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   

The Hemlo gold deposit,Ontario: A geochemical and isotopic study     

Eion M. Cameron  Keiko Hattori 《Geochimica et cosmochimica acta》1985,49(10):2041-2050

The Hemlo deposit, near Marathon, Ontario, is one of the largest gold deposits in North America. It is stratiform within Archean metamorphosed volcano-sedimentary rocks. The main ore zone is composed of pyritic, sericitic schist, and massive barite. This is the first report of stratiform barite in the Archean of North America, but other occurrences have since been found west of Hemlo. The mineralization is substantially enriched in Au, Mo, Sb, Hg, Tl and V and lacks carbonate. Because of metamorphism and deformation of the body its genesis is uncertain.${}^{87}\text{Sr}{}^{86}\text{Sr}$ of .7017 for barite from the deposit is similar to that of the sedimentary barite west of Hemlo and to initial ratios of contemporaneous volcanic rocks. At the base of the main ore zone, barite with δ^34S of +8 to +12%. was deposited with ~0%. pyrite. Upward, both barite and pyrite get isotopically lighter, with minimum values for pyrite, to ?17.5%, in non-baritic schist forming the upper part of the ore zone. In drill section, Au grades correlate with the isotopic composition of pyrite. This, and the association of fractionated sulphide with sulphate, suggests that Au, pyrite and barite were deposited contemporaneously. The linked, asymmetric distributions of S minerals and isotopic distributions, which are continuous from section to section, and the isotopic similarity of the Hemlo and western barites are consistent with a syngenetic depositional model.Two sources for the S minerals are considered. In the first, exogenous sulphate from a restricted basin were partially reduced in a geothermal system to form ³⁴S-depleted sulphide. In the second, the sulphate and sulphide are of magmatic-hydrothermal origin. Sulphate and fractionated sulphide are uncommon in Archean rocks, but one or both occur with unusual frequency in major Archean gold deposits. Hydrothermal fluids of moderately high , containing sulphate and permitting isotopic fractionation between oxidized and reduced S species, may have favoured the dissolution, transport and precipitation of Au.  相似文献   

Stable sulfur and nitrogen isotopic compositions of crude oil fractions from Southern Germany     

A.V Hirner  W Graf  R Treibs  A.N Melzer  P Hahn-Weinheimer 《Geochimica et cosmochimica acta》1984,48(11):2179-2186

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 (${}^{34}\text{S}{}^{32}\text{S}$ and ${}^{15}\text{N}{}^{14}\text{N}$, 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   

Rates of reaction of pyrite and marcasite with ferric iron at pH 2     

C.L Wiersma  J.D Rimstidt 《Geochimica et cosmochimica acta》1984,48(1):85-92

The relative reactivities of pulverized samples (100–200 mesh) of 3 marcasite and 7 pyrite specimens from various sources were determined at 25°C and pH 2.0 in ferric chloride solutions with initial ferric iron concentrations of 10^?3 molal. The rate of the reaction: was determined by calculating the rate of reduction of aqueous ferric ion from measured oxidation-reduction potentials. The reaction follows the rate law: where m_Fe³⁺ is the molal concentration of uncomplexed ferric iron, k is the rate constant and $\text{A}\text{M}$ is the surface area of reacting solid to mass of solution ratio. The measured rate constants, k, range from 1.0 × 10^?4 to 2.7 × 10^?4 sec^?1 ± 5%, with lower-temperature/early diagenetic pyrite having the smallest rate constants, marcasite intermediate, and pyrite of higher-temperature hydrothermal and metamorphic origin having the greatest rate constants. Geologically, these small relative differences between the rate constants are not significant, so the fundamental reactivities of marcasite and pyrite are not appreciably different.The activation energy of the reaction for a hydrothermal pyrite in the temperature interval of 25 to 50°C is 92 kJ mol^?1. This relatively high activation energy indicates that a surface reaction controls the rate over this temperature range. The BET-measured specific surface area for lower-temperature/early diagenetic pyrite is an order of magnitude greater than that for pyrite of higher-temperature origin. Consequently, since the lower-temperature types have a much greater $\text{A}\text{M}$ ratio, they appear to be more reactive per unit mass than the higher temperature types.  相似文献   

Experimental paleotemperature equation for planktonic foraminifera     

Jonathan Erez  Boaz Luz 《Geochimica et cosmochimica acta》1983,47(6):1025-1031

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: $\text{t = ?0.07 + 1.01}\text{t}\text{?}\text{(r= 0.95)}$ where t is the actual growth temperature and $\text{t}\text{?}$ 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: $\text{t}\text{?}\text{= 17.0 ? 4.52(δ}{}^{18}\text{Oc ? δ}{}^{18}\text{Ow) + 0.03(δ}{}^{18}\text{Oc ? δ}{}^{18}\text{Ow)}{}^2$$\text{t}\text{?}\text{, δ}{}^{18}\text{Oc}$ 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   

Geochimie et teneurs isotopiques des systèmes saisonniers de dissolution de la calcite dans un sol sur craie     

L. Dever  R. Durand  J.Ch. Fontes  P. Vachier 《Geochimica et cosmochimica acta》1982,46(10):1947-1956

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 ($\text{δ}{}_{\mathrm{tidc}}{}^{13}\text{C = ?12,2\%0}$) 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: $\text{δ}{}_{\mathrm{G}}{}^{13}\text{C = ?21,5\%0}$; $\text{A}{}_{\mathrm{G}}{}^{14}\text{C = 118\%}$; $\text{δ}{}_{\mathrm{M}}{}^{13}\text{C = +2,9\%0}$; $\text{A}{}_{\mathrm{M}}{}^{14}\text{C = 28\%}$).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 δ_{L mes} = from ?9,4%0 to ?11,5%0, δ_{l calc} = from ?9,8%0 to ?13,9%0 A_{L mes} = 119%, A_{L 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   

Precambrian sulfur isotopes and a possible role for sulfite in the evolution of biological sulfate reduction     

G.W. Skyring  T.H. Donnelly 《Precambrian Research》1982,17(1):41-61

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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   

Progression in sulfur isotopic compositions from coal to fly ash: Examples from single-source combustion in Indiana     

Yaofa Jiang  Erika R. Elswick  Maria Mastalerz   《International Journal of Coal Geology》2008,73(3-4):273-284

Sulfur occurs in multiple mineral forms in coals, and its fate in coal combustion is still not well understood. The sulfur isotopic composition of coal from two coal mines in Indiana and fly ash from two power plants that use these coals were studied using geological and geochemical methods. The two coal beds are Middle Pennsylvanian in age; one seam is the low-sulfur (< 1%) Danville Coal Member of the Dugger Formation and the other is the high-sulfur (> 5%) Springfield Coal Member of the Petersburg Formation. Both seams have ash contents of approximately 11%. Fly-ash samples were collected at various points in the ash-collection system in the two plants. The results show notable difference in δ³⁴S for sulfur species within and between the low-sulfur and high-sulfur coal. The δ³⁴S values for all sulfur species are exclusively positive in the low-sulfur Danville coal, whereas the δ³⁴S values for sulfate, pyritic, and organic sulfur are both positive and negative in the high-sulfur Springfield coal. Each coal exhibits a distinct pattern of stratigraphic variation in sulfur isotopic composition. Overall, the δ³⁴S for sulfur species values increase up the section in the low-sulfur Danville coal, whereas they show a decrease up the vertical section in the high-sulfur Springfield coal. Based on the evolution of δ³⁴S for sulfur species, it is suggested that there was influence of seawater on peat swamp, with two marine incursions occurring during peat accumulation of the high-sulfur Springfield coal. Therefore, bacterial sulfate reduction played a key role in converting sulfate into hydrogen sulfide, sulfide minerals, and elemental sulfur. The differences in δ³⁴S between sulfate sulfur and pyritic sulfur is very small between individual benches of both coals, implying that some oxidation occurred during deposition or postdeposition.The δ³⁴S values for fly ash from the high-sulfur Springfield coal (averaging 9.7‰) are greatly enriched in ³⁴S relative to those in the parent coal (averaging 2.2‰). This indicates a fractionation of sulfur isotopes during high-sulfur coal combustion. By contrast, the δ³⁴S values for fly-ash samples from the low-sulfur Danville coal average 10.2‰, only slightly enriched in ³⁴S relative to those from the parent coal (average 7.5‰). The δ³⁴S values for bulk S determined directly from the fly-ash samples show close correspondence with the δ³⁴S values for SO₄^− 2 leached from the fly ash in the low-sulfur coal, suggesting that the transition from pyrite to sulfate occurred via high-temperature oxidation during coal combustion.  相似文献   

A study of strontium in core 119K,Discovery deep,Red Sea     

M.O.U. Ikpeama  P.D. Boger  G. Faure 《Chemical Geology》1974,13(1):11-22

The isotopic composition of strontium of pore water and of authigenic minerals leached from the sediment of core 119K with hot aqua regia is similar to that of the brine in the Discovery deep and differs from that of normal seawater. The average ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of strontium removed by acid leaching is 0.7077 ± 0.0007 (1σ) compared to a value of 0.70904 for the Red Sea. The detrital silicate fraction exhibits an approximate inverse correlation between ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios and strontium concentrations which provides tentative support for a model in which the detrital silicate fraction of deep-sea sediment is considered to be a mixture of terrigenous dust of sialic composition enriched in radiogenic ⁸⁷Sr and of volcanogenic material of basaltic composition and low ⁸⁷Sr abundance. The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of the shells of foraminifers and pteropods, expressed as δ ⁸⁷Sr‰ relative to 0.70904 for seawater, decrease from $\text{?0.23 ± 0.17‰}$ at 90 cm to $\text{?0.82 ± 0.17‰}$ at 273 cm and remain constant at this value to a depth of 450 cm. The lowering of the δ ⁸⁷Sr values is attributed both to the presence of aragonite overgrowths on pteropod shells and to possible isotope exchange with strontium in the connate fluid.  相似文献   

The distribution and isotopic composition of sulfur in coal     

J.W. Smith  B.D. Batts 《Geochimica et cosmochimica acta》1974,38(1):121-133

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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   

Carbon,nitrogen and sulfur in lunar fines 15012 and 15013: abundances,distributions and isotopic compositions     

S. Chang  J. Lawless  M. Romiez  I.R. Kaplan  C. Petrowski  H. Sakai  J.W. Smith 《Geochimica et cosmochimica acta》1974,38(6):853-872

Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. In the former case, it was released by mineral grains to which it was adsorbed or from cavities within which it had been captured. Hydrogen released during hydrolysis had largely resulted from dissolution of metallic iron.By comparison of the distribution frequencies of C, N, S, H₂ and Fe with ⁴He, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteoritic contribution to these samples.Solar wind interaction also has a marked effect on the stable isotope distribution of ¹³C/¹²C, ¹⁵N/¹⁴N, and ³⁴S/³²S. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction. During stepwise pyrolysis, CH₄, CO₂, CO and N₂ were obtained at different temperatures and displayed different isotopic ratios. The carbon fraction most enriched in ¹³C, was CH₄ liberated at 600–800°C with $\text{δ}{}^{13}\text{C = +45.7\%.}$. Between 400 and 600°C, N₂ was liberated with (δ¹⁵N ≈ +119% and at 600–800°C, N₂ was liberated with $\text{δ}{}^{15}\text{N = +75\%.}$ relative to terrestrial atmospheric nitrogen.  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   

The statistical analysis and interpretation of imperfectly-fitted Rb-Sr isochrons from polymetamorphic terrains     

M. Cameron  K.D. Collerson  W. Compston  R. Morton 《Geochimica et cosmochimica acta》1981,45(7):1087-1097

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Use of Pitzer's equations to determine the media effect on the formation of lead chloro complexes     

Frank.J. Millero  Robert H. Byrne 《Geochimica et cosmochimica acta》1984,48(5):1145-1150

The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl₂ and CaCl₂ solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl⁺, PbCl₂⁰ and PbCl₃^? have been determined for the various media. Values of $\text{K}{}_1\text{= 30.0 ± 0.6}$, $\text{K}{}_2\text{= 106.7 ± 2.1}$ and $\text{K}{}_3\text{= 73.0 ± 1.5}$ were obtained for the cumulative formation constants. [$\text{Pb}{}^{\mathrm{2+}}\text{+ nCl}{}^{\mathrm{?}}\text{→ PbCl}{}_{\mathrm{n}}{}^{\mathrm{2?n}}\text{)}$]. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb²⁺ in an artificial seawater solution.  相似文献   

Precambrian sedimentary carbonates: carbon and oxygen isotope geochemistry and implications for the terrestrial oxygen budget   总被引：2，自引：0，他引：2  

Manfred Schidlowski  Rudolf Eichmann  Christian E. Junge 《Precambrian Research》1975,2(1):1-69

Carbon isotope values of 260 Precambrian limestones and dolomites (most of them being substantially unaltered) have yielded an overall mean of $\text{δ}{}^{13}\text{C}\text{= +0.4 ± 2.7‰}$ vs. PDB; the corresponding oxygen values average at $\text{δ}{}^{13}\text{O = +20.0 ± 4.2‰}$ 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 $\text{δ}{}^{13}\text{C}\text{= +9.4 ± 2.0‰}$ 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 C_org/C_total ? 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 C_org 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   

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   

Hydrogen,oxygen and carbon isotopic evidence for the origin of rodingites in serpentinized ultramafic rocks     

David B. Wenner 《Geochimica et cosmochimica acta》1979,43(4):603-614

$\text{D}\text{H}$, ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ 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 $\text{D}\text{H}$ 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 $\text{D}\text{H}$ 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 $\text{D}\text{H}$ 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 ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ 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   

Delivery of transuranic elements by rain to the Mediterranean Sea     

M. Thein  S. Ballestra  A. Yamato  R. Fukai 《Geochimica et cosmochimica acta》1980,44(8):1091-1097

The concentrations of ²³⁸Pu, ^{239 + 240}Pu, ²⁴¹Am and ¹³⁷Cs were determined in rain samples collected at Monaco in the course of 1978–1979. Based on these data, the annual deliveries of these radionuclides to the Mediterranean by rain are computed to be 0.18 ± 0.01 pCim^?2 for ²³⁸Pu, 8.1 ± 0.1 pCim^?2 for ^{239 + 240}Pu, 0.58 ± 0.02 pCim^?2 for ²⁴¹Am and 351 ± 4 pCim^?2 for ¹³⁷Cs.Comparing the delivery data with the mixed layer inventories of ^{239 + 240}Pu and ²⁴¹Am in the Mediterranean, the upper limits of the mean residence time of these radionuclides in the mixed layer were estimated to be 12.3 yr for ^{239 + 240}pu and 2.9 yr for ²⁴¹Am. These values are consistent with the conclusion deduced from the vertical distribution pattern of these transuranic elements in the Mediterranean.Based on delivery values, the annual activity ratios for ${}^{238}\text{pu}{}^{\mathrm{239\; +\; 240}}\text{Pu}$, ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ and ${}^{\mathrm{239\; +\; 240}}\text{pu}{}^{137}\text{Cs}$ are found to be 0,022, 0.072 and 0.023 respectively. The ${}^{238}\text{pu}{}^{\mathrm{239\; +\; 240}}\text{pu}$ and ${}^{\mathrm{239\; +\; 240}}\text{Pu}{}^{137}\text{Cs}$ activity ratios vary within relatively narrow ranges with time, while a much wider variation was observed for the ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ activity ratio. The cause of the wider variation of the ${}^{241}\text{Am}{}^{\mathrm{239\; +\; 240}}\text{Pu}$ ratio may be related to the difference in the mean age of fallout brought down in different seasons.  相似文献