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1.
Carbon and oxygen isotopic covariations in hydrothermal calcites   总被引：5，自引：0，他引：5  
Isotopic covariations of carbon and oxygen in hydrothermal calcites are quantitatively modeled in terms of the following three mixing processes: (1) mixing between two different fluids which leads to the precipitation of calcite; (2) mixing between fluid and rock: (a) calcite precipitation due to fluid/rock interaction, (b) secondary alteration of primary calcite by interaction with a subsequent fluid. The models are derived from mass balance equations. A distinction among the three mixing processes can be made on a 13C vs 18O diagram, which places important constraints on the genesis of hydrothermal mineralization. The variables which control the ultimate isotopic composition of hydrothermal calcites include the composition of the initial fluid and the wallrock, temperature, and dissolved carbon species. Owing to significant temperature-dependent fractionation effects during equilibrium precipitation of calcite from a hydrothermal fluid, the mixing processes may be distinguished by telltale patterns of isotopic data in 13C vs 18O space. In particular, caution must be exercised in postulating the fluid mixing as the cause for mineral deposition. This is demonstrated for hydrothermal Pb-Zn deposits in the western Harz Mountains, Germany. A positive correlation between 13C and 18O values is observed for calcites from the Bad Grund deposit in the Upper Harz. Two sample profiles through calcite veins show similar correlations with the lowest -values at the center of the veins and the highest -values at the vein margins. Because the correlation array has a greater slope than for calcite precipitation at equilibrium in a closed system and because fluid mixing may not proceed perpendicular to the vein strike, it is assumed that a fluid/rock interaction is responsible for the observed correlation and thus for the precipitation of calcite. A deep-seated fluid is inferred with a 13C value of — 7% and a 18O value of +10%., as well as H2CO3 as the dominant dissolved carbon species; precipitation temperatures of the calcites are estimated to be about 280 170°C. Quite different isotopic distributions are observed for calcites from the St. Andreasberg deposit in the Middle Harz. An alteration model is suggested based mainly on the isotopic distribution through a calcite vein. In addition to a primary fluid which has the same isotopic composition as that in the Bad Grund deposit and thus seems to be responsible for the precipitation of calcite associated with sulfides, an evolved, HCO 3 - -dominant subsurface fluid with 13C about -20 — 15% and 18O 0% is deduced to alter the primary calcite at low temperatures of 70 40°C.  相似文献   

2.
The Jurassic Notch Peak granitic stock, western Utah, discordantly intrudes Cambrian interbedded pure limestones and calcareous argillites. Contact metamorphosed argillite and limestone samples, collected along traverses away from the intrusion, were analyzed for 18O, 13C, and D. The 13C and 18O values for the limestones remain constant at about 0.5 (PDB) and 20 (SMOW), respectively, with increasing metamorphic grade. The whole rock 18O values of the argillites systematically decrease from 19 to as low as 8.1, and the 13C values of the carbonate fraction from 0.5 to –11.8. The change in 13C values can be explained by Rayleigh decarbonation during calcsilicate reactions, where calculated is about 4.5 permil for the high-grade samples and less for medium and low-grade samples suggesting a range in temperatures at which most decarbonation occurred. However, the amount of CO2 released was not anough to decrease the whole rock 18O to the values observed in the argillites. The low 18O values close to the intrusion suggest interaction with magmatic water that had a 18O value of 8.5. The extreme lowering of 13C by fractional devolatilization and the lowering of 18O in argillites close to the intrusion indicates oxgen-equivalent fluid/rock ratios in excess of 1.0 and X(CO2)F of the fluid less than 0.2. Mineral assemblages in conjunction with the isotopic data indicate a strong influence of water infiltration on the reaction relations in the argillites and separate fluid and thermal fronts moving thru the argillites. The different stable isotope relations in limestones and argillites attest to the importance of decarbonation in the enhancement of permeability. The flow of fluids was confined to the argillite beds (argillite aquifers) whereas the limestones prevented vertical fluid flow and convective cooling of the stock.  相似文献   

3.
Stable isotope data have been determined for 13 Mesozoic and Tertiary plutons in eastern Nevada and nearby Utah. In the southern Snake Range of eastern Nevada, where relations are best exposed and have been most intensively studied, D, 18O, and apparent K-Ar ages depend on proximity to the Snake Range decollement. Where stresses resulting from late movement on the decollement have caused cataclasis of Oligocene (37 Ma) granitoid rock, 18O, D, and K-Ar age values as low as –2.5, –155, and 18 Ma, respectively, have been determined. Where there has been no cataclasis, 18O values of Jurassic, Cretaceous, and Oligocene granitoid rocks are apparently unaffected, but both D values and K-Ar ages have been modified for distances of tens of meters below the decollement.Results similar to those in the southern Snake Range have been observed in other eastern Nevada granitoid rocks spatially related to regional thrust faults, as in the Kern Mountains, the Toana Range, and the northern Egan Range. In each of these areas cataclasis or deformation of granitoid rocks has resulted in lowered 18O, D, and K-Ar age values. Where there has been no cataclasis or deformation, 18O values are unaffected, but both D and K-Ar age values have been lowered by stresses resulting from postcrystallization movement along overlying thrust faults.Many of the plutons discussed have not been deeply eroded, and spatially related thrust faults crop out. Where thrust faults are not in evidence and the granitoid rocks give D values lower than about –130 along with spuriously low K-Ar age results, modification of the D and K-Ar age values may have been caused by stresses related to late movement along an overlying (now eroded) thrust fault.  相似文献   

4.
Carbon and oxygen isotope analyses were made of representative samples of calcite and quartz from the carbonate deposits in the Tolfa Mountains mining district. Measurements were also made of hydrogen isotope compositions, filling temperatures and salinities of fluid inclusions in these minerals. There are three stages of mineralization at Tolfa. In stage I, characterized by calc-silicate hornfels, the carbonates have relatively high 18O values of 14.5 to 21.6 suggesting a rather low water/rock ratio. 13C values of –0.3 to 2.1 indicate that appreciable decarbonation or introduction of deep-seated carbon did not occur. Stage II is marked by phanerocrystalline carbonates; 18O values of 13.1 to 20.0 and 13C values of 0.7 to 5.0 identify them as hydrothermal veins rather than marbles. D values of –56 to –50 for inclusion fluids suggest a possible magmatic component to the hydrothermal fluid. Filling temperatures of coarse-grained samples of Calcite II are 309° to 362° C with a salinity range of 5.3 to 7.1 weight percent NaCl. Calculated 18O values of 11–12 for these fluids are again indicative of low water/rock ratios. The sparry calcites of stage III have 18O and 13C values of 8.1 to 12.9 and –1.7 to 3.2, respectively. D values of inclusion fluids are –40 to –33, clearly heavier than in earlier stages and similar to values of modern local ground waters. A salinity measurement of <0.1 weight percent NaCl in a sample of Calcite III is compatible with a relatively unaltered ground water origin for this fluid. Precipitation of the sparry calcite took place at much lower temperatures, around 160° C. For quartz, 18O values of 9.3 to 12.4 and D values for inclusions of –53 to –28 are consistent with its late occurrence and paragenetic link with associated carbonates.  相似文献   

5.
The 620 M.y.-old in Hihaou (In Zize) magmatic complex located at the north-western boundary of the Archaean In Ouzzal block (western Ahaggar), is composed of massive alkaline rhyo-ignimbrites and rhyolitic domes, which are intruded by a granophyric and granitic body. The whole is preserved in a cauldron structure. Extrusive rocks are strongly 18O-depleted, with -values as low as –1.5/SMOW, while granophyres are less depleted (minimum -18O value=+2.0/SMOW. The granite has values around + 6/SMOW. D/H compositions are rather low, with D–90 to –110/SMOW. Isotopic zoning of quartz phenocrysts, 18O/16O fractionation among coexisting phases, and heterogeneity of the whole-rock -18O values, suggest that the volcanic rocks have interacted with meteoric water after the eruption. Several mechanisms of isotopic alteration are discussed. The hydrothermal alteration does not seem to have been controlled by the granitic intrusion, but rather seems to have followed the deposition of thick pyroclastic deposits on permeable arkosic sandstones and fluvio-glacial conglomerates. Pervasive circulation of water through the cooling volcanic deposits could have produced the observed 18O depletion.  相似文献   

6.
The stable isotope composition of veins, pressure shadows, mylonites and fault breccias in allochthonous Mesozoic carbonate cover units of the Helvetic zone show evidence for concurrent closed and open system of fluid advection at different scales in the tectonic development of the Swiss Alps. Marine carbonates are isotopically uniform, independent of metamorphic grade, where 13C=1.5±1.5 (1 ) and 18O=25.4±2.2 (1 ). Total variations of up to 2 in 13C and 1.5 in 18O occur over a cm scale. Calcite in pre- (Type I) and syntectonic (Type II) vein arrays and pressure shadows are mostly in close isotopic compliance with the matrix calcite, to within ±0.5, signifying isotopic buffering of pore fluids by host rocks during deformation, and closed system redistribution of carbonate over a cm to m scale. This is consistent with microstructural evidence for pressure solution — precipitation deformation.Type III post-tectonic veins occur throughout 5 km of structural section, extend several km to the basement, and accommodate up to 15% extension. Whereas the main population of Type III veins is isotopically undistinguishable from matrix carbonates, calcite in the largest of these veins is depleted in 18O by up to 23 but acquired comparable 13C values. This generation of veins involved geopressurized hydrothermal fluids at 200 to 350° C where 18O H2O=–8 to +20, representing variable mixtures of 18O enriched pore and metamorphic fluids, with 18O depleted meteoric water. Calc-mylonites ( 18O=25 to 11) at the base of the Helvetic units, and syntectonic veins from the frontal Pennine thrust are characterized by a trend of 18O depletion relative to carbonate protoliths, due to exchange with an isotopically variable reservoir ( 18O H2O=20 to 4). The upper limiting value corresponds to carbonate-buffered pore fluid, whereas the lower value is interpreted as 18O-depleted formation brines tectonically expelled at lithostatic pressure from the crystalline basement. Carbonate breccias in one of the large scale late normal faults exchanged with infiltrating 18O-depleted meteoric surface waters ( 18O=–8 to –10).During the main ductile Alpine deformation, individual lithological units and associated tectonic vein arrays behaved as closed systems, whereas mylonites along thrust faults acted as conduits for tectonically expelled lithostatically pressured reservoirs driven over tens of km. At the latest stages, marked by 5 to 15 km uplift and brittle deformation, low 18O meteoric surface waters penetrated to depths of several km under hydrostatic gradients.  相似文献   

7.
A systematic study of the auriferous quartz veins of the Val-dOr vein field, Abitibi, Quebec, Canada, demonstrates that the C, O, S isotope composition of silicate, carbonate, borate, oxide, tungstate and sulphide minerals have a range in composition comparable to that previously determined for the whole Superior Province. The oxygen isotope composition of quartz from early quartz–carbonate auriferous veins ranges from 9.4 to 14.4 whereas later quartz-tourmaline-carbonate veins have 18Oquartz values ranging from 9.2 to 13.8 . Quartz-carbonate veins have carbonate (18O: 6.9–12.5 ; 13C: –6.2– –1.9 ) and pyrite (34S: 1.2 and 1.9 ) isotope compositions comparable to those of quartz-tourmaline-carbonate veins (18O: 7.9–11.7 ; 13C: –8.0 – –2.4 ; 34S: 0.6–6.0 ). 18Oquartz values in quartz-tourmaline-carbonate veins have a variance comparable to analytical uncertainty at the scale of one locality, irrespective of the type of structure, the texture of the quartz or its position along strike, across strike or down-dip a vein. In contrast, the oxygen isotope composition of quartz in quartz-tourmaline-carbonate veins displays a regional distribution with higher 18O values in the south-central part of the vein field near the Cadillac Tectonic Zone, and which 18O values decrease regularly towards the north. Another zone of high 18O values in the northeast corner of the region and along the trace of the Senneville Fault is separated by a valley of lower 18O values from the higher values near the Cadillac Tectonic Zone. Oxygen isotope isopleths cut across lithological contacts and tectonic structures. This regional pattern in quartz-tourmaline-carbonate veins is interpreted to be a product of reaction with country rocks and mixing between (1) a deep-seated hydrothermal fluid of metamorphic origin with minimum 18O=8.5 , 13C=0.6 and 34S=–0.4 , and (2) a supracrustal fluid, most likely Archean seawater with a long history of water-rock exchange and with maximum 18O=3.9 , 13 C=–5.6 and 34S=5.0 .  相似文献   

8.
Oxygen and carbon isotope compositions were determined for calcites from the Green Tuff formations of Miocene age in Japan. Values of 18O from 24 calcites in altered rocks from 5 districts range from –2 to +16SMOW, in most cases from 0 to +8SMOW. The low 18O values rule out the possibility of their low-temperature origin or any significant contribution of magmatic fluid in the calcite precipitation. These values, coupled with their mineral assemblages, suggest that the calcites formed from meteoric hydrothermal solutions which caused propylitic alteration after the submarine strata became emergent.Values of 13C from the calcites show a wide variation from –17 to 0PDB. Calcites from different districts have different ranges of 13C values, indicating that there was no homogeneous reservoir of carbon at the time the calcite formed, and that the carbon had local sources. Carbon isotopic compositions of calcite within ore deposits in the Green Tuff formations range from –19 to 0PDB, similar to those of calcite in the altered rocks in the same district, suggesting that the carbon in ore calcites was likely supplied from the surrounding rocks through activity of meteoric hydrothermal solutions.  相似文献   

9.
Isotopic compositions were determined for quartz, sericite and bulk rock samples surrounding the Uwamuki no. 4 Kuroko ore body, Kosaka, Japan. 18O values of quartz from Siliceous Ore (S.O.), main body of Black Ore B.O.) and the upper layer of B.O. are fairly uniform, +8.7 to +10.5. Formation temperatures calculated from fractionation of 18O between sericite and quartz from B.O. and upper S.O. are 250° to 300° C. The ore-forming fluids had 18O values of +1 and D values of –10, from isotope compositions of quartz and sericite.Tertiary volcanic rocks surrounding the ore deposits at Kosaka have uniform 18O values, +8.1±1.0 (n=50), although their bulk chemical compositions are widely varied because of different degrees of alteration. White Rhyolite, which is an intensely altered rhyolite occurring in close association with the Kuroko ore bodies, has also uniform 18O values, +7.9±0.9 (n=19). Temperatures of alteration are estimated to be around 300° C from the oxygen isotope fractionation between quartz and sericite. Paleozoic basement rocks phyllite and chert, have high 18O values, +18 and +19. The Sasahata formation of unknown age, which lies between Tertiary and Paleozoic formations, has highly variable 18O, +8 to +16 (n=4). High 18O values of the basement rocks and the sharp difference in 18O at their boundary suggest that the hydrothermal system causing Kuroko mineralization was mainly confined within permeable Tertiary rocks. D values of altered Tertiary volcanic rocks are highly variable ranging from –34 to –64% (n=12). The variation of D does not correlate with change of chemical composition, 18O values, nor distance from the ore deposits. The relatively high D values of the altered rocks indicate that the major constituent of the hydrothermal fluid was sea water. However, another fluid having lower D must have also participated. The fluid could be evolved sea water modified by interaction with rocks and the admixture of magmatic fluid. The variation in D may suggest that sea water mixed dispersively with the fluid.  相似文献   

10.
Boron isotope variations in nature: a synthesis   总被引：9，自引：0，他引：9  
The large relative mass difference between the two stable isotopes of boron, 10B and 11B, and the high geochemical reactivity of boron lead to significant isotope fractionation by natural processes. Published 11B values (relative to the NBS SRM-951 standard) span a wide range of 90. The lowest 11B values around — 30 are reported for non-marine evaporite minerals and certain tourmalines. The most 11B-enriched reservoir known to date are brines from Australian salt lakes and the Dead Sea of Israel with 11B values up to +59. Dissolved boron in present-day seawater has a constant world-wide 11B value of + 39.5. In this paper, available 11B data of a variety of natural fluid and solid samples from different geological environments are compiled and some of the most relevant aspects, including possible tracer applications of boron-isotope geochemistry, are summarized.
Résumé La grande différence relative de masse entre les isotopes stables du bore, 10B et 11B, et la grande réactivité geochimique du bore ont pour conséquence un fractionnement isotopique naturel important. Les valeurs de 11B publiées (par rapport au standard NBS SRM-951) varient de 90. Les valeurs de 11B les plus basses (–30) correspondent aux evaporites non-marines et à certaines tourmalines. Le réservoir le plus enrichi en 11B est représenté par les saumures des lacs salés d' Australie et par la Mer Morte en Israël, qui ont des valuers de 11B allent jusqu'à + 59. L'eau de mer a une valeur de 11B mondialement constante de + 39.5. Des valeurs de 11B des solutions naturelles ainsi que des roches et minéraux de différentes origines, publiées jusqu'à présent, sont présentées ici. En outre quelques aspects importants concernant la géochimie des isotopes du bore y compris quelques applications sont exposés.
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11.
REE (rare-earth-element) and Th mineralization at the Rodeo de Los Molles deposit occurs within an elliptical body of hydrothermally altered rocks (fenite) located in a biotite monzogranite of the Las Chacras batholith. Ore assemblages are found as isolated patches of intergrown britholite, allanite, apatite, bastnaesite, fluorite, sphene, quartz, and aegirine-augite, as well as nodules of uranothorite and late-stage veins of calcite, fluorite, and bastnaesite. Composition-volume computations suggest that the fenite was produced by alteration of the biotite monzogranite by addition of K and Na, and loss of Ca and Sr. Petrographic evaluations indicate that microcline and plagioclase have been replaced by perthite, and biotite was converted to aggregates of clinochlore, anatase, kaolinite, and hematite. Relict biotite is characterized by lower Fe/(Fe+Mg) and Ti values with progressive alteration. Fluorine-rich phlogopite is present in mineralized areas, but textural evidence suggests that it was not produced via biotite alteration. Mass-balance constraints also show that Ca and Mg in ore zones may result from redistribution, rather than their being a result of external derivation. The 18O values of quartz (8.6–11.1) and feldspar (7.8–10.6) suggest that feldspar continued to exchange oxygen isotopes with a fluid to lower temperatures than did quartz. Feldspars equilibrated with a fluid of 18O8 at a fluid/rock ratio less than 1. The 18O values of quartz and aegirine-augite that crystallized during REE mineralization also suggest equilibration with a fluid of 18O8. The D values of biotite (-83 to-120) are relatively low for igneous rocks and are thought to have resulted from exsolution of a D-enriched magmatic vapor. The D values of both mineralized and barren fenites are consistent with equilibration with fluid of magmatic origin. Meteoric water was involved in the production of calcite and clinochlore alteration, and late-stage calcite-fluorite-bastnaesite veins. The 13C values of calcite and bastnaesite (-7.8 to-13.5%) suggest that carbon was derived by leaching of carbon from igneous and/or enclosing metamorphic rock types, and that a majority of carbon ultimately was derived from sedimentary organic meterial.  相似文献   

12.
Strata-bound sulfide deposits associated with clastic, marine sedimentary rocks, and not associated with volcanic rocks, display distributions of S34 values gradational between two extreme types: 1. a flat distribution ranging from S34 of seawater sulfate to values about 25 lower; and 2. a narrow distribution around value S34 (sulfide)=S34 (seawater sulfate) –50, and skewed to heavier values. S34 (seawater sulfate) is estimated from contemporaneous evaporites. There is a systematic relation between the type of S34 distribution and the type of depositional environment. Type 1 occurs in shallow marine or brackish-water environments; type 2 occurs characteristically in deep, euxinic basins. These distributions can be accounted for by a model involving bacterial reduction of seawater sulfate in systems which range from fully-closed batches of sulfate (type 1) to fully open systems in which fresh sulfate is introduced as reduction proceeds (type 2). The difference in the characteristic distributions requires that the magnitude of the sulfate-sulfide kinetic isotope effect on reduction be different in the two cases. This difference has already been suggested by the conflict between S34 data for modern marine sediments and laboratory experiments. The difference in isotope effects can be accounted for by Rees' (1973) model of steady-state sulfate reduction: low nutrient supply and undisturbed, stationary bacterial populations in the open system settings tend to generate larger fractionations.
Zusammenfassung Schichtgebundene Sulfid-Lagerstätten in Begleitung von klastischen, marinen Sedimentgesteinen ohne Beteiligung vulkanischer Gesteine zeigen kontinuierliche Verteilungen der S34-Werte zwischen zwei Extremtypen: 1. Eine flache Verteilung im Bereich von S34-Werten des Seewasser-Sulfats bis zu Werten, die etwa 25 niedriger liegen. 2. Eine eng begrenzte Verteilung um den S34 (Sulfid)-Wert=S34 (Seewasser-Sulfat) –50 und asymmetrischer Verteilungskurve mit stärkerer Besetzung bei den schwereren Werten. Das S34 (Seewasser-Sulfat) wird von gleichaltrigen Evaporiten abgeleitet. Es besteht eine systematische Beziehung zwischen der Art der S34-Verteilung und dem Milieu des Ablagerungsraumes. Typ 1 tritt im marinen Flachwasser oder in brackischer Umgebung auf. Typ 2 ist charakteristisch für tiefe euxinische Becken. Diese Verteilungen können erklärt werden mit Hilfe eines Modells mit bakterieller Reduktion von Meerwasser-Sulfat in Systemen, die von völlig abgeschlossenen Sulfat-Mengen (Typ 1) bis zu völlig offenen Systemen reichen, in die bei fortschreitender Reduktion frisches Sulfat zugeführt wird (Typ 2). Der Unterschied in den charakteristischen Verteilungen setzt voraus, daß die Stärke der kinetischen Sulfat-Sulfid-Isotopen-Wirkung auf die Reduktion in beiden Fällen verschieden ist. Dieser Unterschied wurde bereits wegen der Widersprüche zwischen den verschiedenen S34-Werten heutiger mariner Sedimente und Laborexperimente vermutet. Der Unterschied in der Isotopen-Wirkung kann durch das Modell von Rees (1973) für kontinuierlich ablaufende Sulfat-Reduktion erklärt werden. Geringes Nahrungsangebot und ungestörte, gleichbleibende Bakterien-Populationen in offenen Systemen neigen zur Erzeugung stärkerer Fraktionierungen.
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13.
The world-class Idrija mercury deposit (western Slovenia) is hosted by highly deformed Permocarboniferous to Middle Triassic sedimentary rocks within a complex tectonic structure at the transition between the External Dinarides and the Southern Alps. Concordant and discordant mineralization formed concomitant with Middle Triassic bimodal volcanism in an aborted rift. A multiple isotopic (C, O, S) investigation of host rocks and ore minerals was performed to put constraints on the source and composition of the fluid, and the hydrothermal alteration. The distributions of the 13C and 18O values of host and gangue carbonates are indicative of a fracture-controlled hydrothermal system, with locally high fluid-rock ratios. Quantitative modeling of the 13C and 18O covariation for host carbonates during temperature dependent fluid-rock interaction, and concomitant precipitation of void-filling dolomites points to a slightly acidic hydrothermal fluid (13C–4 and 18O+10), which most likely evolved during isotopic exchange with carbonates under low fluid/rock ratios. The 34S values of hydrothermal and sedimentary sulfur minerals were used to re-evaluate the previously proposed magmatic and evaporitic sulfur sources for the mineralization, and to assess the importance of other possible sulfur sources such as the contemporaneous seawater sulfate, sedimentary pyrite, and organic sulfur compounds. The 34S values of the sulfides show a large variation at deposit down to hand-specimen scale. They range for cinnabar and pyrite from –19.1 to +22.8, and from –22.4 to +59.6, respectively, suggesting mixing of sulfur from different sources. The peak of 34S values of cinnabar and pyrite close to 0 is compatible with ore sulfur derived dominantly from a magmatic fluid and/or from hydrothermal leaching of basement rocks. The similar stratigraphic trends of the 34S values of both cinnabar and pyrite suggest a minor contribution of sedimentary sulfur (pyrite and organic sulfur) to the ore formation. Some of the positive 34S values are probably derived from thermochemical reduction of evaporitic and contemporaneous seawater sulfates.Editorial handling: P. Lattanzi  相似文献   

14.
Mineralogical, textural and geochemical investigations were made to determine the post-depositional evolution of Devonian and Early Carboniferous carbonates from Valle de Tena. The carbonate association is made up of low-Mg calcite, which occurs as micrite, spar cements, neomorphic patches and spar filling veinlets. Non-stoichiometric dolomite and ankerite occur as cements (dolomite also as replacements) in the Middle Devonian, post-dating calcite types. All these phases pre-date tectonic stylolites, indicating compaction after stabilization of the carbonate minerals. Strontium concentrations indicate that Early Devonian and Early Carboniferous micrites initially precipitated as aragonite; Middle and Late Devonian micrites precipitated as high-Mg calcites. Both precursors were diagenetically stabilized to low-Mg calcites through interaction with meteoric waters in phreatic environments. Trace elements in dolomite and ankerite indicate precipitation from Sr-enriched meteoric water. All studied carbonates, except Middle Devonian limestones, precipitated in reducing environments, which favoured incorporation of Fe and Mn. Late calcite generations precipitated from more saline waters than micrites. Light 18O values in micrites suggest alteration mainly in meteoric-phreatic environments. The dolomites and ankerites precipitated from more 18O-depleted fluids than the calcites, suggesting a greater contribution from meteoric waters. Variations in 13C of micrites represent primary secular trends, according to published 13C variations. The 13C oscillations within each succession probably relate to sea-level oscillations. Strontium isotopes also point to a meteoric origin of diagenetic fluids. Model calculations suggest that O and Sr isotopes equilibrated between calcites and fluid at relatively low water/rock ratios, whereas C isotopic signatures are inherited from limestones.  相似文献   

15.
Sulfur isotope analyses were made on 14 alunites from volcanic and sedimentary rocks widely different in chemistry and age from southern Tuscany and northern Latium, central Italy. The 34S values range from +0.7 to +9.6, and appear not to be related to the nature of the host rock. Geological and isotopic evidence suggests that all the alunites formed by supergenic oxidation of sulfides. Sulfides occurring with alunites in the volcanic rocks of Latium can be divided into an isotopically light group of probably magmatic origin (34S=–1.5 to +3.4) and a heavy one with 34S=+6.0 to +10.3, tentatively interpreted as deposited by hydrothermal fluids that leached sulfides of similar 34S/32S from the deep basement. Such an interpretation is consistent with recent studies indicating that in the perityrrhenian belt of Latium exists a continuation, at depth, of the Tuscan stratigraphic series, rich in sulfides with 34 from +6 to +12.  相似文献   

16.
Temperatures of the formation of mud-volcanic waters are determined based on concentrations of some temperature-dependent components (Na–Li, Mg–Li). Estimates obtained for the Taman and Kakhetia regions are similar and range from 45 to 170°, which correspond to depths of 1–4.5 km. The calculated temperatures correlate with the chemical (Li, Rb, Cs, Sr, Ba, B, I, and HCO3) composition of water and 13 (2) and 13 (CH4) values in spontaneous gases. The isotope values indicate that mechanisms of the formation of 13-rich gases, i.e., gases with high 13 values (up to +16.0 in 2 and –23.4 in CH4) in mud-volcanic systems of Taman and Kakhetia are governed by fluid-generation temperatures rather than the supply of abyssal gases. The 11 value was determined for the first time in mud-volcanic products of the Caucasus region. This value ranges from +22.5 to +39.4 in the volcanic water of Georgia, from –1.2 to +7.4 in the clayey pulp of Georgia, and from –7.6 to +13.2 in the clayey pulp of Taman. It is shown that the 11 value in clay correlates with the fluid-generation temperature and 11 correlates with 13 in carbon-bearing gases. These correlations probably testify to the formation of different phases of mud-volcanic emanations in a single geochemical system and suggest the crucial role of temperature in the development of isotope-geochemical features.  相似文献   

17.
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 ( 18O SMOW) of emeralds shows a strong enrichment in18O and is remarkably uniform at + 15.6 ± 0.4 (1,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 (D = –51 to –32 SMOW) than the other inclusion waters (D = –96 to –70 SMOW). Similarly the oxygen isotopic compositions of tourmaline and fuchsite are relatively constant ( 18O = + 13 to + 14 SMOW) and show enrichment in18O. The 18O values of quartz, ranging from + 15.1 to + 19.1 SMOW, are also high (+ 16.9 ± 1.4 1, n = 7). The meanD of channel waters measured from emerald (–42 ± 6.6 SMOW) and that of fluid calculated from hydrous mineralsDcalculated (–47 ± 7.1 SMOW) are consistent with both metamorphic and magmatic origin. However, the close similarity between the measuredD 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 ( 13 –3.2 ± 0.7%, PDB; 18O + 17.9 ± 1.27 SMOW). On the basis of the isotopic composition of fluid ( 13C –1.8 ± 0.7 PDB; 18O + 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.  相似文献   

18.
Isotopic compositions of carbon and oxygen are studied in different (rhodochrosite, calcareous-rhodochrosite, and chlorite–rhodochrosite) types of manganese carbonate ores from the Usa deposit (Kuznetskii Alatau). The 13C value varies from –18.4 to –0.7, while the 18O value ranges between 18.4 and 23.0. Host rocks are characterized by higher values of 13C (–1.9 to 1.0) and 18O (21.2 to 24.3). The obtained isotope data suggest an active participation of oxidized organic carbon in the formation of manganese carbonates. Manganese carbonate ores of the deposit are probably related to metasomatic processes.  相似文献   

19.
The carbon and oxygen isotopic composition of Fe-carbonate ore and its calcitic to dolomitic Devonian host rocks at the Steirischer Erzberg siderite deposit (Greywacke zone, Upper Austroalpine Unit) were determined in order to constrain the source and nature of the Fe-rich mineralizing fluid. The 18O-values obtained for various Fe-carbonate generations and the carbonate host lie within a similar range between + 14.6 and + 21.6 (V-SMOW). No good correlation exists between the relative ages of the carbonate phases and their O isotopic composition. The variation in 18O-values is due to metamorphic recrystallization with locally variable fluid/rock ratios. The average 13C-value of the carbonate host is +0.5 ± 1.2 (PDB) which corresponds well to worldwide Phanerozoic marine carbonate values. The first Fecarbonate generation has slightly lower 13C-values, on average -1.4 ± 0.8 (PDB). Recrystallization of both the carbonate host minerals and the ankerite/siderite led to significantly lower 13C-values of -4.2 ± 0.6 and-4.7 ± 0.7, respectively. Within the basal breccia of the post-Hercynian transgression series matrix calcite/ dolomite shows an average 13C-value of -2.9 ± 0.7, and matrix siderite/ankerite an average value of-4.1 ± 0.4. These data, together with Sr isotope data published previously, strongly support a late-diagenetic or epigenetic first Fe-mineralization from convecting formation waters. They ascended along extension faults and were driven by an increased heat flow caused by crustal thinning during a Devonian rifting phase that initiated the separation of the Noric terrane from Africa. A potential source of the Fe could have been the underlying Ordovician acid volcanics. Regional metamorphism related to collision tectonics in the Late Carboniferous (Hercynian) and later during the Alpine orogeny, caused intensive recrystallization and partial mobilization of the various carbonate phases.  相似文献   

20.
Sulfur isotope ratios have been determined in 27 selected volcanic rocks from Iceland together with their whole rock chemistry. The 34S of analyzed basalts ranges from –2.0 to +0.4 with an average value of –0.8 Tholeiitic and alkaline rocks exhibit little difference in 34S values but the intermediate and acid rocks analyzed have higher 34S values up to +4.2 It is suggested that the overall variation in sulfur isotope composition of the basalts is caused by degassing. The small range of the 34S values and its similarity to other oceanic and continental basalts, suggest that the depleted mantle is homogeneous in its sulfur isotope composition. The 34S of the depleted mantle is estimated to be within the range for undegassed oceanic basalts, –0.5 to +1.0  相似文献   

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