Coupling among the terrestrial sulfur,carbon and oxygen cycles: numerical modeling based on revised Phanerozoic carbon isotope record     

Manfred Schidlowski  Christian E Junge 《Geochimica et cosmochimica acta》1981,45(4):589-594

Numerical modeling of the terrestrial oxygen budget based on the revised δ¹³C_carb 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 ${}^{13}\text{C}{}^{12}\text{C}$ and ${}^{34}\text{S}{}^{32}\text{S}$ trends.  相似文献   

Growth pattern and 13C12C isotope fractionation of Cyanidium caldarium and hot spring algal mats     

J. Seckbach  I.R. Kaplan 《Chemical Geology》1973,12(3):161-169

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 ($\text{δ}{}^{13}\text{C}\text{< ?30‰}{}_{\mathrm{<mtext>PDB</mtext>}}$) in Precambrian kerogen presumably derived from algal mats.  相似文献   

Origin of epigenetic calcite in coal from Antarctica and Ohio based on isotope compositions of oxygen,carbon and strontium     

Gunter Faure  George Botoman 《Chemical Geology》1984,46(4):313-324

Isotopic compositions of oxygen, carbon and strontium of calcite cleats in coal seams of southern Victoria Land, Antarctica, and Tuscarawas County, Ohio, contain a record of the conditions a the time of their formation. The Antarctic calcites (δ ¹⁸O(SMOW) = +9.14 to +11.82%₀) were deposited from waters enriched in ¹⁶O whose isotopic composition was consistent with that of meteoric precipitation at low temperature and high latitude. The carbon of the calcite cleats (δ ¹³C(PDB) = ?15.6 to ?16.9%₀) was derived in part from the coal (δ ¹³C(PDB) = ?23.5 to ?26.7%₀) as carbon dioxide and by oxidation of methane or other hydrocarbon gases. The strontium (${}^{87}\text{Sr}{}^{86}\text{Sr}\text{= 0.71318–0.72392)}$ originated primarily from altered feldspar grains in the sandstones of the Beacon Supergroup.Calcite cleats in the Kittaning No. 6 coal seam of Ohio (δ ¹⁸O(SMOW) = +26.04 to +27.79%₀) were deposited from waters that had previously exchanged oxygen, possibly with marine carbonate at depth. The carbon (δ ¹³C(PDB) = 0.9 to +2.4%₀) is enriched in ¹³C even though that cleats were deposited in coal that is highly enriched in ¹²C and apparently originated from marine carbonates. Strontium in the cleats ($\text{Sr}\text{87}$ 0.71182–0.71260) is not of marine origin but contains varying amounts of radiogenic ⁸⁷Sr presumably derived from detrital Rb-bearing minerals in the adjacent sedimentary rocks. The results of this study suggest that calcite cleats in coal of southern Victoria Land, Antarctica, were deposited after the start of glaciation in Cenozoic time and that those in Ohio precipitated from formation waters derived from the underlying marine carbonate rocks, probably in the recent geologic past.  相似文献   

Carbon isotope geochemistry of the 3.7 × 10⁹-yr-old Isua sediments,West Greenland: implications for the Archaean carbon and oxygen cycles     

Manfred Schidlowski  Peter W.U Appel  Rudolf Eichmann  Christian E Junge 《Geochimica et cosmochimica acta》1979,43(2):189-199

One hundred and twenty-four carbonate samples from the meta-sedimentary sequence of the 3.7 × 10⁹ yr old Isua supracrustal belt (W-Greenland) have yielded a δ¹³C_carb average of ?2.5 ± 1.7%. vs PDB and a δ¹⁸O_carb average of +13.0 ± 2.5%. vs SMOW. The oxygen mean comes fairly close to the averages of other early Precambrian carbonates. The carbon average, however, is some 2%. more negative than those of younger marine carbonates. In terms of a simple terrestrial ¹³C mass balance, if δ¹³C_carb values are original sedimentary values, this more negative δ¹³C average would imply a considerably smaller $\text{C}{}_{\mathrm{org}}\text{C}{}_{\mathrm{carb}}$ ratio in the sedimentary shell during Isua times, and would thus support the concept of a gradual buildup of a sedimentary reservoir of organic carbon during the early history of the Earth. Since, however, the Isua supracrustal rocks have experienced amphibolite-grade metamorphism, which in other areas has been shown to lower δ¹³C_carb values, it is most likely that the original values of these rocks were approx 0%.. This indicates that C_orx and C_carb were present in the ancient carbon reservoir in about ‘modern’ proportions. Unless this early stabilization of the terrestrial carbon cycle in terms of a constant partitioning of carbon between the reduced and oxidized species is shown to have been caused by some inorganic geochemical process, a considerably earlier start of chemical evolution and spontaneous generation of life must be considered than is presently accepted.  相似文献   

The enrichment of 34S in the solfataras of the Nea Kameni volcano,Santorini archipelago,Greece     

H.W. Hubberten  H. Nielsen  H. Puchelt 《Chemical Geology》1975,16(3):197-205

Sulfur isotope investigations carried out on elemental sulfur and sulfates of the Nea Kameni solfataras, Santorini, Aegean Sea, Greece, show a clear enrichment in the heavy sulfur isotope ³⁴S against the assumed primordial ${}^{32}\text{S}{}^{34}\text{S}$ ratio of 22,220. Within the same crater, different vents, only a few meters apart from each other, produced δ differences up to 10‰, which remained constant for several years. This enrichment is most probably due to contamination by heavy sulfur from a nonvolcanic source. An enrichment in the same order of magnitude was observed in sulfur of recent and older lavas ($\text{δ}{}^{34}\text{S}\text{= ?1 ? +11‰}$).Potential contaminants like sulfide sulfur in hydrothermal ore veins of Athinios has a δ ³⁴S mean value close to 0‰, sulfide and sulfate in the sedimentary basement has a δ ³⁴S mean value of $\text{+2.6‰.}$ Seawater sulfate from the area gives a value of $\text{δ}{}^{34}\text{S}\text{= 20‰}$, while sulfide from bacterial reduction of pore-water sulfate in recent iron ore sediments has δ ³⁴S values between ?8 and $\text{?5‰.}$ Sulfate remaining in the pore solutions gave $\text{δ}{}^{34}\text{S}\text{= +27‰}$.The most probable explanation for the observed high δ ³⁴S values in the solfataric sulfur and in some of the lavas of the Santorini area is contamination of the volcanic vents by Mediterranean Sea water.  相似文献   

Carbon content and carbonate ¹³C abundances in the Early Precambrian Swaziland sediments of South Africa     

Bartholomew Nagy  Steven M. Kunen  John E. Zumberge  Austin Long  Carleton B. Moore  Charles F. Lewis  Carl R. Anhaeusser  Desmond A. Pretorius 《Precambrian Research》1974,1(1):43-48

Carbon content (0.02–0.68% organic), carbonate content (0–69.7%) and carbonate ¹³C abundances (${}^{\mathrm{?}}\text{7.5?+2.3‰}$) were obtained on samples from the Swaziland sediments of South Africa, which are among the oldest known sedimentary rocks on earth (> 3·10⁹ years old). The carbon chemistry of these sediments may serve as evidence for early life and/or for products of chemical evolution. The variation of organic and carbonate carbon concentrations in different sedimentary horizons seems to be controlled by differences in depositional and diagenetic histories. The carbonate δ ¹³C values did not vary significantly from the ordinary range of Phanerozoic limestone values.  相似文献   

An electrochemical study of Ni²⁺, Co²⁺, and Zn²⁺ ions in melts of composition CaMgSi₂O₆     

Krystyna W. Semkow  Ronald A. Rizzo  Larry A. Haskin  David J. Lindstrom 《Geochimica et cosmochimica acta》1982,46(10):1879-1889

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.  相似文献   

Diffusivity of oxygen in jadeite and diopside melts at high pressures     

N. Shimizu  I. Kushiro 《Geochimica et cosmochimica acta》1984,48(6):1295-1303

The diffusivity of oxygen was determined in melts of Jadeite (NaAlSi₂O₆) and diopside (CaMgSi₂O₆) compositions using diffusion couples with ¹⁸O as a tracer. In the Jadeite melt, the diffusivity of oxygen increases from $\text{6.87}{}_{\mathrm{?0.25}}{}^{\mathrm{+0.28}}\text{× 10}{}^{\mathrm{?10}}\text{cm}{}^2\text{/}\text{sec}$ at 5 Kb to $\text{1.32 ± 0.08 × 10}{}^{\mathrm{?9}}\text{cm}{}^2\text{/}\text{sec}$ at 20 Kb at constant temperature (1400°C), whereas in the diopside melt at 1650°C, the diffusivity decreases from $\text{7.30}{}_{\mathrm{?0.18}}{}^{0.29}\text{× 10}{}^{\mathrm{?7}}\text{cm}{}^2\text{/}\text{sec}$ at 10 Kb to $\text{5.28}{}_{\mathrm{?0.55}}{}^{\mathrm{+0.60}}\text{× 10}{}^{\mathrm{?7}}\text{cm}{}^2\text{/}\text{sec}$ at 17 Kb. These results demonstrate that the diffusivity is inversely correlated with the viscosity of the melt. For the jadeite melt, in particular, the inverse correlation is very well approximated by the Eyring equation using the diameter of oxygen ions as a unit distance of translation, suggesting that the viscous flow is rate-limited by the diffusion of individual oxygen ions. In the diopside melt, the activation volume is slightly greater than the molar volume of oxygen ion, indicating that the individual oxygen ion is the diffusion unit. The negative activation volume obtained for the jadeite melt is interpreted as the volume decrease associated with a diffusive jump of an oxygen ion due to local collapse of the network structure.  相似文献   

Hydrogen and carbon isotopes of petroleum and related organic matter     

Hsueh-Wen Yeh  Samuel Epstein 《Geochimica et cosmochimica acta》1981,45(5):753-762

$\text{D}\text{H}$ and ${}^{13}\text{C}{}^{12}\text{C}$ ratios were measured for 114 petroleum samples and for several samples of related organic matter. δD of crude oil ranges from ?85 to ?181‰, except for one distillate (?250‰) from the Kenai gas field; δ¹³C of crude oil ranges from ?23.3 to ?32.5‰, Variation in δD and δ¹³C values of compound-grouped fractions of a crude oil is small, 3 and 1.1%., respectively, and the difference in δD and δ¹³C between oil and coeval wax is slight. Gas fractions are 53–70 and 22.6–23.2‰ depleted in D and ¹³C, respectively, relative to the coexisting oil fractions.The δD and δ¹³C values of the crude oils appear to be largely determined by the isotopic compositions of their organic precursors. The contribution of terrestrial organic debris to the organic precursors of most marine crude oils may be significant.  相似文献   

Light hydrocarbons in Red Sea brines and sediments     

Roger A. Burke  James M. Brooks  William M. Sackett 《Geochimica et cosmochimica acta》1981,45(5):627-634

Light hydrocarbon (C₁-C₃) concentrations in the water from four Red Sea brine basins (Atlantis II, Suakin, Nereus and Valdivia Deeps) and in sediment pore waters from two of these areas (Atlantis II and Suakin Deeps) are reported. The hydrocarbon gases in the Suakin Deep brine (T = ~ 25°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 85‰}$, $\text{CH}{}_4\text{=}\text{~ 71}\text{1}$) are apparently of biogenic origin as evidenced by $\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3$) ratios of ~ 1000. Methane concentrations (6–8 μl/l) in Suakin Deep sediments are nearly equal to those in the brine, suggesting sedimentary interstitial waters may be the source of the brine and associated methane.The Atlantis II Deep has two brine layers with significantly different light hydrocarbon concentrations indicating separate sources. The upper brine (T = ~ 50°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 73‰}$, CH₄ = ~ 155 μl/l) gas seems to be of biogenic origin [$\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{) = ~1100}$], whereas the lower brine (T = ~ 61°C, $\text{Cl}{}^{\mathrm{?}}\text{= ~ 155‰}$, CH₄ = ~ 120μl/l) gas is apparently of thermogenic origin [$\text{C}{}_1\text{(C}{}_2\text{+ C}{}_3\text{) = ~ 50}$]. The thermogenic gas resulting from thermal cracking of organic matter in the sedimentary column apparently migrates into the basin with the brine, whereas the biogenic gas is produced in situ or at the seawater-brine interface. Methane concentrations in Atlantis II interstitial waters underlying the lower brine are about one half brine concentrations; this difference possibly reflects the known temporal variations of hydrothermal activity in the basin.  相似文献   

Annual periodicity of the 18O16O and 13C12C ratios in the coral Montastrea annularis     

Richard G. Fairbanks  Richard E. Dodge 《Geochimica et cosmochimica acta》1979,43(7):1009-1020

The isotopic ratios ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ show an annual periodicity in the coral Montastrea annularis from Bermuda, Jamaica and Barbados. The abundances of ¹⁸O and ¹³C are positively correlated in the Jamaica and Barbados samples, but inversely related in the Bermuda sample. Annual high density growth bands are formed during the season of warmest water temperature at all 3 sites and are enriched in ¹⁶O. M. Annularis has a constant displacement from oxygen isotopic equilibrium and accurately records seasonal temperature variations via the temperature-dependent aragonite-water fractionation factor. Light intensity, through the activity of the coral's endosymbiotic algae, regulates the depth-dependent and seasonal variations in the skeletal carbon isotopic composition.  相似文献   

Interstellar organic matter in meteorites     

Jongmann Yang  Samuel Epstein 《Geochimica et cosmochimica acta》1983,47(12):2199-2216

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 $\text{D}\text{H}$ 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 $\text{D}\text{H}$ ratios are greater than 30 × 10^?5. If the $\text{D}\text{H}$ 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 $\text{D}\text{H}$ 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 $\text{D}\text{H}$ ratios in organic compounds in interstellar clouds are typically 180 × 10^?5 and range between about 40 × 10^?5 and 5000 × 10^?5. The $\text{D}\text{H}$ 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 $\text{D}\text{H}$ ratios.In contrast, the $\text{D}\text{H}$ 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 ${}^{13}\text{C}{}^{12}\text{C}$ ratios of organic matter, irrespective its $\text{D}\text{H}$ ratio, lie well within those observed for the earth. If organic matter originated in the interstellar medium, our data would indicate that the ${}^{13}\text{C}{}^{12}\text{C}$ 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 $\text{D}\text{H}$ 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   

Stable carbon isotope constraints on mixing and mass balance of CO2 in an urban atmosphere: Dallas metropolitan area,Texas, USA     

《Applied Geochemistry》2003,18(1):75-95

  相似文献   

Carbon and oxygen isotopes in epigenetic hydrothermal rocks from Hamam-el-Farun,Sinai     

Mordechai Magaritz  Arie Issar 《Chemical Geology》1973,12(2):137-146

Rock samples from an Eocene cliff above the thermal spring of Hamam-el-Farun (west coast of Sinai) show various degrees of dolomitization and calcitization ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ ratios indicate that dolomite and secondary calcite precipitated from hot brines.  相似文献   

Secular variations in kerogen structure and carbon,nitrogen and phosphorus concentrations in pre-Phanerozoic and Phanerozoic sedimentary rocks     

Togwell A. Jackson  Carleton B. Moore 《Chemical Geology》1976,18(2):107-136

Variations in the chemical composition of sedimentary rocks and the nature of kerogen through geologic time were investigated in order to obtain information on biological and environmental evolution during the pre-Phanerozoic eon. Rock samples differing in lithology, depositional environment, and age were pulverized, pre-extracted with organic solvents, and analyzed for total nitrogen (N), phosphorus (P) and organic carbon (org. C or C_T). Variations in the molecular structure of kerogen were measured by determining the ratio of org. C content after pyrolysis (C_R) to org. C content before pyrolysis (C_T), the $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio being considered an index of the degree of condensed-aromatic (as opposed to aliphatic) character. The rocks included mudstones (Early Archean (> 3 · 10⁹ years old) to Miocene), carbonate rocks (mid-Proterozoic (1.3 · 10⁹ years old) to Eocene), cherts (Early Archean (> 3 · 10⁹ years old) to Late Proterozoic (0.8 · 10⁹ years old)), and coal (Archean (> 2.7 · 10⁹ years old) to Early Proterozoic (～1.8 · 10⁹ years old)).The mudstones and carbonates showed progressive increase in org. C content with decreasing age, as reported by other investigators, but the cherts unexpectedly showed a decrease in org. C content with decreasing age. In all samples, a simple inverse correlation between $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio and org. C was observed, each rock type forming its own trend separate from but parallel to those of the other rock types. Thus, the older cherts tend to be richer in org. C and have lower $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratios, but the older carbonates and mudstones are poorer in org. C and have higher $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratios. For a given org. C concentration, chert has the highest $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio and carbonate rock the lowest, mudstone being intermediate; this may mean that chert is relatively ineffective as a catalyst for the thermal cracking of kerogen or that it inhibits cracking. N appears to be correlated with org. C. The relationship between $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio and org. C or N suggests that the concentrations of org. C and N in sedimentary rocks are largely determined by selective elimination of labile aliphatic and nitrogenous groups of kerogen during post-depositional maturation, although the nature, abundance and depositional environment of the organic source material must be taken into consideration as well. The observed secular variations of org. C, N and $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio may be ascribed to several possible causes, including age-dependent post-depositional alteration of kerogen, secular decrease in the $\text{CO}{}_2\text{O}{}_2$ ratio of the atmosphere and hydrosphere during pre-Phanerozoic time, secular increase in rates of accumulation of organic matter in sediments and evolutionary changes in the composition of the biological source material. The secular variations of the carbonates and mudstones could be accounted for by age-dependent cumulative effects of post-depositional alteration alone, whereas the secular variations of the cherts probably reflect changes in the nature of the biological source material and the composition of the atmosphere and hydrosphere. The available evidence suggests that primary characteristics of kerogen are better preserved in chert than in the other types of sediment.The $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratios of the carbonates and cherts correlate negatively with the $\text{A}{}_{\mathrm{<mtext>465</mtext><mtext>m</mtext><mtext>\mu </mtext>}}\text{A}{}_{\mathrm{<mtext>665</mtext><mtext>m</mtext><mtext>\mu </mtext>}}$ absorbance ratios of “humic matter” extracted from the same rock samples with benzene—methanol. Thus, the greater the degree of condensed-aromatic character of the kerogen, the greater the degree of condensed-aromatic character of the solvent-extractable bituminous “humic matter” with which it is associated. In addition, the ratio of aliphatic to carbonyl-type groups ($\text{CH}{}_2\text{C=O}$) in the extractable “humic matter” of carbonates and cherts correlates with the non-extractable org. C content of the rocks, suggesting that the org. C data are related to the degree of aliphatic character of the kerogen. The chemical similarity between extractable “humic matter” and its associated kerogen is evidence that the “humic matter” is as old as its rock matrix and can be accepted as a valid chemical fossil. It also suggests that information obtainable from kerogen may be gotten more easily, rapidly and cheaply from solvent-extractable organic matter. The mudstones showed little or no relationship between $\text{A}{}_{\mathrm{<mtext>465</mtext><mtext>m</mtext><mtext>\mu </mtext>}}\text{A}{}_{\mathrm{<mtext>665</mtext><mtext>m</mtext><mtext>\mu </mtext>}}$ ratio and $\text{C}{}_{\mathrm{<mtext>R</mtext>}}\text{C}{}_{\mathrm{<mtext>T</mtext>}}$ ratio, or between $\text{CH}{}_2\text{C=O}$ ratio and org. C content. The data are consistent with the hypothesis that the kerogen in the carbonates and cherts is autochthonous, whereas the kerogen in the mudstones is partly allochthonous, implying the existence of soil humus and soil organisms in pre-Phanerozoic times. Moreover, the existence of coal in Archean sediments is consistent with the existence of very shallow-water and possibly terrestrial microfloras possessing adaptations for protection against ultraviolet solar radiation.The P content of the sediments showed a complicated zig-zag pattern of variation through geologic time. All the different suites of samples gave similar results, indicating that the variations represent phenomena whose effects were worldwide and independent of local environment. P levels are low in the early pre-Phanerozoic but rise with decreasing age until ～ 1 · 10⁹ years B.P., then fall to a minimum at (～0.7–0.8) · 10⁹ years B.P., and rise again to a lower Paleozoic (Ediacarian?) maximum, decline to a later Paleozoic minimum, and then rise again. The low P content of early pre-Phanerozoic sediments could be due to several factors, including high CO₂ content of seawater, anaerobic conditions in the sea, absence of stable-shelf environments, and low rates of primary production. The minimum in the Late Proterozoic is tentatively attributed to the Late Proterozoic glaciations. The data are consistent with the theory that the glacial episode was of worldwide extent.  相似文献   

Etude systématique des isotopes de l'oxygène,du carbone et du strontium dans les carbonatites     

Françoise Pineau  Marc Javoy  Claude J Allegre 《Geochimica et cosmochimica acta》1973,37(11):2363-2377

${}^{18}\text{O}{}^{16}\text{O}$, ${}^{13}\text{C}{}^{12}\text{C}$ and ${}^{87}\text{Sr}{}^{86}\text{Sr}$ 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   

Stable carbon isotopes of graphite from Bogala Mine,Sri Lanka     

Albert Dobner  Wolfgang Graf  Paula Hahn-Weinheimer  Alfred Hirner 《Lithos》1978,11(3):251-255

The ratios of the carbon isotopes ¹³C and ¹²C of twenty-four graphite samples from Bogala Mine, Sri Lanka have been determined. The graphites are isotopically very similar (mean value $\text{?7.76? °}{}^{13}\text{C}{}_{\mathrm{PDB}}$; range $\text{<2?}$). Three models for the biogenic or abiogenic origin of the graphite deposit are discussed.  相似文献   

Rutile solubility and titanium coordination in silicate melts     

James E Dickinson  Paul C Hess 《Geochimica et cosmochimica acta》1985,49(11):2289-2296

The solubility of rutile has been determined in a series of compositions in the K₂O-Al₂O₃-SiO₂ system ($\text{K}{}^1\text{=}\text{K}{}_2\text{O}\text{(K}{}_2\text{O}$ + Al₂O₃) = 0.38–0.90), and the CaO-Al₂O₃-SiO₂ system ($\text{C}{}^1\text{=}\text{CaO}\text{(CaO + Al}{}_2\text{O}{}_3\text{)}\text{= 0.47–0.59}$). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the $\text{K}{}^1$ ratio. For example, at 1475°C the amount of TiO₂ required for rutile saturation varies from 9.5 wt% ($\text{K}{}^1\text{= 0.38}$) to 11.5 wt% ($\text{K}{}^1\text{= 0.48}$) to 41.2 wt% ($\text{K}{}^1\text{= 0.90}$). In the CAS system at 1475°C, rutile solubility is not a strong function of $\text{C}{}^1$. The amount of TiO₂ required for saturation varies from 14 wt% ($\text{C}{}^1\text{= 0.48}$) to 16.2 wt% ($\text{C}{}^1\text{= 0.59}$).The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K⁺ in excess of that needed to charge balance Al³⁺. The suggested stoichiometry of this complex is K₂Ti₂O₅ or K₂Ti₃O₇. In CAS melts, the data suggest that Ca²⁺ in excess of A1³⁺ is not as effective at complexing with Ti as is K⁺. The greater solubility of rutile in CAS melts when $\text{C}{}^1$ is less than 0.54 compared to KAS melts of equal $\text{K}{}^1$ ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiK_β x-ray emission spectra of KAS glasses ($\text{K}{}^1\text{= 0.43–0.60}$) with 7 mole% added TiO₂, rutile, and Ba₂TiO₄, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba₂TiO₄, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules.  相似文献   

Comment on “the statistical analysis and interpretation of imperfectly-fitted Rb-Sr isochrons from polymetamorphic terrains” by M. Cameron et al.     

Håakon Austrheim 《Geochimica et cosmochimica acta》1983,47(3):655-658

Cameronet al. (1981) proposed a “Free Line Model” for calculating formation ages for rock systems that have undergone local scale homogenization by ⁸⁷Sr migration. This model is valid only if the variation in the ${}^{87}\text{Rb}{}^{86}\text{Sr}$ ratio is independent of the variation in Sr-content within the rock system. If Sr increases linearly with increasing ${}^{87}\text{Rb}{}^{86}\text{Sr}$ the calculated age will be too high. If Sr decreases linearly with increasing ${}^{87}\text{Rb}{}^{86}\text{Sr}$, the calculated age will be systematically too low. If the rate of change in Sr with increasing ${}^{87}\text{Rb}{}^{86}\text{Sr}$ varies systematically through a rock system the “isochron” will be curved and the calculated ages will be younger or older than the real age, depending on the position of samples in relation to the curvature of the “isochron.” This problem with the “Free Line Model” is inherited in both the “Bulk Earth Model 1” and the “Bulk Earth Model 2.”  相似文献   

Precise age determinations and petrogenetic studies using the KCa method     

B.D. Marshall  D.J. DePaolo 《Geochimica et cosmochimica acta》1982,46(12):2537-2545

High precision mass spectrometric determination of calcium isotope ratios allows the ⁴⁰K → ⁴⁰Ca radioactive decay to be used for dating a much broader range of geologic materials than is suggested by previous work. ${}^{40}\text{Ca}{}^{42}\text{Ca}$ is used to monitor enrichments in ⁴⁰Ca and can be measured to ±0.01% (2σ) using an exponential mass discrimination correction (Russell et al., 1978) and large ion currents. The earth's mantle has such a low $\text{K}\text{Ca}$ (～0.01) that it has retained “primordial” ${}^{40}\text{Ca}{}^{42}\text{Ca}\text{= 151.016}$ ± 0.011 (normalized to ${}^{42}\text{Ca}{}^{44}\text{Ca}\text{= 0.31221}$), as determined by measurements on two meteorites, pyroxene from an ultramafic nodule, metabasalt, and carbonatite. ${}^{40}\text{Ca}{}^{42}\text{Ca}$ ratios can be conveniently expressed relative to this value as ?_Ca in units of 10^?4. To test the method for age dating, a mineral isochron has been obtained on a sample of Pikes Peak granite, which has been shown to have concordant KAr, RbSr, and UPb ages. Plagioclase, K-feldspar, biotite, and whole rock yield an age of 1041 ± 32 m.y. (2σ) in agreement with previous age determinations (λ_K = 0.5543 b.y.^?1, $\text{λ}{}_{\mathrm{\beta ?}}\text{λ}{}_{\mathrm{<mtext>K</mtext>}}\text{= 0.8952}$, ⁴⁰K = 0.01167%). The initial ${}^{40}\text{Ca}{}^{42}\text{Ca}$ of 151.024 ± 0.016 (?_Ca = +0.5 ± 1.0), indicates that assimilation of high K/Ca crust was insufficient to affect calcium isotopes. Measurements on two-mica granite from eastern Nevada indicate that the magma sources had K/Ca ≈ 1, similar to intermediate-composition crustal rocks. These results show that the KCa system can be used as a precise geochromometer for common felsic igneous and metamorphic rocks, and may prove applicable to sedimentary rocks containing authigenic K minerals. The relatively short half-life of ⁴⁰K, the non-volatile daughter, and the fact that potassium and calcium are stoichiometric constituents of many minerals, make the KCa system complementary to other dating methods, and potentially applicable to a variety of geologic problems.  相似文献