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1.
Isotope geochemistry of caliche developed on basalt   总被引：1，自引：0，他引：1  
Enormous variations in oxygen and carbon isotopes occur in caliche developed on < 3 Ma basalts in 3 volcanic fields in Arizona, significantly extending the range of δ18O and δ13C observed in terrestrial caliche. Within each volcanic field, δ18O is broadly co-variant with δ13C and increases as δ13C increases. The most 18O and 13C enriched samples are for subaerial calcite developed on pinnacles, knobs, and flow lobes that protrude above tephra and soil. The most 18O and 13C depleted samples are for pedogenic carbonate developed in soil atmospheres. The pedogenic caliche has δ18O fixed by normal precipitation in local meteoric waters at ambient temperatures and has low δ13C characteristic of microbial soil CO2. Subaerial caliche has formed from 18O-rich evapoconcentrated meteoric waters that dried out on surfaces after local rains. The associated 13C enrichment is due either to removal of 12C by photosynthesizers in the evaporating drops or to kinetic isotope effects associated with evaporation. Caliche on basalt lava flows thus initially forms with the isotopic signature of evaporation and is subsequently over-layered during burial by calcite carrying the isotopic signature of the soil environment. The large change in carbon isotope composition in subsequent soil calcite defines an isotopic biosignature that should have developed in martian examples if Mars had a “warm, wet” early period and photosynthesizing microbes were present in the early soils. The approach can be similarly applied to terrestrial Precambrian paleocaliche in the search for the earliest record of life on land. Large variations reported for δ18O of carbonate in Martian meteorite ALH84001 do not necessarily require high temperatures, playa lakes, or flood runoff if the carbonate is an example of altered martian caliche.  相似文献   

2.
Soils overlying two porphyry Cu deposits (Spence, Gaby Sur) and the Pampa del Tamarugal, Atacama Desert, Northern Chile were collected in order to investigate the extent to which saline groundwaters influence “soil” chemistry in regions with thick Miocene and younger sediment cover. Soil carbonate (calcite) was analyzed for C and O isotopes and pedogenic gypsum for S isotopes. Soil calcite is present in all soils at the Spence deposit, but increases volumetrically above two fracture zones that cut the Miocene gravels, including gravels that overlie the deposit. The C isotope composition of carbonate from the soils overlying fracture zones is indistinguishable from pedogenic carbonate elsewhere at the Spence deposit; all δ13CVPDB values fall within a narrow range (1.40–4.23‰), consistent with the carbonate having formed in equilibrium with atmospheric CO2. However, δ18OVPDB for carbonate over both fracture zones is statistically different from carbonate elsewhere (average δ18OVPDB = 0.82‰ vs. −2.23‰, respectively), suggesting involvement of groundwater in their formation. The composition of soils at the Tamarugal anomaly has been most strongly affected by earthquake-related surface flooding and evaporation of groundwater; δ13CVPDB values (−4.28‰ to −2.04‰) are interpreted to be a mixture of dissolved inorganic C (DIC) from groundwater and atmospheric CO2. At the Spence deposit, soils only rarely contain sufficient SO4 for S isotope analysis; the SO4-bearing soils occur only above the fracture zones in the gravel. Results are uniform (3.7–4.9‰ δ34SCDT), which is near the middle of the range for SO4 in groundwater (0.9–7.3‰). Sulfur in soils at the Gaby Sur deposit (3.8–6.1‰ δ34SCDT) is dominated by gypsum, which primarily occurs on the flanks and tops of hills, suggesting deposition from SO4-rich fogs. Sulfate in Gaby Sur deposit gypsum is possibly derived by condensation of airborne SO4 from volcanic SO2 from the nearby Andes. At the Gaby Sur deposit and Tamarugal anomaly, pedogenic stable isotopes cannot distinguish between S from porphyry or redeposited SO4 from interior salars.The three sites studied have had different histories of salt accumulation and display variable influence of groundwater, which is interpreted to have been forced to the surface during earthquakes. The clear accumulation of salts associated with fractures at the Spence deposit, and shifts in the isotopic composition of carbonate and sulfate in the fractures despite clear evidence of relatively recent removal of salts indicates that transfer from groundwater is an ongoing process. The interpretation that groundwaters can influence the isotopic composition of pedogenic calcrete and gypsum has important implications for previous studies that have not considered this mechanism.  相似文献   

3.
MIS 11 is often considered to be the best climatic analogue for the Holocene. Many studies have suggested, however, that it is a period of extreme climate warmth comparable in temperatures to the Middle and Late Pliocene. In Britain deposits of the Hoxnian interglacial are correlated to MIS 11 and multi-proxy techniques can be used to reconstruct the climate of this interglacial. Soil, groundwater and freshwater carbonates are common in Hoxnian deposits and the stable isotopic composition of these precipitates can be used to increase our understanding of MIS 11 environments in Britain. Carbonates from Marks Tey, Clacton, Swanscombe, Elveden and West Stow are studied, the stratigraphic context of which indicates that their formation is broadly synchronous (in the mid-Hoxnian, pollen zones Ho II to Ho III). The carbon isotopic composition of groundwater and pedogenic carbonates is typically depleted with respect to δ13C (ca −9 to −8‰ VPDB) reflecting uptake of plant respired CO2 during water migration/recharge. The carbon isotopic composition of lacustrine carbonate is more enriched with respect to δ13C (ca 0-1‰VPDB) reflecting the equilibration of lake waters with atmospheric CO2. The δ18O of groundwater and pedogenic carbonates is slightly more enriched than modern soil carbonates but not as enriched as soil carbonates formed under interglacials that were warmer than the Holocene (i.e. the Cromerian). The stable isotopic composition of Hoxnian carbonates does not, therefore, indicate that this interglacial was characterised by uniquely warm climates in the context of other Middle Pleistocene interglacials and the Holocene. This is contrary to many marine and littoral records from around the world but consistent with environmental records from Britain and Europe.  相似文献   

4.
The morphology and geochemistry of pedogenic carbonate found in vertic claystone palaeosols in the Devonian Catskill Formation in central Pennsylvania preserve a record of the physical and chemical environment of carbonate precipitation. The carbonate is characterized by three distinct petrographic generations. Pedogenic rhizoliths and nodules are the earliest precipitated generation, and typically consist of dull red-brown luminescent micrite. Clear, equant calcite spar cement fills voids in the centres of rhizoliths, as well as circumgranular cracks and septarian voids in nodules. Early spar cements are non-luminescent to dull luminescent, whereas later spar cements exhibit bright yellow-orange luminescence. Late stage pedogenic fractures are always occluded with very bright yellow-orange luminescent spar cements. The incorporation of progressively higher concentrations of Mn (up to 34000 ppm) into successively younger calcite spar cements, without concomitant increases in Fe, suggests carbonate precipitation from an evolving meteoric water in which Mn2+ became increasingly mobile over time. The increased mobility is possibly due to decreasing Eh, resulting from oxidation of organic matter after rapid soil burial on the floodplain. The amount of Fe2+ available for incorporation into calcite was limited because most iron was immobile, having been earlier oxidized and bound to the palaeosol clay matrix as a poorly crystallized ferric oxide or oxyhydroxide mineral. Carbon isotope compositions of pedogenic carbonate correlate with the inferred depth of carbonate precipitation. Rhizoliths preserved below the lowest stratigraphic occurrences of pedogenic slickensides are consistently depleted in 13C relative to nodules, which formed stratigraphically higher, within the zone of active soil shrink and swell processes. Nodular carbonate, precipitated in proximity to deep cracks in the soil, is enriched due to increased gas exchange with isotopically heavy atmospheric CO2. Accordingly, rhizolith compositions will most accurately estimate palaeoatmospheric levels of CO2; the use of nodule compositions may result in overestimation of PCO2 by as much as 30%.  相似文献   

5.
Abstract Positive shifts in global seawater δ13CDIC are related to changes in the ratio of organic relative to inorganic carbon burial in oceanic basins, whereas factors such as climatic cooling and the accumulation of polar ice are known to cause positive shifts in δ18O. Here, an alternative model is proposed for the formation of local positive isotope shifts in shallow-marine settings. The model involves geochemically altered platform-top water masses and the effects of early meteoric diagenesis on carbonate isotopic composition. Both mechanisms are active on modern (sub)tropical carbonate platforms and result in low carbonate δ13C and δ18O relative to typical oceanic values. During high-amplitude transgressive events, the impact of isotopically light meteoric fluids on the carbonate geochemistry is much reduced, and 13C-depleted platform-top water mixes with open oceanic water masses having higher isotope values. Both factors are recorded as a transient increase in carbonate 13C and 18O relative to low background values. These processes must be taken into consideration when interpreting the geochemical record of ancient epeiric seas.  相似文献   

6.
The Berriasian Rupelo Formation of the W Cameros Basin consists of a 2–200 m thickness of marginal and open lacustrine carbonate and associated deposits. Open lacustrine facies contain a non-marine biota with abundant charophytes (both stems and gyrogonites), ostracods, gastropods and rare vertebrates. Carbonate production was mainly biogenic. The associated marginal lacustrine (‘palustrine’) facies show strong indications of subaerial exposure and exhibit a wide variety of pedogenic fabrics. Silicified evaporites found near to the top of the sequence reflect a short hypersaline phase in the lake history. The succession was laid down in a low gradient, shallow lake complex characterized by wide fluctuations of the shoreline. Carbon and oxygen stable isotope analyses from the carbonates show non-marine values with ranges of δ13 from ? 7 to ? 11‰and δ18 from ? 3 to ? 7.5‰. Differences in the isotopic composition of open lacustrine carbonates are consistent with sedimentary evidence of variation in organic productivity within the lake. Analyses from the entire sample suite plot on a linear trend; isotopic compositions become lighter with increasing evidence of pedogenic modification. This suggests progressive vadose zone diagenesis and influence of meteoric waters rich in soil-derived CO2. The stable isotope data thus support evidence from petrography and facies relations that ‘palustrine’limestones form through pedogenic modification of lake carbonates.  相似文献   

7.
Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.  相似文献   

8.
Studies of the δ13C of pore water dissolved inorganic carbon (δ13C-DIC) were carried out in shallow water carbonate sediments of the Great Bahamas Bank (GBB) to further examine sediment-seagrass relationships and to more quantitatively describe the couplings between organic matter remineralization and sediment carbonate diagenesis. At all sites studied δ13C-DIC provided evidence for the dissolution of sediment carbonate mediated by metabolic CO2 (i.e., CO2 produced during sediment organic matter remineralization); these observations are also consistent with pore water profiles of alkalinity, total DIC and Ca2+ at these sites. In bare oolitic sands, isotope mass balance further indicates that the sediment organic matter undergoing remineralization is a mixture of water column detritus and seagrass material; in sediments with intermediate seagrass densities, seagrass derived material appears to be the predominant source of organic matter undergoing remineralization. However, in sediments with high seagrass densities, the pore water δ13C-DIC data cannot be simply explained by dissolution of sediment carbonate mediated by metabolic CO2, regardless of the organic matter type. Rather, these results suggest that dissolution of metastable carbonate phases occurs in conjunction with reprecipitation of more stable carbonate phases. Simple closed system calculations support this suggestion, and are broadly consistent with results from more eutrophic Florida Bay sediments, where evidence of this type of carbonate dissolution/reprecipitation has also been observed. In conjunction with our previous work in the Bahamas, these observations provide further evidence for the important role that seagrasses play in mediating early diagenetic processes in tropical shallow water carbonate sediments. At the same time, when these results are compared with results from other terrigenous coastal sediments, as well as supralysoclinal carbonate-rich deep-sea sediments, they suggest that carbonate dissolution/reprecipitation may be more important than previously thought, in general, in the early diagenesis of marine sediments.  相似文献   

9.
《Quaternary Science Reviews》1999,18(4-5):501-513
Terrestrial stable isotope records (13C/12C, 18O/16O, and D/H ratios) of late Quaternary paleoclimates in the eastern Mediterranean region are reviewed. Significant paleoclimatic reconstructions come from a variety of isotopic studies. Paleogroundwaters, although they cannot be accurately dated, show oxygen and hydrogen isotopic compositions highly depleted in heavier isotopes compared to modern meteoric waters in arid regions of southern Israel, Sinai and northeastern Africa and attest to a major difference in climatic regime some time in the Pleistocene. Th-U dating of land snails showing a similar 18O depletion indicates ages of 100,000 yr and ≥300,000 yr for this climatic regime in the Negev Desert of southern Israel. Carbon isotope records of organic matter have not been studied extensively in the region, except for the record of Holocene land snails in the Negev. These document a southward shift in pure C3 plant communities in the middle and early Holocene relative to their present distribution and indicate wetter conditions at those times. An oxygen isotope curve for the Holocene, reflecting changes in the isotopic composition of precipitation, has been established from analysis of carbonate materials—land snail shells and speleothems. The curve indicates a depletion of ca. 2‰ in 18O centered around 7000 cal yr bp, with modern levels being reached by 5000 cal yr bp. Carbon isotope analysis of soil carbonates in paleosols developed in loess in the Negev show the existence of dramatic north–south climatic gradients at the times of formation of the soils (ca. 13,000, 28,000, and ≥37,000 14C yr bp), as occur also today due to the waning influence of Mediterranean to the south. Some isotopic methods, widely used in other regions, have received little or no attention in the eastern Mediterranean region. These include oxygen and hydrogen isotopes in wood, phosphate oxygen and organic carbon in bones and teeth, and carbon in soil organic matter.  相似文献   

10.
Combined stable isotope (δ18O and δ13C) and trace element (Mg, Sr) geochemistry from bulk tufa calcite and ostracod shell calcite from an early Holocene British tufa reveal clear records of Holocene palaeoclimatic change. Variation in δ18O is caused principally by change in the isotopic composition of Holocene rainfall (recharge), itself caused mainly by change in air temperature. The δ13C variability through much of the deposit reflects increasing influence of soil‐zone CO2, owing to progressive woodland soil development. Bulk tufa Mg/Ca and Sr/Ca are controlled by their concentrations in the spring water. Importantly, Mg/Ca ratios are not related to δ18O values and thus show no temperature dependence. First‐order sympathetic relationships between δ13C values and Mg/Ca and Sr/Ca are controlled by aquifer processes (residence times, CO2 degassing and calcite dissolution/reprecipitation) and probably record intensity of palaeorainfall (recharge) effects. Stable isotope records from ostracod shells show evidence of vital effects relative to bulk tufa data. The ostracod isotopic records are markedly ‘spiky’ because the ostracods record ‘snapshots’ of relatively short duration (years), whereas the bulk tufa samples record averages of longer time periods, probably decades. The δ18O record appears to show early Holocene warming, a thermal maximum at ca. 8900 cal. yr BP and the global 8200 yr BP cold event. Combined δ13C, Mg/Ca and Sr/Ca data suggest that early Holocene warming was accompanied by decreasing rainfall intensity. The Mg/Ca data suggest that the 8200 yr BP cold event was also dry. Warmer and wetter conditions were re‐established after the 8200 yr BP cold event until the top of the preserved tufa sequence at ca. 7100 cal. yr BP. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   

11.
High sedimentation-rate basins are characteristic of the continental margins, where sedimentation rates up to 500m/Ma and more are no exception. The sediments are rich in organic matter and undergo a well-established sequence of bacterial oxidation reactions, starting at the sediment/water interface with: (1) the oxidation zone (absent in euxinic basins), which is followed downwards by (2) the nitrate reduction zone, (3) the sulfate reduction zone, (4) the carbonate reduction zone, (5) the fermentation zone and (6) the decarboxylation zone, which marks the onset of thermocatalytic reactions characteristic of the intermediate stage (and deeper stages) of diagenesis. This sequence of bacterially mediated organic-matter decomposition reactions in rapidly deposited sediments on the continental margins is well reflected in the vertical trends of pore-water chemistry. Carbon isotopic fractionation permits to distinguish between zones (1) to (3) with negative δ13C values for the CO2 generated, and between zones (4) and (5) with increasingly heavier carbon-isotopes in CO2 (up to + 15 to + 25‰ δ13C). The formation of gas-hydrates causes characteristic chemical and isotopic signatures in pore waters retrieved from hydrate-bearing sediments. After hydrate decomposition (in the sampling process or at the base of hydrate zones) marked chlorimity decreases accompanied by increases in heavy oxygen isotopes are observed. These are distinctly different from the effects of meteoric water influx, which are not accompanied by positive δ18O values. The opposite trend of increasing salinity at shallow burial depths, rather than pore-waters freshening, is observed in the vicinity of evaporites.  相似文献   

12.
Several drill cores were obtained from a laminated, actively forming flowstone from a shallow cave in Austria. Highly resolved petrographic and geochemical analyses combined with multi‐annual cave monitoring reveal a distinct sensitivity of flowstone growth and composition to late Holocene meteoric precipitation. The regular sub‐millimetre‐scale lamination consists of thicker, translucent laminae and thinner (organic) inclusion‐rich laminae. There is also a macroscopic millimetre‐scale banding of darker and lighter bands comprising several laminae. Stable isotope analyses of drill cores and modern calcite precipitates show a pronounced positive covariation of δ13C and δ18O values indicative of kinetic isotope effects. Comparing the isotope values with petrography shows gradual changes across several of the annual laminae, i.e. changes of several per mille on a multi‐annual to decadal timescale. The stable isotope and trace‐element composition, as well as the flowstone petrography, are mainly controlled by the variable drip‐water discharge controlling the water‐film thickness and water residence time on the flowstone surface and consequently the intensity of CO2‐degassing, kinetic isotope enrichment and concomitant calcite precipitation. Drill core PFU6 provides an isotope record of the last ca. 3000 years at near‐annual resolution. A distinct phase of low C and O isotope values – interpreted as increased discharge and hence higher meteoric precipitation – occurred from ca. 300 to 140 a b2k (second half of the Little Ice Age) and another wet interval occurred around 700 a, corresponding to reported Medieval glacier advances. The Roman Warm Period was also dominated by relatively wet conditions, although significant decadal variability prevailed. Increased precipitation further characterized the intervals from ca. 2480 to 2430 and 2950 to 2770 a. Dry conditions persisted during the Medieval Climate Anomaly, although this trend towards reduced precipitation started earlier. The highest C isotope values of the last 2 ka are recorded around 750 a and another dry phase is centred at 1480 a. This new record shows that inter‐annual to decadal oscillations are a dominant mode of variation during the last 3 ka in the Alps. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

13.
Stable isotope data (δ18O, δ13C) were obtained for magnesite (MgCO3) from Holocene salt lake deposits of the Taoudenni–Agorgott basin, Mali, in which it is the only carbonate mineral present. The deposits have a high glauberite content (Na2Ca(SO4)2), representing a type of continental evaporite formation that is commonly magnesite‐bearing. Samples from seven different levels in a 5 m long sequence were analysed. δ18OV‐PDB values are between +3.17 and +5.91‰, which is lower than might be expected for evaporitic environments, recording reduced 18O enrichment at high salinity. δ13CV‐PDB values are between −1.32‰ and −4.79‰, showing an influence of carbon derived from the decomposition of organic matter rather than from exchange with atmospheric CO2. Covariance between δ18O and δ13C is strong for the lower part of the sequence, recording coupled 18O and 13C enrichment as commonly observed for closed basins. Covariance is lacking for the upper part of the sequence, with only periodic massive magnesite deposition in a more shallow lake. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

14.
The Gordon Group carbonates consist of biota of the Chlorozoan assemblage, diverse non‐skeletal grains and abundant micrite and dolomite, similar to those of modern warm water carbonates. Cathodoluminescence studies indicate marine, meteoric and some burial cements. Dolomites replacing burrows, mudcracks and micrite formed during early diagenesis.

δ18O values (‐5 to ‐7%ō PDB) of the non‐luminescent fauna and marine cement are lighter than those of modern counterparts but are similar to those existing within low latitudes during the Ordovician because of the light δ18O values of Ordovician seawater (‐3 to ‐5%o SMOW). The δ18O difference (2%o) between marine and meteoric calcite indicates that Ordovician meteoric water was similar to that in modern subtropics. Values of δ13C relative to δ18O indicate that during the Early Ordovician there were higher atmospheric CO2 levels than at present but during the Middle and Late Ordovician they became comparable with the present because of a change from ‘Greenhouse’ to glacial conditions. δ18O values of Late Ordovician seawater were heavier than in the Middle Ordovician mainly because of glaciation.

Dolomitization took place in marine to mixed‐marine waters while the original calcium carbonate was undergoing marine to meteoric diagenesis.  相似文献   

15.
Pedogenic goethites in each of two Early Permian paleosols appear to record mixing of two isotopically distinct CO2 components—atmospheric CO2 and CO2 from in situ oxidation of organic matter. The δ13C values measured for the Fe(CO3)OH component in solid solution in these Permian goethites are −13.5‰ for the Lower Leonardian (∼283 Ma BP) paleosol (MCGoeth) and −13.9‰ for the Upper Leonardian (∼270 Ma BP) paleosol (SAP). These goethites contain the most 13C-rich Fe(CO3)OH measured to date for pedogenic goethites crystallized in soils exhibiting mixing of the two aforementioned CO2 components. δ13C measured for 43 organic matter samples in the Lower Leonardian (Waggoner Ranch Fm.) has an average value of −20.3 ± 1.1‰ (1s). The average value yields a calculated Early Permian atmospheric Pco2 value of about 1 × PAL, but the scatter in the measured δ13C values of organic matter permits a calculated maximum Pco2 of 11 × PAL (PAL = present atmospheric level). Measured values of the mole fraction of Fe(CO3)OH in MCGoeth and SAP correspond to soil CO2 concentrations in the Early Permian paleosol profiles of 54,000 and 50,000 ppmV, respectively. Such high soil CO2 concentrations are similar to modern soils in warm, wet environments.The average δ13C values of pedogenic calcite from 9 paleosol profiles stratigraphically associated with MCGoeth (Waggoner Ranch Fm.) range from −6.5‰ to −4.4‰, with a mean δ13C value for all profiles of −5.4‰. Thus, the value of Δ13C between the pedogenic calcite data set and MCGoeth is 8.1 (±0.9)‰, which is in reasonable accord with the value of 7.7‰ expected if atmospheric Pco2 and organic matter δ13C values were the same for both paleosol types. Furthermore, the atmospheric Pco2 calculated for the Early Permian from the average measured carbon isotopic compositions of the paleosol calcite and organic matter is also analytically indistinguishable from 1 × PAL, with a maximum calculated atmospheric Pco2 (permitted by one standard deviation of the organic matter δ13C value) of ∼5 × PAL.If, however, measured average δ13C values of the plant organic matter are more positive than the original soil organic matter as a result of diagenetic loss of 13C-depleted, labile organic compounds, calculated Permian atmospheric Pco2 using these 13C-enriched organic values would underestimate the actual atmospheric Pco2 using either goethite or calcite. This is the first stratigraphically constrained, intrabasinal study to compare ancient atmospheric CO2 concentrations calculated from pedogenic goethite and calcite. These results demonstrate that the two different proxies record the same information about atmospheric CO2.The Fe(CO3)OH component in pedogenic goethite from a Triassic paleosol in Utah is significantly enriched in 13C relative to Fe(CO3)OH in goethites from soils in which there are mixtures of two isotopic CO2 components. Field-relationships and the δ13C value (−1.9‰) of the Triassic goethite indicate that this ancient paleosol profile experienced mixing of three isotopically distinct CO2 components at the time of goethite crystallization. The three components were probably atmospheric CO2, CO2 from in situ oxidation of organic matter and CO2 from in situ dissolution of preexisting calcite. Although mixing of three isotopically distinct CO2 components, as recorded by Fe(CO3)OH in goethite, has been described in modern soil, this is the first example from a documented paleosol. Its preservation affirms the need for careful, case-by-case assessment of ancient paleosols to establish that goethite in any particular soil is likely to be a valid proxy of atmospheric Pco2.  相似文献   

16.
The Pongkor gold–silver deposit is the largest low‐sulfidation epithermal precious metal deposit in Indonesia, and is of Pliocene age. The deposit consists of nine major subparallel quartz–adularia–carbonate veins with very low sulfide content. Vein infill records five paragenetic sequences, dominated by calcite in the early stage and quartz in the later stage of the hydrothermal evolution. Fluid inclusions in hydrothermal calcite and quartz of all stages indicate a temperature ranging from 180 to 220°C and a meteoric water origin (very low salinity close to 0 wt% NaCl equivalent). Carbon isotope data on calcite display a narrow range from ?6.5 to ?3.0‰δ13C. The oxygen isotope values have a wider range of +4.6 to +10.1‰δ18O. The broadly positive correlation of the δ13C versus δ18O plot suggests that the carbon species, which equilibrated during the formation of calcite, is dominated by H2CO3 not far from equilibrium with HCO3?. The abundance of rare earth and yttrium (REY) in carbonate samples is very low (>REY mostly <2 ppm). However, there is always a positive Eu anomaly, which indicates a deeper fluid reservoir at >250°C.  相似文献   

17.
The differentiated Mesozoic alkali dolerite Prospect Intrusion contains a wide range of secondary minerals, including carbonates (primarily calcite), laumontite, prehnite and heulandite, whose stability relationships imply a formation temperature of <200°C. The δ18O data for carbonates define a higher temperature (160 – 195°C) suite, and a lower temperature (51 – 73°C) suite. The δ13C, δ18O and 87Sr/86Sr isotope systematics for these carbonates suggest derivation of the higher temperature group from magmatic fluids, whereas the other group had a major meteoric component that probably originated from porewater in the country rock. Source fluids for prehnite were meteoric rather than magmatic in origin based on their δD and δ18O ratios. Early in the intrusion's emplacement, CO2-rich hydrothermal fluids formed a carbonate rind sealing the upper part of the hydrothermal system and produced the higher temperature carbonates (calcite) and laumontite. Later, cooler fluids with a meteoric component infiltrated vesicles and fractures, depositing the lower temperature carbonates (calcite, aragonite), heulandite and prehnite.  相似文献   

18.
Modern terrestrial speleothem-like calcareous deposits in streams draining a disused lime quarry on Black Mountain, South Wales have anomalously negative δ18O and δ13C compositions compared with other similar European deposits. Black Mountain water chemistry is unusual only in its locally very high pH (> 11.5) and carbonate ion concentrations. The high pH is caused by dissolution of lime spoil, resulting in high OH– concentrations. This high alkalinity causes uptake of atmospheric CO2 and strong fractionation of both carbon and oxygen stable isotopes, resulting in calcite precipitates with unusually negative isotopic compositions. Since shifts in δ18O of < 1° are highly significant for Holocene palaeoclimate reconstructions, depletions caused by hyperalkaline waters must be avoided. While extreme lime spoil contamination should be obvious, less heavily affected sites will record smaller fractionation effects and might escape detection. Even small depletions from low-level contamination will have large effects on palaeotemperatures based on carbonate crust δ18O values.  相似文献   

19.
The Neoproterozoic Doushantuo Formation on the Yangtze Platform, South China, documents a sedimentary succession with different sedimentary facies from carbonate platform to slope and to deep sea basin, and hosts one of the world-class phosphorite deposits. In these strata, exquisitely preserved fossils have been discovered： the Weng＇an biota. This study presents carbon isotope geochemistry which is associated paired carbonate and organic matter from the Weng＇an section of a carbonate platform （shelf of the Yangtze Platform, Guizhou Province） from the Songtao section and Nanming section of a transition belt （slope of the Yangtze Platform, Guizhou Province） and from the Yanwutan section （basin area of the Yangtze Platform, Hunan Province）. Environmental variations and bio-events on the Yangtze Platform during the Late Neoproterozoic and their causal relationship are discussed. Negative carbon isotope values for carbonate and organic carbon （mean δ^13Corg = -35.0‰） from the uppermost Nantuo Formation are followed by an overall increase in δ^13C up-section. Carbon isotope values vary between -9.9‰ and 3.6‰ for carbonate and between -35.6‰ and -21.5‰ for organic carbon, respectively. Heavier δ^13Ccarb values suggest an increase in organic carbon burial, possibly related to increasing productivity （such as the Weng＇an biota）. The δ^13C values of the sediments from the Doushantuo Formation decreased from the platform via the slope to basin, reflecting a reduced environment with minor dissolved inorganic carbon possibly due to a lower primary productivity. It is deduced that the classical upwelling process, the stratification structure and the hydrothermal eruption are principally important mechanisms to interpret the carbon isotopic compositions of the sediments from the Doushantuo Formation.  相似文献   

20.
In this study, we investigate the geochronological, geochemical and isotopic characteristics of two travertine sites surrounded by Quaternary eruption centres in central Anatolia with ample palaeo-eruption records. High-resolution carbonate precipitation records, revealed by U-Th dating, are clustered around 5–35, 60–100 and 120–170 ka and are well correlated with the dataset on eruptions as well as the position of fractures related to the volcanic centres. Syn-eruptive carbonate precipitation seems to occur due to the circulation of CO2-rich fluids along the extensional fracture systems aligned tangentially to the related volcanic conduit and, therefore, the study of this system could be an alternative technique for the reconstruction of palaeo-eruptions. δ18O values of the studied travertines are within the range of meteogene fluids. Oxygen isotope compositions at around 130 ka match well with Glacial Termination II that is also recorded by climate proxies in various cave and benthic deposits throughout the world. It is likely that the studied carbonates were precipitated under similar fluid circulation conditions which are represented by a high rate of dilatation followed by a meteoric water influx into the extensional fractures.  相似文献   

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