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1.
The early Pliocene Shirahama Limestone is a grainstone-packstone principally composed of fragments of algae, bryozoa, and echinoderm and subordinate volcanic rocks. The limestone was variously dolomitized and the regional distribution of dolomite is patchy. Dolomite occurs as isolated crystals filling pores, moulds, and solution vugs, and mosaic aggregates replacing bioclasts. Calcite occurs as rim and pore-filling sparry cements, and as calcareous skeletons. Isotopically, the dolomites are classified into a heavy oxygen group (?2 to ? 3.5%0 PDB) and a light oxygen group (?5.5 to ? 7.5%0 PDB). Calcite associated with heavy oxygen dolomite has δ18O of ? 6.5 to ?8.5%0 PDB, whereas those associated with light oxygen dolomite have a wide range from ?7.5 to ?14%0 PDB. Calcite in dolomite-free limestone has an oxygen isotopic composition of ?2 to ?8.5%0 PDB. Textures, chemistry, and isotopic evidence indicate that heavy oxygen calcite formed in freshwater, and heavy oxygen dolomite in a meteoric-marine mixture of 10–30% seawater. Light oxygen calcite and dolomite precipitated from modified hydrothermal fluids at approximately 30–65°C. Petrographic features, and both isotopic and chemical evidence suggest that the Shirahama Limestone was exposed to freshwater soon after deposition. Subsequently blocky calcite precipitated (Stage I). The limestone was locally submerged in the meteoric-marine mixture due to gradual subsidence or eustatic movement. This led to the precipitation of heavy oxygen, zoned dolomite and dolospar (Stage II). Hydrothermal alterations occurred in the area a few Myr ago, and related hydrothermal fluids and mixed meteoric-hydrothermal waters caused dedolomitization of some zoned dolomite, partial dissolution of vuggy dolomite, precipitation of limpid dolomite and recrystallization of some earlier dolomites (Stage III). Zeolites were also precipitated from these fluids. Finally, the Shirahama Limestone was exposed again to freshwater and sparry calcite precipitated to plug some of the remaining pores (Stage IV).  相似文献   

2.
The Early to Middle Cambrian Red Heart Dolomite and lower Arthur Creek Formation of the southern portion of the Georgina Basin, Australia, is an entirely dolomitized succession of shallow-water evaporitic mudflat and deeper-water subtidal lithologies. Three types of dolomite have been identified and are interpreted as: (1) syndepositional dolomite; (2) regional replacement dolomite; and (3) void-filling dolomite (cement). Syndepositional dolomite, derived from saline pore fluids developed in a sabkha environment, is a minor dolomite type with very fine crystal mosaics and has a mottled, non-zoned cathodoluminescence. The widespread regional replacement dolomite ranges from fine- to medium-crystalline forming mainly planar-s and non-planar-a crystal mosaics, and displays blotchy, mottled, non-zoned cathodoluminescence. Void-filling dolomite commonly forms planar-s to planar-e, medium to very coarse crystal mosaics. Rare non-planar-c, very coarsely crystalline saddle dolomite also exists. Void-filling dolomite has a successively zoned cathodoluminescence pattern from non-, to brightly, to dully luminescent. Geochemically, the syndepositional dolomite has δ18O (PDB) values ranging between ? 5.3 and ? 8.6%o. Regional replacement dolomites exhibit a wide range of δ18O values from ? 3.3 to ? 10.9%o whereas void-filling dolomite has δ18O values ranging from ? 10.8 to ? 14.3%o. All three dolomite types have similar δ13C (PDB) values, in the range between +1.7 and ?1.7%o. Three initial dolomitization episodes are interpreted: (1) a sabkha stage, forming the syndepositional dolomite and dolomitizing the evaporitic mudflat lithologies; (2) a brine-reflux stage, replacing the subtidal lithologies; and (3) a burial stage, forming the void-filling dolomite type. Final dolomite stabilization occurred during burial, at elevated temperatures, in the presence of basinal fluids, resulting in progressive recrystallization and stabilization of the earlier-formed syndepositional and replacement dolomites. Both textural and geochemical evolution should be taken into account when studying the origin of dolomites, based on their present geochemical composition. Sulphates are represented by very fine-crystalline syndepositional anhydrite in association with the syndepositional dolomite, and coarse to very coarse anhydrite cement. Evaportic mudflat (sabkha) and burial environments are inferred for the origin of the former and the latter anhydrite types, respectively. Evaporite dissolution breccias, indicative of the former presence of evaporites, are common throughout the succession.  相似文献   

3.

Sideritic ironstones in Tertiary lacustrine oil shale from the Lowmead and Duaringa Basins in Queensland, contain two distinctive types of siderite in the ironstone bands: sphaerosiderite in the mudstone and coal, and finely crystalline siderite in the lamosite. The petrological evidence indicates that the siderite in the ironstone bands formed eogenetically by growing displacively within the soft sediment. Chemically the siderite is very pure though the sphaerosiderite sometimes shows compositional zoning. Stable oxygen and carbon isotope analyses of the siderite show a wide range of values from ‐12.8‰ to ‐2.4 %0 δ18O (PDB) and ‐5.5‰ to +12.9‰ δ13C (PDB) for the Lowmead Basin; and ‐9.6‰ to ‐1.2‰ δ18O (PDB) and ‐18.6‰ to +16.4‰ δ13C (PDB) for the Duaringa Basin. The oxygen isotope data indicate that the siderite formed in freshwater environments but not in isotopic equilibrium with the formation waters. Kinetic factors offer the most plausible explanation for the anomalously light δ18O values of many of the siderites. The carbon isotope data show that the carbonate for the formation of the siderite originated predominantly from methanogenic fermentation processes but there was also the varying influence of bacterial oxidation processes. The different petrological and isotopic characteristics of the ironstones broadly reflect variations in their depositional environments and the variable eogenetic conditions in which the siderite formed. There is no suitable single model to explain the genesis of all the different types of ironstones other than that a synsedimentary iron‐enrichment process is involved.  相似文献   

4.
ABSTRACT Gravity cores of Holocene sediments from a shallow ephemeral lake in the Coorong region (Pellet Lake, southeastern coastal Australia) show a mineral assemblage and sequence particular to its hydrology. The mineralogical sequence above an initial dolomitic siliciclastic sand reflects conditions of increasing salinity in the lower portions of the core (i.e. organic-rich aragonite to magnesite + hydromagnesite + aragonite) followed by a relative decrease in salinity (i.e. magnesite + aragonite + hydromagnesite to aragonite + hydromagnesite) in the upper portions of the core. This sequence is capped by ? 0.4 m of micritic dolomite and minor amounts of hydromagnesite, with the relative abundance of dolomite increasing upwards. Three stratigraphically and spatially distinct dolomite units (upper, lower and margin) are recognized using stable carbon and oxygen isotope data, unit cell calculations and MgCO3 mole per cent data of the dolomite. Detailed X-ray diffraction (XRD) analyses of samples with more than 80% dolomite shows that the dolomite is ordered. Average unit cell parameters, calculated from the XRD patterns, indicate that the upper dolomite unit has crystal lattices expanded in the co direction (co= 16.09 Å) relative to ideal dolomite (co= 16.02 Å) and contracted in the ao direction (ao= 4.796 Å) relative to ideal dolomite (ao= 4.812 Å). The mol fraction of MgCO3 in the upper dolomite shows up to 4.0 ±M 2.0 mole per cent excess Mg in the dolomite crystal lattice (calculated from XRD). This unusual dolomite crystal chemistry is probably generated by rapid precipitation from solutions which have greatly elevated Mg/Ca ratios. Transmission electron microscopy reveals that the upper dolomite has a heterogeneous microstructure which also suggests rapid precipitation from solution. The modulated microstructure found in calcium-rich dolomite is completely lacking. Dolomite ordering reflections are present in electron diffraction patterns, but are weak. Stable oxygen and carbon isotope values of the upper dolomite are tightly grouped (ave. δ18O ～+ 7.55%o, δ13C ～+ 4.10%o), yet show three upward-lightening oxygen cycles. The oxygen cycles correlate with three upward decreases in the calculated Mg content of the dolomite zone. These cycles may indicate the increased importance of rain-water dilution of the brine at times when the water in the lake was at its shallowest levels. Analyses of the lower dolomite and the margin dolomite suggest that these units precipitated more slowly from less evaporitic brines than the upper dolomite unit. The lower dolomite is close to stoichiometric, has less evaporitic stable isotope values than the upper dolomite, and has only a slightly expanded co-axis. The margin dolomite is Ca-rich, has a more homogeneous microstructure, and has expanded ao and co axes. The abundance of relatively soluble Mg-bearing phases, such as hydromagnesite and magnesite, may supply additional magnesium for the dolomitization of aragonite and calcite during subsequent diagenesis and burial of the sediment. This process may leave a finely laminated dolomicrite deposit which retains little, if any, evidence of evaporite minerals.  相似文献   

5.
Three major types of dolomite occur in the Trenton Formation (Mid-Ordovician) of the Michigan Basin. These are: (1) ‘regional dolomite’ which is confined to the extreme western edge of the basin; (2) ‘cap dolomite’ which occurs in the upper portion of the Trenton and is confined to the basin's southern margin; and (3) ‘fracture-related’ dolomite which occurs in association with both large- and small-scale faults and fractures. These three dolomite types can be distinguished from one another by their major element chemistry, oxygen isotope ratios and rock texture. The regional dolomite is fine-grained, has <0.34 mol% FeCO3, and mean δ18O of ?6·8‰OPBD. The cap dolomite is texturally similar to regional dolomite but contains 3–13·0 mol% FeCO3 and has a mean δ18O of ?7·7‰. Fracture-related dolomites are coarse-grained, low in iron, and have the most depleted δ18O ratios (x?=–9·0%PDB). Petrographic relationships imply that the regional dolomite, formed prior to the cap dolomite probably during early diagenesis. The cap dolomite formed at relatively shallow depths as a result of the interaction of the overlying Utica Shale and the Trenton Limestone. Fracture-related dolomites post-date the cap dolomite and formed during deeper burial. A temperature of precipitation of approximately 80°C was calculated for fracture-related dolomites using oxygen isotope data. The distribution of the cap dolomite was controlled by the availability of Fe2? which was in turn controlled by the availability of S2?. In the centre of the basin Trenton-Utica deposition was continuous. The upper Trenton contained relatively high concentrations of organic matter which was used by sulphate reducing bacteria to produce H2S from seawater sulphate. The precipitation of iron sulphides (pyrite + iron monosulphide) followed and used up most of the available Fe2?. As a result only small amounts of ferroan dolomite formed. On the periphery of the basin, subaerial exposure resulted in the oxidation of most of the available organic matter. Sulphate reducing bacteria were therefore limited and produced limited amounts of H2S. As a result only a minor amount of iron sulphide (iron monosulphide) formed. The remaining Fe2- was then available for the formation of the ferroan cap dolomite. This model is supported by the following: (1) In the southern margin of the basin, the contact between Trenton cap dolomite and the overlying Utica Shale is sharp and probably unconformable. In the centre of the basin the contact is gradational. (2) In the centre of the basin, the total organic carbon content in the upper Trenton is an order of magnitude higher than in the cap dolomite. (3) The whole-rock concentration of iron is high in both the cap dolomite and in slightly dolomitized equivalent beds in the basin centre. (4) Iron sulphides are abundant in the centre of the basin and mostly in the form of pyrite. In the cap dolomite, iron sulphide is minor and primarily in the form of iron monosulphide.  相似文献   

6.
The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ18OSMOW=+24.4 to +26.5‰δ13CPDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ18OSMOW=+18.4 to +25.8‰; δ13CPDB=?2.1 to +0.2‰), and calcite (δ18OSMOW=+21.3 to +32.6‰; δ13CPDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ18O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ18O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.  相似文献   

7.
《Chemical Geology》2006,225(1-2):137-155
Carbon stable isotopes from carbonate minerals (mainly dolomite) from six wells from the Lower Triassic Sherwood Sandstones of the Corrib Gas Field, Slyne Basin, west of Ireland, allow stratigraphic correlation. The results also provide information on palaeoenvironmental change during the deposition of these continental redbed sedimentary rocks. The Triassic reservoir rocks have been buried to > 4000 m and heated to > 165 °C and now contain methane-rich gas. Although the oxygen isotopic signal has been at least partially reset during burial and heating, a primary carbon isotopic signal appears to have survived diagenesis. The carbon isotope ratio varies from − 3.2‰ to + 2.1‰. All six wells show similar stratigraphic changes when all the carbon isotope data are plotted relative to a major playa horizon. δ13C increases from about − 3‰ at the base of the Sherwood to about + 2‰ 170 m above the base. δ13C then decreases to about − 2‰ for the next 70 m and remains steady for the following 50 m. The top 20 m of the Sherwood contains carbonate with a δ13C values decreasing to about − 3‰. The occurrence of a stratigraphically-correlatable carbon isotope pattern implies that the primary evolution signal has been preserved. The change in δ13C correlates with indicators of aridity and biological stress such that the highest δ13C values are in sedimentary rocks deposited in a playa lake (arid times); these rocks contain the greatest quantity of dolomite cement. Conversely, the lowest δ13C values correspond to sedimentary rocks deposited from well-developed rivers (relatively humid times) from the lowest quantity of dolomite cement. The same carbon isotope evolution has been found in another well in the Slyne basin and in Belgium, suggesting that the palaeoenvironmental isotope signal in the Triassic sedimentary rocks of the Corrib Field may have a regional significance.  相似文献   

8.
Carbon isotope measurements carried out on 67 dolomite samples from the Middle Precambrian Lomagundi Group (Rhodesia) have yielded a δ13C mean of +8.2 ± 2.6%. vs PDB. With the outcrop of these dolomites extending over a distance of almost 300 km, the Lomagundi dolomite faces is likely to represent the largest isotopically anomalous sedimentary carbonate province ever recorded. It is concluded that the anomalous carbonates formed in a closed basin whose δ13C level had been substantially increased as a result of a preferential removal (within sedimentary organics) of the light carbon isotope.  相似文献   

9.
The Swan Hills Formation (Middle-Upper Devonian) of the Western Canada Basin is host to several NW-SE-trending gas fields developed in massive replacement dolostone. One of these, the Rosevear Field, contains two major dolostone trends along opposing margins of a marine channel that penetrates into a platform-reef complex. Dolostones consist predominantly of branching and bulbous strdmatoporoid floatstones and rudstones with well-developed moldic and vuggy porosity. Replacement dolomite is coarsely crystalline (100-600 μm), inclusion-rich, composed of euhedral through anhedral crystals and has a blotchy to homogeneous red cathodoluminescence. Geochemically, replacement dolomite is characterized by (i) nearly stoichiometric composition (50.1-51.1 mol% CaCO3), (ii) negative δ18O values (mean=-7.5‰, PDB) and (iii) variable 87Sr/86Sr ratios ranging from values similar to Late Devonian-Early Mississippian seawater (～0.7082) to radiogenic compositions comparable to saddle dolomite cements (>0.7100). Dolomitization began after widespread precipitation of early, equant calcite spar and after the onset of pressure solution, implying that replacement dolomite formed in a burial environment. Oxygen isotope data suggest that dolomite formed at 35-75°C, temperatures reached during burial in Late Devonian through Jurassic time, at minimum depths of 450 m. The linear NW-SE orientation of most dolomite fields in the Swan Hills Formation is suggestive of fault control on fluid circulation. Two models are proposed for fault-controlled circulation of dolomitizing fluids at the Rosevear Field. In the first, compaction-driven, updip fluid migration occurred in response to basin tilting commencing in the Late Palaeozoic. Deep basinal fluids migrating updip were focused into channel-margin sediments along fault conduits. The second model calls upon fault-controlled convective circulation of (i) warm Devonian-Mississippian seawater or (ii) Middle Devonian residual evaporitic brines. The overlap in 87Sr/86Sr and δ18O compositions, and similar cathodoluminescence properties between replacement and saddle dolomites provide evidence for neomorphism of some replacement dolomite. Quantitative modelling of Sr and O isotopes and Sr abundances suggests partial equilibration of some replacement dolomite with hot radiogenic brines derived during deep burial of the Swan Hills Formation in the Late Cretaceous-Palaeocene. Interaction of replacement dolomite with deep brines led to enrichment in 87Sr while leaving δ18O similar to pre-neomorphism values.  相似文献   

10.
Recent (<50 years old) freshwater cyanobacterial carbonates from diverse environments (streams, lakes, waterfalls) throughout Britain and Ireland were analysed for their stable carbon and oxygen isotope compositions. The mean δ18O value of ?5–9‰ PDB for river and stream data represents calcite precipitation in equilibrium with the mean oxygen isotopic composition of precipitation in central Britain (?7–5‰SMOW) assuming a mean water temperature of 9°C. The mean δ18O of lake data, ?4–5‰ PDB, is statistically different, reflecting the effects of residence time and/or variations in the oxygen isotopic composition of rainfall. Carbon isotopes have wide variations in both fluviatile and lake data sets (+ 3 to ?12‰ PDB). These variations are principally controlled in the fluviatile samples by contribution of isotopically light ‘soil zone’ carbon relative to isotopically heavier carbon from limestone aquifer rock dissolution. Lake samples have the heaviest carbon isotope values, reflecting a trend toward isotopic equilibrium between atmospheric CO2 and aqueous HCO?3. We infer that isotopic compositions of ancient cyanobacterial carbonates should also record environmental information, although the effects of stabilization and diagenesis on primary δ18O values will need careful consideration. Primary carbon isotope compositions should be well preserved, although in marine samples values will be buffered by the isotopic composition of aqueous marine bicarbonate.  相似文献   

11.
Thick dolomite-cemented horizons (dolocretes) occur within a fluvial sandstone-mudstone sequence of Late Triassic age in the western part of the Paris Basin, France. Two types of dolomites can be distinguished: (a) nodular dolomitic beds less than a few metres thick, which formed within mottled overbank siltstones and mudstones; and (b) massive dolomite up to 16 m thick, which occurs in coarse grained channel sandstones and conglomerates. The majority of the dolomite consists of a finely crystalline groundmass of dolomicrospar and, less commonly, dolomicrite. Glaebules, irregular spar-filled cracks, spheroidal dolomite, silicification and vuggy porosity are locally abundant in the massive dolomite. In contrast, biologically induced micromorphological features such as rhizocretions and alveolar-septal fabrics were observed in the thin, nodular dolomite beds. The dolomite is near stoichiometric, well ordered and non-ferroan. 18O values range from ?7·7 to ?0·4%o PDB and 18O values range from ?5·1 to + 1·8%0 PDB and no obvious difference in the stable isotopic composition between both types of dolomites was observed. Sr isotope ratios range from 0·7101 to 0·7126 and are invariably higher than the contemporary Triassic sea water. A vadose—pedogenic origin for the thin dolocrete layers is indicated by the occurrence of rhizocretions and other biological structures. Several features, however, argue against a pedogenic origin for the massive carbonates, most notably the absence of biologically induced structures, the occurrence in coarse grained channel (and not overbank) deposits, and the great thickness. These units are thus interpreted as groundwater in origin. Phreatic calcretes of Quaternary age, widespread in inland Australia, are regarded as a modern analogue for the Triassic Paris Basin dolocretes. Petrographic observations argue in favour of primary (proto)dolomite precipitation, although early diagenetic replacement of calcite by (proto)dolomite cannot be ruled out. Strontium and carbon isotope data of early diagenetic dolocrete cements and oxygen isotope data of early diagenetic silica indicate an entirely non-marine, continental origin for the groundwaters. The poorly ordered and non-stoichiometric protodolomite probably underwent stabilization upon further burial resulting in a near-stoichiometric, well ordered dolomite that clearly lacks evidence for pervasive recrystallization.  相似文献   

12.
ALI M'RABET 《Sedimentology》1981,28(3):331-352
Combined field, sedimentological, mineralogical, isotopic and geochemical study of the Lower Cretaceous dolomites of Central Tunisia has demonstrated considerable diversity in origin. Environments of dolomite formation include deep phreatic, karst, lacustrine and evaporitic sabkha. All four groups of dolomite are composed of non-stoichiometric and/or disordered crystals which are more or less rich in calcium and in iron. Petrographic fabrics are of three types: replacement, recrystallization and cementation. These three fabrics are proposed among the various criteria for the different environments of dolomitization. Average isotope (δ18 O and δ13 C) contents for these four dolomite groups range from ?10·5 to +0·4%o (PDB) and ?3·9 to + 3·7%o respectively. The distribution of strontium is related both to the degree of recrystallization and to the palaeosalinity. Ferrous iron, also very common, is regarded as an indicator of relatively deep reducing conditions, mainly in meteoric groundwaters. Sodium distribution is related to inclusions within the dolomite, its distribution being relatively constant in all four groups; it cannot be regarded as a reliable criterion for palaeosalinity of dolomitizing fluids. This study confirms that dolomitization may occur under widely different palaeoenvironments, either at the surface or during burial. With the exception of the sabkha environment, dolomitizing fluids seem to have been essentially meteoric.  相似文献   

13.
This paper describes the occurrence of dolomite and the mechanism of dolomitization of the Upper Triassic-Lower Jurassic K?z?loren Formation in the autochthonous Bolkardag? unit of the middle Taurus Mountains in south western Turkey. Dolomites were analyzed for geochemical, isotopic and crystallographic variation. Dolomites occur as a replacement of precursor carbonate and cement. The dolomite crystals range from <10 to ~1000 μm existing as both replacements and cements. Sr concentrations range between 84 and 156 ppm, and the molar Sr/Ca ratios of dolomitizing fluids are estimated to range between 0.0066 to 0.013 ratios. Dolomites are Ca-rich (with average CaCO3 and MgCO3 equal to 56.43 and 43.57 mol%, respectively) and they are non-stoichiometric, with an average Sr=116 ppm, Na=286 ppm, Mn=81 ppm, Fe=1329 ppm, and δ18O and δ13C ranges from –0.6‰ to –6.1‰ Pee Dee Belemnite [PDB], and +1.2 to +3.9‰ PDB. The North American Shale Composition [NASC]-normalized rare earth element (REE) values of the both limestone and dolomite sample groups show very similar REE patterns characterized by small positive Eu (mean=1.32 and mean=1.42, respectively) and slightly or considerably negative Ce (mean=0.61 and mean=0.72, respectively) anomalies and a clear depletion in all REE species. The K?z?loren Formation dolomites have been formed as early diagenetic from mixing zone fluids at the tidal-subtidal environment and at the late diagenetic from basinal brines at the shallow-deep burial depths.  相似文献   

14.
The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ13C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ18O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ18O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ13C ? 6-8‰.  相似文献   

15.
The Bajiazi deposits of western Liaoning Province, northeastern China, are aligned approximately west-east in an 8-× 15-km district. The Zn-Pb-Ag-FeS2 sulfide ores are hosted in intensively folded and faulted Early Proterozoic carbonates and minor clastic rocks, near their contact with Late Jurassic-Early Cretaceous Bajiazi granite. The ore-bearing strata on both limbs of the Bajiazi syncline can be correlated throughout the district. Orebodies are stratigraphically conformable with the host rocks and mostly parallel the contact metamorphic halo of the granite, in the skarn mineralizing zone. The ores are composed of stratabound and stratiform sulfide lenses and layers, are associated with sediments formed in local depressions of a tectonically active, shallow-marine environment, and are limited to dolomitized tidal flat and lagoonal facies with cryptalgal lamination and to adjacent oolitic grainstones of barrier facies. The ores consist of fine- to medium-grained intergrowths of sulfides in dolomite and locally skarn gangues. Sulfides are intensely recrystallized and annealed in the contact metamorphic halo. Isotopes of sulfur, carbon, oxygen, and lead were examined for genetic interpretation of the sulfides and host rocks. Sulfur isotope values range from ?9.1 to 13.0 per mil for sulfides, suggesting sedimentary exhalative origin, though they were, to some extent, homogenized during late overprinting events. The δ18O values range between ?6 and ?15 per mil PDB, and the δ13C values between +1 and ?5 per mil PDB. Late crystallization generations are enriched in the light isotopes of oxygen and carbon compared to primary ones. Lead isotope ratios in galenas from all Bajiazi ores have means of 206Pb/204Pb = 16.23, 207Pb/204Pb = 15.23, and 208Pb/204Pb = 36.51. These isotope ratios, characterized by a model age of about 1350 Ma, suggest an early Proterozoic, crustal source for the lead in the ores, unrelated to the lead in the Mesozoic granite. All evidence identified in this study suggests that the Bajiazi polymetallic sulfide deposits formed as sedimentary exhalative accumulations in a Lower Proterozoic, shallow-marine sedimentary basin. The present distribution of the ores and their distinctive textures indicate overprinting by. contemporaneous and/or post-depositional tectonic processes, as well as contact metamorphism during the emplacement of the Mesozoic Bajiazi granite.  相似文献   

16.
The Waulsortian Limestone (Lower Carboniferous) of the southern Irish Midlands is dolomitized pervasively over a much larger region than previous studies have documented. This study indicates a complex, multistage, multiple fluid history for regional dolomitization. Partially and completely dolomitized sections of Waulsortian Limestones are characterized by finely crystalline (0·01–0·3 mm) planar dolomite. Planar replacive dolomite is commonly followed by coarse (≥0·5 mm) nonplanar replacive dolomite, and pervasive void‐filling saddle dolomite cement is frequently associated with Zn–Pb mineralization. Planar dolomite has average δ18O and δ13C values (‰ PDB) of –4·8 and 3·9 respectively. These are lower oxygen and slightly higher carbon isotope values than averages for marine limestones in the Waulsortian (δ18O=–2·2, δ13C=3·7). Mean C and O isotope values of planar replacive dolomite are also distinct from those of nonplanar and saddle dolomite cement (–7·0 and 3·3; –7·4 and 2·4 respectively). Fluid inclusions indicate a complex history involving at least three chemically and thermally distinct fluids during dolomite cementation. The petrography and geochemistry of planar dolomites are consistent with an early diagenetic origin, possibly in equilibrium with modified Carboniferous sea water. Where the Waulsortian was exposed to hydrothermal fluids (70–280 °C), planar dolomite underwent a neomorphic recrystallization to a coarser crystalline, planar and nonplanar dolomite characterized by lower δ18O values. Void‐filling dolomite cement is isotopically similar to nonplanar, replacive dolomite and reflects a similar origin from hydrothermal fluids. This history of multiple stages of dolomitization is significantly more complex than earlier models proposed for the Irish Midlands and provides a framework upon which to test competing models of regional vs. localized fluid flow.  相似文献   

17.
Three peritidal carbonate crusts and associated intercrust sediments (total thickness of ～30cm; aged <3000 years BP) on Ambergris Cay, Belize, contain 32–100% calcian dolomite (δx=72·5% dolomite) ranging in composition from 40 to 46 mol% MgCO3 (δx=43·3). Dolomite replaced high Mg calcite foraminiferal muds penecontemporaneously with sedimentation, forming partially dolomitized sediments and lithified crusts. Dolomitization probably occurred in normal to moderately evaporated seawater and is apparently continuing at the present. Detailed scanning electron microscope analysis shows a linear increase in mean dolomite crystal size with depth; 0·4 μm near the top of the section to 1·0 μm near the base of the dolomitized section. This size increase is not accompanied by any significant decrease in porosity. Crystal size distributions appear to be log-normal and become increasingly broad and flat with depth. Rietveld X-ray pattern-fitting structure refinements indicate increasing Ca and Mg concentrations on their respective sites (cation ordering) as a function of increasing depth. Most of the ordering occurs within the first 15 cm of the surface. Stoichiometry does not increase with depth indicating no relationship between the Ca/Mg ratio and cation ordering. Strong geochemical trends were observed down-section in the dolomite, including: (1) increasing Mn content (44 to 274 ppm), and (2) decreasing δ13C values (?0·9 to ?5·5‰ PDB). Oxygen isotope values range from δ18O = 1·3‰ PDB in the upper part of the section to 2·6‰ PDB in the lower part of the section and are interpreted to represent two distinct groups of values rather than a continuous trend. Down-section dolomite crystal size increase and shapes of crystal size distributions are consistent with recrystallization via a surface energy-driven dissolution-reprecipitation process (Ostwald ripening). The observed trends in carbon isotopes and Mn content probably result from geochemical re-equilibration during recrystallization and reflect reducing conditions and an isotopically light, organically derived, carbon source. Oxygen isotope compositions probably reflect relict original dolomite values and are a result of decreasing evaporation due to rising sea level.  相似文献   

18.
We have developed a quantitative model of CO2 and H2O isotopic mixing between magmatic and hydrothermal gases for the fumarolic emissions of the La Fossa crater (Vulcano Island, Italy). On the basis of isotope balance equations, the model takes into account the isotope equilibrium between H2O and CO2 and extends the recent model of chemical and energy two-end-member mixing by Nuccio et al. (1999). As a result, the H2O and CO2 content and the δD, δ18O, and δ13C isotope compositions for both magmatic and hydrothermal end-members have been assessed. Low contributions of meteoric steam, added at a shallow depth, have been also recognized and quantified in the fumaroles throughout the period from 1988 to 1998. Nonequilibrium oxygen isotope exchange also seems to be occurring between ascending gases and wall rocks along some fumarolic conduits.The δ13CCO2 of the magmatic gases varies around −3 to 1‰ vs. Peedee belemnite (PDB), following a perfect synchronism with the variations of the CO2 concentration in the magmatic gases. This suggests a process of isotope fractionation because of vapor exsolution caused by magma depressurization. The hydrogen isotopes in the magmatic gases (−1 to −‰ vs. standard mean ocean water [SMOW]), as well as the above δ13CCO2 value, are coherent with a convergent tectonic setting of magma generation, where the local mantle is widely contaminated by fluids released from the subducted slab. Magma contamination in the crust probably amplifies this effect.The computed isotope composition of carbon and hydrogen in the hydrothermal vapors has been used to calculate the δD and δ13C of the entire hydrothermal system, including mixed H2O-CO2 vapor, liquid water, and dissolved carbon. We have computed values of about 10‰ vs. SMOW for water and −2 to −6.5‰ vs. PDB for CO2. On these grounds, we think that Mediterranean marine water (δDH2O ≈ 10‰) feeds the hydrothermal system. It infiltrates at depth throughout the local rocks, reaching oxygen isotope equilibrium at high temperatures. Interaction processes between magmatic gases and the evolving seawater also seem to occur, causing the dissolution of isotopically fractionated aqueous CO2 and providing the source for hydrothermal carbon. These results have important implications concerning fluid circulation beneath Vulcano and address the more convenient routine of geochemical surveillance.  相似文献   

19.
Nineteen samples of metamorphosed carbonate-bearing rocks were analyzed for carbon and oxygen isotope ratios by ion microprobe with a ∼5-15 μm spot, three from a regional terrain and 16 from five different contact aureoles. Contact metamorphic rocks further represent four groups: calc-silicate marble and hornfels (6), brucite marble (2), samples that contain a reaction front (4), and samples with a pervasive distribution of reactants and products of a decarbonation reaction (4). The average spot-to-spot reproducibility of standard calcite analyses is ±0.37‰ (2 standard deviations, SD) for δ18O and ±0.71‰ for δ13C. Ten or more measurements of a mineral in a sample that has uniform isotope composition within error of measurement can routinely return a weighted mean with a 95% confidence interval of 0.09-0.16‰ for δ18O and 0.10-0.29‰ for δ13C. Using a difference of >6SD as the criterion, only four of 19 analyzed samples exhibit significant intracrystalline and/or intercrystalline inhomogeneity in δ13C at the 100-500 μm scale, with differences within individual grains up to 3.7‰. Measurements are consistent with carbon isotope exchange equilibrium between calcite and dolomite in five of six analyzed samples at the same scale. Because of relatively slow carbon isotope diffusion in calcite and dolomite, differences in δ13C can survive intracrystalline homogenization by diffusion during cooling after peak metamorphism and likely represent the effects of prograde decarbonation and infiltration. All but 2 of 11 analyzed samples exhibit intracrystalline differences in δ18O (up to 9.4‰), intercrystalline inhomogeneity in δ18O (up to 12.5‰), and/or disequilibrium oxygen isotope fractionations among calcite-dolomite, calcite-quartz, and calcite-forsterite pairs at the 100-500 μm scale. Inhomogeneities in δ18O and δ13C are poorly correlated with only a single mineral (dolomite) in a single sample exhibiting both. Because of relatively rapid oxygen isotope diffusion in calcite, intracrystalline inhomogeneities in δ18O likely represent partial equilibration between calcite and fluid during retrograde metamorphism. Calcite is in oxygen isotope exchange equilibrium with forsterite in one of four analyzed samples, in equilibrium with dolomite in none of six analyzed samples, and in equilibrium with quartz in neither of two analyzed samples. There are no samples of contact metamorphic rock with analyzed reactants and products of an arrested metamorphic reaction that are in oxygen isotope equilibrium with each other. The degree of departure from equilibrium in analyzed samples is variable and is often related, at least in part, to alteration of δ18O of calcite during retrograde fluid-rock reaction. In situ sub-grain-scale carbon and oxygen isotope analyses of minerals are advisable in the common applications of stable isotope geochemistry to metamorphic petrology. Correlation of sub-mm scale stable isotope data with imaging will lead to improved understanding of reaction kinetics, reactive fluid flow, and thermal histories during metamorphism.  相似文献   

20.
Thin (<10 m), extensive dolostones conformably capping late Precambrian glaciogenic rocks in the Kimberley region and the Adelaide Geosyncline commonly comprise micritic dolomite apparently of ‘primary’ or early diagenetic origin. Their aphanitic texture, the presence of algal and cryptalgal lamination, tepee structures and intraclastic rocks, and the lack of saline evaporites or their pseudomorphs, suggest deposition mainly in supratidal to lagoonal environments under a seasonally evaporitic/humid climate. Less common oolitic or pelletal rocks and a finely laminated shaly dolostone facies also suggest peritidal to marine influences.

The ‘cap’ dolostones (omitting possible large erratics) have a δ18O mean of —6.4 ± 1.9% vs. PDB and a δ13C mean of —1.9 ± 2.1% vs. PDB. The oxygen mean is comparable to that determined for other late Precambrian ‘primary’ or early diagenetic dolostones not associated with glaciogenic rocks and presumably deposited under warm conditions. The carbon mean, in contrast, is lighter than that determined for other late Precambrian dolostones.

The sedimentological and oxygen‐isotope data are consistent with relatively high formation‐temperatures for the cap dolostones. Abrupt climatic warming at the close of late Precambrian glacial epochs is implied.  相似文献   

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