Diagenetic overprinting of the sphaerosiderite palaeoclimate proxy: are records of pedogenic groundwater δ18O values preserved?

Meteoric sphaerosiderite lines (MSLs), defined by invariant δ¹⁸O and variable δ¹³C values, are obtained from ancient wetland palaeosol sphaerosiderites (millimetre‐scale FeCO₃ nodules), and are a stable isotope proxy record of terrestrial meteoric isotopic compositions. The palaeoclimatic utility of sphaerosiderite has been well tested; however, diagenetically altered horizons that do not yield simple MSLs have been encountered. Well‐preserved sphaerosiderites typically exhibit smooth exteriors, spherulitic crystalline microstructures and relatively pure (> 95 mol% FeCO₃) compositions. Diagenetically altered sphaerosiderites typically exhibit corroded margins, replacement textures and increased crystal lattice substitution of Ca²⁺, Mg²⁺ and Mn²⁺ for Fe²⁺. Examples of diagenetically altered Cretaceous sphaerosiderite‐bearing palaeosols from the Dakota Formation (Kansas), the Swan River Formation (Saskatchewan) and the Success S2 Formation (Saskatchewan) were examined in this study to determine the extent to which original, early diagenetic δ¹⁸O and δ¹³C values are preserved. All three units contain poikilotopic calcite cements with significantly different δ¹⁸O and δ¹³C values from the co‐occurring sphaerosiderites. The complete isolation of all carbonate phases is necessary to ensure that inadvertent physical mixing does not affect the isotopic analyses. The Dakota and Swan River samples ultimately yield distinct MSLs for the sphaerosiderites, and MCLs (meteoric calcite lines) for the calcite cements. The Success S2 sample yields a covariant δ¹⁸O vs. δ¹³C trend resulting from precipitation in pore fluids that were mixtures between meteoric and modified marine phreatic waters. The calcite cements in the Success S2 Formation yield meteoric δ¹⁸O and δ¹³C values. A stable isotope mass balance model was used to produce hyperbolic fluid mixing trends between meteoric and modified marine end‐member compositions. Modelled hyperbolic fluid mixing curves for the Success S2 Formation suggest precipitation from fluids that were < 25% sea water.     

Subaerial exposure and deposition of shallowing upward sequences: evidence from stable isotopes of Purbeckian peritidal carbonates (basal Cretaceous), Swiss and French Jura Mountains

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.     

An alternative model for positive shifts in shallow-marine carbonate δ13C and δ18O

Abstract Positive shifts in global seawater δ¹³C_DIC 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.     

Carbon and oxygen isotope compositions of the carbonate facies in the Vindhyan Supergroup, central India

The Vindhyan sedimentary succession in central India spans a wide time bracket from the Paleoproterozoic to the Neoproterozoic period. Chronostratigraphic significance of stable carbon and oxygen isotope ratios of the carbonate phase in Vindhyan sediments has been discussed in some recent studies. However, the subtle controls of facies variation, depositional setting and post-depositional diagenesis on stable isotope compositions are not yet clearly understood. The Vindhyan Supergroup hosts four carbonate units, exhibiting a wide variability in depositional processes and paleogeography. A detailed facies-specific carbon and oxygen isotope study of the carbonate units was undertaken by us to investigate the effect of these processes and to identify the least altered isotope values. It is seen that both carbon and oxygen isotope compositions have been affected by early meteoric water diagenesis. The effect of diagenetic alteration is, however, more pronounced in case of oxygen isotopes than carbon isotopes. Stable isotope compositions remained insensitive to facies only when sediments accumulated in a shallow shelf setting without being exposed. Major alteration of original isotope ratios was observed in case of shallow marine carbonates, which became exposed to meteoric fluids during early diagenetic stage. Duration of exposure possibly determined the magnitude of alteration and shift from the original values. Moreover, dolomitization is found to be accompanied by appreciable alteration of isotope compositions in some of the carbonates. The present study suggests that variations in sediment depositional settings, in particular the possibility of subaerial exposure, need to be considered while extracting chronostratigraphic significance from δ¹³C data.     

Isotopic signature of burial diagenesis and primary lithological contrasts in periplatform carbonates (Miocene, Great Bahama Bank)

The stable isotope geochemistry of Miocene sediments from the leeward margin of the Great Bahama Bank was examined to investigate burial diagenetic processes in periplatform carbonates. Data indicate that, in addition to differences in bulk proportions of neritic and pelagic carbonate along the slope, rhythmic variation in primary carbonate content has controlled patterns of burial diagenesis and associated geochemical signatures throughout much of the succession examined. The present study focuses on Ocean Drilling Program Sites 1006 and 1007, the most distal of five sites drilled from marginal to deep basin environments during Leg 166. These Miocene sections are characterized by their cyclic appearance, manifest as decimetre‐ to metre‐scale alternations between light‐coloured ooze/chalk/limestone and dark‐coloured marl/marlstone. The section at Site 1006 contains a high proportion of pelagic carbonate and is unlithified to a subbottom depth of ～675 m. Fluctuations in δ¹⁸O and δ¹³C values at this site are independent of lithological variation and reflect primary conditions. At Site 1007, located at the toe‐of‐slope and composed of a mixture of bank‐derived and pelagic carbonate, limestones are densely cemented, show little evidence of compaction and have δ¹⁸O values up to 2‰ higher than coeval sediments at Site 1006. Marlstones at Site 1007 are poorly cemented, exhibit an increase in compaction‐related features with depth and have lower and more variable δ¹⁸O values that are similar to those of coeval sediments at Site 1006. Isotopic and petrographic characteristics of limestone interbeds result from cement precipitation from cold sea water during the first ～100 m of burial. Higher proportions of insoluble materials and pelagic carbonate seem to have inhibited diagenetic alteration in adjacent marlstones; in spite of significant compaction and pressure solution during burial, original isotopic compositions appear to be best preserved in these intervals at Site 1007. The documented contrasts in petrographic and isotopic patterns illustrate the role of primary sediment composition in controlling lithification processes in periplatform carbonates and stress the importance of considering such factors when interpreting geochemical data from ancient shelf and slope limestones.     

Lithofacies associations and stable isotopes of palustrine and calcrete carbonates: examples from an Indian Maastrichtian regolith

Detailed information on semi‐arid, palustrine carbonate–calcrete lithofacies associations in a sheetwash‐dominated regolith setting is sparse. This is addressed by studying the Lower Limestone of the Lameta Beds, a well‐exposed Maastrichtian regolith in central India. The general vertical lithofacies assemblage for this unit comprises: (a) basal calcareous siltstones and marls with charophytes, ostracods and gastropods; (b) buff micritic limestones associated in their upper parts with calcretized fissure‐fill sandstones; (c) sheetwash as fissure‐fill diamictites and thin pebbly sheets, locally developed over a few metres; and (d) sandy, nodular, brecciated and pisolitic calcretes at the top. The sequence is ‘regressive’, with upsection filling of topographic lows by increased sheetwash. Lateral lithofacies change is marked, but there are no permanent open‐water lake deposits. In topographic lows close to the water table, marshy palustrine or groundwater calcretes formed, whereas on better drained highs, brecciation and calcretization occurred. Prolonged exposure is implied, suggesting that shrinkage was the main cause of brecciation. Evidence for rhizobrecciation and other biological calcrete fabrics is sparse, contrasting with the emphasis on root‐related brecciation in many studies of palustrine lithofacies. Stable isotope (δ¹⁸O and δ¹³C) values are consistent with the palustrine limestones being fed from meteoric‐derived groundwater with a strong input of soil‐zone carbon. There is overlap of both δ¹⁸O and δ¹³C values from the various palustrine and calcrete fabrics co‐occurring at outcrop. This suggests that, in groundwater‐supported wetlands, conversion from palustrine carbonate to calcrete need not show isotopic expression, as the groundwater source and input of soil‐zone carbon are essentially unchanged. Cretaceous–Tertiary δ¹⁸O and δ¹³C values from palustrine lithofacies and associated calcretes appear to be strongly influenced by the inherited values from lakes and wetlands. Hydrologically closed lakes and marine‐influenced water bodies tend to result in low negative palustrine δ¹⁸O and δ¹³C values. During brecciation and calcretization, the degree of isotopic inheritance depends on whether or not alteration occurs in waters that are different from those of the original water body or wetland. Marked biological activity (e.g. rhizobrecciation or root mat development) during calcretization may lower δ¹³C values where C₃ plants are abundant but, in shrinkage‐dominated systems, δ¹³C values will be largely inherited from the palustrine limestones.     

Lacustrine carbonates and pedogenesis: sedimentology and origin of palustrine deposits from the Early Cretaceous Rupelo Formation, W Cameros Basin, N Spain

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.     

Isotope geochemistry of caliche developed on basalt

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.     

Microfacies and geochemistry of the Ilam Formation in the Tang-E Rashid area, Izeh, S.W. Iran

The Ilam Formation (Santonian–Campanian in age), part of the Bangestan Group, is disconformably overlain by the Sarvak Formation and underlain by the Gurpi Formation in the Tang-E Rashid, Peyon area, Izeh (Zagros), southwest of Iran.Facies analyses indicate that the Ilam carbonates formed in four microfacies belts: tidal flat, lagoon, shoal and open marine, in a platform ramp environment. Major and minor elements and carbon and oxygen isotope values were used to determine the original carbonate mineralogy of the Ilam Formation. Petrographic evidence and elemental and oxygen and carbon isotope values indicate that aragonite was the original carbonate mineralogy in the Ilam Formation. The elemental and isotopic compositions of the Ilam carbonates also illustrate that they have stabilized in the marine phreatic environment. Variations of Sr/Ca and δ¹⁸O values versus Mn suggest that diagenetic alteration occurred in a closed system. Temperature calculation based on the oxygen isotope value of the least-altered sample indicates that the very early shallow burial fluid temperature was around 28 °C.Recognition of the exact boundary between the Ilam and Sarvak Formations is difficult, due to similar lithologies and the absence of the Surgah Formation in the study area. However, elemental and oxygen and carbon isotope analysis were used to determine the boundary between these formations. The δ¹⁸O and δ¹³C values, along with elemental results, clearly indicate a subaerial exposure surface, below which meteoric diagenesis affected the sediments.     

Carbon,oxygen and strontium isotope geochemistry of Proterozoic carbonate rocks of the Vindhyan Basin,central India

Carbon, oxygen and strontium isotope compositions of carbonate rocks of the Proterozoic Vindhyan Supergroup, central India suggest that they can be correlated with the isotope evolution curves of marine carbonates during the latter Proterozoic. The carbonate rocks of the Lower Vindhyan Supergroup from eastern Son Valley and central Vindhyan sections show δ¹³C values of ∼0‰ (V-PDB) and those from Rajasthan section are enriched up to +2.8‰. In contrast, the carbonate rocks of the Upper Vindhyan succession record both positive and negative shifts in δ¹³C compositions. In the central Vindhyan section, the carbonates exhibit positive δ¹³C values up to +5.7‰ and those from Rajasthan show negative values down to –5.2‰. The δ¹⁸O values of most of the carbonate rocks from the Vindhyan Supergroup show a narrow range between –10 and –5‰ (V-PDB) and are similar to the ‘best preserved’ ¹⁸O compositions of the Proterozoic carbonate rocks. In the central Vindhyan and eastern Son Valley sections, carbonates from the Lower Vindhyan exhibit best-preserved ⁸⁷Sr/⁸⁶Sr compositions of 0.7059±6, which are lower compared to those from Rajasthan (0.7068±4). The carbonates with positive δ¹³C values from Upper Vindhyan are characterized by lower ⁸⁷Sr/⁸⁶Sr values (0.7068±2) than those with negative δ¹³C values (0.7082±6). A comparison of C and Sr isotope data of carbonate rocks of the Vindhyan Supergroup with isotope evolution curves of the latter Proterozoic along with available geochronological data suggest that the Lower Vindhyan sediments were deposited during the Mesoproterozoic Eon and those from the Upper Vindhyan represent a Neoproterozoic interval of deposition.     

Stable isotope signatures associated with palaeosols, Pennsylvanian Holder Formation, New Mexico

The Holder Formation (Pennsylvanian, Virgilian) of southern New Mexico, USA, consists of limestones interbedded with siliciclastics. It was deposited during times of glacio-eustatic sea-level change and was exposed subaerially during multiple sea-level lowstands. Microcomponents and whole-rock samples of limestones were analysed for δ¹³C and δ¹⁸O values to examine the method of whole-rock isotopic analysis for detecting subaerial exposure events and to determine the diagenetic processes acting during subaerial exposure. Whole-rock isotopic shifts are not consistently present across petrographically identified subaerial exposure surfaces. Apparently, whole-rock isotopic shifts do not result from wholesale replacement of the host sediment during soil formation. However, the isotopic shifts are present in calcareous, soil-precipitated microcomponents, such as rhizoliths, laminated crusts, and soil-precipitated cements. The components are heterogeneous in isotopic composition, but converge on a meteoric calcite line at about δ¹⁸O=?5.5‰. These microcomponents are heterogeneous in distribution and may either dominate or be a minor constituent of the whole rock at a single stratigraphic horizon. Without petrographic selection of palaeosol components, the detection of whole-rock isotopic shifts may depend on the selection or chance sampling of a rock containing abundant microcomponents precipitated in a soil environment. Only minor whole-rock isotopic shifts come from those rocks bearing no evidence of exposure and bearing lithological characteristics suggesting subaerial exposure was unlikely.     

Sr chemostratigrphy, δ<Superscript>13</Superscript>C,and δ<Superscript>18</Superscript>O of rocks in the Crimean carbonate platform (Late Jurassic,northern Peri-Tethys)

The paper presents the results of study of the Sr, C, and O isotope compositions in Upper Jurassic carbonate rocks of the Baidar Valley and Demerdzhi Plateau in the Crimean Mountains represented by different facies of the carbonate platform at the northern active margin of the Tethys. The ⁸⁷Sr/⁸⁶Sr value in them varies from 0.70699 to 0.70728. Based on the Sr chemostratigraphic correlation, the age of massive and layered limestones in the western part of the Ai-Petri and Baidar yailas (pastures) is estimated as late Kimmeridgian–early Tithonian, whereas the age of flyschoids of the Baidar Valley are estimated as late Tithonian–early Berriasian. The nearly synchronous formation of carbonate breccias of the Baidar Valley and Demerdzhi Plateau in late Tithonian–early Berriasian is substantiated. A summary section of Upper Jurassic rocks is compiled based on the Sr chemostratigraphic data. It has been established that δ¹⁸O values in the studied carbonate sediments vary from–2.9 to 1.3‰ (V-PDB). At the same time, shallow-water sediments in the internal part and the edge of the Crimean carbonate platform are depleted in ¹⁸O (–2.9 to +0.1‰) relative to sediments on the slope and foothill (–0.5 to +1.3‰). It is demonstrated that δ¹³C values do not depend on the facies properties and decrease in younger carbonate sediments from 3–3.5‰ to 1–1.5‰ in line with the Late Jurassic general trend. The δ¹³C values obtained for the Crimean carbonate platform turned out to be 0.5–1‰ higher than the values typical of the deep-water marine setting at the western margin of the Tethys. These discrepancies are likely related to peculiarities of water circulation and high bioproductivity in marine waters of the northern Peri-Tethys.     

Carbon and Oxygen Isotopic Signatures in Albian-Danian Limestones of Cauvery Basin, Southeastern India

The Albian-Danian limestones of Cauvery Basin show a wide range of d¹³C and d¹⁸O values (–13.2 to +1.1% and –9.0 to –2.5%, respectively). The cement samples show negative carbon and oxygen isotope values (–18.9 to –3.9% and –9.0 to –4.3%, respectively). The petrographic study reveals the presence of algae, molluscs, bryozoans, foraminifers and ostracods as major framework constituents. The limestones have microspar and equant sparry calcite cements. The pore spaces and vugs are filled with sparry calcite cement. The bivariate plot of d¹³C and d¹⁸O suggests that most of the samples fall in the freshwater limestone and meteoric field, while few samples fall in the marine limestone and soil calcite fields. The presence of sparry calcite cement, together with negative carbon and oxygen isotope values, indicates that these limestones have undergone meteoric diagenesis.     

Cyclostratigraphy and high-frequency carbon isotope fluctuations in Upper Cretaceous shallow-water carbonates, southern Italy

Abstract A detailed carbon isotope study has been carried out on a Santonian (Upper Cretaceous) carbonate platform succession that crops out at Monte Sant'Erasmo (southern Italy). Previous centimetre‐scale studies on this succession have shown that high‐frequency eustatic changes, resulting from the Earth's orbital fluctuations, controlled the hierarchical organization of the depositional and early diagenetic features in elementary cycles, bundles (groups of three to five elementary cycles) and superbundles (groups of three or four bundles). The elementary cycles, which correspond to single beds, suggest a control caused by Earth's precession; the bundles and superbundles record the short (≈ 100 kyr) and long (≈ 400 kyr) eccentricity periodicity respectively. The δ¹³C signal of the Monte Sant'Erasmo succession is cyclic in nature and may be considered to be a reliable proxy for the sedimentary evolution (and related sea‐level history) of the analysed sequence. The carbon isotope cyclicity is recorded at bundle and superbundle level, but it is not evident at the scale of the elementary cycles, at least with the sampling interval used in this study. Spectral analysis of the δ¹³C record shows two main peaks corresponding to the short‐ and long‐eccentricity periodicity, whereas the precession signal is not evident in the power spectrum. In addition, lithofacies analysis shows that, in each bundle (and superbundle), higher C isotope values occur in sediments characterized by marine cements, whereas lower values are normally found in more restricted deposits overprinted by early meteoric diagenesis. Early diagenesis, driven by periodic sea‐level fluctuations, developed in either shallow‐subtidal (marine diagenesis) or subaerial‐exposed (meteoric overprint) sedimentary environments and directly influenced the carbon isotope signature. As a consequence, the δ¹³C record at Monte Sant'Erasmo reflects high‐frequency climatic oscillations controlling both environmental and early diagenetic changes. The long‐term isotopic record is similar to that of contemporaneous pelagic sections in England and elsewhere in Italy. It is concluded that the δ¹³C signature of shallow‐water carbonates, such as those of Monte Sant'Erasmo, offers great potential for correlation with coeval sections, including those of the pelagic realm.     

Changes to depositional palaeoenvironments within the Qikou depression (Bohaiwan Basin,China): carbon and oxygen isotopes in lacustrine carbonates of the Palaeogene Shahejie Formation

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.     

Geochemistry of meteoric calcite cements in some Pleistocene limestones

In this study, the stable isotope and trace element geochemistries of meteoric cements in Pleistocene limestones from Enewetak Atoll (western Pacific Ocean), Cat Island (Bahamas), and Yucatan were characterized to help interpret similar cements in ancient rocks. Meteoric calcite cements have a narrow range of δ¹⁸O values and a broad range of δ¹³C values in each geographical province. These Pleistocene cements were precipitated from water with stable oxygen isotopic compositions similar to modern rainwater in each location. Enewetak calcite cements have a mean δ¹⁸O composition of ?6.5%₀ (PDB) and δ¹³C values ranging from ?9.6 to +0.4%0 (PDB). Sparry calcite cements from Cat Island have a mean δ¹⁸O composition of ?4.1%₀ and δ¹³C values ranging from ?6.3 to + 1.1%₀. Sparry cements from Yucatan have a mean δ¹⁸O composition of ?5.7%₀ and δ¹³C values of ?8.0 to ?2.7%₀. The mean δ¹⁸O values of these Pleistocene meteoric calcite cements vary by 2.4%₀ due to climatic variations not related directly to latitude. The δ¹³C compositions of meteoric cements are distinctly lower than those of the depositional sediments. Variations in δ¹³C are not simply a function of distance below an exposure surface. Meteoric phreatic cements often have δ¹³C compositions of less than —4.0%₀, which suggests that soil-derived CO₂ and organic material were washed into the water table penecontemporaneous with precipitation of phreatic cements. Concentrations of strontium and magnesium are quite variable within and between the three geographical provinces. Mean strontium concentrations for sparry calcite cements are, for Enewetak Atoll, 620 ppm (σ= 510 ppm); for Cat Island, 1200 ppm (σ= 980 ppm); and for Yucatan, 700 ppm (σ= 390 ppm). Equant cements, intraskeletal cements, and Bahamian cements have higher mean strontium concentrations than other cements. Equant and intraskeletal cements probably precipitated in more closed or stagnant aqueous environments. Bahamian depositional sediments had higher strontium concentrations which probably caused high strontium concentrations in their cements. Magnesium concentrations in Pleistocene meteoric cements are similar in samples from Enewetak Atoll (mean =1.00 mol% MgCO₃; σ= 0.60 mol% MgCO₃) and Cat Island (mean = 0.84 mol% MgCO₃; σ= 0.52mol% MgCO₃) but Yucatan samples have higher magnesium concentrations (mean = 2.20 mol% MgCO₃: σ= 0.84mol% MgCO₃). Higher magnesium concentrations in some Yucatan cements probably reflect precipitation in environments where sea water mixed with fresh water.     

Behavior of carbonate-associated sulfate during meteoric diagenesis and implications for the sulfur isotope paleoproxy

Although carbonate-associated sulfate (CAS) is used widely as a proxy for the sulfur isotope composition of ancient seawater, little is known about the effects of diagenesis on retention of primary δ³⁴S signals. Our case study of the Key Largo Limestone, Pleistocene, Florida, is the first systematic assessment of the impact of meteoric diagenesis on CAS properties. Geochemical and petrographic data show that meteoric diagenesis has affected the exposed coralline facies to varying degrees, yielding differences now expressed as sharp reaction fronts between primary and secondary carbonate minerals within individual coral heads. Specifically, analyses across high-resolution transects in the Key Largo Limestone show that concentrations of strontium and sodium decrease across the recrystallization front from original aragonite to meteoric low-magnesium calcite by factors of roughly 5 and 10, respectively. Predictably, δ¹⁸O values decrease across these same fronts. The δ¹³C relationships are more complex, with the most depleted values observed in the latest-formed calcite. Such trends likely reflect carbon isotope buffering capacity that decreased as reaction progressed, as well as protracted development of soil profiles and the associated terrestrial biomass and thus depleted δ¹³C during sea-level lowstand. Conversely, δ³⁴S values of CAS vary within a narrow ‘buffered’ range from 20.6 to 22.6‰ (compared to 20.8-22.0‰ of coeval Pleistocene seawater) across the same mineralogical transition, despite sulfate concentrations that drop in the diagenetic calcite by an average factor of 12. Collectively, these data point to robust preservation of primary δ³⁴S for carbonates that have experienced intense meteoric diagenesis, which is encouraging news for those using the isotopic composition of CAS as a paleoceanographic proxy. At the same time, the vulnerability of CAS concentrations to diagenetic resetting is clear.     

Carbonate diagenesis of the upper Jurassic successions in the west of Binalud — Eastern Alborz (NE Iran)

The upper Jurassic carbonate settings in Iran are widely exposed in north and northeastern parts. Five stratigraphic columns were selected in the north eastern Iran. Their thickness ranges from 330 to 500 m. The various diagenetic processes identified include, micritization, cementation, compaction (physical and chemical), dissolution, neomorphism, pyritization, hematitization, silicification and dolomitization, which affected these carbonates. Elemental and stable isotopes analysis indicated that these deposits have undergone both meteoric and burial diagenesis in a relatively open system with moderate water-rock interaction. The positive trend between trace elements and oxygen isotope depletion also support these burial conditions. Lighter δ^l8O values of the dolomite samples may be related to an increase in temperature during the burial, which correspond to coarser euhedral crystals. Relatively higher δ¹⁸O values in finer dolomite crystals indicate their formation at lower burial depths relative to coarser crystals. Petrographic evidences such as coarse euhedral crystals with bright and dull zonation prove this interpretation. Chert nodules also have lighter ¹⁸O values relative to carbonate host rock, thus indicating the influence of burial diagenetic processes in their formation. The average environmental palaeotemperature was estimated to be 26°C on the basis of oxygen isotope values of less altered lime-mudstones.     

Reconstruction of Holocene paleohydrological and sedimentological characteristics of Umm Ar-Rimam basin (northern Kuwait)

The paleohydrological and sedimentological characteristics of a playa lake in northern Kuwait (Arabian Gulf) are reconstructed using sedimentological, geochemical, and isotopic techniques. The sequence consists of up to 8 cycles of S-poor, alluvial sediments capped by a thin organic soil interbedded with gravity-fall calcrete sediments. The succession is locally derived from mainly Quaternary sediments and is regressive with upsection filling of the subsiding basin by cycles of sheetwash flow in response to climatic change. There is no natural, open-water lake water as indicated by low total organic carbon (TOC) data, but the presence of incised calcrete yardangs suggests that more extensive open-water conditions were operative in the past. Stable isotope (δ¹⁸O‰ and δ¹³C‰) values of the authigenic carbonates indicate the following three distinct processes: evaporation, meteoric fluid infiltration, and rapid per-descensum flow (rapid downward movement of water and playa sediment through pipes) through a porous, clastic sequence. Because evaporites are scarce, other factors besides evaporation action control chemical and isotopic compositions of the per-decensum lake fluids. Consequently, the isotopic composition cannot be interpreted exclusively as an indicator of salinity or evaporation ratio. The degassing of CO₂ during groundwater discharge may explain the enriched carbon isotope values for the authigenic carbonates precipitated in the sediments. Hydrologically closed lake water bodies tend to show low negative carbonate oxygen and carbon isotopic signatures. Isotopically negative δ¹³C values imply a strong input of soil-zone carbon to the groundwater of the top 60 cm of the sediment. Lakes that are hydrologically closed and evaporate or equilibrate with atmospheric CO₂ will tend to have low negative δ¹⁸O and δ¹³C values in the carbonates as reported by Talbot (Chem Geol: Isotope Geosci Sect 80(4):261–279, 1990). Biologically active lakes will tend toward lower δ¹³C of dissolved carbon due to the photosynthetic effects of ¹²C withdrawal as reported by Dunagan and Driese (J Sed Res 69:772–783, 1999). Increased biological activity during sedimentation may account for low carbon isotope values where plants were abundant, but in shrinkage-dominated systems (those of clay-rich soil subjecting to wet-dry conditions), carbon isotopes will be largely inherited from the calcretic limestones in the land extending landward of the coast and not influenced by coastal processes (known as hinterland), such as Umm Ar-Rimam depression. This basin does not fit the classic shallow playa-type basins of the Arabian Peninsula but rather the recharge playas of the southwestern USA.     

Lake carbonate-δ18O records from the Yukon Territory,Canada: Little Ice Age moisture variability and patterns

A 1000-yr history of climate change in the central Yukon Territory, Canada, is inferred from sediment composition and isotope geochemistry from small, groundwater fed, Seven Mile Lake. Recent observations of lake-water δ¹⁸O, lake level, river discharge, and climate variations, suggest that changes in regional effective moisture (precipitation minus evaporation) are reflected by the lake’s hydrologic balance. The observations indicate that the lake is currently ¹⁸O-enriched by summer evaporation and that during years of increased precipitation, when groundwater inflow rates to the lake increase, lake-water δ¹⁸O values decrease. Past lake-water δ¹⁸O values are inferred from oxygen isotope ratios of fine-grained sedimentary endogenic carbonate. Variations in carbonate δ¹⁸O, supplemented by those in carbonate and organic δ¹³C, C/N ratios, and organic carbon, carbonate and biogenic silica accumulation rates, document changes in effective moisture at decadal time scales during the early Little Ice Age period to present. Results indicate that between ～AD 1000 and 1600, effective moisture was higher than today. A shift to more arid climate conditions occurred after ～AD 1650. The 19th and 20th centuries have been the driest of the past millennium. Temporal variations correspond with inferred shifts in summer evaporation from Marcella Lake δ¹⁸O, a similarly small, stratified, alkaline lake located ～250 km to the southwest, suggesting that the combined reconstructions accurately document the regional paleoclimate of the east-central interior. Comparison with regional glacial activity suggests differing regional moisture patterns during early and late Little Ice Age advances.