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1.
The oxygen and hydrogen isotopic composition of Eocene and Miocene freshwater cherts in the western United States records regional climatic variation in the Cenozoic. Here, we present isotopic measurements of 47 freshwater cherts of Eocene and Miocene age from the Great Basin of the western United States at two different sites and interpret them in light of regional climatic and tectonic history. The large range of δ18O of terrestrial cherts measured in this study, from 11.2‰ to 31.2‰ (SMOW: Standard Mean Ocean), is shown to be primarily the result of variations in δ18O of surface water. The following trends and patterns are recognized within this range of δ18O values. First, in Cenozoic rocks of northern Nevada, chert δ18O records the same shift observed in authigenic calcite between the Eocene and Miocene that has been attributed to regional surface uplift. The consistent covariation of proxies suggests that chert reliably records and retains a signal of ancient meteoric water isotopic composition, even though our analyses show that chert formed from warmer waters (40°C) than coexisting calcite (20°C). Second, there is a strong positive correlation between δ18O and δD in Eocene age chert from Elko, Nevada and Salina, Utah that suggests large changes in lake water isotopic composition due to evaporation. Evaporative effects on lake water isotopic composition, rather than surface temperature, exert the primary control on the isotopic composition of chert, accounting for 10‰ of the 16‰ range in δ18O measured in Eocene cherts. From authigenic mineral data, we calculate a range in isotopic composition of Eocene precipitation in the north-central Great Basin of −10 to −14‰ for δ18O and −70 to −100‰ for δD, which is in agreement with previous estimates for Eocene basins of the western United States. Due to its resistance to alteration and record of variations in both δ18O and δD of water, chert has the potential to corroborate and constrain the cause of variations in isotope stratigraphies.  相似文献   

2.
Quartz-eye keratophyric tuffs at Aljustrel, S. Portugal, Iberian Pyrite Belt possess unusually high, uniform whole rock δ-values up to 18.1%. with a mean of 16.7 ± 0.7%.. Because the quartz eye cores have δ18O 12.0 to 13.5%. the felsic tuffs may have had an original whole rock oxygen isotope composition of 10 to 11%. The deduced enrichments of up to +8%. in keratophyric derivatives is attributed to isotope exchange with abundant marine water under temperatures which diminished to ≤ 100°C, during thermally driven convective cooling. The isotopic uniformity requires elevated permeability of ～ 10?8 cm2, such that the second critical Rayleigh number was exceeded, and drifting, non steady state convection cells dominated, with relatively smooth thermal structures.In mineralised counterparts of the tuffs beneath the Feitais-Estacao Zn-Pb-Cu massive sulphide orebodies, whole rock δ-values are ~12%. and quartz (13.3–15.4%.)-chlorite (3.2–6.3%.) fractionations correspond to temperatures of 220–270°C, and a calculated fluid δ18O of 1.4 to 5.7%. This local isotopic overprinting in vent domains of the regionally high 18O was induced by a stable, second stage convective regime imposed by drastic reduction of permeability accompanying capping of the geothermal discharge by hydrothermal cherts, and/or progressive spilitisation of the tuffs. At lower water/rock coupled with higher temperatures, the recirculating marine water underwent variable 18O enrichment up to 5.7%. by exchange with the high 18O tuffs. An upwards increase in δ18O quartz and δ-quartz reflects progressive cooling of the geothermal discharge from 15.4%. 270°C in the stockwork, through 18.3%. 220–240°C in the orebody, to 20.1%. 110–130°C in overlying hydrothermal cherts, probably induced by entrainment of ambient marine bottom water in sub-seafloor aquifers.  相似文献   

3.
δD and δ18O values have been determined for fluid inclusions in 45 samples of Permian halite. The inclusions are enriched in 18O relative to the meteoric water line but are depleted in D relative to ocean water. Inclusions with the more positive δ-values coincide with the isotopic composition expected for evaporating sea water which follows a hooked trajectory on a δD-δ18O diagram. Inclusions with more negative δ-values may represent more highly evaporated sea water but probably reflect synsedimentary or diagenetic mixing of meteoric water with evaporite brines. The isotope systematics in these inclusions are sufficiently similar to those of a modern evaporite pan to indicate that Permian sea water was isotopically similar to modern sea water.Connate evaporite brines can have negative δ-values because of the probable hooked isotope trajectory of evaporating sea water and/or synsedimentary mixing of evaporite brines with meteoric waters. Subsurface formation waters composed of mixtures of remnant primary evaporite brines and later meteoric waters may be more common than previous isotopic evidence has suggested.  相似文献   

4.
Oxygen isotopic compositions of chert and calcite cements in the Lake Valley Formation indicate that these diagenetic features cannot be equilibrium co-precipitates in spite of their coexistence in the same interstices. Petrography of megaquartz and non-ferroan calcite cements indicates that both are original precipitates that formed during pre-Pennsylvanian time at shallow burial depths (< 215m) implying precipitation temperatures less than 30°C. Under these constraints the δ18Os of megaquartz (mean =+27.00/00 SMOW; range =+ 24.8 to + 28.90/00) and calcite (mean =+ 28.00/00 SMOW; range =+ 27.3 to + 28.40/00) are best interpreted as unaltered since precipitation; thus, they must reflect the oxygen isotopic composition of pre-Pennsylvanian pore waters. Microquartz and chalcedony are interpreted to have formed from recrystallization of pre-Pennsylvanian opal-CT precursors, and therefore probably re-equilibrated during recrystallization in late or post-Mississippian time. We propose a model integrating the isotopic data with regional petrographic and sedimentological data that explains the greater consistency and generally greater δ18Os values of the calcites compared to those of the cherts. This model is one of chertification and calcite cementation in a regional meteoric phreatic ground-water system, the seaward terminus of which moved southward during lowering of pre-Pennsylvanian sea level. The calcite cements and some of the opal-CT precursor to microquartz and chalcedony are interpreted to have formed in the more seaward portions of the groundwater system. The megaquartz precipitated in the more inland parts of the phreatic groundwater system where rainfall was isotopically lighter and more variable. As such, the δ18Os of the megaquartz reflect the isotopic composition of groundwaters in areas undersaturated with respect to calcite.  相似文献   

5.
Analyses of 230 Franciscan rock and mineral samples, including the San Luis Obispo ophiolite, show that metamorphism produces no change in the δ18O of the graywackes (+11 to +14), but that igneous rocks become enriched in 18O by 2–6% and the cherts depleted by 5–10%. The shales are of two types, a high-18O type (+16 to +20) associated with chert and a low-18O type isotopically and mineralogically similar to the graywackes. The vein quartz (δ = + 15 to + 20) is invariably richer in 18O than the host rock quartz and in most of the rocks the δ18O of the clastic quartz is similar to the δ18O of the whole rock. Mineral assemblages are typically not in isotopic equilibrium. Although the δ18O values are very uniform (+13 to +16). the δ13C of vein aragonite and calcite is widely variable (0 to ? 14), implying that a major source of the carbon is oxidized organic material. The δD values of 83 igneous and sedimentary rocks are -45 to -80, exceptions are the Fe-rich minerals howieite and deerite, which have δD = ?100. All of these samples could have equilibrated with H2O having δD ≈ +10 to ?20 and δ18O ≈ ?3 to +8. assuming temperatures of 100–300°C. However, the serpentines (δD ≈ ?85 to ?110) and the vein minerals (δD = ?23 to ?55) are exceptions. The vein minerals are 10–20%, richer in deuterium than the adjacent wall rocks; they formed from a relatively D-rich metamorphic water, typically at lower temperatures than did their host rocks. The isotopic compositions of the other Franciscan rocks were affected by three distinct events: (1) hydrothermal alteration of the ophiolite complexes and volcanic rocks as a result of submarine igneous activity at a spreading center or in an island-arc environment; (2) low-temperature, high-pressure regional metamorphism and diagenesis; and (3) a late-stage, very low temperature (<100°C) alteration of the ultramafic bodies by meteoric ground waters, producing lizardite-chrysotile serpentine. In the first two cases, the pore fluid involved in the alteration of the Franciscan rocks was sea water. However, this water became somewhat depleted in D and enriched in 18O during blueschist metamorphism, evolving to values of δD ≈ ? 20 and δ18O ≈ + 6 to + 8 at the highest grades. Except for one graywacke sample, the meteoric waters that affected the serpentinites did not significantly change the DH ratios of the OH-bearing minerals in any other Franciscan rock.The δ18O values of orogenic andesites are too low for such magmas to have formed by direct partial melting of Franciscan-type materials in a subduction zone. Andesites either form in some other fashion, or the melts must undergo thorough isotopic exchange with the upper mantle. The great Cordilleran granodiorite-tonalite batholiths, however, are much richer in 18O and may well have formed by large-scale melting or assimilation of Franciscan-type rocks. The range of δD values of Franciscantype rocks is identical to the ?50 to ?80 range shown by most igneous rocks. This suggests that ‘primary magmatic H2O’ throughout the world may be derived mainly by partial melting of Franciscantype materials, or by dehydration of such rocks in the deeper parts of a Benioff zone.  相似文献   

6.
The Late Cretaceous to Early Eocene, dominantly micritic, Amuri Limestone Group (ALG) was deposited in an approximately NW trending trough, in eastern Marlborough, New Zealand. The ALG comprises: the Mead Hill Formation; the Teredo, Lower and Middle Limestone formations; and the Upper and Lower Marl formations. Chert and dolomite are concentrated in the Mead Hill Formation, which contains five of six recognized diagenetic zones: Zone I at the base of the ALG consists almost entirely of chert; Zone II consists solely of chert and dolomite; Zone III comprises chert and limestone; Zone IV is composed of chert plus dolomite; Zone V is a chertified mudstone; and the minor amounts of chert found in the Middle Limestone Formation comprise Zone VI. With the exception of Zones IV and V, chert decreases stratigraphically upwards and away from the basin centre. All the dolomites are composed of <1 mm diameter rhombohedra in discontinuous beds and lenses. Generally Ca-rich, and non- to slightly ferroan, the dolomite contains approximately 500–900 ppm Mn and 200–400 ppm Sr. δ13C values average 1–2%PDB with δ18O ratios of about -4%PDB. Mass balance calculations indicate that the Mg2+ for dolomitization was derived from sea water. Sr, Fe and Mn concentrations are interpreted as indicating dolomite formation in the marine environment, with no influence from meteoric waters. The intimate association with pyrite implies dolomite formation in association with sulphate reduction, in the upper sediment column. δ18O data show that the bulk of the dolomite formed at temperatures below 50°C. All chert samples contain in excess of 90 wt% SiO2, about 1 wt% Al2O3 and 1 wt% from losses on ignition. Generally all other major elements total less than 2 wt% oxide. δ18O values range from 26·8 to 29·0%SMOW. Chert chemistry is consistent with the replacement of host carbonate and expulsion of carbonate-bound components from the site of chertification, and the effective dilution by SiO2 of non-carbonate-bound insoluble residues. δ18O data indicate that chert formed in fluids of similar composition and temperature as the dolomite. The abundance of disseminated pyrite in cherts implies an association with sulphate reduction. Silica for chertification is thought to have initially come from dissolution of siliceous organisms. However, there is insufficient biogenic silica available to form the volumes of chert observed. It is suggested that the bulk of the silica came from SiO2-rich pore waters generated by clay mineral reactions in the thick underlying mudstones. The ALG compacted down through these pore waters. Chert and dolomite nucleation are considered to have been penecontemporaneous. Dolomitization was initially probably the faster process, continuing as long as sulphate reduction prevailed and there was an adequate supply of Mg2+. The nucleation of chert, although initially slower (probably due to a relatively lower initial SiO2 supply), continued after cessation of dolomitization to the extent of completely chertifying the dolomite intercrystalline matrix. The amount of chertification decreased progressively as SiO2 supplies diminished, both stratigraphically upwards and away from the basin centre.  相似文献   

7.
Upper Visean limestones in the Campine Basin of northern Belgium are intensively fractured. The largest and most common fractures are cemented by non-ferroan, dull brown-orange luminescent blocky calcite. First melting temperatures of fluid inclusions in these calcites are around -57°C, suggesting that precipitation of the cements occurred from NaCl-CaCl2-MgCl2 fluids. The final melting temperatures (Tmice) are between -5 and -33°C. The broad range in the Tmice data can be explained by the mixing of high salinity fluids with meteoric waters, but other hypotheses may also be valid. Homogenization temperatures from blocky calcite cements in the shelf limestones are interpreted to have formed between 45 and 75°C. In carbonates which were deposited close to and at the shelf margin, precipitation temperatures were possibly in the range 70-85°C and 72-93°C, respectively. On the shelf, the calcites have a δ18O around -9.3‰ PDB and they are interpreted to have grown in a fluid with a δ18O between −3.5 and +1.0‰ SMOW. At the shelf margin, blocky calcites (δ18O∼ - 13.5‰ PDB) could have precipitated from a fluid with a δ18O betweenn -4.0 and -1.1‰ SMOW. The highest oxygen isotopic compositions are comparable to those of Late Carboniferous marine fluids (δ18O= - 1‰ SMOW). The lowest values are more positive than a previously reported composition for Carboniferous meteoric waters (δ18O= -7‰ SMOW). Precipitation is likely to have occurred in marine-derived fluids, which mixed with meteoric waters sourced from near the Brabant Massif. Fluids with a similar negative oxygen isotopic composition and high salinity are actually present in Palaeozoic formations. The higher temperature range in the limestones near the shelf margin is explained by the upward migration of fluids from the ‘basinal’ area along fractures and faults into the shelf.  相似文献   

8.
We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ18OSMOW and δ13CPDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ18O =?12‰, δ13C =?10‰) and a deep high temperature water (300°C, δ18O =?5‰, δ13C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ18O and δ13C indicate that the carbonates precipitated from H2CO3‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.  相似文献   

9.
Oxygen and hydrogen isotope analyses were made of Jurassic-age chert nodules from the Holy Cross Mountains, SE Poland, along radial transects at high spatial resolution. There is a radial “sigmoidal” periodicity for both isotope ratios, but the two are out of phase, with high δD values corresponding to low δ18O values. Periodicity for a 100- to 120-mm diameter nodule is approximately 16 mm, increasing slightly toward the rim, with amplitudes approaching 20 and 3.0‰ for hydrogen and oxygen, respectively. The combined hydrogen-oxygen isotope data for one nodule fall on a published curve for chert forming in equilibrium with seawater (Knauth and Epstein, 1976); the range of delta values corresponds to temperature variations of ∼10°C. Data for a second chert fall on a subparallel δD-δ18O line with δD values that are almost 50‰ lower. The δD-δ18O patterns for the nodules cannot be explained by periodic mixing of meteoric and ocean water because the hydrogen and oxygen isotope data are out of phase. Two possible explanations for the antiphase periodicity are (a) cyclical temperature variations, perhaps related to an unstable convection system (e.g., Bolton et al., 1999), and (b) self-organizing catalytic precipitation (e.g., Wang and Merino, 1990). The systematic isotopic variations are difficult to explain by diagenesis and strongly suggest that primary isotopic compositions are preserved. The isotopic data provide important information on the thermal history of the sedimentary basin, if temperature variations are the cause of the isotopic periodicity.  相似文献   

10.
Stable isotope geochemistry of deep sea cherts   总被引：1，自引：0，他引：1  
Seventy four samples of DSDP recovered cherts of Jurassic to Miocene age from varying locations, and 27 samples of on-land exposed cherts were analyzed for the isotopic composition of their oxygen and hydrogen. These studies were accompanied by mineralogical analyses and some isotopic analyses of the coexisting carbonates. δ18O of chert ranges between 27 and 39%. relative to SMOW, δ18O of porcellanite—between 30 and 42%.. The consistent enrichment of opal-CT in porcellanites in 18O with respect to coexisting microcrystalline quartz in chert is probably a reflection of a different temperature (depth) of diagenesis of the two phases.δ18O of deep sea cherts generally decrease with increasing age, indicating an overall cpoling of the ocean bottom during the last 150 m.y. A comparison of this trend with that recorded by benthonic foraminifera (Douglas and Savin, 1975) indicates the possibility of δ18O in deep sea cherts not being frozen in until several tens of millions of years after deposition. Cherts of any Age show a spread of δ18O values, increasing diagenesis being reflected in a lowering of δ18O. Drusy quartz has the lowest δ18O values.On-land exposed cherts are consistently depleted in 18O in comparison to their deep sea time equivalent cherts.Water extracted from deep sea cherts ranges between 0.5 and 1.4 wt %. δD of this water ranges between ?78 and ?95%. and is not a function of δ18O of the cherts (or the temperature of their formation).  相似文献   

11.
Niutuozhen geothermal field is located in the Jizhong graben, belonging to the northern part of Bohai Bay Basin in North China. Chemical and isotopic analyses were carried out on 14 samples of the geothermal fluids discharged from Neogene Minghuazhen (Nm), Guantao (Ng), and Jixianian Wumishan (Jxw) formations. The δ2H and δ18O in water, δ13C in CH4, δ13C in CO2, and 3He/4He ratio in the gases were analyzed in combination with chemical analyses on the fluids in the Niutuozhen geothermal field. The chemical and isotopic compositions indicate a meteoric origin of the thermal waters. The reservoir temperatures estimated by chemical geothermometry are in the range between 60 and 108 °C. The results show that the gases are made up mainly by N2 (18.20–97.42 vol%), CH4 (0.02–60.95 vol%), and CO2 (0.17–25.14 vol%), with relatively high He composition (up to 0.52 vol%). The chemical and isotopic compositions of the gas samples suggest the meteoric origin of N2, predominant crustal origins of CH4, CO2, and He. The mantle-derived He contributions are calculated to be from 5 to 8% based on a crust–mantle binary mixing model. The deep temperatures in the Jxw reservoir were evaluated based on gas isotope geothermometry to be in the range from 141 to 165 °C. The mantle-derived heat fraction in the surface heat flow is estimated to be in the range of 48–51% based on 3He/4He ratios.  相似文献   

12.
Nodular chert from the middle and upper Arbuckle Group (Early Ordovician) in the Slick Hills, SW Oklahoma, was formed by selective replacement of grainstones, burrow fillings, algal structures, and evaporite nodules. Chert nodules are dominantly microquartz with minor fibrous quartz (both quartzine and chalcedony), megaquartz, and microflamboyant quartz. Lepisphere textures of an opal-CT precursor are preserved in many (especially in finely-crystalline) chert nodules. The δ18O values of microquartz chert range from +23.4 to + 28.80/00 (SMOW), significantly lower than those of Cenozoic and Mesozoic microquartz chert formed both in the deep sea and from near-surface sea water. The δ18O values of chert decrease with increasing quartz crystal size. Silicification in the Arbuckle Group occurred during early diagenesis, with the timing constrained by the relative temporal relationships among silicification, burial compaction, and early dolomite stabilization. Silica for initial chert nucleation may have been derived from both dissolution of sponge spicules and silica-enriched sea water. Chert nucleation appears to have been controlled by the porosity, permeability, and organic matter content of precursor sediments. This conclusion is based on the fact that chert selectively replaced both porous grainstones and burrows and algal structures enriched in organic matter. Growth of chert probably occurred by a maturation process from opal-A(?), to opal-CT, to quartz, as indicated by the presence of opal-CT precursor textures in many chert nodules. Although field and petrographic evidence argues for an early marine origin for chert in the Arbuckle Group, the light δ18O values are inconsistent with this origin. Meteoric resetting of the δ18O values of the chert during exposure of the carbonate platform best explains the light δ18O values because: (i) the δ18O values of chert nodules decrease with decreasing δ18O values of host limestones, and (ii) chert nodules from early dolomite, which underwent more extensive meteoric modification than associated limestones, have lighter δ18O values than chert nodules from limestones. Increasing recrystallization of chert nodules by meteoric water resulted in progressive 18O depletion and (quartz) crystal enlargement.  相似文献   

13.
The isotopic composition and parameters for deuterium excess of brines, which were sampled in the Si-chuan Basin, show obvious regularities of distribution. The brine isotopic composition shows distinct two systems of marine and terrestrial deposits, with the Middle Triassic strata as the boundary. Brine hydrogen isotopic composition of marine deposits is lower while oxygen isotopic composition is higher than that of the SMOW, respectively, indicating that the brines were derived from seawater with different evaporating degrees at different times. From the Sinian strata, up to the Cambrian, Permian Maokou Formation and the Triassic Jialingjiang Formation, the δD values of brines tend to become relatively positive with the strata becoming younger. Brines of terrestrial deposits are considered to have been derived from precipitation and their isotopic composition is close to the globe meteoric water line (GMWL). Brines of transitional deposits between marine and terrestrial ones (the Upper Triassic Xujiahe Formation) have δD and δ18O values falling between the two end members of marine deposit brines and precipitation, indicating that the brines are a mixture of precipitation and vaporing seawater. Water samples from the brine-bearing strata of different ages show various deuterium excesses (d) with an evident decreasing trend as the age of strata gets older and older. Brine-bearing strata of the Triassic Leikoupo-Jialingjiang Formation, the Permian Maokou Formation, the Cambrian and Sinian strata are all carbonate rocks which have experienced intensive water/rock reaction and the deuterium excess essentially changes with time. All brine-bearing-strata surrounding the basin or faults, as well as those brine wells exploited for resources, have been obviously influenced by the precipitation supply. Therefore, the deuterium excesses of their brines have increased to different extents, depending on the amount of involvement of meteoric water. The variation and distribution of d values of the brines from different Triassic strata are related to the embedded depth of the strata. The deuterium excesses of brines become lower with increasing burial depth of the strata.  相似文献   

14.
Well-developed dissolution pores occur in the dolomites of the Sinian Dengying Formation, which is an important oil and gas reservoir layer in the Sichuan Basin and adjacent areas in southern China. The pores are often filled with quartz, and some dolomites have been metasomatically altered to siliceous chert. Few studies have documented the characteristics, source or origin of silica-rich fluids and their effects on the dolomite reservoir. The peak homogenisation temperatures(T_h) of fluid inclusions in pore-filling quartz are between 150℃ and 190℃, with an average of 173.7℃. Gases in the inclusions are mainly composed of CO_2, CH_4 and N_2. Compared with host dolomite, pore-filling quartz and metasomatic chert contain higher amounts of Cr, Co, Mo, W and Fe, with average concentrations of 461.58, 3.99, 5.05, 31.43 and 6666.83 ppm in quartz and 308.98, 0.99, 1.04, 13.81 and 4703.50 ppm in chert, respectively. Strontium levels are lower than that in the host dolomite, with average concentrations in quartz and chert of 4.81 and 11.06 ppm, respectively. Rare earth element compositions in quartz and chert display positive Eu anomalies with a maximum δEu of 5.72. The δD_(SMOW) values of hydrogen isotopes in water from quartz inclusions vary from-85.1‰ to-53.1‰ with an average of-64.3‰, whereas the δ~(18)O_(SMOW) values range from 7.2‰ to 8.5‰ with an average of 8.2‰. The average ~(87)Sr/~(86)Sr ratios in quartz and chert are 0.711586 and 0.709917, respectively, which are higher than that in the host dolomite. The fluid inclusions, elemental and isotopic compositions demonstrate that the formation of quartz and chert was related to silica-rich hydrothermal fluid and that the fluid was the deep circulation of meteoric water along basement faults. Interactions with silica-rich hydrothermal fluids resulted in densification of dolomite reservoirs in the Dengying Formation through quartz precipitation and siliceous metasomatism. However, it increased the resistance of the host dolomite to compaction, improving the ability to maintain reservoir spaces during deep burial. Evidence for silica-rich hydrothermal activity is common in the Yangtze Platform and Tarim Basin and its influence on deep dolomite reservoirs should be thoroughly considered.  相似文献   

15.
Calcite is a common fracture inflilling mineral in the Grenville gneisses of the Chalk River area, Ontario, Canada. It exhibits a variety of occurrences and textures which suggests calcite has precipitated under different hydrogeochemical conditions that may be identified through a detailed chemical and isotopic investigation of the calcite and associated infilling minerals.The δ18O of these calcites range over 20%. but the δ13C varies over a narrow range of 5%.. None of the calcites analyzed is in isotopic equilibrium with both the δ18O and δ13C of the present day ground water. The lightest δ18O calcites (near 0%. SMOW) are present in sealed fractures and are sometimes associated with laumontite. This suggests that these light calcites formed from hydrothermal solutions (at temperatures less than about 300°C) shortly after the period of metamorphism that formed the gneisses. This interpretation is supported by relatively unradiogenic87Sr/86Sr ratios near 0.709 and δ13C values of −5 to −6%..Most of the Chalk River calcites, however, are considerably heavier in18O and lighter in13C than the hydrothermal end member. This may be the result of low temperature recrystallization of the hydrothermal calcites by meteoric waters under variable water/rock ratios. The13C contents and87Sr/86Sr ratios of these younger, low temperature calcites appear to be partially buffered by the isotopic composition of the original hydrothermal calcite.Pyrite is often associated with the fracture calcites. These pyrites display a wide range in δ34S values of about 70%., which suggests that sulphide precipitation occurred under semi-closed conditions. These data indicate that fracture permeability has been a major control on the isotopic composition of fracture minerals since formation of the gneiss.  相似文献   

16.
The Vil-car-1 flowstone core from Villars cave (SW France) provides one of the first European speleothem records extending back to 180 ka, based on U–Th TIMS and MC-ICP-MS measurements. The core offers a continuous record of Termination II and the Last Interglacial. The penultimate deglaciation is characterized by a prominent 5‰ depletion in calcite δ18O. Determining which specific environmental factors controlled such a large oxygen isotopic shift offers the opportunity to assess the impact of various factors influencing δ18O variations in speleothem calcite.Oxygen isotope analyses of fluid inclusions indicate that drip water δ18O remained within a very narrow range of ±1‰ from Late MIS6 to the MIS5 δ18O optimum. The possibility of such a stable behaviour is supported by simple calculations of various effects influencing seepage water δ18O.Although this could suggest that the isotopic shift in calcite is mainly driven by temperature increase, attempts to quantify the temperature shift from Late MIS6 to the MIS5 δ18O optimum by assuming an equilibrium relationship between calcite and fluid inclusion δ18O yield unreasonably high estimates of ～20 °C warming and Late MIS6 cave temperatures below 0 °C; this suggests that the flowstone calcite precipitated out of thermodynamic equilibrium at this site.Using a method proposed by Guo et al. (submitted for publication) combining clumped isotope measurements, fluid inclusion and modern calcite δ18O analyses, it is possible to quantitatively correct for isotopic disequilibrium and estimate absolute paleotemperatures. Although the precision of these absolute temperature reconstructions is limited by analytical uncertainties, the temperature rise between Late MIS6 and the MIS5 optimum can be robustly constrained between 13.2 ± 2.6 and 14.6 ± 2.6 °C (1σ), consistent with existing estimates from Western Europe pollen and sea-surface temperature records.  相似文献   

17.
Abstract: The origin of mineralizing fluids responsible for the Hishikari vein-type epithermal Au deposits was studied on the basis of the hydrogen isotopic ratio (δD) of the inclusion fluid from vein quartz and adularia. The origin of hydrothermal fluids was estimated by combination of the present δ values and the oxygen isotopic ratios (δ18O) previously reported by Shikazono and Nagayama (1993). The water in the fluid inclusions was extracted by means of decrepitation of quartz at 500°C. Hydrogen was obtained by reduction of the collected water with Zn shot at 450°C. The δD values were determined by mass spectrometer. The δD values of inclusion fluid obtained from quartz range from –61 to –114%. These are significantly lower than the δD value of the thermal water presently venting from the Hishikari deposits and that of local meteoric water. Hydrogen isotopic fractionation between water and amorphous silica, which might have initially precipitated from the hydrothermal fluids at least partly, is not a probable cause of this isotopic depletion, while some water might have been released from the initial hydrous amorphous silica during recrystallization to quartz observed presently. Thus, a part of ore fluids for the Hishikari deposits is supposed to have been originated from the water having anomalous δD values of lower than –100%. Such D depletion cannot be caused by simple oxygen-shift of meteoric water or by contribution of magmatic volatiles. The δD values of water released from the shale samples of the Shimanto–Supergroup, a major host to the Hishikari veins range from –132 to –148%. Therefore, the anomalous δD values of inclusion fluids from some vein quartz and adularia suggest that the water released from hydrous minerals of the sedimentary basement rocks by dehydration or the groundwater isotopically exchanged with sedimentary rocks at elevated temperatures during circulation, partly contributed to the hydrothermal fluids responsible for the Hishikari deposits.  相似文献   

18.
Bulk carbonate samples of hemipelagic limestone–marl alternations from the Middle and Upper Triassic of Italy are analysed for their isotopic compositions. Middle Triassic samples are representative of the Livinallongo Formation of the Dolomites, while Upper Triassic hemipelagites were sampled in the Pignola 2 section, within the Calcari con Selce Formation of the Southern Apennines in Southern Italy. Triassic hemipelagites occur either as nodular limestones with chert nodules or as plane‐bedded limestone–marl alternations which are locally silicified. In the Middle Triassic Livinallongo Formation, diagenetic alteration primarily affected the stable isotopic composition of sediment surrounding carbonate nodules, whereas the latter show almost pristine compositions. Diagenesis lowered the carbon and oxygen isotope values of bulk carbonate and introduced a strong correlation between δ13C and δ18O values. In the Middle Triassic successions of the Dolomites, bulk carbonate of nodular limestone facies is most commonly unaltered, whereas carbonate of the plane‐bedded facies is uniformly affected by diagenetic alteration. In contrast to carbonate nodules, plane‐bedded facies often show compaction features. Although both types of pelagic carbonate rocks show very similar petrographic characteristics, scanning electron microscopy studies reveal that nodular limestone consists of micrite (< 5 μm in diameter), whereas samples of the plane‐bedded facies are composed of calcite crystals ca 10 μm in size showing pitted, polished surfaces. These observations suggest that nodular and plane‐bedded facies underwent different diagenetic pathways determined by the prevailing mineralogy of the precursor sediment, i.e. probably high‐Mg calcite in the nodular facies and aragonite in the case of the plane‐bedded facies. Similar to Middle Triassic nodular facies, Upper Triassic nodular limestones of the Lagonegro Basin are also characterized by uncorrelated δ13C and δ18O values and exhibit small, less than 5 μm size, crystals. The alternation of calcitic and aragonitic precursors in the Middle Triassic of the Dolomites is thought to mirror rapid changes in the type of carbonate production of adjacent platforms. Bioturbation and dissolution of metastable carbonate grains played a key role during early lithification of nodular limestone beds, whereby early stabilization recorded the carbon isotopic composition of sea water. The bulk carbonate δ13C values of Middle and Upper Triassic hemipelagites from Italy agree with those of Tethyan low‐Mg calcite shells of articulate brachiopods, confirming that Triassic hemipelagites retained the primary carbon isotopic composition of the bottom sea water. A trend of increasing δ13C from the Late Anisian to the Early Carnian, partly seen in the data set presented here, is also recognized in successions from tropical palaeolatitudes elsewhere. The carbon isotopic composition of Middle and Upper Triassic nodular hemipelagic limestones can thus be used for chemostratigraphic correlation and palaeoenvironmental studies.  相似文献   

19.
Carbonate cements in late Dinantian (Asbian and Brigantian) limestones of the Derbyshire carbonate platform record a diagenetic history starting with early vadose meteoric cementation and finishing with burial and localized mineral and oil emplacement. The sequence is documented using cement petrography, cathodoluminescence, trace element geochemistry and C and O isotopes. The earliest cements (Pre-Zone 1) are locally developed non-luminescent brown sparry calcite below intrastratal palaeokarsts and calcretes. They contain negligible Fe, Mn and Sr but up to 1000 ppm Mg. Their isotopic compositions centre around δ18O =?8.5‰, δ13C=?5.0‰. Calcretes contain less 13C. Subsequent cements are widespread as inclusion-free, low-Mg, low-Fe crinoid overgrowths and are described as having a‘dead-bright-dull’cathodoluminescence. The‘dead’cements (Zone 1) are mostly non-luminescent but contain dissolution hiatuses overlain by finely detailed bright subzones that correlate over several kilometres. Across‘dead'/bright subzones there is a clear trend in Mg (500–900 ppm), Mn (100–450 ppm) and Fe (80-230 ppm). Zone 1 cements have isotopic compositions centred around δ18O =?8.0‰ and δ13C=?2.5‰. Zone 2 cement is bright, thin and complexly subzoned. It is geochemically similar to bright subzones of Zone 1 cements. Dull Zone 3 cement pre-dates pressure dissolution and fills 70% or more of the pore space. It generally contains little Mn, Fe and Sr but can have more than 1000 ppm Mg, increasing stratigraphically upwards. The δ18O compositions range from ?5.5 to ?15‰ and the δ13C range is ?1 to + 3.20/00. Zone 4 fills veins and stylolite seams in addition to pores. It is synchronous with Pb, Ba, F ore mineralization and oil migration. Zone 4 is ferroan with around 500 ppm Fe, up to 2500 ppm Mg and up to 1500 ppm Mn. Isotopic compositions range widely; δ15O =?2.7 to ?9‰ and δ13C=?3.8 to+2.50‰. Unaltered marine brachiopods suggest a Dinantian seawater composition around δ15O = 0‰ (SMOW), but vital isotopic effects probably mask the original δ13C (PDB) value. Pre-Zone 1 calcites are meteoric vadose cements with light soil-derived δ13C and light meteoric δ18O. An unusually fractionated‘pluvial’δ15O(SMOW) value of around — 6‰ is indicated for local Dinantian meteoric water. Calcrete δ18O values are heavier through evaporation. Zone 1 textures and geochemistry indicate a meteoric phreatic environment. Fe and Mn trends in the bright subzones indicate stagnation, and precipitation occurred in increments from widespread cyclically developed shallow meteoric water bodies. Meteoric alteration of the rock body was pervasive by the end of Zone 1 with a general resetting of isotopic values. Zone 3 is volumetrically important and external sources of water and carbonate are required. Emplacement was during the Namurian-early Westphalian by meteoric water sourced at a karst landscape on the uplifted eastern edge of the Derbyshire-East Midland shelf. The light δ18O values mainly reflect burial temperatures and an unusually high local heat flow, but an input of highly fractionated hinterland-derived meteoric water at the unconformity is also likely. Relatively heavy δ13C values reflect the less-altered state of the source carbonate and aquifer. Zone 4 is partly vein fed and spans burial down to 2000 m and the onset of tectonism. Light organic-matter-derived δ13C and heavy δ18O values suggest basin-derived formation water. Combined with textural evidence of geopressures, this relates to local high-temperature ore mineralization and oil migration. Low water-to-rock ratios with host-rock buffering probably affected the final isotopic compositions of Zone 4, masking extremes both of temperature and organic-matter-derived CO2.  相似文献   

20.
The clay fractions of sedimentary kaolin deposits representing different ages (Carboniferous and Cretaceous), types (pisolitic flint and plastic), and localities (Sinai and Aswan) from Egypt were analyzed for their H and O isotopic compositions to examine the paleoclimate conditions during their formation. The δD values of the Carboniferous deposits in Sinai range between −67‰ and −88‰, while the values for the Cretaceous deposits in Sinai range between −59‰ and −75‰. The δ18O values of the Carboniferous deposits range from 17.9‰ to 19.4‰ and the values for the Cretaceous deposits range between 19.2‰ and 20.4‰. The relatively low δD and δ18O values of the Carboniferous deposit at the Abu Natash area (−67‰ and 17.9‰, respectively) compared to other Carboniferous deposits (averages of −83.3‰, and 18.8‰ for δD and δ18O, respectively) could be due to isotopic exchange between this deposit and the adjacent dolomite and/or the enclosed hydrothermally-formed Mn ores of the Carboniferous Um Bogma Formation. The δD and δ18O values of the Cretaceous pisolitic flint kaolin deposit from Aswan (averages of −65‰ and 20.3‰, respectively) and plastic kaolin from the same area (averages of −66‰ and 19.5‰, respectively) are almost identical. The differences in the δ18O values between the clay fractions of the pisolitic flint kaolin (20.3‰) and the previously analyzed bulk kaolin of the same deposit (average of 17.5‰) suggest a significant effect of non-clay minerals on the isotopic compositions of the kaolin deposits.The H and O isotopic compositions plot close to the kaolinite line that marks the isotopic composition of kaolinite in equilibrium with meteoric water at 20 °C. This indicates that the kaolinite from both the Carboniferous and Cretaceous deposits in Egypt formed by meteoric water weathering of the source rock(s). The δD and δ18O values also suggest that kaolinite of these deposits formed under warm-temperate to tropical conditions. The slight deviations of some samples from the kaolinite line suggest post-depositional modifications of the isotopic compositions of studied deposits probably due to the interaction between earlier-formed kaolinite and downward percolating meteoric water.The δD and δ18O values of the Cretaceous and Carboniferous deposits from all localities suggest that both deposits formed under similar climatic conditions due to the location of Egypt at almost the same distance from the equator either to the south during the Carboniferous or to the north during the Cretaceous.  相似文献   

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