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1.
We evaluate the impact of exceptionally sparse plant cover (0-20%) and rainfall (2-114 mm/yr) on the stable carbon and oxygen composition of soil carbonate along elevation transects in what is among the driest places on the planet, the Atacama Desert in northern Chile. δ13C and δ18O values of carbonates from the Atacama are the highest of any desert in the world. δ13C (VPDB) values from soil carbonate range from −8.2‰ at the wettest sites to +7.9‰ at the driest. We measured plant composition and modeled respiration rates required to form these carbonate isotopic values using a modified version of the soil diffusion model of [Cerling (1984) Earth Planet. Sci. Lett.71, 229-240], in which we assumed an exponential form of the soil CO2 production function, and relatively shallow (20-30 cm) average production depths. Overall, we find that respiration rates are the main predictor of the δ13C value of soil carbonate in the Atacama, whereas the fraction C3 to C4 biomass at individual sites has a subordinate influence. The high average δ13C value (+4.1‰) of carbonate from the driest study sites indicates it formed—perhaps abiotically—in the presence of pure atmospheric CO2.δ18O (VPDB) values from soil carbonate range from −5.9‰ at the wettest sites to +7.3‰ at the driest and show much less regular variation with elevation change than δ13C values. δ18O values for soil carbonate predicted from local temperature and δ18O values of rainfall values suggest that extreme (>80% in some cases) soil dewatering by evaporation occurs at most sites prior to carbonate formation. The effects of evaporation compromise the use of δ18O values from ancient soil carbonate to reconstruct paleoelevation in such arid settings.  相似文献   

2.
Surface carbonate and land-derived deposits in the sea off southern Chile were investigated for their mineralogical and geochemical composition. The data were related to environmental features and compared with those of similar temperate and polar carbonate deposits from Tasmania, New Zealand, Arctica, and Antarctica. The mineralogy of the siliciclastic fraction is typical of cold areas and is mainly composed of chlorite, mica, quartz, feldspars and amphibole. The CaCO3 content varies from 30 to 90%; carbonate mineralogy is made up of low-Mg calcite, high-Mg calcite and minor amounts of aragonite. The Ca, Mg, Sr, Fe, and Mn contents of bulk carbonates and some selected skeletal hard parts are comparable to those of carbonates from Tasmania. The elemental composition is mainly related to carbonate mineralogy, skeletal components, and seawater conditions. The δ13C and δ18O values of carbonates are positive, and their field falls between the “seafloor diagenesis” and “upwelling water” trend lines, because the sediments are likely to be in equilibrium with waters of Antarctic origin. The mineralogical, elemental, and isotopic compositions of carbonates from southern Chile show better similarities with the “temperate” carbonates from Tasmania and New Zealand than with the “polar” carbonates from Arctica and Antarctica. Carbonate deposition is allowed by the low terrigenous input, the low SPM concentration and, probably, the upwelling of seawater from Antarctica.  相似文献   

3.
《Quaternary Science Reviews》2007,26(11-12):1670-1689
Given the growing interest in carbonate deposits from polar regions as paleoclimatic proxies, this review paper first provides a classification of the various types of cold-climate carbonate precipitates followed by a summary of the 13C and 18O composition of the carbonate deposits and parent water from which the carbonates precipitated. The cold-climate carbonate precipitates were classified into three broad categories: powders, crusts and speleothem. The carbonate powders include those that precipitated in relation to aufeis aggradation (cryogenic aufeis calcite) and in relation to the growth of various annual/perennial ice formations in freezing caves (cryptocrystalline calcite and calcite pearls). The carbonate crusts can be further subdivided based on their lithic environment; those that precipitated on the upper surface of bedrock/clasts (i.e. subglacially precipitated calcite and evaporative calcite crusts); those that are located on the underside of clasts (i.e. pedogenic carbonates); and those that precipitated in rock outcrop fissures (i.e. endostromatolites). The cold-climate carbonate precipitates have a highly variable isotopic composition with δ18O values ranging between −6.5‰ and 28‰ VSMOW and δ13C values in the −10–20‰ VPDB range. However, each type of carbonate precipitates has a specific δ13C and δ18O range, suggesting that their environmental setting and the mechanism by which they formed controls their 13C and 18O signature. It was found that carbonate deposits that precipitated under equilibrium physico-chemical conditions had a δ13C value that is in equilibrium with that of the parent water, while its δ18O composition was more variable, as it is in part controlled by the temperature of reaction and by the δ18O and calcite saturation state of the parent water. By contrast, the δ18O composition of biologically precipitated carbonate deposits (endostromatolites) reflect that of the parent water, while its δ13C composition was enriched over that of the parent water due to bacterial methanogenesis. In the case of kinetically precipitated carbonate deposits, the δ18O and δ13C values are out-of-equilibrium relative to that of the parent water due to the faster rate of reaction.  相似文献   

4.
The evolution of carbonate groundwaters may occur in a so-called open or closed system or under conditions between the extremes. In order to distinguish between the cases the chemistry of the water and the carbon isotope composition of the dissolved carbonate, the carbonate rock and the soil CO2 of the recharge area must be known. Model calculations based on measurements of the above parameters show that ground-waters in the “Schwäbische Alb”, Federal Republic of Germany, are evolved essentially under closed-system conditions. The average measured carbon isotope composition of the water is δ 13C = ?13.7%0 vs. calculated values of δ 13C = ?13.5%0 and δ 13C = ?18.5%0 assuming a closed and an open system, respectively. In model calculations for closed-system conditions the origin of sulfate ions has to be considered.  相似文献   

5.
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   

6.
Stable isotopes were measured in the carbonate and organic matter of palaeosols in the Somma–Vesuvius area, southern Italy in order to test whether they are suitable proxy records for climatic and ecological changes in this area during the past 18000 yr. The ages of the soils span from ca. 18 to ca. 3 kyr BP. Surprisingly, the Last Glacial to Holocene climate transition was not accompanied by significant change in δ18O of pedogenic carbonate. This could be explained by changes in evaporation rate and in isotope fractionation between water and precipitated carbonate with temperature, which counterbalanced the expected change in isotope composition of meteoric water. Because of the rise in temperature and humidity and the progressive increase in tree cover during the Holocene, the Holocene soil carbonates closely reflect the isotopic composition of meteoric water. A cooling of about 2°C after the Avellino eruption (3.8 ka) accounts for a sudden decrease of about 1‰ in δ18O of pedogenic carbonate recorded after this eruption. The δ13C values of organic matter and pedogenic carbonate covary, indicating an effective isotope equilibrium between the organic matter, as the source of CO2, and the pedogenic carbonate. Carbon isotopes suggest prevailing C3 vegetation and negligible mixing with volcanogenic or atmospheric CO2. Copyright © 2000 John Wiley & Sons, Ltd.  相似文献   

7.
C and O isotope composition of Middle-Upper Miocene and Lower Pliocene carbonates from Kerch-Taman Region (Eastern Paratethys) have been studied in order to reconstruct palaeoenvironmental variability and post-sedimentation changes. The δ13C and δ18О values of the Upper Sarmatian to Lower Pliocene organogenic carbonates reflect the desalinization of paleobasins, global Late Miocene Cooling, and increase in seasonal temperature fluctuations. Isotopic composition of the Middle Sarmatian organogenic carbonates was strongly influenced by evaporation processes, high bioproductivity, and local submarine methane emissions. Warm climate and low bioproductivity together with unstable hydrological regime during the Late Chokrakian and the Karaganian times influenced the isotope composition of primary carbonates. Calcite shell of Spiratella sp. (δ13C =–0.4‰ and δ18О =–0.4‰) from Tarkhanian sediments was formed in warm marine environment. Dolomitization prevails over other secondary mineralization in the studied carbonate rocks. Two groups of secondary dolomites that are characterized by negative and positive δ13C values have been recognized. Lowe δ13C values (up to–31.4‰) in dolomites indicate the influence of both dissolved inorganic carbon (DIC) from oxidized organic matter (Сorg) and methane. Dolomites with positive δ13C values (7.0 and 7.8‰) associat with migration of CO2- and CH4-containing saline groundwater.  相似文献   

8.
The first detailed isotope-geochemical study of carbonate deposits has been performed in the Lower Famennian stratotype section of the northwestern Kuznetsk Basin (Kosoy Utyos), which was localized in the middle latitudes of the Northern Hemisphere in the Late Devonian. The δ13Ccarb, δ13Corg, and δ18O variation curves were constructed for the section deposits. Geochemical and petrographic studies of carbonates allowed allocation of samples that underwent postsedimentation alteration and exclude them from further interpretation. Compared with coeval sections in the other world's regions, the Kosoy Utyos section is characterized by higher δ13Ccarb values, up to 5.4‰, whereas the maximum value in subequatorial area sections is 4‰. The isotope shift amplitude of the studied section reaches 4.6‰, which is 1.5‰ higher than those in other regions. The δ18O values are 3‰ lower than the ones of the world's coeval sections. The results obtained show that δ13C and δ18O variation trends differ from those of coeval subequatorial sections. The high shift amplitude and maximum δ13Ccarb values in the Kosoy Utyos section are due to the shallow-water carbonate sedimentation environments on the Siberian continental shelf and, probably, the lower temperatures of waters in the middle latitudes as compared with the subequatorial areas.  相似文献   

9.
Authigenic carbonates were sampled in piston cores collected from both the Tunica Mound and the Mississippi Canyon area on the continental slope of the northern Gulf of Mexico during a Marion Dufresne cruise in July 2002. The carbonates are present as hardgrounds, porous crusts, concretions or nodules and shell fragments with or without carbonate cements. Carbonates occurred at gas venting sites which are likely to overlie gas hydrates bearing sediments. Electron microprobe, X-ray diffraction (XRD) and thinsection investigations show that these carbonates are high-Mg calcite (6–21 mol% MgCO3), with significant presence of framboidal pyrite. All carbonates are depleted in 13C (δ13C = − 61.9 to − 31.5‰ PDB) indicating that the carbon is derived mainly from anaerobic methane oxidation (AMO). Age estimates based on 14C dating of shell fragments and on regional sedimentation rates indicate that these authigenic carbonates formed within the last 1000 yr in the Mississippi Canyon and within 5500 yr at the Tunica Mound. The oxygen isotopic composition of carbonates ranges from + 3.4 to + 5.9‰ PDB. Oxygen isotopic compositions and Mg2+ contents of carbonates, and present in-situ temperatures of bottom seawater/sediments, show that some of these carbonates, especially from a core associated with underlying massive gas hydrates precipitated in or near equilibrium with bottom-water. On the other hand, those carbonates more enriched in 18O are interpreted to have precipitated from 18O-rich fluids which are thought to have been derived from the dissociation of gas hydrates. The dissociation of gas hydrates in the northern Gulf of Mexico within the last 5500 yr may be caused by nearby salt movement and related brines.  相似文献   

10.
Morphological characters and multi-element isotopic compositions of carbonates from the loess-paleosol sequences in Northwestern China are examined to explore the origin of the minerals. Samples are collected from various sections ranging from Holocene to 0.9 Ma within the sequences and fractions with grain sizes >45 and <2 μm are separated from the bulk soil and examined by SEM and TEM. The results show that the grains >45 μm exhibit an almost perfect spherical shape while those <2 μm are dominated by nano-rods having diameters of 30-50 nm and lengths of 0.3-2 μm, presumably indicating the detrital origin of the coarse fractions and the authigenic characters of the fine ones. Such implications are corroborated by the multi-elemental isotopic compositions of the carbonate minerals. A comparison of the δ13C and δ18O values between minerals and biologically originated samples indicates that the <2 μm fractions have a similar composition to those of coexisting land snail shells. Additional differences between the two size fractions also manifest in the ratios of 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb, and 87Sr/86Sr. These results suggest the utility of fine carbonate particles in the soil profile in reconstructing a potentially higher resolution δ13C and δ18O time series to elucidate the paleoclimatic fluctuation in the Chinese Loess Plateau during Pleistocene. The discovery of the nano-rod calcite in Chinese loess, together with previous findings of the similar mineral form in Asian dust, strongly suggests the possibility that these highly reactive CaCO3 form may alter the aerosol properties during transport.  相似文献   

11.
Sequences of laminated limestones found within thin Carboniferous carbonate strata of northeastern Kentucky were studied to determine their origin and palaeo-environmental significance. These laminated zones are strikingly similar to Holocene and Pleistocene surficial calcareous crusts (caliche) profiles that occur in various parts of the world. Carboniferous laminated carbonates are associated with shallow marine carbonate units, palaeokarst, and overlying palaeosol zones. A typical laminated profile ranges in thickness from 1 to 2 m and contains brecciated, light olive-grey to brown micrite that lacks distinctive bedding. Structures and textures common in most profiles include: (1) calcareous and silicious laminae (laminae form diffuse, alternating light and dark bands that generally parallel bedding but often fill fractures and vugs within the rocks); (2) particles (allochems, and micrite and microspar fragments) coated by brown microcrystalline calcite; (3) brecciated texture; (4) circular to elliptical fossil moulds (occur in sinuous patterns and fill fractures within the rocks); (5) large and small scale fracture patterns. Subaerial weathering and vadose diagenesis of carbonate mud banks or islands is suggested as a mechanism for the formation of these Carboniferous calcareous crust profiles. These ‘crusts’ formed by a combination of solution (karsting), brecciation, and soil development that transformed an exposed marine biomicrite (‘host’ rock) into a porous subsoil rubble. Laminated ‘crusts’ and coated particles developed as the result of dissolution and reprecipitation of CaCO3 and SiO3 from the soil and carbonate bedrock. Carboniferous laminated carbonates in northeastern Kentucky are often referred to as ‘algal limestones’ because of their superficial similarity to some modern and ancient algal structures. This study, however, reveals numerous characteristics that can only be explained by diagenesis in a subaerial environment.  相似文献   

12.
《International Geology Review》2012,54(15):1909-1921
This paper reports the carbon and oxygen isotope compositions of lacustrine carbonate sediments from the Palaeogene Shahejie Formation, Qikou depression, Bohaiwan Basin, with the aim of determining the palaeoenvironmental conditions in the region. Results from Es2, the second member of the Shahejie Formation, showed values of δ13C and δ18O from –1.2‰ to +2.4‰ (average +0.6‰) and from –6.8‰ to –4.7‰ (average –5.7‰), respectively, suggesting a relatively hot climate attending deposition. The slightly closed nature of the lake, which contains brackish water, resulted in higher carbonate δ13C and δ18O values than in a meteoric environment. The values of δ13C and δ18O preserved within the carbonates of the overlying lower Shahejie I (Es1) varied between +1.3‰ and +4.9‰ (average +3.2‰) and from ?4.4‰ to ?1.8‰ (average ?3.1‰), respectively, indicating that the climate became colder at that time. Subsequently, a marine transgression caused the salinity of the lake water to increase. The values of δ13C and δ18O were controlled by salinity. The high δ13C values were also influenced by the rapid burial of the lake organisms and by algal photosynthesis. Values of δ13C and δ18O from carbonates in upper Es1 ranged from ?8.0‰ to +11.0‰ (average +10.1‰) and from ?5.0‰ to ?1.5‰ (average ?3.4‰), respectively, indicating a slight increase in the temperature over time. In the closed and reducing environment, extremes in δ13C values resulted from biochemical fermentation. The positive δ13C excursion recorded in the carbonates of the Shahejie Formation in the Qikou depression indicates that the palaeoclimate underwent a significant transformation during the Eocene and the Oligocene.  相似文献   

13.
Radiocarbon and 230Th-234U dates of calcic horizons from calciorthid soil profiles in the Mojave Desert were used to calculate the rate of deposition of pedogenic CaCO3. A major period of CaCO3 deposition appears to have occurred about 20000 yBP forming calcic horizons below 100-cm depth during a climatic regime with greater effective rainfall than in the present. The overall rate of deposition has been 1.0 to 3.5 g CaCO3/m2/yr during soil formation. This rate is consistent with present-day rates, assuming that the atmospheric deposition of Ca limits the process. Stable isotope ratios in calcic horizons indicate that CaCO3 precipitated from a soil environment with CO2 of ? 15.5%. 13C12C (vs. PDB) and H2O of + 2.0%. 18O16O (vs. SMOW). These values suggest that CaCO3 precipitates when seasonal drought simultaneously lowers soil pore pCO2 and enriches soil water 18O by evaporation. The role of soil calcic horizons in the global geochemical cycle of carbon is discussed.  相似文献   

14.
UWE BRAND 《Sedimentology》1982,29(1):139-147
The aragonitic molluscs and lime-mud of the Pennsylvanian Buckhorn asphalt (Deese Group) of southern Oklahoma precipitated calcium carbonate in oxygen and carbon isotopic equilibrium with ambient sea-water. In addition, δ18O values indicate that the pelecypods precipitated their shells during the warmer months of the year. The coiled nautiloids probably precipitated their shells in the warm surface water and throughout the year. For the orthocone nautiloids, the δ18O values suggest that they precipitated their shells in deeper/cooler water. The low-Mg calcite brachiopods of the Mississippian Lake Valley Formation of New Mexico precipitated shells in oxygen and carbon isotopic equilibrium with ambient sea-water. The δ18O and δ13C values of the Buckhorn and Lake Valley faunas, in conjunction with other published results, suggest that Carboniferous sea-water was, on a average, depleted in δ18O by 1·5 ± 2‰, PDB, relative to Recent sea-water. However, the δ13C value of +2.6 ± 2‰, PDB, for average Carboniferous sea-water is similar to that of Recent ocean water. Early diagenetic alteration of metastable carbonates probably occurs in a meteoric-sea-water mixing zone. In this zone the oxygen and carbon isotopic compositions of these components are increased by about 2-4‰, PDB over their marine composition.  相似文献   

15.
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   

16.
A reassessment of the abundance of dolomite in carbonate sediments has confirmed that carbonates deposited during the past 150 Ma contain, on average, less dolomite than Proterozoic and Paleozoic carbonates. The lower dolomite content of the more recent carbonate sediments results from the increase in the deposition of CaCO3 in deep-sea sediments, and to the difficulty of dolomitizing deep-sea CaCO3 by reaction with cold, unevaporated seawater. The decrease in the rate of dolomite formation during the past 150 Ma has led to an increase in the output of oceanic Mg+2 by the reaction of seawater with clay minerals and with ocean-floor basalts. The increase in the output of marine Mg+2 into these reservoirs has been brought about by an increase in the Mg+2 concentration of seawater. During the past 40 Ma, the concentration of Mg+2 in seawater has probably increased by ～18 mmol/kg, and probably has been accompanied by an equimolar increase in the concentration of SO4?2.  相似文献   

17.
The oxygen (δ18O, δ17O) and carbon (δ13C, FMOD14C-the fraction of modern 14C) isotopic compositions of carbonate were measured for a set of paired Antarctic CM chondrites (EET 96006, EET 96016, EET 96017, and EET 96019). While the oxygen isotopic compositions do not plot on the terrestrial fractionation line and indicate that a component of the carbonate minerals has an extraterrestrial origin, they also do not fall on the array defined for carbonates by CM falls and are thus consistent with the presence of a terrestrial carbonate component. The δ13C and FMOD14C measurements of carbonate suggest the presence of at least two carbon sources: carbonate derived from atmospheric CO2 that is inferred to have been produced as a result of silicate weathering reactions and carbonate derived from another carbon source that is either old or non-atmospheric. The relationships between oxygen and carbon isotope data provide additional constraints on the weathering process, and allow the possibility that rock-dominated weathering of the meteorite caused the oxygen isotopic composition of Antarctic water added to the meteorite to evolve away from the terrestrial mass-fractionation array, leading to formation of low temperature terrestrial alteration products that do not lie on the terrestrial fractionation line.  相似文献   

18.
Purbeckian (lowermost Cretaceous) peritidal carbonates are characterized by open marine, lagoonal, intertidal and lacustrine facies arranged in Milankovitch-type shallowing upward sequences. Shallowing upward sequences typically consist of 2–6 individual beds. The sequences may be (i) complete, (ii) incomplete or (ii) pedogenetically overprinted, reflecting the duration of subaerial exposure and/or the extent of erosion and pedogenetic modification at the cycle tops. The stable isotopic composition of the peritidal micrites reveals homogenous δ18O values attributed to diagenetic stabilization in a meteoric, water-buffered system. Carbon isotopes show three distinctly different carbon isotope patterns dependent on the completeness of the shallowing upward sequences. Complete shallowing upward sequences consist of 4–6 individual carbonate beds. The carbon isotope values show a facies-dependent pattern: open marine carbonate muds record enriched δ13C values of +0·28‰ while lagoonal (−0·82‰), intertidal (−2·46‰) and lacustrine micrites (−2·96‰) are increasingly depleted. This distinct pattern is explained by carbonate mud deposition in environments of differing salinity and marine influence. Incomplete sequences (2–5 carbonate beds) are characterized by depleted δ13C values below subaerial exposure surfaces that become progressively enriched in 13C with increasing depth. Pedogenetically overprinted sequences (1–3 carbonate beds) show strong 13C depletion throughout the sequence with little variation in the carbon isotopic composition. The depleted values (−4·5‰) of the pedogenetically altered micrites suggest that modification during subaerial exposure was associated with equilibration with meteoric solutions enriched in isotopically light soil gas CO2. The duration of subaerial exposure is the most crucial factor determining the extent of pedogenetic alterations, the completeness of the shallowing upward sequences and the carbon isotope pattern. The recorded patterns clearly illustrate that micrites have a good potential for the preservation of their primary carbon isotopic composition if the duration of subaerial exposure is rather brief. Otherwise, the recorded carbon isotope patterns may support sequence stratigraphic analysis by providing a refinement of the time-stratigraphic interpretation.  相似文献   

19.
The oxygen (δ18Oc) and carbon (δ13Cc) isotope compositions of the structural carbonate group (CO3) in apatites from lateritic profiles were investigated. The weathering profiles, located in southern Brazil and in western Senegal, are developed on three different types of apatite-rich parent rock: carbonatite, metamorphosed marine phosphorite and sedimentary marine phosphorite. The parent rock apatites are of magmatic, hydrothermal, metamorphic and sedimentary origins. The in situ formation of apatite of weathering origin in the profiles is well documented petrographically and geochemically.The overall range of measured δ18Oc and δ13Cc values of apatites of weathering origin (22 to 27 SMOW for δ18Oc and −15 to −10 PDB for δ13Cc) is much smaller than the range of measured and/or published isotope compositions of parent rock apatites (4–35 for δ18Oc and −11 to +1 for δ13Cc). In any profile, the apatites of weathering origin can exhibit lower, similar or higher δ18Oc values than parent rock apatites. In contrast, their δ13Cc values are systematically and significantly lower than those of the parent rock apatites. Apatites formed as a result of weathering in laterites can therefore be readily distinguished from apatites of other origin on the basis of their isotope composition.Assuming that apatite CO3 fractionates O in a way similar to calcite CO3, the structural carbonate group of the apatites of weathering origin appears to form in approximate isotopic equilibrium with the weathering solutions. The very low δ13Cc values exhibited by these apatites indicate that the dominant sources of dissolved CO2 in the soil water are organic. The isotope composition of structural carbonate in apatite of weathering origin in lateritic profiles may provide useful information for paleoenvironmental studies.  相似文献   

20.
The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ18O. Interpreting speleothem δ18O records in terms of absolute paleotemperatures and δ18O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ47 (a geochemical variable reflecting the statistical overabundance of 13C18O bonds in CO2 evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ47 value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation.Here we report Δ47 values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ47 and heavier δ18O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ47 disequilibrium and that of δ18O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ18O and Δ47 values, probably inherited from prior degassing within the cave system.In addition to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ47 in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ47 in inorganic carbonates.  相似文献   

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