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1.
In the Amba Dongar diatreme, “ferrocarbonatite” is not a single unit of late differentiate of calciocarbonatite magma but it is a family with variation on field occurrence, mineralogy and chemistry of each unit. The family includes dikes of ankeritic carbonatites (phase I and II), plugs of ankeritic carbonatite within sövite ring dike, dikes of sideritic carbonatite in ankeritic carbonatite plug and rödberg veins. Their intrusive relations are very clear in the field and each phase has characteristic mineralogy and trace and REE geochemistry. According to the nomenclature suggested by Harmer and Gittins (1997) majority of “ferrocarbonatites” of Amba Dongar plot in field of “ferruginous calciocarbonatite” and only siderite and rödberg plot in the field of “ferrocarbonatite”. Within these family members, their trace and REE show clear increase from early phase to last phase of sideritic carbonatite. The present short communication discusses various aspects of “ferrocarbonatites”.  相似文献   

2.
The Siriwasan carbonatite-sill along with associated alkaline rocks and fenites is located about 10 km north of the well-known Amba Dongar carbonatite-alkaline rocks diatreme, in the Chhota Udaipur carbonatite-alkaline province. Carbonatite has intruded as a sill into the Bagh sandstone and overlying Deccan basalt. This resulted in the formation of carbonatite breccia with enclosed fragments of basement metamorphics, sandstone and fenites in the matrix of ankeritic carbonatite. The most significant are the plugs of sövite with varied mineralogy that include pyroxene, amphibole, apatite, pyrochlore, perovskite and sphene. REE in sövites is related to the content of pyrochlore, perovskite and apatite. The carbon and oxygen isotopic compositions of some sövite samples and an ankeritic carbonatite plot in the “mantle box” pointing to their mantle origin. However, there is also evidence for mixing of the erupting carbonatite magma with the overlying Bagh limestone. The carbonatites of Siriwasan and Amba Dongar have the same Sr and Nd isotopic ratios and radiometric age, suggesting the same magma source. On the basis of available chemical analyses this paper is aimed to give some details of the Siriwasan carbonatites. The carbonatite complex has good potential for an economic mineral deposit but this is the most neglected carbonatite of the Chhota Udaipur province.  相似文献   

3.
The Cobre–Babilonia vein system formed during a single major hydrothermal stage and is part of the Taxco district in Guerrero, southern Mexico. Homogenization and ice melting temperatures range from 160 to 290 °C and from − 11.6 to − 0.5 °C, respectively. We determined an approximate thermal gradient of 17 to 20 °C per 100 m using fluid inclusions. A thermal peak marked by the 290 °C isotherm is interpreted as a major feeder channel to the veins. The highest content of Zn + Pb in ore coincides with the 220 and 240 °C isotherms. Salinities of mineralizing fluids range from 0.8 to 15.6 wt.% NaCl equiv, and are distributed in two populations that can be related with barren or ore-bearing vein sections, with 0.8 to 6 wt.% NaCl equiv and 7 to 15.6 wt.% NaCl equiv, respectively. δ13C and δ18O water values from calcite from the Cobre–Babilonia vein system and the Esperanza Vieja and Guadalupe mantos range − 5.4‰ to − 10.4‰ and 9.9‰ to 13.4‰, respectively. δ34S values range from 0‰ to 3.2‰ and − 0.7‰ to − 4.3‰ in sphalerite, − 4‰ to 0.9‰ in pyrite, and − 1.4‰ to − 5.5‰ in galena. Both fluid inclusion and stable isotope data are compatible with magmatic and meteoric sources for mineralizing fluids. Also, sulfur isotope compositions suggest both magmatic and sedimentary sources for sulfur.  相似文献   

4.
Stable carbon- and oxygen-isotope compositions of calcite and dolomite cements have been used to understand porewater evolution in the Upper Tertiary Hazeva Formation within the Dead Sea Graben, southern Israel. Sandstone samples were obtained from four boreholes in three tectonic blocks of the graben over depths of 253–6448 m, a variation that largely reflects differential subsidence of individual fault-bounded blocks. Early carbonate cements dominate diagenesis. Calcite occurs at <1600 m, but was replaced by dolomite at greater depths. Dolomite at 1600–2700 m is Fe-poor (<0.8 mol% FeCO3), and at 4700–6200 m, Fe-rich (0.5–7.2 mol% FeCO3). Magnesite, anhydrite and halite are the final diagenetic phases. Calcite has positively correlated δ18O (+21‰ to +25‰) and δ13C (−6‰ to −2‰) values that generally decrease with depth. Dolomite has a wider variation in δ18O (+18‰ to +30‰) and δ13C (−8‰ to −1‰) values, which also generally are lower with increasing depth. However, the δ13C and δ18O values of dolomite from the uppermost 400 m of the Hazeva Formation in the Sedom Deep-1 borehole are anomalous in spanning the entire range of stable carbon and oxygen isotopic compositions over this relatively small interval.The decreasing dolomite δ13C values likely indicate an increased contribution of carbon from organic sources with increasing depth. Except for the uppermost 400 m, Hazeva Formation dolomite in the Sedom Deep-1 borehole has stable carbon-isotope compositions that imply initial dolomitization at much shallower levels, prior to the preferential subsidence of this tectonic block. The oxygen isotopic compositions of the calcite cement are best explained by equilibration at present burial temperatures (≤55 °C) with porewater of meteoric origin. Its δ18O values increased from −5‰ at the shallowest depths to 0‰ at 1600 m. The dolomite oxygen isotopic compositions also reflect equilibration at present burial temperatures with porewaters ranging from 0‰ at 1600 m to +7‰ at 3600 m (100 °C). In the deepest fault block (Sedom Deep-1 borehole), however, increasingly Fe-rich dolomite has (re)equilibrated with porewater whose δ18O values decreased from +9‰ at 4750 m (120 °C) to +1‰ to +2‰ by 6200 m (150 °C).Much of the dolomite likely formed at relatively shallow depths from saline brines derived from precursors to the Dead Sea. These infiltrated the Hazeva Formation, mixing with and largely displacing meteoric water, and dolomitizing calcite. Rock–water ratios tended to be high during these processes. However, the upper 400 m of the Hazeva Formation in the deepest fault block were likely deposited during its rapid tectonic subsidence, and largely escaped the initial style of dolomitization pervasive elsewhere in the study area. These sediments were also capped by evaporites. This relatively thin interval likely became a preferential conduit for brines that escaped underlying and overlying strata, including the Fe-rich, lower 18O fluids (evolved seawater?) present in the deepest part of the graben. These rocks present the most promising target for the passage and accumulation of hydrocarbons in the study area.  相似文献   

5.
Tin-polymetallic greisen-type deposits in the Itu Rapakivi Province and Rondônia Tin Province, Brazil are associated with late-stage rapakivi fluorine-rich peraluminous alkali-feldspar granites. These granites contain topaz and/or muscovite or zinnwaldite and have geochemical characteristics comparable to the low-P sub-type topaz-bearing granites. Stockworks and veins are common in Oriente Novo (Rondônia Tin Province) and Correas (Itu Rapakivi Province) deposits, but in the Santa Bárbara deposit (Rondônia Tin Province) a preserved cupola with associated bed-like greisen is predominant. The contrasting mineralization styles reflect different depths of formation, spatial relationship to tin granites, and different wall rock/fluid proportions. The deposits contain a similar rare-metal suite that includes Sn (±W, ±Ta, ±Nb), and base-metal suite (Zn–Cu–Pb) is present only in Correas deposit. The early fluid inclusions of the Correas and Oriente Novo deposits are (1) low to moderate-salinity (0–19 wt.% NaCl eq.) CO2-bearing aqueous fluids homogenizing at 245–450 °C, and (2) aqueous solutions with low CO2, low to moderate salinity (0–14 wt.% NaCl eq.), which homogenize between 100 and 340 °C. In the Santa Bárbara deposit, the early inclusions are represented by (1) low-salinity (5–12 wt.% NaCl eq.) aqueous fluids with variable CO2 contents, homogenizing at 340 to 390 °C, and (2) low-salinity (0–3 wt.% NaCl eq.) aqueous fluid inclusions, which homogenize at 320–380 °C. Cassiterite, wolframite, columbite–tantalite, scheelite, and sulfide assemblages accompany these fluids. The late fluid in the Oriente Novo and Correas deposit was a low-salinity (0–6 wt.% NaCl eq.) CO2-free aqueous solution, which homogenizes at (100–260 °C) and characterizes the sulfide–fluorite–sericite association in the Correas deposit. The late fluid in the Santa Bárbara deposit has lower salinity (0–3 wt.% NaCl eq.) and characterizes the late-barren-quartz, muscovite and kaolinite veins. Oxygen isotope thermometry coupled with fluid inclusion data suggest hydrothermal activity at 240–450 °C, and 1.0–2.6 kbar fluid pressure at Correas and Oriente Novo. The hydrogen isotope composition of breccia-greisen, stockwork, and vein fluids (δ18Oquartz from 9.9‰ to 10.9‰, δDH2O from 4.13‰ to 6.95‰) is consistent with a fluid that was in equilibrium with granite at temperatures from 450 to 240 °C. In the Santa Bárbara deposit, the inferred temperatures for quartz-pods and bed-like greisens are much higher (570 and 500 °C, respectively), and that for the cassiterite-quartz-veins is 415 °C. The oxygen and hydrogen isotope composition of greisen and quartz-pods fluids (δ18Oqtz-H2O=5.5–6.1‰) indicate that the fluid equilibrated with the albite granite, consistent with a magmatic origin. The values for mica (δ18Omica-H2O=3.3–9.8‰) suggest mixing with meteoric water. Late muscovite veins (δ18Oqtz-H2O=−6.4‰) and late quartz (δ18Omica-H2O=−3.8‰) indicate involvement of a meteoric fluid. Overall, the stable isotope and fluid inclusion data imply three fluid types: (1) an early orthomagmatic fluid, which equilibrated with granite; (2) a mixed orthomagmatic-meteoric fluid; and (3) a late hydrothermal meteoric fluid. The first two were responsible for cassiterite, wolframite, and minor columbite–tantalite precipitation. Change in the redox conditions related to mixing of magmatic and meteoric fluids favored important sulfide mineralization in the Correas deposit.  相似文献   

6.
The genesis of Lower Eocene calcite-cemented columns, “pisoid”-covered structures and horizontal interbeds, clustered in dispersed outcrops in the Pobiti Kamani area (Varna, Bulgaria) is related to fossil processes of hydrocarbon migration. Field observations, petrography and stable isotope geochemistry of the cemented structures and associated early-diagenetic veins, revealed that varying seepage rates of a single, warm hydrocarbon-bearing fluid, probably ascending along active faults, controlled the type of structure formed and its geochemical signature. Slow seepage allowed methane to oxidize within the sediment under ambient seafloor conditions (δ18O = − 1 ± 0.5‰ V-PDB), explaining columns' depleted δ13C ratios of − 43‰. Increasing seepage rates caused methane to emanate into the water column (δ13C = − 8‰) and raised precipitation temperatures (δ18O = − 8‰). Calcite-cemented conduits formed and upward migrating fluids also affected interbed cementation. Even higher-energy fluid flow and temperatures likely controlled the formation of “pisoids”, whereby sediment was whirled up and cemented.  相似文献   

7.
Twenty two samples of calcretes from seven depth-profiles in the Menindee catchment, Broken Hill region, Australia were analysed for their inorganic and organic carbon contents and inorganic carbon and oxygen isotopes. The organic carbon content is very low (from 0.06 to 0.31 wt.%) while inorganic carbon (carbonate) is up to 3.9 wt.%. Both δ13C and δ18O become more positive closer to the surface. Carbon isotopes vary from − 8.5‰ to −5.5‰ PDB. Oxygen isotopes vary from − 6‰ to − 1.8‰ V-PDB. Depth-related δ13C and δ18O variations correlate over at least 15 km and show no significant variation along the flow path. δ13C values increase by 3‰ and δ18O values increase by 4‰ with decreasing depth in a 1.40 m thick soil profile. The variation is interpreted to indicate an increasingly elevated air temperature, greater water stress and subsequently an aridification of the area through time. The Broken Hill calcrete data confirm that climatic evolution can be deduced from isotopic series and be applied successfully to the Broken Hill region.  相似文献   

8.
Petrological data provide evidence that framboidal pyrite, Fe-carbonates and kaolinite are the major diagenetic minerals developed during burial diagenesis in the Tertiary Niger Delta sandstones and associated mudrocks. The pyrite sulphur, carbonate carbon and oxygen and kaolinite oxygen and hydrogen isotope compositions have been determined. These data (pyrite, δ34S = −24.8 to 21.0‰; “siderite”, δ13C(PDB) = −14.7 to +5.0‰, δ18O(PDB) = −19.1 to −0.6‰; Fe-calcite, δ13C(PDB) = +17.5 to 17.9‰, δ18O(PDB) = −8.3 to −8.0‰; kaolinite, δ18O(SMOW) = +14.7 to 17.5‰, δD (SMOW) = −86 to −43‰) have been used to interpret the isotopic compositions of the precipitating pore fluids and/or the temperatures of mineral formation. The interpretation of these results indicate that in the deltaic depositional setting the syndepositional pore waters had a significant but variable marine influence that favoured the early formation of pyrite. Subsequently the subsurface influence of meteoric waters, showing varying degrees of modification involving organic and/or water-rock reactions, played an increasingly significant role in the development of later diagenetic cements in the sediments when abundant authigenic carbonates and kaolinites were formed.  相似文献   

9.
This study was undertaken to determine whether wallrocks around the Twin Creeks Carlin-type gold deposits exhibit oxygen isotope haloes similar to those found around other types of hydrothermal deposits. Mineralization at Twin Creeks is hosted by Ordovician Sequence shales containing some carbonate minerals and by Pennsylvanian–Permian Etchart Formation limestone. Analysis of orthophosphate-soluble carbonate from these rocks shows that oxygen isotope haloes are detectable in Ordovician Sequence shales but not in Etchart Formation limestone. The soluble fraction of Ordovician Sequence shales at Twin Creeks has δ18O values of 12 to 24‰ and δ13C values of 0 to −10‰. Most samples fall along a poorly defined trend that extends from δ18O of about 24‰ and δ13C values of about 0, which are typical of unaltered limestones, toward lower values for both isotope systems, which are typical of rocks that have undergone alteration by hydrothermal fluids. Plots of these values along two sections through the ore body show that δ18O values of wallrocks are lowest in the ore zone and increase outward, forming a halo several hundred meters in size. In the same plots, δ13C values of the wallrocks do not show systematic spatial variations. The soluble fraction of Etchart Formation limestones at Twin Creeks have δ18O values of 25 to 5‰ and δ13C values of 4 to −10‰, but do not show any systematic spatial variation relative to mineralization at the scale of our samples. Failure of the Etchart Formation samples to show detectable haloes is probably related to deposition of post-ore carbonate minerals or lower ore fluid : rock ratios. Material balance calculations used to model the isotopic composition of average Ordovician Sequence shales indicate that changes in temperature and water : rock ratio were probably not sufficient to account for the wide range of isotope compositions observed in these rocks. The most likely additional factor contributing to this range of values was a change in the composition of the altering fluid, probably by mixing of the ore fluid with surrounding meteoric water. These results suggest that Carlin-type gold deposits are surrounded by haloes of low δ18O values, but that detection of these haloes could be complicated by local compositional variations and post-ore modification of the wallrocks.  相似文献   

10.
The 1.27 Ga old Ivigtut (Ivittuut) intrusion in South Greenland is world-famous for its hydrothermal cryolite deposit [Na3AlF6] situated within a strongly metasomatised A-type granite stock. This detailed fluid inclusion study characterises the fluid present during the formation of the cryolite deposit and thermodynamic modelling allows to constrain its formation conditions.Microthermometry revealed three different types of inclusions: (1) pure CO2, (2) aqueous-carbonic and (3) saline-aqueous inclusions. Melting temperatures range between − 23 and − 15 °C for type 2 and from − 15 to − 10 °C for type 3 inclusions. Most inclusions homogenise between 110 and 150 °C into the liquid.Stable isotope compositions of CO2 and H2O were measured from crushed inclusions in quartz, cryolite, fluorite and siderite. The δ13C values of about − 5‰ PDB are typical of mantle-derived magmas. The differences between δ18O of CO2 (+ 21 to + 42‰ VSMOW) and δ18O of H2O (− 1 to − 21.7‰ VSMOW) suggest low-temperature isotope exchange. δD (H2O) ranges from − 19 to − 144‰ VSMOW. The isotopic composition of inclusion water closely follows the meteoric water line and is comparable to Canadian Shield brines. Ion chromatography revealed the fluid's predominance in Na, Cl and F. Cl/Br ratios range between 56 and 110 and may imply intensive fluid–rock interaction with the host granite.Isochores deduced from microthermometry in conjunction with estimates for the solidification of the Ivigtut granite suggest a formation pressure of approximately 1–1.5 kbar for the fluid inclusions. Formation temperatures of different types of fluid inclusions vary between 100 and 400 °C. Thermodynamic modelling of phase assemblages and the extraordinary high concentration in F (and Na) may indicate that the cryolite body and its associated fluid inclusions could have formed during the continuous transition from a volatile-rich melt to a solute-rich fluid.  相似文献   

11.
Miocene igneous rocks (diorites, andesites, dacites, rhyolites and microgranites) of Chetaibi and Cap de Fer massif, NE Algeria, are high-K calc-alkaline to shoshonitic rocks. Fresh diorites have δ34S and δ18O values ranging between −2.5‰ and +5.9‰, +6.5‰ and +6.7‰ respectively, indicating a mantle origin. The relatively low δ34S values (−5.4‰ to −12.2‰) and high δ18O (+8.3‰ to +9.0‰) of altered diorites indicate the input of a crustal component to the initial magma. The microgranites’ I-type signature is indicated by the geochemical data and the δ34S and δ18O values of −1.2‰ and −3.6‰, and +7.8‰ to +10.4‰ respectively. The andesites show a large variation of δ34S, between −33.2‰ and +25.7‰. Massive andesites with δ34S between +6.8‰ and +7.6‰ preserve a 34S-enriched mantle signature. The δ34S of the lava flows between +25.7‰ and +25.8‰ are attributed to open system magma degassing, whereas the low δ34S of two andesitic dyke samples (−13.7‰ and −33.2‰) strongly suggest a crustal sulphur input. High δ18O (+9.2‰ to +15.7‰) of andesites indicate post-magmatic alteration (mainly silicification); the flyschs with δ18O between of +13.3‰ and +21.7‰ are most likely the contaminant. Quartz veins within the andesites gave a δ18O value of +23.0‰ while silica-filling vesicles yielded a value of +13.8‰. Initial Sr-isotope data are rather high for all the rocks (diorites: 0.707–0.708, andesites: 0.707–0.710, and microgranites and rhyolites: 0.717–0.719), and because geochemical and stable isotope data do not indicate a substantial amount of crustal assimilation, an extensive enrichment of the mantle source by subducted sediments is called for. A metasomatized-mantle source, characterized by high radiogenic Sr and relatively high δ18O, has also been indicated for the genesis of similar Tertiary igneous rocks in the Western Mediterranean basin, e.g. the Volcanic Province of southeasten Spain [Benito, R., Lopez-Ruiz, J., Cebria, J.M., Hertogen, J., Doblas M., Oyarzun, R., Demaiffe, D., 1999. Sr and O isotope constraints on source and crustal contamination in the high-K calc-alkaline and shoshonitic neogene volcanic rocks of SE Spain. Lithos 46, 773–802] and some plutons of northeastern Algeria [Ouabadi, A., 1994. Pétrologie, géochimie et origine des granitoïdes peralumineux à cordiérite (Cap Bougaroun, Béni-Touffout et Filfila), Algérie nord-orientale. Thèse de Doctorat, Université de Rennes I, France, 257p; Fourcade, S., Capdevila, R., Ouabadi, A., Martineau, F., 2001. The origin and geodynamic significance of the Alpine cordierite-bearing granitoids of northern Algeria. A combined petrological, mineralogical, geochemical and isotopic (O, H, Sr, Nd) study. Lithos 57, 187–216].  相似文献   

12.
The calcite cement in the Lower Ordovician Majiagou Formation in the Ordos basin in northern China can be subdivided into three groups based on preliminary results of oxygen and carbon isotopes and fluid inclusion microthermometry. Group 1 has low oxygen isotopes (− 14‰ to − 18‰), low Th values (92–103 °C), and low salinities (1.7–4.9 wt.% NaCl equivalent) and is interpreted to have precipitated during early burial from porewater influenced by meteoric water. Group 2 has much higher oxygen isotope values (− 5‰ to − 8‰), which, coupled with the higher Th values (136–151 °C), suggest that the calcite was precipitated from fluids that were significantly enriched in 18O, possibly resulting from fluid–rock reaction during burial. Group 3 occurring along fractures is characterized by high salinities (21–28 wt.% NaCl equivalent) and is interpreted to have been precipitated from locally preserved residual evaporitic brines. The occurrence of primary hydrocarbon inclusions and its low carbon isotopes (− 11‰ to − 15‰) suggest that precipitation of group 3 calcite took place in the presence of hydrocarbons.  相似文献   

13.
Large-scale atmospheric circulation patterns determine the quantity and seasonality of precipitation, the major source of water in most terrestrial ecosystems. Oxygen isotope (δ18O) dynamics of the present-day hydrologic system in the Palouse region of the northwestern U.S.A. indicate a seasonal correlation between the δ18O values of precipitation and temperature, but no seasonal trends of δ18O records in soil water and shallow groundwater. Their isotope values are close to those of winter precipitation because the Palouse receives  75% of its precipitation during winter. Palouse Loess deposits contain late Pleistocene pedogenic carbonate having ca. 2 to 3‰ higher δ18O values and up to 5‰ higher carbon isotope (δ13C) values than Holocene and modern carbonates. The late Pleistocene δ18O values are best explained by a decrease in isotopically light winter precipitation relative to the modern winter-dominated infiltration. The δ13C values are attributed to a proportional increase of atmospheric CO2 in soil CO2 due to a decrease in soil respiration rate and 13C discrimination in plants under much drier paleoclimate conditions than today. The regional climate difference was likely related to anticyclonic circulation over the Pleistocene Laurentide and Ice Sheet.  相似文献   

14.
The middle Cenomanian–lower Turonian deposits of Ohaba-Ponor section (Southern Carpathians) were studied from biostratigraphic and isotopic points of view. Both the qualitative and semiquantitative nannofloral analyses, as well as the stable isotope (δ13C and δ18O) data support significant palaeoenvironmental changes in the investigated interval. Two δ13C positive excursions were recognized: (1) an excursion up to 1.8‰ (PDB) within the middle/late Cenomanian boundary; (2) an excursion up to 2.2‰ (PDB) in the Cenomanian/Turonian boundary interval. The oldest δ13C positive excursion recorded (placed within the Acanthoceras jukes-brownei/Eucalycoceras pentagonum Ammonite Zone boundary interval, and in the NC11 Calcareous Nannofossil Zone respectively) could be assigned to the middle Cenomanian Event II (MCEII). During the above-mentioned event, significant increase in abundance of Watznaueria barnesae, followed by successive blooms of Biscutum constans and Eprolithus floralis, were observed. The youngest δ13C positive excursion was identified in the Cenomanian/Turonian boundary interval (in the NC12 and lower part of the NC13 Calcareous Nannofossil Zones). Even the amplitude of this δ13C positive excursion is lower in the Ohaba-Ponor section, as generally reported, this may represent the regional record of the OAE2. The successive peaks of the nannofossils Biscutum constans, Zeugrhabdotus erectus and Eprolithus floralis indicate episodes of cooler surface water and high fertility, which preceded and lasted the Cenomanian/Turonian boundary event. Additionally, fluctuations of δ18O values between −2 and −6‰ suggest also cooler conditions within the Cenomanian/Turonian boundary interval.  相似文献   

15.
A case study of three springs in Switzerland is used to demonstrate the value of geochemical time-series data as a powerful tool to study the dynamics of groundwater systems. Values of repeatedly measured parameters revealed intermixings of two water types: (a) a 29°C water, circulating to a depth of 1100 m and containing approximately 700 mg/l Ca, 2000 mg/l SO4, 700 mg/l HCO3, 20 mg/l of Na and Cl, 6 mg/l Fe, at least 47 mg/l SiO2, and with an isotopic composition of δD = − 73.0‰ and δ18 O = −10.9‰, and (b) a 12°C or colder water, shallow, and of a post-1953 age, containing 420 mg/l TDI or less, very low in Na and Cl (4 mg/l or less), isotopic values of δD = −71.0‰ and δ18 O = −10.5‰ and tritium as in recent (post-bomb) precipitation.  相似文献   

16.
Fluid inclusion studies combined with the isotope geochemistry of several generations of fracture calcite from the Olkiluoto research site, Finland, has been used to better understand the past thermal and fluid history in the crystalline rock environment. Typically, fracture mineral investigations use O and C isotopes from calcite and an estimate of the isotopic composition of the water that precipitated the calcite to perform δ18O geothermometry calculations to estimate past temperature conditions. By combining fluid inclusion information with calcite isotopes, one can directly measure the temperature at which the calcite formed and can better determine past fluid compositions. Isotopic, petrologic and fluid inclusion studies at the Olkiluoto research site in Finland were undertaken as part of an investigation within the Finnish nuclear waste disposal program. The study revealed that four fluids were recorded by fracture calcites. From petrologic evidence, the first fluid precipitated crystalline calcite at 151–225°C with a δ13C signature of −21 to −13.9‰ PDB and a δ18O signature of 12.3–13.0‰ SMOW. These closed fracture fillings were found at depths greater than 500 m and were formed from a high temperature, low salinity, Na–Cl fluid of possible meteoric water altered by exchange with wallrock or dilute basinal origin. The next fluid precipitated crystalline calcite with clay at 92–210°C with a δ13C signature of −2.6 to +3.8‰ PDB and a δ18O signature of 19.4–20.7‰ SMOW. These closed fracture fillings were found at depths less than 500 m and were formed from a moderate to high temperature, low to moderate salinity, Na–Cl fluid, likely of magmatic origin. The last group of calcites to form, record the presence of two distinct fluid types. The platy (a) calcite formed at 95–238°C with a δ13C signature of −12.2 to −3.8‰ PDB and a δ18O signature of 14.9–19.6‰ SMOW, from a high temperature, low salinity, Na–Cl fluid of possible magmatic origin. The platy (b) calcite formed at 67–98°C with a δ13C signature of −13.0 to −6.2‰ PDB and a δ18O signature of 15.1–20.1‰ SMOW, from a low temperature, high salinity, Ca–Na–Cl fluid of possible basinal brine origin. The two calcites are related through a mixing between the two end members. The source of the fluids for the platy grey (a) calcites could be the olivine diabase dykes and sills that cut through the site. The source of fluids for the platy (b) calcites could be the Jotnian arkosic sandstone formations in the northern part of the site. At the Olkiluoto site, δ18O geothermometry does not agree with fluid inclusion data. The original source of the water that forms the calcite has the largest effect on the isotopic signature of the calcites formed. Large isotopic shifts are seen in any water by mineral precipitation during cooling under rock–water equilibrium fractionation conditions. Different calcite isotopic signatures are produced depending on whether cooling occurred in an open or closed system. Water–rock interaction, at varying W/R ratios, between a water and a host rock can explain the isotopic shifts in many of the calcites observed. In some cases it is possible to shift the δ18O of the water by +11.5‰ (SMOW) using a realistic water–rock ratio. This process still does not explain some of the very positive δ18O values calculated using fluid inclusion data. Several other processes, such as low temperature recrystallization, boiling, kinetic effects and dissolution of calcite from fluid inclusion walls can affect isotopic signatures to varying degrees. The discrepancy between fluid inclusion data and δ18O geothermometry at the Olkiluoto site was most likely due to poor constraint on the original source of the water.  相似文献   

17.
Cryogenic cave carbonate (CCC) represents a specific type of speleothem. Its precipitation proceeds at the freezing point and is triggered by freezing-induced concentration of solutes. Compared to classical speleothems (stalagmites, flowstones), CCC occurs as accumulations of loose uncemented aggregates. The grain sizes range from less than 1 μm to over 1 cm in diameter. Karst groundwater chemistry and its freezing rate upon entering the cave are responsible for highly variable grain morphology. Rapid freezing of water results in the formation of CCC powders with grain size typically below 50 μm. Slow freezing of water in caves (usually in systems where the CO2 escape is partly restricted; e.g., ice covered water pools) results in the formation of large mineral grains, with sizes from less than 1 mm to about 20 mm. The range of carbon and oxygen stable isotope compositions of CCC is larger than for a typical carbonate speleothem. Rapid freezing of water accompanied by a quick kinetic CO2 degassing results in large ranges of δ13C of the CCC powders (between –10‰ and +18‰ PDB). Slow freezing of water, with a restricted CO2 escape results in gradual increase of δ13C values (from −9‰ to +6‰ PDB; data ranges in individual caves are usually much more restricted), accompanied by a δ18O decrease of the precipitated carbonate (overall range from −10‰ to −24‰ PDB). These unusual trends of the carbonate δ18O evolution reflect incorporation of the heavier 18O isotope into the formed ice. New isotope data on CCC from three Romanian ice caves allow better understanding of the carbon and oxygen isotope fingerprint in carbonates precipitated from freezing of bulk water. CCCs are proposed as a new genetic group of speleothems.  相似文献   

18.
We have measured the boron concentration and isotope composition of regionally expansive borate deposits and geothermal fluids from the Cenozoic geothermal system of the Argentine Puna Plateau in the central Andes. The borate minerals borax, colemanite, hydroboracite, inderite, inyoite, kernite, teruggite, tincalconite, and ulexite span a wide range of δ11B values from −29.5 to −0.3‰, whereas fluids cover a range from −18.3 to 0.7‰. The data from recent coexisting borate minerals and fluids allow for the calculation of the isotope composition of the ancient mineralizing fluids and thus for the constraint of the isotope composition of the source rocks sampled by the fluids. The boron isotope composition of ancient mineralizing fluids appears uniform throughout the section of precipitates at a given locality and similar to values obtained from recent thermal fluids. These findings support models that suggest uniform and stable climatic, magmatic, and tectonic conditions during the past 8 million years in this part of the central Andes. Boron in fluids is derived from different sources, depending on the drainage system and local country rocks. One significant boron source is the Paleozoic basement, which has a whole-rock isotopic composition of δ11B=−8.9±2.2‰ (1 SD); another important boron contribution comes from Neogene-Pleistocene ignimbrites (δ11B=−3.8±2.8‰, 1 SD). Cenozoic andesites and Mesozoic limestones (δ11B≤+8‰) provide a potential third boron source.  相似文献   

19.
Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO3 type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ18O of − 8.3‰, δD of − 48.2‰,δ11B of 1.5‰, and 87Sr/86Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO4 type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ18O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ11B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and 87Sr/86Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO4 type water with the highest TDS (249.1 g/l, brine) and has δ18O of − 2.8‰, δD of − 45.8‰,δ11B of 21.2‰, and 87Sr/86Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ11B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.  相似文献   

20.
Lime mortar and plaster were sampled from Roman, medieval and early modern buildings in Styria. The historical lime mortar and plaster consist of calcite formed in the matrix during setting and various aggregates. The stable C and O isotopic composition of the calcite matrix was analyzed to get knowledge about the environmental conditions during calcite formation. The δ13Cmatrix and δ18Omatrix values range from −31 to 0‰ and −26 to −3‰(VPDB), respectively. Obviously, such a range of isotope values does not represent the local natural limestone assumed to be used for producing the mortar and plaster. In an ideal case, the calcite matrix in lime mortar and plaster is isotopically lighter in the exterior vs. the interior mortar layer according to the relationship δ18Omatrix = 0.61 · δ13Cmatrix − 3.3 (VPDB). Calcite precipitation by uptake of gaseous CO2 into alkaline Ca(OH)2 solutions shows a similar relationship, δ18Ocalcite = 0.67 · δ13Ccalcite − 6.4 (VPDB). Both relationships indicate that the 13C/12C and 18O/16O values of the calcite reflect the setting behaviour of the lime mortar and plaster. Initially, CO2 from the atmosphere is fixed as calcite, which is accompanied by kinetic isotope fractionation mostly due to the hydroxylation of CO2 (δ13Cmatrix ≈  −25‰ and δ18Omatrix ≈ −20‰). As calcite formation continued the remaining gaseous CO2 is subsequently enriched in 13C and 18O causing later formed calcite to be isotopically heavier along the setting path in the matrix. Deviations from such an ideal isotopic behaviour may be due to the evolution of H2O, e.g. evaporation, the source of CO2, e.g. from biogenic origin, relicts of the natural limestone, and secondary effects, such as recrystallization of calcite. The results of the field and experimental study suggest that isotope values can be used as overall proxies to decipher the origin of carbonate and the formation conditions of calcite in the matrix of ancient and recent lime mortar and plaster. Moreover, these proxies can be used to select calcite matrix from historical lime mortar and plaster for 14C dating.  相似文献   

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