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1.
Statistical evaluation of 3056 δ13C measurements in carbonate rocks and fossils shows that they record a 2‰ 13C depletion from the late Proterozoic to the early Paleozoic, a 2.5‰ enrichment to the Permian, and a 1.5‰ depletion to the Cenozoic. These variations, not controlled primarily by facies or alteration phenomena, correlate negatively with the δ34S sulfate secular trend, as confirmed by collation of 1083 δ34S measurements. The correlation suggests that the biologically mediated redox fluxes of the C and S cycles have been approximately balanced through this long span of geological time, generally levelling available oxygen. Such a redox system is consistent with the controlling mechanism proposed by Garrels and Perry (1974). Consequently, the sedimentary reservoirs of Corganic as well as Sbacteriological'have varied through geological time.  相似文献   

2.
3.
Partial fluorination experiments developed on a 26 mg sample of Luna 16 fines show a big 18O enrichment in the first oxygen evolved similar to those observed by Epstein and Taylor on Apollo samples and probably related to the high solar wind content of this sample.  相似文献   

4.
Auger electron spectroscopy has been used to study K-feldspar that has been reacted with both aqueous 10% HF and a 50% mixture of a 10% HF/0.1 N H2SO4 solution. In the feldspar/HF system, the resulting feldspar surface was shown to have been fluorinated; depth profiling, using argon ion sputtering, showed the fluorination to have occurred substantially into the mineral bulk. In the feldspar/ HFH2SO4 system, the resulting surface contained both fluorine and sulfur. The fluorination had again penetrated into the bulk, but the sulfur could be removed with mild argon ion sputtering. The AlF signal ratio was much lower on the feldspar surface treated with the 10% HF/0.1 N H2SO4 solution than the feldspar surface treated with the weaker 10% HF acid solution.  相似文献   

5.
The δC13 value for sedimentary organic carbon in four estuaries of the Gulf of Mexico increases with radial distance from the river mouth. Mass balance calculations indicate that terrestrial organic carbon is limited to sediments within a relatively short distance from the river mouth. This distance is a function of the discharge rate of the river. For the Mississippi River, terrestrial organic carbon is limited to sediments within 69 km of the mouth of Pass à Loutre and 61 km of South Pass. These data indicate that the low δC13 (< ?22%.) values reported for Pleistocene sediments in the Gulf of Mexico may be the result of factors in addition to the postulated large influx of terrestrial organic carbon.  相似文献   

6.
Results of an 40Ar39ArAr age spectrum obtained on a sample of the Kirin chondrite (K-5-13) show a similar character to previous published analyses of Kirin samples K-1 and K-2. The K-5-13 age spectrum shows clear evidence of having been substantially outgassed during a presumed collisional event about 0.5 Ga, ago, in good agreement with the estimate obtained from K-2, The differing amounts of 40Ar loss registered by K-2 and K-5-13 during the 0.5 Ga event of about 60 and 50%, respectively, allows calculation of their vertical separation in the parent body at about 10cm.  相似文献   

7.
A modified Redlich-Kwong equation of state is used to calculate the solubility of CO2 in methane at various temperatures and pressures. From the solubility of CO2 in CH4 at the triple point and at final melting (Th < Tfm), and the molar volume of solid CO2, the volume of solid at the triple point, and the molar volume of the inclusion can be calculated using a mass balance. The pressure at the melting point is calculated from the equation of state.The algorithm predicts composition, molar volume, pressure at final melting and the isochor pressure (for a given temperature of trapping) for CO2-CH4 fluid inclusions for the case Th < Tfm, given Th, Tfm and experimental data on Ph and dco2 (solid) at Th.  相似文献   

8.
Sapphirine, coexisting with quartz, is an indicator mineral for ultrahigh‐temperature metamorphism in aluminous rock compositions. Here a new activity‐composition model for sapphirine is combined with the internally consistent thermodynamic dataset used by THERMOCALC, for calculations primarily in K2O‐FeO‐MgO‐Al2O3‐SiO2‐H2O (KFMASH). A discrepancy between published experimentally derived FMAS grids and our calculations is understood with reference to H2O. Published FMAS grids effectively represent constant aH2O sections, thereby limiting their detailed use for the interpretation of mineral reaction textures in compositions with differing H2O. For the calculated KFMASH univariant reaction grid, sapphirine + quartz assemblages occur at P–T in excess of 6–7 kbar and 1005 °C. Sapphirine compositions and composition ranges are consistent with natural examples. However, as many univariant equilibria are typically not ‘seen’ by a specific bulk composition, the univariant reaction grid may reveal little about the detailed topology of multi‐variant equilibria, and therefore is of limited use for interpreting the P–T evolution of mineral assemblages and reaction sequences. Calculated pseudosections, which quantify bulk composition and multi‐variant equilibria, predict experimentally determined KFMASH mineral assemblages with consistent topology, and also indicate that sapphirine stabilizes at increasingly higher pressure and temperature as XMg increases. Although coexisting sapphirine and quartz can occur in relatively iron‐rich rocks if the bulk chemistry is sufficiently aluminous, the P–T window of stability shrinks with decreasing XMg. An array of mineral assemblages and mineral reaction sequences from natural sapphirine + quartz and other rocks from Enderby Land, Antarctica, are reproducible with calculated pseudosections. That consistent phase diagram calculations involving sapphirine can be performed allows for a more thorough assessment of the metamorphic evolution of high‐temperature granulite facies terranes than was previously possible. The establishment of a a‐x model for sapphirine provides the basis for expansion to larger, more geologically realistic chemical systems (e.g. involving Fe3+).  相似文献   

9.
The oxygen isotopic compositions of over 100 Archean clastic metasedimentary, felsic metavolcanic and gneissic rocks from selected areas within the Superior Province have been determined. δ18O values of low grade, immature clastic metasediments range from 8.0 to 13.3%. and hence are somewhat depleted in 18O relative to other clastic metasediments. The lower 18O content is attributed to the large proportion of unaltered rock fragments in the Archean metasediments. Felsic metavolcanics have a similar range of δ18O values (7.3 to 13.0%..δ18O values for the middle amphibolite facies Pakwash paragneiss (8.8–11.7%.) are higher than those determined for the amphibolite to granulite facies Twilight paragneiss (7.3–9.2%.). Archean orthogneisses such as the Clay Lake gneiss (7.0–9.0%.), the Cedar Lake gneiss (7.4–8.7%.) and the Footprint gneiss (5.9-8.8%.) have δ18O values similar to those of the Twilight paragneiss. Therefore, at least at metamorphic grades higher than middle amphibolite facies, Archean metasedimentary gneisses may have δ18O values that are indistinguishable from those of Archean orthogneisses, and hence are no longer isotopically recognizable as metasedimentary rocks.  相似文献   

10.
Silica‐undersaturated, sapphirine‐bearing granulites occur in a large number of localities worldwide. Such rocks have historically been under‐utilized for estimating PT evolution histories because of limited experimental work, and a consequent poor understanding of the topology and PT location of silica‐undersaturated mineral equilibria. Here, a calculated PT projection for sapphirine‐bearing, silica‐undersaturated metapelitic rock compositions is constructed using THERMOCALC for the FeO‐MgO‐Al2O3‐SiO2 (FMAS) and KFMASH (+K2O + H2O) chemical systems, allowing quantitative analysis of silica‐undersaturated mineral assemblages. This study builds on that for KFMASH sapphirine + quartz equilibria [Kelsey et al. (2004) Journal of Metamorphic Geology, vol. 22, pp. 559–578]. FMAS equilibria are significantly displaced in PT space from silicate melt‐bearing KFMASH equilibria. The large number of univariant silica‐undersaturated KFMASH equilibria result in a PT projection that is topologically more complex than could be established on the basis of experiments and/or natural assemblages. Coexisting sapphirine and silicate melt (with or without corundum) occur down to c. 900 °C in KFMASH, some 100 °C lower than in silica‐saturated compositions, and from pressures of c.≤1 to ≥12 kbar. Mineral compositions and composition ranges for the calculated phases are consistent with natural examples. Bulk silica has a significant effect on the stability of sapphirine‐bearing assemblages at a given PT, resulting in a wide variety of possible granulite facies assemblages in silica‐undersaturated metapelites. Calculated pseudosections are able to reproduce many naturally occurring silica‐undersaturated assemblages, either within a single assemblage field or as the product of a PT trajectory crossing several fields. With an understanding of the importance of bulk composition on sapphirine stability and textural development, silica‐undersaturated assemblages may be utilized in a quantitative manner in the detailed metamorphic investigation of high‐grade terranes.  相似文献   

11.
The relative abundance of 226Ra and 228Ra were determined in the groundwater from 125 drilled wells containing from < 0.1 to 51.3 pCi/l of 226Ra. The determination of 228Ra was carried out with a liquid scintillation counter by measuring only the weakly energetic β particles emitted from 228Ra. Thus the interference from the daughter nuclides of 226Ra was avoided, without specific separation of 228Ac. The direct measurement of 228Ra made the method decisively simpler and faster in terms of the chemistry involved.The concentration of 228Ra was found to be independent of the amount of 226Ra present in the samples. The concentrations of 228Ra were nearly the same over the whole range of 226Ra concentrations and the average sol226Ra228Ra ratio sharply increased as the 226Ra content of water increased. The 226Ra228Ra ratio in the drilled wells varied from 0.3 to 26. Abnormally high 226Ra228Ra ratios were found in areas with known uranium deposits as well as in several drilled wells at other locations. The abnormally high 226Ra228Ra ratios present in groundwater suggest that the radioactivity anomaly is caused by uranium deposits and not by common rocks. In samples with a low radioactivity level the average 226Ra228Ra ratio was slightly below unity, corresponding to the typical U/Th ratio of granite, the most common kind of rock in the study area. The samples from the rapakivi area proved to be exceptional in that they had a low 226Ra228Ra ratio independent of the concentration of 226Ra.  相似文献   

12.
Speleothem from West Virginia, ranging in age from 2000 to 200,000 yr B.P. contains uranium with U234U238 ratios significantly greater than unity. This ratio varies from one speleothem to another, as does average U content. Initial ratios, corrected for age, are remarkably constant for a given speleothem. By contrast, U234U238 ratios in seepage waters vary significantly from month to month at a given drip site, and their average values differ from that of the speleothem which they are depositing. This discrepancy is attributed either to long-term averaging-out of fluctuations, or fractional precipitation on the speleothem of a chemical species of uranium with a more constant ratio. Constancy of initial U234U238 ratios from Th230U234. datable portions of speleothems should permit U234U238-dating of older portions of the same speleothem, back to about 106 yr B.P., with estimated precision of ±5 per cent.  相似文献   

13.
We report data for trace elements Ag, Au, Bi, Cd, Co, Cs, Ga, In, Rb, Se, Te, Tl and Zn determined by radiochemical neutron activation analysis in L4–6 chondrites with undisturbed 40Ar release patterns or with patterns showing some disturbance in the 4.4–4.6 Gyr plateau indicating shock-induced loss. Mean concentrations are lower, many significantly so, in 16 chondrites with disturbed patterns than in 4 with undisturbed ones, consistent with shock-induced mobilization. Similar trends were noted earlier in L4–6 chondrites having mineralogically observable shock indicators: mean concentrations are lower in strongly shocked (i.e. > 22 GPa) than in mildly shocked (<22 GPa) samples. From trace element contents, L4–6 chondrites with undisturbed 40Ar release patterns are mildly shocked but chondrites with disturbed patterns are more strongly heated, on average, than those of shock facies d-f (i.e. 22 to > 57 GPa). Pooling these populations, significantly lower mean concentrations of nearly all trace elements in 26 strongly shocked L4–6 chondrites than in 14 mildly shocked ones indicate loss in shock-formed FeS-Fe eutectic and/or by vaporization during cooling of shock-heated collisional debris. Two-element correlations and the pattern of them, i.e. correlation profiles, are also consistent with this picture. Trace elements can act as thermometers for collisional episodes in L4–6 chondrites but not for earlier thermal fractionations, unless compensation can be made for late shock heating.  相似文献   

14.
The possible importance of SiF4 in volcanic and magmatic gases has been neglected due to the convention of reporting analyses and basing calculations on the presence of HF. Calculated HFSiF4 ratios for natural gas compositions serve to justify this convention by showing that SiF4 is not a significant F-bearing molecular species at high temperatures.  相似文献   

15.
40Ar39Ar age spectrum analyses of three microcline separates from the Separation Point Batholith, northwest Nelson, New Zealand, which cooled slowly (~5°C-Ma?1) through the temperature zone of partial radiogenic 40Ar accumulation are characterized by a linear age increase over the first 65 percent of gas release with the lowest ages (~80 Ma) corresponding to the time that the samples cooled below about 100°C. The last 35 percent of 39Ar released from the microclines yields plateau ages (103,99 and 93 Ma) which reflect the different bulk mineral ages, and correspond to cooling temperatures between about 130 to 160°C. Theoretical calculations confirm the likelihood of diffusion gradients in feldspars cooling at rates ≤5°C-Ma?1. Diffusion parameters calculated from the 39Ar release yield an activation energy, E = 28.8 ± 1.9 kcal-mol?1, and a frequency factor/grain size parameter, D0l2 = 5.6?3.9+14sec?1. This Arrhenius relationship corresponds to a closure temperature of 132 ± 13°C which is very similar to the independently estimated temperature. From the observed diffusion compensation correlation, this D0l2 implies an average diffusion half-width of about 3 μm, similar to the half-width of the perthite lamellae in the feldspars. The range in microcline K-Ar ages from the Separation Point Batholith is the result of relatively small temperature differences within the pluton during cooling. Comparison of the diffusion laws determined for microcline with those for anorthoclases and other homogeneous K-feldspars (E = 40 to 52 kcal-mol?1) reveals that Ar diffusion is more highly temperature dependent in the disordered structural state than in the ordered structural state. Previously published U-shaped age spectra are probably the result of the superimposition of excess 40Ar upon diffusion profiles of the kind described here.  相似文献   

16.
Olivine tholeiites, the youngest Tertiary units (about 8–11 m.y. old) at five widely spaced localities in northeastern Nevada, are geologically related to the basalts of the Snake River Plain, Idaho, to the north and are similar in major element and alkali chemistry to mid-ocean ridge basalts (MORB) and island arc tholeiites. The measured K (1250–3350 ppm), Rb (1·9–6·2 ppm) and Sr (140–240 ppm) concentrations overlap the range reported for MORB. Three of the five samples have low, unfractionated rare earth element (REE) patterns, the other two show moderate light-REE enrichment. Barium concentration is high and variable (100–780 ppm) and does not correlate with the other LIL elements. The rocks have 87Sr/86Sr = 0·7052–0·7076, considerably higher than MORB (~0·702–0·703). These samples are chemically distinct (i.e. less alkalic) from the olivine tholeiites from the adjacent Snake River Plain, but their Sr isotopic compositions are similar. They contain Sr that is distinctly more radiogenic than the basalts from the adjacent Great Basin. About 10 b.y. would be required for the mean measured Rb/Sr (~ 0·02) of these samples to generate, in a closed system, the radiogenic Sr they contain. The low alkali content of these basalts makes crustal contamination an unlikely mechanism. If the magma is uncontaminated, the time-averaged Rb/Sr of the source material must have been ~0·04. A significant decrease in Rb/Sr of the source material (a factor 2?) thus most probably occurred in the relatively recent (1?09 yr) past. Such a decrease of Rb/Sr in the mantle could accompany alkali depletion produced by an episode of partial melting and magma extraction. In contrast, low 87Sr86Sr ratios indicate that the source material of the mid-ocean ridge basalts may have been depleted early in the Earth's history.  相似文献   

17.
Eclogite facies metarodingites occur as deformed dykes in serpentinites of the Zermatt‐Saas ophiolite (Western Alps). They formed during the subduction of the Tethys oceanic lithosphere in the Early Tertiary. The metarodingites developed as a consequence of serpentinization of the oceanic mantle. Three major types of metarodingites (R1, R2 & R3) can be distinguished on the basis of their mineralogical composition. All metarodingites contain vesuvianite, chlorite and hydrogrossular in high modal amounts. In addition they contain: R1 – diopside, tremolite, clinozoisite, calcite; R2 – hydroandradite, diopside, epidote, calcite; and R3 – hydroandradite. Both garnets contain a small but persistent amount of hydrogarnet component. The different metarodingites reflect different original dyke rocks in the mantle. In each group of metarodingite, textural relations suggest that reactions adjusted the assemblages along the P–T path travelled by the ophiolite during subduction and exhumation. Reactions and phase relations derived from local textures in metarodingite can be modelled in the eight‐component system: SiO2‐Al2O3‐Fe2O3‐FeO‐MgO‐CaO‐CO2‐H2O. This permits the analysis of redox reactions in the presence of andradite garnet and epidote in many of the rocks. Within this system, the phase relations in eclogite facies metarodingites have been explored in terms of TXCO2, T–μ(SiO2), μ(Cal)–μ(SiO2) and P–T sections. It was found that rodingite assemblages are characterized by low μ(SiO2) and low XCO2 conditions. The low SiO2 potential is externally imposed onto the rodingites by the large volume of antigorite‐forsterite serpentinites enclosing them. Moreover, μ(SiO2) decreases consistently from metarodingite R1 to R3. The low μ(SiO2) enforced by the serpentinites favours the formation of hydrogarnet and vesuvianite. Rodingite formation is commonly associated with hydrothermal alteration of oceanic lithosphere at the ocean floor, in particular to ocean floor serpentinization. Our analysis, however, suggests that the metarodingite assemblages may have formed at high‐pressure conditions in the subduction zone as a result of serpentinization of oceanic mantle by subduction zone fluids.  相似文献   

18.
19.
The diagenesis and geochemical evolution of deep-sea sediments are controlled by the interaction between sediments and their associated pore waters. With increasing depth, the pore water of Hole 149 (DSDP) exhibits a strong depletion in Mg and a corresponding enrichment in Ca, while the alkalinity remains relatively constant. Dissolved SiO2 is nearly constant in the upper 100 m of sediment, but is highly enriched in the deepest pore waters. The pore waters exhibit a depletion in K with increasing depth, and O18O16 pore water ratios also decrease.The sediment section has three zones of sedimentary regimes with increasing depth in the drill hole: an upper 100 m section of detrital clays, a middle section enriched in calc-akalic volcanics which have undergone submarine weathering to a smectite phase, and a lower section of siliceous ooze which still has a diagenetic smectite phase. The quartz-feldspar ratios and O18O16 composition of the silicate phases are in agreement with these interpretations.The submarine weathering of volcanics to a smectite can account for the observed pore water gradients. Volcanics release Ca and Mg to the pore waters causing the alkalinity values to increase. Smectite is formed, depletes the pore waters in Mg and O18 and causes the alkalinity to decrease. The net reaction allows for the observed relationship between pore water Ca and Mg gradients with little net change in alkalinity. Given the abundance of volcanics in many deep-sea sediments, especially in lower sections which often form near ridge crests, the submarine formation of smectite may be an additional oceanic Mg sink which has not yet been fully considered.  相似文献   

20.
Determinations of 40Ar39Ar ages are reported for seven severely shock-heated chondrites. Shaw gives a plateau age of 4.29 Gyr. Louisville, Farmington, and Wickenburg give well-defined intercept ages of 0.5–0.6 Gyr. Orvinio, Arapahoe, and Lubbock show complex 40Ar39Ar release curves, with age minima of 0.7–1.0 Gyr. Degassing times of 0.5–1.0 Gyr are suggested for these meteorites. Most severely shocked chondrites were apparently not totally degassed of 40Ar by the event, but retained from ~ 2 to ~45% of their 40Ar. When calculated values of the diffusion parameter, Da2, for Ar are examined in Arrhenius plots, they show two distinct linear relationships, which apparently correspond to the degassing of different mineral phases with distinct KCa ratios and different average temperatures for Ar release. The experimentally determined values of Da2 for the high temperature phase of several severely shocked chondrites are ~10?7 to 10?5sec?1 for their determined shock-heating temperatures of ~950°C to ~ 1200°C. The inferred reheating temperatures, Da2 values, and fraction of 40Ar loss during the reheating event for these seven chondrites suggest post-shock cooling rates and burial depth of ~ 10?2 10?4°C/sec and ~0.5–2m, respectively. For three chondrites these cooling rates agree with those determined from Ni diffusion in metal grains: for five chondrites the cooling rates derived from 40Ar and Ni disagree by a factor of ~105. It is suggested that five of these severely shocked chondrites were part of large ejecta blankets containing hot material and cold clasts with a distribution of sizes and that the cooling rate of this ejecta appreciably decreased as a function of time.  相似文献   

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