatite in the western part. We determined metamorphic stages using textural relations and electron microprobe analyses. Furthermore, chemical microprobe ages of monazites were obtained in order to associate the inferred stages of mineral growth to metamorphic events. All three migmatites show evidence for a polymetamorphic evolution (pre-Variscan, Variscan) and only the Winnebach migmatite shows evidence for a P-accentuated Eo-Alpine metamorphic overprint in the central ÖC. The P-T data range from 670–750 °C and < 2.8 kbar for the pre-Variscan event, 550–650 °C and 4–7 kbar for the Variscan event and 430–490 °C and ca. 8.5 kbar for the P-accentuated Eo-Alpine metamorphic overprint. U-Th-Pb electron microprobe dating of monazites from the leucosomes from all three migmatites provides an average age of 441 ± 18 Ma, thus indicating a pervasive Ordovician-Silurian metamorphic event in the ÖC.     

The thermal history of equilibrated ordinary chondrites and the relationship between textural maturity and temperature

The compositions and textures of phases in eleven equilibrated ordinary chondrites from the H, L, and LL groups spanning petrographic types 4-6 were studied and used to constrain the thermal histories of their parent bodies. Based on Fe-Mg exchange between olivine and spinel, average equilibration temperatures for type 4-6 chondrites encompass a small range, 586-777 °C, relative to what is commonly assumed for peak temperatures (600-950 °C). The maximum temperatures recorded by individual chondrites, which are minima relative to peak metamorphic temperatures, increase subtly but systematically with metamorphic type and are tightly clustered for H4-6 (733-754 °C) and LL4-6 (670-777 °C). For the Ls, Ausson (L5) records a higher maximum olivine-spinel temperature (761 °C) than does the L4 chondrite Saratov (673 °C) or the L6 chondrite Glatton (712 °C). Our data combined with olivine-spinel equilibration temperatures calculated for other equilibrated ordinary chondrites using mineral compositions from the literature demonstrate that, in general, type 4 chondrites within each chemical group record temperatures lower than or equal to those of types 5-6 chondrites.For H chondrites, the olivine-spinel closure temperature is a function of spinel grain size, such that larger grains, abundant in types 5-6 chondrites, record temperatures of ∼740 °C or more while smaller grains, rare in types 5-6 but abundant in type 4 chondrites, record lower temperatures. Olivine-spinel temperatures in the type 6 chondrites Guareña and Glatton are consistent with rapid (50-100 °C/Myr) cooling from high temperatures in the ordinary chondrite parent bodies. With one exception (∼500 °C/Myr), olivine-spinel data for St.-Séverin (LL6) are consistent with similar cooling rates. Cooling rates of order 100 °C/Myr at ∼750 °C for type 6 chondrites are considerably higher than previously determined cooling rates for lower temperatures (?550 °C) based on metallography, fission tracks, and geochronology. For H chondrites, current thermal models of an “onion shell” parent body are inconsistent with a small range of peak temperatures based on olivine-spinel and two pyroxene thermometry combined with a wide dispersion of cooling rates at low temperatures. Equilibrated chondrites may have sampled regions near a major transition in physical properties such as near the base of a regolith pile.     

Le facies granulite en norvege meridionale: I. Les associations minéralogiques

The basement of Southern Norway is a genetically homogeneous migmatite complex in which old supracrustals produced granitic and granodioritic ‘neosome’ during a late Precambrian (10⁹ years ago) regional metamorphism. Observed isograds of critical minerals: muscovite, cordierite, orthopyroxene indicate that the Telemark amphibolite facies in the North passes into the coastal Bamble granulite facies in the South. The data of expeimental petrology suggest that the transition, which took place at temperatures of 700–800°C, is essentially due to a decrease of the partial water pressure. P_H2O was equal to total pressure P_s in the amphibolite facies and lower than 2 kb in the granulite facies.     

Fluids in low-pressure migmatites: a fluid inclusion study of rocks from the Gennargentu Igneous Complex (Sardinia, Italy)

Summary The low-pressure emplacement of a quartz diorite body in the metapelitic rocks of the Gennargentu Igneous Complex (Sardinia, Italy) produced a contact metamorphic aureole and resulted in migmatisation of part of the aureole through partial melting. The leucosome, formed by dehydration melting involving biotite, is characterised by granophyric intergrowth and abundant magnetite crystals. A large portion of the high temperature contact aureole shows petrographic features that are intermediate between quartz diorite and migmatite s.s. (i.e. hybrid rocks). A fluid inclusion study has been performed on quartz crystals from the quartz diorite and related contact aureole rocks, i.e. migmatite sensu stricto (s.s.) and hybrid rocks. Three types of fluid inclusions have been identified: I) monophase V inclusions, II) L + V, either L-rich or V-rich aqueous saline inclusions and III) multiphase V + L + S inclusions. Microthermometric data characterised the trapped fluid as a complex aqueous system varying from H₂O–NaCl–CaCl₂ in the quartz diorite to H₂O–NaCl–CaCl₂–FeCl₂ in the migmatite and hybrid rocks. Fluid salinities range from high saline fluids (50 wt% NaCl eq.) to almost pure aqueous fluid. Liquid-vapour homogenisation temperatures range from 100 to over 400 °C with an average peak around 300 °C. Temperatures of melting of daughter minerals are between 300 and 500 °C. Highly saline liquid- and vapour-rich inclusions coexist with melt inclusions and have been interpreted as brine exsolved from the crystallising magma. Fluid inclusion data indicate the formation of fluid of high iron activity during the low-pressure partial melting and a fluid mixing process in the hybrid rocks.     

Clumped isotope composition of marbles from the Backbone Range of Taiwan

The clumped isotope composition of carbonates provides a new way to retrieve temperatures for ancient geological systems without knowing the isotopic compositions of co‐existing fluid/minerals. The application of this new thermometer in the past decade, however, has been largely restricted to low‐temperature (<~250 °C) geological processes. In this study, we present clumped isotope analyses for marbles collected from the Backbone Range of Taiwan, which has been subjected to greenschist facies metamorphism during the ongoing arc–continent collision. We find that the ∆₄₇ temperatures either indicate temperatures of the last dynamic open‐system recrystallization of marbles due to tectonic movement/stress or signify closed‐system closure temperatures during rock exhumation, demonstrating that clumped information from marbles has great potential for revealing process characteristics during mountain building.     

The miscibility gap between rhodonite and bustamite along the join MnSiO3-Ca0.60Mn0.40SiO3

The miscibility gap between rhodonite and bustamite has been experimentally determined at temperatures between 600° and 1,100° C. For temperatures below 700° C the resulting limbs have been extrapolated on T-X-diagram as at such low temperatures equilibrium could not be attained. According to microprobe analyses for the natural assemblages of Ravinella di Sotto (Ivrea zone, Italy) and Broken Hill (N.S.W., Australia) equilibrium temperatures are estimated to be at 500° to 550° C. However these assemblages are thought to have re-equilibrated during cooling and the compositions of equilibrium assemblages are also pressure dependent. According to experiments and to molar volume data the rhodonite structure is stabilized by high pressures whereas bustamite by high temperatures. Based on available experimental results and natural data an isobaric T-X _Ca diagram and two isotherm -X _Ca diagrams (for T=400° C and T=600° C) are given.     

Ternary feldspar thermometry in granulites from the Oaxacan Complex,Mexico

Coexisting feldspars from across 2,000 km² of the granulite facies Oaxacan Complex, southern Mexico exhibit variable amounts of solid solution from nearly binary (Ab-An and Ab-Or) to substantially ternary (Ab-An-Or). Reintegrated analyses of 21 coarsely exsolved perthite (AF)-plagioclase (PL) pairs yield AF=Or_30–63 Ab_30–56An_2–15 and PL=Or_1–2Ab_70–84An_11–28. These data have been used to test existing two feldspar geothermometers for this extended composition range.For all compositions, temperature estimates show relatively little spread in value (660° to 795° C, 7 kbar) using the Haselton et al. (1983) calibration (HHHR). These temperatures are in fair agreement with estimates of 750±40° C for feldspar pairs with nearly binary compositions using the Stormer (1975) thermometer (STO). However, STO temperatures increase significantly (to 990° C) with increasing ternary solid solution in AF, suggesting that thermometers derived for binary systems are inaccurate for ternary compositions. Isotherms drawn from HHHR which take into account variable anorthite solution in alkali feldspar show that estimated temperature decreased by 50–100° C for each 5 mole percent anorthite in alkali feldspar.Experimentally determined solvus relations (Seck 1971) require feldspars with significant ternary solid solution to have crystallized or to have equilibrated at higher temperature than feldspars with more binary compositions. However, petrographic and field relations of ternary and binary feldspars in the Oaxacan Complex suggest they were all equilibrated at similar metamorphic pressures and temperatures and do not support a model where ternary feldspars have preserved higher premetamorphic temperatures. The composition of coexisting feldspars from other Precambrian granulite-facies terranes are also inconsistent with Seck's (1971) results. Hence, thermometers which fit Seck's solvus relations may not yield accurate temperatures in high grade metamorphic terranes. Parallel tie-lines for ternary and binary feldspars in the Oaxacan Complex and the consistency of inferred temperatures (HHHR) for many granulite terranes suggest that estimation of temperature using tie-line slopes rather than solvus width may yield more accurate results for these samples.Peak metamorphic conditions in the Oaxacan Complex are inferred to have been 730±50° C, 7±1 kbar. Pressure estimates from four garnet-plagioclase barometers show good agreement. Results of feldspar thermometry are consistent with diopside-forsterite equilibria in marbles which restrict T=720–765° C at P=7 kbar.     

Nikubuchi peridotite body in the sanbagawa metamorphic belt; thermal history of the ‘Al-pyroxene-rich suite’ peridotite body in high pressure metamorphic terrain

Oceanic tholeiite glass has been reacted with natural seawater at 25°–500° C, 1 kbar, with both low (5) and high (50) water/rock mass ratios. Initial experiments were conducted at constant temperatures between 100° C and 500° C (100° intervals) in order to characterize the mineralogy and chemical exchange trends for both water/rock ratios. However, the primary purpose of this investigation was to study the chemical and mineralogical changes that may take place as reacted seawater cools as it traverses a temperature gradient before exiting onto the seafloor, as may happen in some submarine hydrothermal systems. Consequently, a series of cooling or temperature gradient experiments were performed in which seawater that had reacted with basalt at 500° C was cooled to 25° C in a step-wise fashion; mineralogy and fluid chemistry were determined at 100 degree intervals during cooling.For all of the experiments, the elemental exchange trends were the same. With respect to the initial sea-water, Fe, Mn, Ca, Si and H⁺ increased while Na and Mg decreased. However, the extent of the exchange depended heavily on the temperature and water/rock ratio. During cooling, fluid compositions in the temperature gradient runs generally approached those of the constant temperature experiments. Even though fluid compositions were very similar at 500° C for both water/rock ratios, the high water/rock ratio systems were more efficient in leaching transition metals from the rock and maintained substantial concentrations in solution during cooling, even to temperatures as low as 25° C. The Fe/Mn ratio in the fluid, however, was quite different for the two water/rock ratios; consequently, the effective water/rock ratio appears to be one parameter that can control the Fe/Mn ratio in exiting hydrothermal fluids and may influence the Fe/Mn ratio in metal-rich sediments.Alteration minerals produced in these seawater/ basalt experiments are very similar to those found at submarine springs on the East Pacific Rise, 21° N. Iron sulfides, pyrite and pyrrhotite, precipitated during cooling for both water/rock ratios, demonstrating the ore-forming potential of submarine hydrothermal systems.     

Metamorphism of the variegated sequence at Kallithea,Samos, Greece

Summary The variegated sequence at Kallithea, westernmost part of the island of Samos, consists of pure dolomitic marbles, siliceous marbles, calc-silicate rocks and amphibolites. It was formed from a volcano-sedimentary series by a regional metamorphism under amphibolite facies conditions. Assuming a total fluid pressure of 5 kb, temperature may have reached 700°C. In the siliceous marbles, a retrogressive evolution is documented. The intrusion of the Kallithea igneous suite which took place about 10 Ma ago hardly affected the regional metamorphic sequence. The only exception are small veins of wollastonite in a silicate marble. In contrast to the other tectonic units which form the major part of Samos, no traces of high pressure minerals could be detected in the Kallithea metamorphics, suggesting a different geological history. The age and geotectonic position of the variegated sequence is unknown so far.

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Zusammenfassung Die bunte Serie von Kallithea (westlichster Teil der Insel Samos), bestehend aus reinen Dolomitmarmoren, Silikatmarmoren, Kalksilikatfelsen und Amphiboliten, geht auf eine vuikano-sedimentäre Folge zurück, die durch eine Regionalmetamorphose unter amphibolitfaziellen Bedingungen geprägt wurde. Hierbei dürften Temperaturen um 700°C erreicht worden sein, wenn man einen Gesamtdruck (P _fl ) von 5 kb annimmt. In den Silikatmarmoren ist eine Abfolge retrograder Mineralreaktionen dokumentiert. Vor etwa 10 Millionen Jahren intrudierten in die regionalmetamorphe Serie dioritische bis granitische Magmen ohne das Nebengestein kontaktmetamorph zu überprägen. Eine Ausnahme bilden kleine Wollastonitäderchen in einem Silikatmarmor. Im Gegensatz zu den übrigen tektonischen Einheiten, die den größten Teil der Insel aufbauen, lassen sich in den Metamorphiten von Kallithea keine Anzeichen einer Hochdruckmetamorphose nachweisen, was auf eine abweichende geologische Geschichte hindeutet. Alter und geotektonische Stellung der bunten Serie von Kallithea sind bislang noch unbekannt.

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With 5 Figures

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Herrn Professor Dr. Siegfried Matthes zum 70. Geburtstag gewidmet     

Environmental impact of mineral transformations undergone during coal combustion

The mineral transformations undergone by high sulfur coal ash were studied. An X-ray diffraction (XRD) experiment was carried out to reproduce experimentally the mineral transformations produced during coal combustion in coal-fired power stations. We have verified that the anhydrite is the main crystalline phase that contains sulfur in the solid combustion waste from 500°C until its decomposition at 1060±10°C. Thus, this calcium sulfate is the main crystalline phase involved in the sulfur retention in the combustion wastes at high temperatures. Therefore, a considerable proportion of the sulfur would not be emitted into the atmosphere at temperatures lower than 1060°C. Taking as a reference the annual coal consumption of the Teruel Mining District (6 million tons), the mean sulfur content and the anhydrite content at 900°C, it was shown that the SO₂ emissions could be reduced by approximately 13 percent (83,000 ton/yr) provided that the combustion temperature was 900°C.     

Porphyry to epithermal transition in the Agua Rica polymetallic deposit, Catamarca, Argentina: An integrated petrologic analysis of ore and alteration parageneses

Agua Rica (27°26′S–66°16′O) is a world class Cu–Au–Mo deposit located in Catamarca, Argentina. In the E–W 6969400 section examined, the Seca Norte and the Trampeadero porphyries that have intruded the metasedimentary rock are cut by interfingered igneous and hydrothermal heterolithic and monolithic breccias, and sandy dikes. Relic biotite and K-feldspar of the early potassic alteration (370° to > 550 °C) with Cu (Mo–Au) mineralization are locally preserved and encapsulated in a widespread, white mica + quartz + rutile or anatase halo (phyllic alteration) with pyrite + covellite that suggests fluids with temperatures ≤ 360 °C and high f(S₂). The Trampeadero porphyry and the surrounding metasedimentary rock with phyllic alteration have molybdenite in stringers and B-type quartz veinlets and the highest Mo grades (> 1000 ppm).Multistage advanced argillic alteration overprinted the earlier stages. Early andalusite ± pyrite ± quartz is preserved in the roots of the argillic halo rimmed by an alumina–silica material and white micas. This alteration assemblage is considered to have been formed at temperatures ≥ 375 °C from condensed magmatic vapor. At higher levels, pyrophyllite replaces muscovite and illite in clasts of hydrothermal breccias in the center and east sector of the study section, suggesting temperatures of 280 to 360 °C. Clasts of vuggy silica in the uppermost levels of the central breccia, indicates that at lower temperatures (< 250 °C), fluids reached very low pH (pH < 2). In this early stage of the advanced argillic alteration, hydrothermal fluids seem to have not precipitated sulfides or sulfosalts.Hydrothermal brecciation was concurrent with fluid exsolution (↑? V), which precipitated intermediate-temperature advanced argillic alunite (svanbergite + woodhouseite) ± diaspore ± zunyite as breccia cement along with abundant covellite + pyrite + enargite ± native sulfur ± kuramite at intermediate depths and in lateral transitional zones to unbrecciated rocks. This mineral assemblage indicates temperatures near 300 °C, oxidized and silica-undersaturated hydrothermal fluids with high sulfur fugacity to prevent gold precipitation. Multiple generations of pyrite, emplectite, colusite, Pb- and Bi-bearing sulfosalts, and native sulfur with Au and Ag, accompanied by alunite introduction in the upper level breccias, probably occurred at lower temperatures, but still high sulfur and oxygen activity. An independent Zn and Pb (as galena) mineralization stage locally coincides with Au–Ag and sulfosalts, and advanced at depth, controlled by fractures and overprinting much of the previous mineralization. A later paragenesis of veinlets of alunite + woodhouseite + svanvergite + pyrite ± enargite that cut the phyllic halo suggests temperatures ~ 250 °C and without woodhouseite + svanvergite, temperatures ~ 200 °C. Kaolinite occurs in the phyllic halo as a late mineral in clots and in veinlets thus, in this zone, the fluid had cooled enough for its formation.     

Calcite solubility and speciation in supercritical NaCl-HCl aqueous fluids

The solubility of calcite in NaCl-H₂O and in HCl-H₂O fluids was measured using an extraction-quench hydrothermal apparatus. Experiments were conducted at 2 kbar, between 400° C and 600° C. Measurements in NaCl-H₂O were conducted in two ways: 1) at constant pressure and NaCl concentration, as a function of temperature; and 2) at constant pressure and temperature, as a function of NaCl concentration. In both the NaCl-H₂O and the HCl-H₂O systems, the solubility of calcite increases with increasing chlorine concentrations. For example, the log calcium molality in equilibrium with calcite increases from –3.75 at 2 kbar and 500° C, in pure H₂O to –3.10 at 2 kbar and 500° C at log NaCl molality=–1.67. At fixed pressure and NaCl molality, the solubility of calcite is almost constant from 400° C to 550° C, but increases somewhat at higher temperatures. The results can be used to determine the dominant calcium species in the experimental solutions as a function of NaCl concentration and to obtain values for the second dissociation constant of CaCl_2(aq). At 2 kbar, 400° C, 500° C, and 600° C, we calculate values for the log of the dissociation constant of CaCl⁺ of –2.1, –3.2, and –4.3, respectively. The 400° C and 500° C values are consistent with those obtained by Frantz and Marshall (1982) using electrical conductance techniques. However, our 600° C value is 0.8 log units higher than that reported by Frantz and Marshall. The calcite solubilities in the NaCl-H₂O and HCl-H₂O systems are inconsistent with the solubilities of calcite in pure H₂O reported by Walther and Long (1986). They are, however, consistent with the measurements of calcite solubilities in pure H₂O presented in this study. These results allow for the calculation of the solubilities of calcium silicates and carbonates in fluids that contain CO₂ and NaCl.