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1.
Celadonite from the northwestern Mojave Desert area of California was examined by detailed Mössbauer spectroscopy at temperatures from 10 K to 400 K. In addition to the predominant Fe3+ doublet with isomer shift 0.4 mm s–1 and quadrupole splitting 0.4 mm s–1, another Fe3+ doublet with 0.4, 1.2 mm/s and two Fe2+ doublets with 1.1, 1.7, 2.7 mm s–1 at 300 K were distinguished. The minor Fe3+ component is ascribed to dehydroxylated surface sites. Most of the remaining Fe(90%) is M2 cis-OH octahedral in an ordered M+–M2+ array. However, about 10% is M1 trans-OH Fe2+. Isomer shift vs. T gives Debye temperatures of 570 K for Fe3+ in M2 and 380 K for both Fe2+ sites, indicating greater vibrational freedom for Fe2+. Quadrupole splitting vs. T for Fe2+ gives a valence electronic energy splitting of 760 cm–1 between the ground and first excited state for M2. The M1 sites have a more drastic variation in vs. T which indicates not only a lower first excited state but a rhombic distortion at these sites. A proposed explanation is a neighboring M2 site vacancy. The soil clay formed from this celadonite, which is mostly Fe-rich smectite, was also studied by Mössbauer spectroscopy. About half the Fe2+ has been oxidized in the clay, but the isomer shifts and quadrupole splittings are essentially the same as in the original celadonite. A texture orientation in the clay absorber was detected by measuring the absorber at 55° to the source radiation. This texture effect produces asymmetric doublets in the usual 90° measurement.  相似文献   

2.
For the first time 18O and 13C values from carbonates and D values of individual n-alkanes were used to reconstruct palaeohydrological conditions in a lagoon at the southern margin of the Central European Zechstein Basin (CEZB). A 12-m core covering the complete Ca2 interval and adjacent anhydrites (A1 and A2) was analyzed for 18O and 13C values of dolomitized carbonates and D values of individual n-alkanes. 18Ocarb values (+2 to +5 vs. VPDB) were strongly influenced by evaporation and temporal freshwater input into the lagoon. The 13Ccarb values (–1 to +4 vs. VPDB) were controlled mainly by changes in primary production. Both isotopic ratios show an inverse relationship throughout most of the core, contradicting diagenetic alteration, since 13Ccarb values are not altered significantly during dolomitization. Assuming a temperature range of 35–40 °C in the lagoon, 18Ocarb values of +2.5 to +8 (vs. VSMOW) for the lagoonal water can be reconstructed. The lagoon may have desiccated twice during the Ca2 interval, as indicated by very high 18Ocarb and low 13Ccarb values, coinciding with increasing amount of anhydrite in the analyzed sample. These events seem to reflect not just local but a regional intra-Ca2 cyclicity. Measured D values of the short-chain n-alkanes, namely n-C16 and n-C18 which are widely used as indicators for photosynthetic bacterial and algal input, reflect the isotopic composition of the lagoonal water. Assuming constant fractionation during incorporation of hydrogen into lipids of –160, an average D value of +70 (vs. VSMOW) can be reconstructed for the lagoonal water, accounting for very arid conditions. The long-chain n-alkanes n-C27, n-C28, n-C29 and n-C30, thought to be derived from the leaf waxes of terrestrial higher plants, were shown to be depleted in D relative to the short-chain alkanes, therefore indicating a different hydrogen source. Terrestrial plants in arid areas mainly use water supplied by precipitation. By using a smaller fractionation of –120 due to evaporation processes in the leaves, reconstructed values vary between –74 and –9 (vs. VSMOW). These values are not indicating extremely arid conditions, implying that the long-chain n-alkanes were transported trough wind and/or rivers into the lagoon at the Zechstein Sea coast. Dwater values, reconstructed using the n-C16 alkane and 18O water values, independently reconstructed on the same sample using the temperature dependant fractionation for dolomites are good agreement and suggest high amounts of evaporation affecting the coastal lagoon. Altogether, our results indicate that hydrogen isotopic ratios of n-alkanes give information on their origin and are a useful proxy for palaeoclimatic reconstruction.  相似文献   

3.
Hydrothermally-altered mesozonal synmetamorphic granitic rocks from Maine have whole-rock 18O (SMOW) values 10.7 to 13.8. Constituent quartz, feldspar, and muscovite have 18O in the range 12.4 to 15.2, 10.0 to 13.2, and 11.1 to 12.0, respectively. Mean values of Q–F ( 18Oquartz– 18Ofeldspar)=2.4 and Q–M ( 18Oquartz– 18Omuscovite)=3.3 are remarkably uniform (standard deviations of both are 0.2). Measured Q–F and Q–M values demonstrate that the isotopic compositions of the minerals are altered from primary magmatic 18O values but that the minerals closely approached oxygen isotope exchange equilibrium at subsolidus temperatures. Analyzed muscovites have D (SMOW) values in the range –65 to –82.Feldspars in the granitic rocks are mineralogically altered to either (a) muscovite+calcite, (b) muscovite+calcite+epidote, (c) muscovite+epidote, or (d) muscovite only. A consistent relation exists between the assemblage of secondary minerals and the oxygen isotope composition of whole rocks, quartz, and feldspar. Rocks with assemblage (a) have whole-rock 18O>12.1 and contain quartz and feldspar with 18O>13.8 and >11.4, respectively. Rocks with assemblages (b), (c), and (d) have whole-rock 18O<11.4 and contain quartz and feldspar with 18O< 13.1 and <11.0, respectively. The correlation suggests that the mineralogical alteration of the rocks was closely coupled to their isotopic alteration.Three mineral thermometers in altered granite suggest that the hydrothermal event occurred in the temperature range 400°–150° C, 100°–150° C below the peak metamorphic temperature inferred for country rocks immediately adjacent to the plutons. Calculations of mineral-fluid equilibria indicate that samples with assemblage (a) coexisted during the event with CO2-H2O fluids of and 18O=10.8 to 12.2 while samples with assemblages (b), (c), or (d) coexisted with fluids of and 18O=9.4 to 10.1. Compositional variations of the hydrothermal fluids were highly correlated: fluids enriched in CO2 were also enriched in 18O. Because CO2 was added to the granites during hydrothermal alteration and because fluids enriched in CO2 were enriched in 18O, some or all of the variation in 18O of altered granites may have been caused by addition of 18O to the rocks during the hydrothermal event. The source of both the CO2 and 18O could have been high-18O metasedimentary country rocks. The inferred change in isotopic composition of the granites is consistent with depletion of the metacarbonate rocks in 18O close to the plutons and with large volumes of fluid that were inferred from petrologic data to have infiltrated the metacarbonate rocks during metamorphism.A close approach of minerals to oxygen isotope exchange equilibrium in altered mesozonal rocks from Maine is in marked contrast to hydrothermally-altered epizonal granites whose mineral commonly show large departures from oxygen isotope exchange equilibrium. The difference in oxygen isotope systematics between altered epizonal granites and altered mesozonal granites closely parallels a differences between their mineralogical systematics. Both differences demonstrate the important control that depth exerts on the products of hydrothermal alteration. Deeper hydrothermal events occur at higher temperature and are longer-lived. Minerals and fluid have sufficient time to closely approach both isotope exchange and heterogeneous chemical equilibrium. Shallower hydrothermal events occur at lower temperatures and are shorter-lived. Generally there is insufficient time for fluid to closely approach equilibrium with all minerals.  相似文献   

4.
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   

5.
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   

6.
The 18O and D values in mud-volcanic waters of the Taman Peninsula and Kakhetia vary from +0.7 to +10.0 and from –37 to –13 , respectively. These values increase as the Greater Caucasus is approached. The increase in 18O and D also positively correlates with fluid generation temperatures based on hydrochemical geothermometers. This is accompanied by changes in the chemical composition of waters, in which contents of alkali metals, HCO– 3 ion, and boron increase, while the content of halogen ions (Cl, Br, J) decreases. Changes in the isotopic composition of water are also accompanied by the increase of 13 in methane and decrease of 11 B in clays. Analysis of formal models of the evolution of isotopic composition of mud-volcanic waters showed that mud volcanoes are recharged by freshened water from the Maikop paleobasin with an inferred isotopic composition of D –40 and 18 O –6. Based on this assumption, the 18O and D values observed in mud-volcanic waters can be explained not only by processes of distillation and condensation in a closed system, but also by combined processes of isotopic reequilibration in the water-illite-methane system.Translated from Litologiya i Poleznye Iskopaemye, No. 2, 2005, pp. 143–158.Original Russian Text Copyright © 2005 by Lavrushin, Dubinina, Avdeenko.  相似文献   

7.
In closed magma systems SiO2 approximately measures differentiation progress and oxygen isotopes can seem to obey Rayleigh fractionation only as a consequence of the behaviour of SiO2. The main role of 18O is as a sensitive indicator of contamination, either at the start of differentiation ( 18Oinit) or as a proportion of fractionation in AFC. Plots of 18O vs SiO2-allow to determine initial 18O values for different sequences for source comparison. For NBS-28=9.60, the 18O at 48% SiO2-varies between a high 6.4 for Kiglapait (Kalamarides 1984), 5.9 for Transhimalaya, 5.8 for Hachijo-Jima (Matsuhisa 1979), 5.6 for Koloula (Chivas et al. 1982) and a low 5.3 for the Darran Complex, New Zealand. The Transhimalayan batholiths (Gangdese belt) were emplaced in the Ladakh-Lhasa terrane, between the present-day Banggong-Nujiang, and Indus-Yarlung Tsangbo suture zones, after its accretion to Eurasia. The gradient of the least contaminated continuous ( 18O vs SiO2-igneous trend line is similar to that of Koloula, and AFC calculations suggest a low secondary assimilation rate of less than 0.05 times the rate of crystallisation. Outliers enriched in 18O are frequent in the Lhasa, and apparently rare in the Ladakh transsect. Low- 18O (5.0–0) granitoids and andesites on the Lhasa-Yangbajain axis are the result of present day or recent near-surface geothermal activity; their quartzes still trace the granitoids to the Transhimalaya 18O trend line, but the distribution of low total rock or feldspar 18O values could be a guide to more recent heat flow and thermally marked tectonic lineaments. Two ignimbrites from Maqiang show hardly any 18O-contamination by crustal material.  相似文献   

8.
The Etendeka Formation volcanics consist of a bimodal association of basalts and quartz latites. Forty three new whole rock oxygen isotope analyses are reported for all the major magma types. All the rocks except a minor suite of dolerites have higher 18O values than normal mantle. The basic rocks (average of 29=8.8) have significantly different 18O to the acid rocks (average of 10=14.4) These data are apparently consistent with previously published petrogenetic models, which propose that the basalts were affected by crustal contamination and that the quartz latites are crustally derived. However, mineral oxygen data show that there is significant oxygen isotopic disequilibrium between phenocryst and whole rock, the latter being significantly higher in most cases. One of the basic magma types (the Tafelberg basalts) shows mutual positive correlations between 18O, SiO2 and Sr. If these correlations are due to crustal contamination, then as much as 45% contamination is required by material having a 18O value of 15 which is the maximum observed value in the Damaran basement rocks. In the absence of pyroxene phenocryst 18O data for the high Sr Tafelberg basalts (they are aphyric), it is not possible to confirm that contamination has taken place. An alternative explanation is that the correlation between Sr and SiO2 resulted from assimilation coupled with fractional crystallization (AFC) (before emplacement). Post-eruption alteration resulted in a correlation between SiO2 18O because the material with the most Si-O bonds was able to concentrate 18O more effectively. The limited mineral data for the quartz latites suggests that there is some source heterogeneity. A pyroxene 18O value of 10% for a southern Etendeka quartz latite is consistent with a crustal source.  相似文献   

9.
Measurements were made of the hydrogen isotope ratios of hydrous silicates (mica and amphibole) and whole rocks, and the carbon isotope ratios of graphite and carbonaceous matter in the metamorphic rocks from the northern Kiso district in central Japan.D values of hydrous silicates in the graphite-bearing metapelites are always higher than those in graphite-free schists, even though the sample localities of the two rock-types are very close. Hydrogen isotopic equilibrium has been attained between the coexisting minerals.D/H ratios of water in the metamorphic fluids seem to depend strongly on the presence or absence of graphite and seem to be not constant throughout the district. The district is divided into three areas of low (metamorphic zones I, II), medium (zones IIIa–V) and high 13Cgr value (zones VIa–VII) areas. In the high 13Cgr values area, the carbon contents of the graphite-bearing rocks decrease slightly from zones VIa to VII, whereas the 13Cgr values increase sharply from the upper part of zone VIa to VIb. TheD values of biotite in these graphite-bearing rocks are higher than those in the medium 13Cgr area. This suggests that methane enriched inH and12C is produced and liberated by the devolatilization reactions between muscovite, graphite and water. The fluid produced is composed of water, methane and a subordinate amount of carbon dioxide, and its logfO2 value is deduced to be about 1.2 lower than that defined by the FMQ buffer. In the medium 13Cgr area, the 13C values of graphite are nearly constant (–20.8), while the Fe2O3/(Fe2O3 + FeO) ratio of the graphite-bearing rocks apparently decreases with increasing metamorphic grade.D differences in hydrous silicates between graphite-bearing and graphite-free rocks are observed. These facts are interpreted to mean that methane was produced in addition to water and carbon dioxide, and that its generation ( ratio of the fluid was about 2) had practically no isotope effect on the graphite. In the low 13Cgr area, the carbon contents of the rocks decrease clearly from zones I to IIIa. TheD and 13Cgr values of the non-metamorphosed shales are much lower than those of the low grade graphite-bearing metapelites. This suggests that methane is produced and liberated from the rocks even at the incipient stage of metamorphism.  相似文献   

10.
New sulphur and sulphate-oxygen isotope measurements for the main discordant and stratiform lead-zinc-barite orebodies at Silvermines Co. Tipperary, allow reappraisal of previously offered differing interpretations (Graham, 1970; Greig et al., 1971) of the bearing of sulphur isotopes on the genesis of this important Irish deposit. The following aspects of the data are confirmed: barite 34 S-values range from 17–21, similar to lower Carboniferous seawater sulphate: stratiform sulphide lens pyrites have 34 S-values ranging from –13 to –36; vein sulphide 34 S-values range from –8 to 4; sulphide 34 S-values increase upwards and outwards respectively in the related discordant and stratiform G orebodies; galena-sphalerite isotope palaeotemperatures are not too consistent, ranging from 40 to 430°C (using the calibration of Czamanske and Rye (1974). New facts are as follows: barite 18O-values range from –13 to –17, stratiform barites ranging from 13 to 14.5; sulphides separated from a single stratiform ore lens hand specimen usually have 34 Ssl > 34 Sga > 34 Spy; the outward decrease in 34 S-values in the stratiform G orebody is confined to the first few hundred feet only; pyrite 34 S-values progressively increase downwards through one stratiform sulphide orebody; yet variations of 13 occur within a single colloform pyrite structure from another stratiform orebody. It is concluded that there were at least two sources of sulphur, seawater sulphate and deep-seated sulphur. The former was the dominant source of all sulphate and, via biogenic reduction, of the sulphur in the bulk of the stratiform sulphide. The latter was the source of the sulphur in the vein sulphides. There was minimal isotopic interaction between the cool seawater sulphate and the warm unwelling ore fluid sulphur species, even though the latter precipitated under near isotopic equilibrium conditions when the temperature dropped and/or the pH and Eh increased. The lack of isotopic equilibrium between pyrite and ore sulphides in the stratiform ore lenses may result from the latter having precipitated slightly later than the former because of solubility relationships. Overall the present isotopic evidence supports considerable geological evidence favoring a syngenetic origin for the stratiform Silvermines orebodies.  相似文献   

11.
Oxygen isotope analyses of 101 samples from the Marcy Anorthosite Massif (61 from this study, 40 from Taylor 1969), indicate that two major and distinct processes of crustal contamination have affected the massif. Ninety percent of the 93 samples with over 65% plagioclase are enriched in 18O by 2.6 relative to normal anorthosites or gabbros: the average 18O for 83 enriched samples is 9.5 Depletions in 18O occur in 8% of the samples which have values ranging from 3.0 to 5.8 Only 2 of the samples fall within the normal magmatic range for anorthosites.Low 18O values of 3.0 to 5.8 in the anorthosite occur only near contacts, and a gradient in 18O occurs near the contact within the border zone of the massif. Low 18O values in both the anorthosite and adjacent wollastonite skarns (with 18O down to –1.3) were probably caused by isotopic exchange with heated meteoric water when the anorthosite intruded at shallow levels, prior to Grenvilleage ( 1.1 by) granulite facies metamorphism.The 18O-enrichment was ascribed to exchange between anorthosite and 18O-rich marble by means of a pervasive, H2O-CO2 fluid during the regional metamorphism by Taylor (1969). However, a number of lines of evidence argue against this hypothesis: 1) the preservation of premetamorphic low 18O values in anorthosite from the border zone as well as preserved gradients in 18O from a number of localities, 2) mass balance calculations of the amount of marble necessary to produce the 18O enrichment 3) metamorphic phase equilibria which buffer and to low values, and, 4) recent oxygen isotope analyses show homogeneity which indicates that magmatic oxygen isotope compositions have been preserved. We evaluated the importance of magmatic assimilation of country rock at the present level of intrusion as an alternative cause of the 18Oenrichment. Samples from 2 distinct lobes of the massif were analyzed: the NE lobe where xenoliths of metasedimentary country rock are common, and the NW lobe, where xenoliths are scarce and the country rock is dominantly granitic. The mean values of 18O for these two lobes are 9.6 in the NE and 9.3 in the NW. Thus, magmatic assimilation at the present level of exposure probably had only localized and relatively minor effects on the oxygen isotope composition of the massif. This conclusion is supported by Rb/Sr data: variations in Rb content and (87Sr/ 86Sr)i show that such crustal contamination is localized, generally occurring only in samples near the border zone. All of the available results suggest that the 18O-enrichment is a magmatic feature, acquired prior to intrusion at the present level of exposure.  相似文献   

12.
Dalradian metamorphic rocks, Lower Ordovician meta-igneous rocks (MGS) and Caledonian granites of the Connemara complex in SW Connemara all show intense retrograde alteration. Alteration primarily involves sericitization and saussuritization of plagioclase, the alteration of biotite and hornblende to chlorite and the formation of secondary epidote. The alteration is associated with sealed microcracks in all rocks and planes of secondary fluid inclusions in quartz where it occurs, and was the result of a phase of fluid influx into these rocks. In hand specimen K-feldspar becomes progressively reddened with increasing alteration. Mineralogical alteration in the MGS and Caledonian granites took place at temperatures 275±15°C and in the MGS Pfluid is estimated to be 1.5 kbar during alteration. The °D values of alteration phases are:-18 to-29 (fluid inclusions),-47 to-61 (chlorites) and-11 to-31 (epidotes). Chlorite 18O values are +0.2 to +4.3, while 18O values for quartz-K-feldspar pairs show both positively sloped (MGS) and highly unusual negatively sloped (Caledonian granites) arrays, diverging from the normal magmatic field on a - plot. The stable isotope data show that the fluid that caused retrogression continued to be present in most rocks until temperatures fell to 200–140°C. The retrograde fluid had D -20 to-30 in all lithologies, but the fluid 18O varied both spatially and temporally within the range-4 to +7. The fO2 of the fluid that deposited the epidotes in the MGS varied with its 18O value, with the most 18O-depleted fluid being the most oxidizing. The D values, together with low (<0) 18O values for the retrograde fluid in some lithologies indicate that this fluid was of meteoric origin. This meteoric fluid was probably responsible for the alteration in all lithologies during a single phase of fluid infiltration. The variation in retrograde fluid 18O values is attributed to the effects of variable oxygen isotope shifting of this meteoric fluid by fluid-rock interaction. Infiltration of meteoric fluid into this area was most likely accomplished by convection of pore fluids around the heat anomaly of the Galway granite soon after intrusion at 400 Ma. However convective circulation of meteoric water and mineralogical alteration could possible have occurred considerably later.  相似文献   

13.
The oxygen isotope geochemistry and chemical composition of clinopyroxene crystals from Alban Hills pyroclastic deposits constrain the petrological evolution of ultrapotassic Roman-type rocks. Volcanic eruptions in the 560–35 ka time interval produced thick pyroclastic deposits bearing clinopyroxene phenocrysts with recurrent chemical characteristics. Clinopyroxenes vary from Si–Mg-rich to Al–Fe-rich with no compositional break, indicating that they were derived from a continuous process of crystal fractionation. Based on the 18O and trace element data no primitive samples were recovered: monomineralic clinopyroxene cumulates set the oxygen isotope composition of primary magmas in the range of uncontaminated mantle rocks (5.5), but their REE composition resulted from extensive crystal fractionation. Departing from these mantle-like 18OCpx values the effects of crustal contamination of clinopyroxene O-isotope composition were identified and used to monitor chemical variations in the parental magma. 18O values in Si–Mg-rich clinopyroxene are slightly higher than typical mantle values (5.9–6.2), and the low REE contents are representative of early stages of magmatic differentiation. 18O values as high as 8.2 are associated with Al–Fe3+-rich clinopyroxene showing high REE contents. These 18O values are characteristic of crystals formed during the late magmatic stages of each main eruptive phase. Geochemical modelling of 18O values vs. trace element contents indicates that these ultrapotassic magmas were derived from fractional crystallization plus assimilation of limited amounts of carbonate wall rocks starting from a primary melt, and from interaction with CO2 derived from country rocks during crystal fractionation.  相似文献   

14.
In this paper, we present boron isotope analyses of variably degassed rhyolitic glasses from Long Valley, California. The following results indicate that pre-eruptive boron isotopic signatures were preserved in degassed glasses: (1) averaged secondary ionization mass spectrometry (SIMS) measurements of H2O-rich (~3 wt%) melt inclusions from late erupted Bishop Tuff pumice are indistinguishable from positive thermal ionization mass spectrometry (PTIMS) analysis of vesiculated groundmass glass (11B=+5.0±0.9 and +5.4±5, respectively); (2) SIMS spot-analyses on H2O-poor obsidian (~0.15 wt% H2O) from younger Glass Mountain Dome YA (average 11B=+5.2±1.0) overlap with compositionally similar late Bishop Tuff melt inclusions; and (3) four variably degassed obsidian samples from the 0.6 ka Mono Craters (H2O between 0.74 and 0.10 wt%) are homogeneous with regard to boron (average 11B=+3.2±0.8, MSWD=0.4). Insignificant variations in 11B between early and late Bishop Tuff melt inclusion glasses agree with published experimental data that predict minor 11B depletion in hydrous melts undergoing gas-saturated fractional crystallization. Melt inclusions from two crystal-rich post-caldera lavas (Deer Mountain and South Deadman Dome) are comparatively boron-rich (max. 90 ppm B) and have lower 11B values (average 11B=+2.2±0.8 and –0.4±1.0 ) that are in strong contrast to the boron isotopic composition of post-caldera crystal-poor rhyolites (27 ppm B; 11B=+5.7±0.8). These variations in 11B are too large to be caused by pre-eruptive degassing. Instead, we favor assimilation of 11B depleted low-temperature hydrothermally altered intrusive rocks subsequent to fresh rhyolite recharge.Editorial responsibility: J. HoefsAn erratum to this article can be found at  相似文献   

15.
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   

16.
Grenville dolomitic marbles and calc-silicates at Stephen Cross Quarry, Québec, underwent contact metamorphism and metasomatism associated with the intrusion of the Wakefield syenite at ambient pressures of 0.4GPa at 1090–1070Ma. Fluid infiltration produced exoskarns, calcite+periclase+forsterite±diopside±orthoclase assemblages in the marbles, and quartz±calcite±wollastonite±diopside±anorthite assemblages in the calc-silicates. Phase-equilibria in the CaO–MgO–Al2O3–SiO2–H2O–CO2 system suggest that fluid infiltration occurred close to the thermal peak of contact metamorphism (715–815°C) and that the fluids hadXCO20.15. In the metasediments, 18O values of calcite (Cc) are as low as 8.6, suggesting that the fluids were in isotopic equilibrium with the syenites (18O =8.8–10.2). Marble 13C(Cc) values are-0.1 to-3.2; the lack of correlation between 13C(Cc) and 18O(Cc) is consistent with the infiltration of water-rich fluids. The resetting of stable isotopes and the mineralogical changes can be explained by time-integrated fluid fluxes of up to 110 m3/m2 (4×106 mol/m2), corresponding to actual fluxes of 3×10-11 to 3×10-12 m3/m2-s and intrinsic permeabilities of 10-18 to 10-20 m2 for fluid flow lasting 0.1-1Ma. Marble 18O(Cc) values do not correlate well with distance from the syenite, and fluids were probably channelled across lithological layering. The correlation between the degree of resetting of marble 18O(Cc) values with the abundance of submillimetre-wide veins, suggests that fluid focussing may have resulted from variations in fracture density. Late, lower temperature (<500°C), fluid flow formed serpentine (Serp) and brucite (Br) from periclase and forsterite. 18O(Br) and 18O(Scrp) values correlate with 18O(Cc), suggesting that retrogression involved only limited volumes of fluid. The observation that 18O(Cc-Br) and 18O(Cc-Serp) values are higher in marbles that have lower 18O(Cc) values is interpreted as indicating that fluid flow persisted to lower temperatures in those rocks due to higher intrinsic permeabilities. Calcite in the syenite was also formed by the influx of fluids during cooling. Syenite 18O(Cc) values are approximately in isotopic equilibrium with the high-temperature silicate minerals, suggesting that again only minor volumes of fluid were involved. In detail fluid flow was prolonged and complex, creating problems for the application of quantitative fluid flow models.This paper is a contribution to IGCP 304, Lower Crustal Processes  相似文献   

17.
Oxygen and hydrogen isotope studies of a number of granite suites and mineral separates from the New England Batholith indicate that O18 can be used to discriminate the major granite protoliths. The granite suites previously subdivided on the basis of mineralogical and geochemical criteria into S-type (sedimentary) and I-type (igneous) have O18 values consistently higher in the S-type granites (10.4–12.5) than in the spatially related I-type plutons (7.7–9.9). There appears to be a systematic variation in O18 from the most S-type to the most I-type granites, the dividing point between the two occuring at O18 equal to 10. A group of leucocratic granites that form about half of the batholith and difficult to classify mineralogically and geochemically is found to have low O18 values (6.4–8.1), suggesting an affinity to the most I-type granites. A single leucogranite pluton with minor muscovite has a O18 of 9.6 which is significantly higher than other leucogranites indicating a different origin perhaps involving amphibole fractionation.The behavior of D in the plutonic rocks is much less systematic than O18. Excluding samples collected adjacent to major faults, the D values show a rough positive correlation with water content similar to, but less pronounced than, the trend previously observed in the Berridale Batholith, southeastern Australia. This relation is considered to reflect an interaction between meteoric water and the granites, the largest effect being observed in samples with the least amount of water. Of note is the generally lower D values of the upper Paleozoic New England Batholith compared with the Silurian Berridale Batholith. This difference may be related to a near equatorial paleolatitude of 22 °S in the Silurian and near polar paleolatitudes in the late Carboniferous that have been inferred for these regions. Granite samples collected from near major faults, and one ignimbrite sample of rhyodacite composition, have very low D values (less than –120) suggesting a much greater degree of interaction with meteoric water.  相似文献   

18.
The stable carbon isotopic composition of the planktonic foraminifera Globigerinoides sacculifer and G. ruber (white) and sedimentary organic matter from the northern Gulf of Aqaba have been investigated to estimate changes in 13CDIC in surface waters during the last 1,000 years. The high sedimentation rates at the core sites (about 54 cm/Kyear) provide high temporal resolution (~10 years). Recent sediments at the top of the cores reflect conditions younger than 1950. The 13C records of the planktonic foraminifera from three multicores display similar trends, showing a uniform and consistent pattern before the 1750s, and a gradual decrease of approximately 0.63 over the last two centuries. This decrease seems to track the decrease of 13CDIC in surface waters, which is mainly caused by the increase of anthropogenic input of 13C-depleted CO2 into the atmosphere. Similarly, a trend towards lighter values of the carbon isotopic composition of sedimentary organic matter (13Corg) during the last 200 years supports the interpretation obtained from the planktonic foraminiferal 13C. Furthermore, direct measurements of seawater show that 13C of the dissolved inorganic carbon (DIC) in the northern Gulf of Aqaba has decreased by about 0.44 during the period 1979–2000. The average annual decrease is 0.021, which is similar to that observed globally. The 13C values of planktonic foraminifera combined with organic matter 13C from marine sediments are good indicators for reconstructing past changes in atmospheric CO2 concentrations from the northern Gulf of Aqaba.  相似文献   

19.
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   

20.
Peak metamorphic temperatures for the coesite-pyrope-bearing whiteschists from the Dora Maira Massif, western Alps were determined with oxygen isotope thermometry. The 18O(smow) values of the quartz (after coesite) (18O=8.1 to 8.6, n=6), phengite (6.2 to 6.4, n=3), kyanite (6.1, n=2), garnet (5.5 to 5.8, n=9), ellenbergerite (6.3, n=1) and rutile (3.3 to 3.6, n=3) reflect isotopic equilibrium. Temperature estimates based on quartz-garnet-rutile fractionation are 700–750 °C. Minimum pressures are 31–32 kb based on the pressure-sensitive reaction pyrope + coesite = kyanite + enstatite. In order to stabilize pyrope and coesite by the temperature-sensitive dehydration reaction talc+kyanite=pyrope+coesite+H2O, the a(H2O) must be reduced to 0.4–0.75 at 700–750 °C. The reduced a(H2O) cannot be due to dilution by CO2, as pyrope is not stable at X(CO2)>0.02 (T=750 °C; P=30 kb). In the absence of a more exotic fluid diluent (e.g. CH4 or N2), a melt phase is required. Granite solidus temperatures are 680 °C/30 kb at a(H2O)=1.0 and are calculated to be 70°C higher at a(H2O)=0.7, consistent with this hypothesis. Kyanite-jadeite-quartz bands may represent a relict melt phase. Peak P-T-f(H2O) estimates for the whiteschist are 34±2 kb, 700–750 °C and 0.4–0.75. The oxygen isotope fractionation between quartz (18O=11.6) and garnet (18O=8.7) in the surrounding orthognesiss is identical to that in the coesitebearing unit, suggesting that the two units shared a common, final metamorphic history. Hydrogen isotope measurements were made on primary talc and phengite (D(SMOW)=-27 to-32), on secondary talc and chlorite rite after pyrope (D=-39 to -44) and on the surrounding biotite (D=-64) and phengite (D=-44) gneiss. All phases appear to be in nearequilibrium. The very high D values for the primary hydrous phases is consistent with an initial oceanicderived/connate fluid source. The fluid source for the retrograde talc+chlorite after pyrope may be fluids evolved locally during retrograde melt crystallization. The similar D, but dissimilar 18O values of the coesite bearing whiteschists and hosting orthogneiss suggest that the two were in hydrogen isotope equilibrium, but not oxygen isotope equilibrium. The unusual hydrogen and oxygen isotope compositions of the coesite-bearing unit can be explained as the result of metasomatism from slab-derived fluids at depth.  相似文献   

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