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1.
An isotopic type-curve has been defined based on the 13C12C ratios of the saturated, aromatic, heterocomponent (NOSs), and asphaltene fractions of crude oils. These fractions show 13C enrichments with increasing polarity or polarizability. This systematic pattern can be used to estimate the 13C12C ratio of the kerogen from which the oil had been generated. Genetically associated source rock oil pairs have been used to show that the difference between the measured and the estimated δ-values of kerogen is about ?0.5%., and between the δ-values of the kerogen and the asphaltene fraction is approximately +0.6%.  相似文献   

2.
DH and 18O16O ratios have been measured for whole-rock samples and mineral separates from the mafic and ultramatic rocks of the Cambro-Ordovician Highland Border Suite. The H- and O- isotopic compositions of these rocks record individual stages in a relatively complex 500 Myr old hydrothermal/metamorphic history. Lizardite serpentinites (δD ~ ? 105‰; δ18O ~ + 6.2‰) record a premetamorphic history and indicate that parent harzburgites, dunites, and pyroxenites were serpentinized through low-temperature interaction with meteoric waters during cooling. The other rocks of the Highland Border Suite record subsequent interaction with metamorphic fluids. Amphibolite facies hornblende schists were produced through thrust-related (dynamothermal) metamorphism of spilitic pillow lavas. During dehydration, D-enriched fluids were driven off from the spilites thus leaving the hornblende schists to equilibrate with a relatively D-depleted internal fluid reservoir (δD ~ ? 45‰). The expelled D-enriched fluids may have mixed with more typical Dalradian metamorphic waters which then exchanged with the remaining mafic rocks and lizardite serpentinites during greenschist facies regional metamorphism to produce antigorite serpentinites (δD ~ ? 62‰; δ18O ~ + 8‰) and greenschist metaspilites (δD ~ ? 57‰; δ18O ~ + 7.3‰) with similar H- and O-isotopic compositions. Serpentinites which have been only partially metamorphosed show intermediate H-isotopic compositions between that of metamorphic antigorite (δD ~ ? 62‰) and non-metamorphic lizardite δD ~ ? 105‰) end members.  相似文献   

3.
Eleven samples of crude oil from the Molasse Basin of Southern Germany were fractionated and their contents of sulfur and nitrogen as well as the stable isotope compositions of these elements (34S32S and 15N14N, resp.) investigated.According to the δ34S determinations, all crude oils from the Tertiary base of the Western and Eastern Molasse belong to one oil family and differ significantly from the Triassic and Liassic oils in the Western Molasse.An enrichment of 34S was observed with increasing polarity of crude oil fractions. The isotope distributions of sulfur in the polar constituents of the biodegraded oils from the sandstones of Ampfing, however, approach a homogeneous distribution.The nitrogen isotope distribution is rather uniform in Southern German oils. A regional differentiation can be recognized, although the overall isotopic variation is small. The δ15N values of the crudes and asphaltenes do not correlate.  相似文献   

4.
DH, 18O16O and 13C12C analyses were made of 14 whole rock and 28 mineral samples of rodingites associated dominantly with lizardite-chrysotile serpentinites from the West Coast of the U.S.A., New Zealand, and the Northern Appalachian Mtns. The δD values of the rodingite minerals are in three groupings: 5 monomineralic veins of pectolite, ?281 to ?429; 8 monomineralic veins of xonotlite, ?112 to ?135; all other minerals, including hydrogarnet, idocrase, prehnite, actinolite, nephrite, and chlorite, ?34 to ?80. Most calcites in rodingites have δ18O (+9.3 to +14.4) and (δ13C (?6.7 to +0.9) values similar to calcites in other Franciscan rocks, but distinct from the very low temperature calcite veins in serpentinites. The DH data, combined with δ18O values of xonotlite (+5.7 to +10.9) and pectolite (+8.9 to +12.4) suggest formation from meteoric-type waters at low temperatures; the DH depletion of pectolite, however, is anomalous. Rodingite whole rock values range from δ18O = +4.1 to +11.5 and δD = ?50 to ?86; one sample containing minor amounts of lizardite-chrysotile serpentinite has δD = ?92, outside this range. However, most rodingites of basaltic or gabbroic parentage are more restricted in δ18O (+4.1 to +8.6). Such a wide range in δ18O is consistent with the idea that most rodingites form over a relatively broad range of hydrothermal temperatures. Hydrogen isotopic data for most rodingite minerals (except xonotlite and pectolite) and for whole rocks are suggestive of non-meteoric waters. These DH data overlap those observed for veins of hydrous minerals found in Franciscan igneous rocks studied by Margaritz and Taylor (1976, Geochim. Cosmochim. Acta40, 215–234), possibly suggesting evolved D-enriched, connate type metamorphic waters generated during high P, low T Franciscan-type metamorphism at temperatures (250–500°C) comparable to estimates based on mineral stabilities. Such an interpretation is supported by the 18O16O and 13C12C data for calcite in rodingites.The isotope data appear to contradict some of the conclusions derived from geologic and petrologic studies that indicate concomitant metasomatism and serpentinization of their presently observed host rock. These data appear most consistent with the interpretation that most rodingite minerals, with the exception of late-stage veins of xonotlite and possibly pectolite, may involve metasomatism in association with antigorite serpentinization of ultramafic rock. Subsequent upward tectonic transport in many instances may result in incorporation of the rodingites into their presently observed lizarditechrysotile host rock during or subsequent to pervasive shallow level serpentinization by meteoric waters.  相似文献   

5.
For sulfates of Miocene evaporites in the Carpathian Foredeep, the waters of crystallization of gypsum (w.c.g.) have δD = ?38 to ?113%. and δ18O = 0 to ?11%. (SMOW). The δ34S and δ18O values of the sulfates are uniform and consistent with a marine origin. It is proposed that the original w.c.g. was equilibrated with marine water. Subsequently, it re-equilibrated towards very isotopically light water (δD ~ ?100%., δ18O ~ ?14%) during a glacial or postglacial period and is now trending towards current waters circulating through the deposits (δD ~ ?50%., δ18 ~ ?7%). The extent of reequilibration increased with decreasing crystal size.  相似文献   

6.
The Mushandike Sanctuary, near Masvingo (Fort Victoria), Zimbabwe, contains well-preserved, but metamorphosed stromatolitic limestones of Archaean age. Despite the metamorphism, textural preservation is excellent to a scale as fine as c. 100–200μ. Cores recovered from the stromatolites have δ18O = ?15‰ (PDB), approximately, and δ13C = 0.0 to 0.5‰ (PDB), in less weathered samples. The results are consistent with a metamorphic history involving volatile loss at 200°C or less, from an original source rock which may have been isotopically similar to the Cheshire stromatolites, Belingwe.  相似文献   

7.
Small live individuals of Globigerinoides sacculifer which were cultured in the laboratory reached maturity and produced garnets. Fifty to ninety percent of their skeleton weight was deposited under controlled water temperature (14° to 30°C) and water isotopic composition, and a correction was made to account for the isotopic composition of the original skeleton using control groups.Comparison of. the actual growth temperatures with the calculated temperature based on paleotemperature equations for inorganic CaCO3 indicate that the foraminifera precipitate their CaCO3 in isotopic equilibrium. Comparison with equations developed for biogenic calcite give a similarly good fit. Linear regression with Craig's (1965) equation yields: t = ?0.07 + 1.01t? (r= 0.95) where t is the actual growth temperature and t? Is the calculated paleotemperature. The intercept and the slope of this linear equation show that the familiar paleotemperature equation developed originally for mollusca carbonate, is equally applicable for the planktonic foraminifer G. sacculifer.Second order regression of the culture temperature and the delta difference (δ18Oc ? δ18Ow) yield a correlation coefficient of r = 0.95: t? = 17.0 ? 4.52(δ18Oc ? δ18Ow) + 0.03(δ18Oc ? δ18Ow)2t?, δ18Oc and δ18Ow are the estimated temperature, the isotopic composition of the shell carbonate and the sea water respectively.A possible cause for nonequilibnum isotopic compositions reported earlier for living planktonic foraminifera is the improper combustion of the organic matter.  相似文献   

8.
Hydrogen which is highly enriched in deuterium is present in organic matter in a variety of meteorites including non-carbonaceous chondrites. The concentrations of this hydrogen are quite large. For example Renazzo contains 140 μmoles/g of the 10,000‰ δD hydrogen. The DH ratios of hydrogen in the organic matter vary from 8 × 10?5 to 170 × 10?5 (δD ranges from ? 500‰ to 10,000‰) as compared to 16 × 10?5 for terrestrial hydrogen and 2 × 10?5 for cosmic hydrogen. The majority of the unequilibrated primitive meteorites contain hydrogen whose DH ratios are greater than 30 × 10?5. If the DH ratios in these compounds were due to enrichment relative to cosmic hydrogen by isotope exchange reactions, it would require that these reactions take place below 150 K. In addition the organic compounds having DH ratios above 50 × 10?5 would require temperatures of formation of < 120 K. These types of deuterium enrichments must take place by ion-molecule reactions in interstellar clouds where both ionization and low temperatures exist. Astronomically observed DH ratios in organic compounds in interstellar clouds are typically 180 × 10?5 and range between about 40 × 10?5 and 5000 × 10?5. The DH values we have determined are the lower limits for the organic compounds derived from interstellar molecules because all processes subsequent to their formation, including terrestrial contamination, decrease their DH ratios.In contrast, the DH ratios of hydrogen associated with hydrated silicates are relatively uniform for the meteorites we have analyzed with an average value of 14 × 10?5; very similar to the terrestrial value. These phyllosilicates values suggest equilibration of H2O with H2 in the solar nebula at temperatures of about 200 K and higher.The 13C12C ratios of organic matter, irrespective its DH ratio, lie well within those observed for the earth. If organic matter originated in the interstellar medium, our data would indicate that the 13C12C ratio of interstellar carbon five billion years ago was similar to the present terrestrial value.Our findings suggest that other interstellar material, representing various inputs from various stars, in addition to the organic matter is preserved and is present in the meteorites which contain the high DH ratios. We feel that some elements existing in trace quantities which possess isotopic anomalies in the meteorites may very well be such materials.  相似文献   

9.
Eggwaters from the chambered cephalopod Nautilus are depleted in both 18O and deuterium relative to ambient seawater. Eggwaters from six other species, including the related chambered cephalopod Sepia, do not show such depletion. These observations indicate that the previously observed step towards more positive δ18O values in calcium carbonate laid down after Nautilus hatches, relative to carbonate precipitated prior to hatching, can be explained by equilibration of the carbonate with water in the egg before hatching and with seawater after hatching. The presence of an oxygen isotope difference between eggwater and seawater for Nautilus and its absence for Sepia suggest that hatching will be recorded in the δ18O values of shell carbonates for some but not all extinct and extant chambered cephalopods.The δ13C values of the organic fraction of the siphuncle in Nautilus do not show any consistent pattern with regard to the time of formation before or after hatching. This observation suggests that the minimum in δ13C values previously observed for calcium carbonate precipitated after Nautilus hatches is not caused by a change in food sources once the animal becomes free-swimming, as has been suggested.  相似文献   

10.
δ13C values and δ34S values in human kidney stones range from ?24 to ?10 and ?10 to + 20 %., respectively, and depend upon geographical location. Although the distributions overlap, the mean δ13C values in oxalate stones from North America become less negative with decreasing latitude. For Mexico and Hawaii, the distributions appear to be bimodal. Uric acid stones are generally enriched in 13C by up to 7%. in comparison to oxalates from the same location, whereas cystine stones tend to span the ranges of both stone types. The geographical trends can be explained by the relative proportions of dietary carbon derived ultimately from plants undergoing various established photosynthetic mechanisms (C3, C4, CAM). The differences among the various major stone types may reflect isotope fractionation during biochemical conversions.Exogenic oxalates and uric acid are considered to have little role in precipitating the respective minerals. Whereas, the currently available C isotope data support this contention, more data are desirable, particularly for ingested oxalates. In contrast, S isotope data provide strong evidence that cystine stones are derived from ingested organo-S compounds and bear no relation to inorganic sulphate consumed by the individual. In turn, these organic-S compounds were probably derived from sulphate in the hydrosphere at lower levels in the food chain, e.g., by bacterial assimilation.  相似文献   

11.
The carbon isotopic ratios obtained from Athabasca bitumen, asphaltene and maltene have the same value δ13C = ?29.6 per ml. The corresponding values in the Cold Lake deposits are ?30.6, ?30.0 and ?31.6 per ml. The ratios determined for methane collected from the oil sand and its fractions are about 15 per ml lower than the above values. It appears that the Athabasca and Cold Lake Reservoirs have similar histories.  相似文献   

12.
18O16O, 13C12C and 87Sr86Sr ratios have been measured on the same samples for carbonatite complexes. The results show that besides the ‘carbonatite box’ of Tayloret al. (1967) there exist higher δ18O and δ13C values than can be explained by late magmatic or deuteric processes. These processes correspond to high concentrations of CO2 and lead to big enrichments in 18O and 13C as well as in some ‘volatile’ elements. Strontium results are consistent with a model of selective contamination of deep-seated material by highly radiogenic strontium. The whole study leads to the opinion that parent magmas of carbonatites differentiated in a crustal environment with or without significant contamination.  相似文献   

13.
Numerical modeling of the terrestrial oxygen budget based on the revised δ13Ccarb record by Veizeret al. (1980) has shown that total photosynthetic oxygen has varied between ±7% and ±10% of its average reservoir size (~3.2 × 1022 g) during the last 800 myr as a result of oscillations of the sedimentary reservoir of organic carbon. Calculated curves of oxygen evolution display a distinct minimum in the Early Paleozoic framed by two maxima in the Latest Proterozoic and the Mesozoic. The sympathetic relationship observed between the curves of total oxygen evolution and respective functions for the partial reservoir of sulfate-bound oxygen suggests that the O2 required for an additional conversion of sulfide to sulfate was most probably provided by excess burial of organic carbon, the results of the modeling thus adding credence to current interpretations proposed for the negative correlation between the secular 13C12C and 34S32S trends.  相似文献   

14.
The deuterium concentrations (δD vs SMOW) of biogenic methanes from world-wide occurrences range from ?180 to ?280%. and were found to be depleted in deuterium by approx. 160%. compared to the deuterium concentration of their associated waters. Theoretical considerations support this relationship to be the result of bacterial transformation of CO2 to methane and is therefore indicative of the biogenic origin of methane.Thermogenic gases with high C2+ concentrations (wet gases associated with crude oil) have D/H ratios from ?260 to ?150%. with deuterium contents tending to increase with decreasing wetness. Dry gases which are not associated with petroleum are more enriched in deuterium (?180 to ?130%.) and show an increase in deuterium with increasing rank of the source beds as it is similarly known for carbon-13.Many dry gases in young sedimentary basins were found to contain significant amounts of C2+ hydrocarbons. These gases cannot be grouped with either the biogenic or thermogenic gases and their methane is concluded to be of mixed biogenic and thermochemical origin.Using a δ13CδD diagrammatic display of the isotope data of methanes the various genetic groups of natural gases can be defined more clearly.  相似文献   

15.
A study was undertaken with the thermophilic green alga Cyanidium caldarium which grows optimally at low pH and high concentrations of CO2. Carbon-isotope fractionation was not found to be a simple linear function of temperature. Maximum enrichment of 12C in cellular material occurred under optimum growth conditions (at approximately pH 2 and at temperatures between 40–50°C in a CO2 atmosphere). A maximum measured fractionation of ?24‰ may account for low values (δ 13C < ?30‰ PDB) in Precambrian kerogen presumably derived from algal mats.  相似文献   

16.
Six authigenic feldspars and three detrital feldspars in limestones and dolostones of Eocene to Preeambrian ages were analyzed for their O18O16 content. The difference in δO18 between the authigenic feldspars (δO18range = + 18.2 to + 24.7%.) and carbonate host rocks, both limestones and dolostones, was found to be ?0.5 to ?1.4%. Detrital feldspars (δO18 = + 11.2, + 22.5 and + 17.0%.) exhibit Δfeldsparcarbonate values of ?12.0, ?2.4 and ?1.6‰, respectively, and appear to have undergone increased isotopic exchange as a function of decreased grain size under solid-state conditions.  相似文献   

17.
Carbon isotope values of 260 Precambrian limestones and dolomites (most of them being substantially unaltered) have yielded an overall mean of δ 13C = +0.4 ± 2.7‰ vs. PDB; the corresponding oxygen values average at δ 13O = +20.0 ± 4.2‰ vs. SMOW. Like the overall mean, the δ 13C values furnished by individual carbonate occurrences are, as a rule, fairly “modern” and almost constant as from the very beginning of the sedimentary record. A remarkable exception are the “heavy” dolomites of the Middle Precambrian Lomagundi Group, Rhodesia, with δ 13C = +9.4 ± 2.0‰ vs. PDB. As a result of our measurements, the sporadic occurrence in the geological past of anomalously heavy carbonates seems to be established.The approximate constancy around zero per mill of the δ 13C values of marine carbonates through geologic time would imply a corresponding constancy of the relative proportion of organic carbon in the total sedimentary carbon reservoir since about 3.3 · 109 y ago (with Corg/Ctotal ? 0.2). Utilizing this ratio and current models for the accumulation of the sedimentary mass as a function of time, we get a reasonable approximation for the absolute quantity of organic carbon buried in sediments and, accordingly, of photosynthetic oxygen released. Within the constraints of our model (based on a terrestrial degassing constant λ = 1.16 · 10?9 y?1) close to 80% of the amount of oxygen contained in the present oxygen budget should have been released prior to 3 · 109 y ago. Since geological evidence indicates an O2-deficient environment during the Early and most parts of the Middle Precambrian, there is reason to believe that the distribution of this oxygen between the “bound” and the “molecular” reservoir was different from that of today (with effective O2-consuming reactions bringing about an instantaneous transfer to the crust of any molecular oxygen released). Accordingly, the amount of Corg in the ancient sedimentary reservoir as derived from our isotope data is just a measure of the gross amount of photosynthetic oxygen produced, withholding any information as to how this oxygen was partitioned between the principal geochemical reservoirs. As a whole, the carbon isotope data accrued provide evidence of an extremely early origin of life on Earth since the impact of organic carbon on the geochemical carbon cycle can be traced back to almost 3.5 · 109y.  相似文献   

18.
19.
In a soil developed on the Cretaceous chalk of the Eastern Paris basin, calcite dissolution begins at the surface. The soil water is rapidly saturated in calcite. Calcite dissolution follows two different pathways according to seasonal pedoclimatic conditions.During winter: the soil is only partly saturated in water and the CO2 partial pressure is low (Ca 10?3 atm.). As a consequence total inorganic dissolved carbon (TIDC) is a hundred times the carbon content of the gaseous phase. Equilibrium is usually observed between the two phases. It is a closed system. The measured carbon 14 activity (87,5%) and 13C content (δtidc13C = ?12,2%0) of the drainage water are very close to theoretical values calculated for an ideal mixing system between gaseous and mineral phases (respectively characterized by the following isotopic values: δG13C = ?21,5%0; AG14C = 118%; δM13C = +2,9%0; AM14C = 28%).During spring and summer: the soil moisture decreases, the input of biogenic CO2 induces an increase of the soil CO2 partial pressure (Ca from 3.10?3 atm to 7.10?3 atm). The carbon content of the gaseous phase is higher by an order of magnitude compared to winter conditions. Therefore the aqueous phase is undersaturated in CO2 with respect to the latter. This disequilibrium occurs as a result of unbalanced rates of CO2 dissolution and CO2 effusion toward atmosphère. It is an open system. The carbon isotopic ratio of the aqueous phase is regulated by that of the gaseous phase, as demonstrated by the agreement between measured and calculated isotopic compositions (respectively δL mes = from ?9,4%0 to ?11,5%0, δl calc = from ?9,8%0 to ?13,9%0 AL mes = 119%, AL calc = from 119% to 125%).The solutions originating from both systems (open and closed) move downwards without significant mixing together. It has also been observed that no significant variation of the TIDC isotopic composition occurs during precipitation of secondary calcite.  相似文献   

20.
The DH and 13C12C ratios of the cellulose nitrate and saponifiable lipid fractions prepared from eleven annual growth rings of a California redwood were determined. The DH ratios of the two fractions are related to one another for the annual rings in the sapwood portion of the tree, but not for those in the heartwood or in the wood undergoing the transition from sapwood to heartwood. No relationship was observed between the 13C12 ratios of the two fractions. These results suggest that analysis of the hydrogen isotopic composition of the saponifiable lipid fractions in plants will provide information useful for climatic reconstruction provided the initial isotopic record has not been changed by subsequent physiological or diagenetic processes.  相似文献   

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