Characterization of the hydrogen isotopic composition of individual n-alkanes in terrestrial source rocks

In order to characterize the H isotopic compositions of individual lipid compounds from different terrestrial depositional environments, the δD values of C-bound H in individual n-alkanes from typical terrestrial source rocks of the Liaohe Basin and the Turpan Basin, China, were measured using gas chromatography–thermal conversion–isotope ratio mass spectrometry (GC–TC–IRMS). The analytical results indicate that the δD values of individual n-alkanes in the extracts of terrestrial source rocks have a large variation, ranging from −140‰ to −250‰, and are obviously lighter than the δD of marine-sourced n-alkanes. Moreover, a trend of depletion in ²H(D) was observed for individual n-alkanes from different terrestrial depositional environments, from saline lacustrine to freshwater paralic lacustrine, and to swamp. For example, the δD values of n-alkanes from a stratified saline lacustrine environment vary from −140‰ to −200‰, δD for n-alkanes from swamp facies range from −200‰ to −250‰, while those from freshwater paralic lacustrine–lacustrine environments fall between the δD values of the end members. The shift toward lighter δD from saltwater to freshwater environments indicates that the source water δD is the major controlling factor for the H isotopic composition of individual compounds. In addition, H exchange between formation water and sedimentary organic matter may possibly be important in regard to the δD of individual n-alkanes. Therefore, other lines of geochemical evidence must be considered when depositional paleoenvironments of source rocks are reconstructed based on the H isotopic composition of individual n-alkanes.     

Isotopic composition of thermal waters in Chukotka

Twenty three groups of thermomineral springs in eastern Chukotka with the discharge temperature of 2 to 97°C and mineralization of 1.47 to 37.14 g/l are studied and compared with surface freshwater from their localities. The δD and δ¹⁸O values in surface waters vary from ?121.4 to ?89.5‰ and from ?16.4 to ?11.1‰, respectively, while respective values in thermomineral waters range from ?134.2 to ?92.5‰ and from ?17.6 to ?10.5‰. The δD value in surface waters decreases from the east to west, i.e., toward interior areas of the peninsula. Hydrothermal springs most depleted in deuterium (δD < ?120‰) are localized in the geodynamically active Kolyuchinskaya-Mechigmen Depression. According to the proposed formation model of Chukotka thermomineral waters, their observed chemical and isotopic characteristics could result from the mixing (in different proportions) of surface waters with the deep-sourced isotopically light mineralized component (δD ≈ ?138‰, δ¹⁸O ≈ ?19‰, M = 9.5?14.7 g/l). The latter originates most likely from subpermafrost waters subjected to slight cryogenic metamorphism.     

A reexamination of cellulose carbon-bound hydrogen δD measurements and some factors affecting plant-water D/H relationships

The method of Epstein et al. (1976) for analysis of D/H ratios of cellulose carbon-bound hydrogen has been modified. This modified “renitration” method yields δD values which are in agreement with those obtained by the sodium chlorite delignification method. Comparison of results obtained by the renitration method with the published results of Epstein et al. (1976) indicate some differences in the δD values of individual samples. However, the overall plant-water δD relationship determined by Epstein et al., is not greatly changed upon redetermination by the renitration method. Additional data from a variety of plants representing a wide geographical range reveal that relative humidity is an important variable in determining the δD value of cellulose C-H hydrogen on this inter-regional scale. The role of relative humidity can be reasonably explained by a leaf water model that assumes an isotopic steady-state during transpiration. These results reaffirm the conclusion of Epstein et al., that the δD variations of the source water are the dominant control of the δD variations of cellulose C-H hydrogen from naturally grown plants. Thus, there is an expectation that these cellulose δD variations can have climate significance.     

Boron and lithium isotopes as groundwater tracers: a study at the Fresh Kills Landfill,Staten Island,New York,USA

A study was conducted at the Fresh Kills landfill, Staten Island, New York to investigate the use of B and Li isotopes as tracers of mixing and flow in the groundwater environment. Four end-member waters are present at the Fresh Kills: freshwater, seawater, a geochemically distinct transitional groundwater (that occurs in the zone of mixing between seawater and freshwater) and landfill leachate. The δ¹¹B and δ⁶Li values of end-member waters are distinct and have isotopic compositions that reflect the solute sources: freshwater δ¹¹B∼+30‰, δ⁶Li∼−22‰; transition zone groundwaters δ¹¹B∼+20‰, δ⁶Li∼−27‰; seawater δ¹¹B+40 to +75‰, δ⁶Li−37 to−44‰; leachate δ¹¹B∼+10‰ (δ⁶Li not determined). Those wells influenced by seawater exhibited a clear chemical mixing trend, with seawater contributions ranging from 3 to 85%. Well waters with a high percentage of seawater (>30%) had δ¹¹B values that were within 1‰ of the seawater value (+40‰), whereas a trend of increasing δ¹¹B values (+55 to +75‰) was observed for wells with a lower percentage of seawater (<30%). δ⁶Li values for well waters impacted by mixing with seawater ranged from−37 to−44‰, significantly more negative than pure seawater (−31‰). This deviation from the isotopic composition of seawater, for both δ¹¹B and δ⁶Li values, represents non-conservative behavior and is likely the result of isotopic fractionation during ion exchange reactions. The wide range of δ¹¹B and δ⁶Li values and the distinct isotopic compositions of end-member waters makes B and Li isotopes useful for recognizing solute sources, however isotopic fractionation may limit their use as simple tracers of groundwater flow and mixing.     

Stable isotopic studies on chitin. III. The D/H and 18O/16O ratios in arthropod chitin

Stable hydrogen and oxygen isotope ratios are presented for carbon-bound hydrogen and for oxygen in chitin-derived substrates from 57 arthropod species collected in 50 different locations or grown under controlled conditions in the laboratory. No systematic isotopic differences were found among Insecta, Crustacea, and Merostomata. The determination of infra- and interindividual isotopic variabilities in a lobster and among individuals of crustacean populations yielded small variances of about ±3 per mil for δD values and ±0.3 per mil for δ¹⁸O values. Molting stage and sex of crustaceans showed no systematic effects on isotopic composition. The δD and δ¹⁸O values of ambient water showed only weak correlations with the respective δ values of chitin-derived substrates. Positive correlation was observed between δD values and trophic level. No temperature effects on δ¹⁸O and δD values from marine crustaceans were found that exceed the natural isotopic noise level. Taken together, these observations indicate that reconstruction of water isotopic composition from arthropod chitin δD and δ¹⁸O values will require specific information about the habits and habitats of the species involved in the analysis.     

Crassulacean acid metabolism influences D/H ratio of leaf wax in succulent plants

This study sought to characterize hydrogen isotopic fractionation during biosynthesis of leaf wax n-alkanes in succulent plants capable of crassulacean acid metabolism (CAM). The metabolic and physiological features of CAM represent crucial strategies for survival in hot and dry climates and have been hypothesized to impact hydrogen isotope fractionation. We measured the stable carbon and hydrogen isotopic compositions (δ¹³C and δD, respectively) of individual n-alkanes in 20 species of succulent plants from a global collection of the Huntington Botanical Gardens, San Marino, California. Greenhouse conditions and irrigation with water of constant δD value enabled determination of interspecies differences in net D/H fractionation between source water and leaf wax products. Carbon isotope ratios provide constraints on the extent of CAM vs. C₃ photosynthesis and indicate a wide range of CAM use, with δ¹³C values ranging from −33.01‰ to −18.54‰ (C₂₇–C₃₃ n-alkanes) and −26.66‰ to −17.64‰ (bulk tissue). Despite the controlled growth environment, we observed ca. 90‰ interspecies range in δD values from −193‰ to −107‰. A positive correlation between δ¹³C_bulk and δD_C31 values with R² = 0.60 (δ¹³C_C31 and δD_C31 values with R² = 0.41) implicates a metabolic isotope effect as the dominant cause of interspecies variation in the hydrogen isotopic composition of leaf wax n-alkanes in CAM-intermediate plants.     

Biogeochemical implications of the isotopic equilibrium fractionation factor between the oxygen atoms of acetone and water

Carbonyl oxygens of organic molecules undergo isotopic exchange with water during reversible hydration reactions. The equilibrium isotopic fractionation factors between the carbonyl oxygen of acetone and water at 15°, 25°, and 35°C are 1.028, 1.028, and 1.026 respectively. The differences between the δ¹⁸O values of the carbonyl oxygen of acetone and of the water with which it is in equilibrium are similar to the differences that have been observed between the δ¹⁸O values of cellulose and the water used in its synthesis by a variety of aquatic plants and animals. Additionally, the identity of the acetone-water fractionation factors at 15° and 25°C parallels the observation that the difference between the δ¹⁸O values of cellulose and water shows no temperature dependence for individual species of plants grown over the same temperature range. These results are discussed in relation to the proposal that the oxygen isotopic relationship between cellulose and water is established by isotopic exchange occurring during the hydration of carbonyl groups of the intermediates of cellulose synthesis.     

Hydrogen and carbon isotopes of petroleum and related organic matter

$\text{D}\text{H}$ and ${}^{13}\text{C}{}^{12}\text{C}$ ratios were measured for 114 petroleum samples and for several samples of related organic matter. δD of crude oil ranges from ?85 to ?181‰, except for one distillate (?250‰) from the Kenai gas field; δ¹³C of crude oil ranges from ?23.3 to ?32.5‰, Variation in δD and δ¹³C values of compound-grouped fractions of a crude oil is small, 3 and 1.1%., respectively, and the difference in δD and δ¹³C between oil and coeval wax is slight. Gas fractions are 53–70 and 22.6–23.2‰ depleted in D and ¹³C, respectively, relative to the coexisting oil fractions.The δD and δ¹³C values of the crude oils appear to be largely determined by the isotopic compositions of their organic precursors. The contribution of terrestrial organic debris to the organic precursors of most marine crude oils may be significant.     

Significant seasonal variation in the hydrogen isotopic composition of leaf-wax lipids for two deciduous tree ecosystems (Fagus sylvativa and Acerpseudoplatanus)

Compound specific hydrogen isotope ratios (δD) of long chain sedimentary n-alkanes, which mostly originate from the leaf waxes of higher terrestrial plants, are increasingly employed as paleoclimate proxies. While soil water is the ultimate hydrogen source for these lipids and the isotopic fractionation during biosynthesis of lipids is thought to remain constant, environmental parameters and plant physiological processes can alter the apparent hydrogen isotopic fractionation between leaf-wax lipids and a plant’s source water. However, the magnitude and timing of these effects and their influence on the isotopic composition of lipids from higher terrestrial plants are still not well understood. Therefore we investigated the seasonal variability of leaf-wax n-alkane δD values for two different temperate deciduous forest ecosystems that are dominated by two different tree species, Beech (Fagus sylvatica) and Maple (Acerpseudoplatanus).We found significant seasonal variations for both tree species in n-alkane δD values of up to 40‰ on timescales as short as one week. Also, the isotopic difference between different n-alkanes from the same plant species did vary significantly and reached up to 50‰ at the same time when overall n-alkane concentrations were lowest.Since δD values of soil water at 5 and 10 cm depth, which we assume represent the δD value of the major water source for the investigated beech trees, were enriched in autumn compared to the spring by 30‰, whereas n-alkane δD values increased only by 10‰, we observed variations in the apparent fractionation between beech leaf derived n-alkanes and soil water of up to 20‰ on a seasonal scale. This observed change in the apparent fractionation was likely caused by differences in leaf water isotopic enrichment. Based on mechanistic leaf water models we conclude that changes in the isotopic difference between water vapor and soil water were the most likely reason for the observed changes in the apparent fractionation between n-alkanes and soil water.The large variability of n-alkane concentrations and δD values over time implies a continuous de novo synthesis of these compounds over the growing season with turnover times possibly as short as weeks. The signal to reach the soil therefore represents an integrated record of the last weeks before leaf senescence. This holds true also for the sedimentary record of small catchment lakes in humid, temperate climates, where wind transport of leaf-wax lipids is negligible compared to transfer through soil and the massive input of leaves directly into the lake in autumn.     

Investigation on the hydrodynamics of Ganga Alluvial Plain using environmental isotopes: a case study of the Gomati River Basin, northern India

An investigation using environmental isotopes (δ¹⁸O and δD) was conducted to gain insight into the hydrological processes of the Ganga Alluvial Plain, northern India. River-water, shallow-groundwater and lake-water samples from the Gomati River Basin were analyzed. During the winter season, the δ¹⁸O and δD compositions of the Gomati River water ranged from ?1.67 to ?7.62 ‰ and ?25.08 to ?61.50 ‰, respectively. Deuterium excess values in the river water (+0.3 to ?13 ‰) and the lake water (?20 ‰) indicate the significance of evaporation processes. Monthly variation of δ¹⁸O and δD values of the Gomati River water and the shallow groundwater follows a similar trend, with isotope-depleted peaks for δ¹⁸O and δD synchronized during the monsoon season. The isotopically depleted peak values of the river water (δ¹⁸O?=??8.30 ‰ and δD?=??57.10 ‰) can be used as a proxy record for the isotopic signature of the monsoon precipitation in the Ganga Alluvial Plain.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.     

The concentration and isotopic composition of hydrogen,carbon and nitrogen in carbonaceous meteorites

Concentrations and isotopic compositions were determined for H₂, N₂ and C extracted by stepwise pyrolysis from powdered meteorites, from residues of meteorites partially dissolved with aqueous HF, and from residues of meteorites reacted with HF-HCl solutions. The meteorites treated were the carbonaceous chondrites, Orgueil, Murray, Murchison, Renazzo and Cold Bokkeveld. Data determined for whole rock samples are in approximate agreement with previously published data. Acidification of the meteorites removed the inorganic sources of H₂, so that H₂ in the HF-HCl acid residues came primarily from insoluble organic matter, which makes up 70–80% fraction of the total carbon in carbonaceous meteorites. The δD in the organic matter differs markedly from previously determined values in organic matter in meteorites. The δD values of organic matter from acid residues of C1 and C2 carbonaceous chondrites range from +650 to + 1150%. The acid residues of the Renazzo meteorite, whose total H₂ has a δD of +930‰, gave a δD value of +2500‰. Oxidation of the HF-HCl residue with H₂O₂ solution removes the high δD and the low δ¹⁵N components. The δ¹³C values range between ?10 and ?21 and δ¹⁵N values range between +40 and ?11. The δ¹⁵N of Renazzo is unusual; its values range between +150 and ?190.There is good correlation between δD and the concentration of H₂ in the acid residues, but no correlation exists between δD, δ¹³C and δ¹⁵N in them. A simple model is proposed to explain the high δD values, and the relationships between δD values and the concentration of H₂. This model depends on the irradiation of gaseous molecules facilitating reaction between ionic molecules, and indicates that an increase in the rate of polymerization and accumulation of organic matter on grains would produce an increase in the deuterium concentration in organic matter.     

Fractionation of hydrogen,oxygen and carbon isotopes in n-alkanes and cellulose of three Sphagnum species

Compound-specific isotope measurements of organic compounds are increasingly important in palaeoclimate reconstruction. Searching for more accurate peat-based palaeoenvironmental proxies, compound-specific fractionation of stable C, H and O isotopes of organic compounds synthesized by Sphagnum were determined in a greenhouse study. Three Sphagnum species were grown under controlled climate conditions. Stable isotope ratios of cellulose, bulk organic matter (OM) and C₂₁–C₂₅ n-alkanes were measured to explore whether fractionation in Sphagnum is species-specific, as a result of either environmental conditions or genetic variation. The oxygen isotopic composition (δ¹⁸O) of cellulose was equal for all species and all treatments. The hydrogen isotopic composition (δD) of the n-alkanes displayed an unexpected variation among the species, with values between −154‰ for Sphagnum rubellum and −184‰ for Sphagnum fallax for the C₂₃ n-alkane, irrespective of groundwater level. The stable carbon isotopic composition (δ¹³C) of the latter also showed a species-specific pattern. The pattern was similar for the carbon isotope fractionation of bulk OM, although the C₂₃ n-alkane was >10‰ more depleted than the bulk OM. The variation in H fractionation may originate in the lipid biosynthesis, whereas C fractionation is also related to humidity conditions. Our findings clearly emphasize the importance of species identification in palaeoclimate studies based on stable isotopes from peat cores.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Leaf cellulose δD and δO trends with elevation differ in direction among co-occurring, semiarid plant species

The potential to reconstruct paleoclimate from analyses of stable isotopes in fossil leaf cellulose could be enhanced by adequate calibration. This potential is likely to be particularly great in mid-latitude deserts, where a rich store of fossil leaves is available from rodent middens. Trends in δD and δ¹⁸O of leaf cellulose were examined for three species growing across climatic gradients caused by elevation and slope aspect in southeastern Utah, USA. The species differed in morphology (Pinus edulis vs. Yucca glauca), photosynthetic pathway (C₃Y. glauca vs. CAM Yucca baccata) or both (P. edulis vs. Y. baccata). The δD_LCN (leaf cellulose nitrate) and δ¹⁸O_LC (leaf cellulose) values of P. edulis decreased with elevation. Stem water δD values either increased (in spring) or did not change with elevation (in summer). Needle water δD values usually decreased with elevation and differed greatly with leaf age. These results suggest that δ cellulose values of P. edulis record the effects of climate on the isotopic composition of leaf water but not climate effects on meteoric water. In contrast to P. edulis, δD_LCN values of Y. glauca increased with elevation. The δ¹⁸O_LC values of Y. glauca also increased with elevation but less significantly and only on south-facing slopes. The δ cellulose values in both P. edulis and Y. glauca were most significantly related to changes in temperature, although temperature and precipitation were negatively correlated in the study area. Where all three species co-occurred, their δD_LCN values differed but their δ¹⁸O_LC values were the same. The disparity in δD_LCN between Y. baccata and the other species corresponds to differences in biochemical fractionations associated with photosynthetic pathway. Biochemical fractionations may also contribute to differences between the two C₃ species. Knowledge of factors affecting responses of individual plant species to environment may be required to infer climate from δD_LCN and δ¹⁸O_LC.     

δC and δD identification of sources of lipid biomarkers in sediments of Lake Haruna (Japan)

Organic materials in lacustrine sediments are from multiple terrestrial and aquatic sources. In this study, carbon (δ¹³C) and hydrogen isotopic compositions (δD) of phytol, various sterols, and major n-fatty acids in sediments at Lake Haruna, Japan, were determined in their solvent-extractable (free) and saponification-released forms (bound). The δ¹³C-δD distributions of these lipid molecules in sediments are compared with those of terrestrial C3 and C4 plants, aquatic C3 plants, and plankton to evaluate their relative contributions. δ¹³C-δD of free phytol in sediments is very close to that of phytol in plankton samples, whereas δ¹³C-δD of bound phytol in sediments is on a mixing line between terrestrial C3 plant and plankton material. Unlike phytol, no significant δ¹³C-δD difference between free and bound forms was found in sterols and n-fatty acids. δ¹³C-δD values of algal sterols such as 24-methylcholesta-5,22-dien-3β-ol in sediments are close to those of plankton, whereas δ¹³C-δD of multiple-source sterols such as 24-ethylcholest-5-en-3β-ol and of major n-fatty acids such as n-hexadecanoic acid in sediments are between those of terrestrial C3 plants and plankton samples. Thus, δ¹³C-δD distributions clearly indicate the specific source contributions of biomarkers preserved in a lacustrine environment. Free phytol and algal sterols can be attributed to phytoplankton, and bound phytol, multiple source sterols, and major n-fatty acids are contributed by both terrestrial C3 plants and phytoplankton.     

Hydrogen and oxygen isotopic compositions of sedimentary kaolin deposits,Egypt: Paleoclimatic implications

The clay fractions of sedimentary kaolin deposits representing different ages (Carboniferous and Cretaceous), types (pisolitic flint and plastic), and localities (Sinai and Aswan) from Egypt were analyzed for their H and O isotopic compositions to examine the paleoclimate conditions during their formation. The δD values of the Carboniferous deposits in Sinai range between −67‰ and −88‰, while the values for the Cretaceous deposits in Sinai range between −59‰ and −75‰. The δ¹⁸O values of the Carboniferous deposits range from 17.9‰ to 19.4‰ and the values for the Cretaceous deposits range between 19.2‰ and 20.4‰. The relatively low δD and δ¹⁸O values of the Carboniferous deposit at the Abu Natash area (−67‰ and 17.9‰, respectively) compared to other Carboniferous deposits (averages of −83.3‰, and 18.8‰ for δD and δ¹⁸O, respectively) could be due to isotopic exchange between this deposit and the adjacent dolomite and/or the enclosed hydrothermally-formed Mn ores of the Carboniferous Um Bogma Formation. The δD and δ¹⁸O values of the Cretaceous pisolitic flint kaolin deposit from Aswan (averages of −65‰ and 20.3‰, respectively) and plastic kaolin from the same area (averages of −66‰ and 19.5‰, respectively) are almost identical. The differences in the δ¹⁸O values between the clay fractions of the pisolitic flint kaolin (20.3‰) and the previously analyzed bulk kaolin of the same deposit (average of 17.5‰) suggest a significant effect of non-clay minerals on the isotopic compositions of the kaolin deposits.The H and O isotopic compositions plot close to the kaolinite line that marks the isotopic composition of kaolinite in equilibrium with meteoric water at 20 °C. This indicates that the kaolinite from both the Carboniferous and Cretaceous deposits in Egypt formed by meteoric water weathering of the source rock(s). The δD and δ¹⁸O values also suggest that kaolinite of these deposits formed under warm-temperate to tropical conditions. The slight deviations of some samples from the kaolinite line suggest post-depositional modifications of the isotopic compositions of studied deposits probably due to the interaction between earlier-formed kaolinite and downward percolating meteoric water.The δD and δ¹⁸O values of the Cretaceous and Carboniferous deposits from all localities suggest that both deposits formed under similar climatic conditions due to the location of Egypt at almost the same distance from the equator either to the south during the Carboniferous or to the north during the Cretaceous.     

Diagenesis and reservoir quality of the Aldebaran Sandstone, Denison Trough, east-central Queensland, Australia

The Lower Permian Aldebaran Sandstone is the principal hydrocarbon reservoir in the Denison Trough (Bowen Basin), east-central Queensland, Australia. It accumulated in a wide range of fluvio-deltaic and nearshore marine environments. Detailed petrological study of the unit by thin section, X-ray diffraction, scanning electron microscopy, electron microprobe and isotopic analysis reveals a complex diagenetic history which can be directly related to depositional environment, initial composition and burial-temperature history. Early diagenetic effects included the precipitation of pyrite, siderite and illite-smectite rims (δ¹⁸O (SMOW) =+8.9 to + 11.3‰). Deep burial effects included physico-chemical compaction and the formation of quartz overgrowths, siderite (δ¹³C(PDB) =?34.0 to + 11.5‰, δ¹⁸O =?0.7 to +22.7‰), illite/illite-smectite and ankerite (δ¹³C=?9.3 to ?4.9‰) δ¹⁸O=+ 7.6 to + 14.4‰). Involved fluids were in part ‘connate meteoric’ water derived from compaction of the underlying freshwater Reids Dome beds. Important post-maximum burial effects, controlled by deep meteoric influx from the surface, were ankerite and labile grain dissolution and formation of kaolinite (δ¹⁸O=+7.8 to +8.9‰, δD=?115 to ?99‰), calcite (δ¹³C=?9.5 to +0.9‰, δ¹⁸O=+9.0 to +20.0‰) and dawsonite (δ¹³C=?4.0 to +2.3‰, δ¹⁸O=+9.8 to +19.8‰), the formation of dawsonite reflecting eventual stagnation of the aquifer. Entrapment of contained hydrocarbons was a relatively recent event which may be continuing today. Reservoir quality varies from marginal to good in the west to poor in the east, with predictable trends being directly linked to depositional environment and diagenesis.     

Isotope (δD, δ<Superscript>18</Superscript>О) systematics in waters of the Russian Arctic seas

Oxygen and hydrogen isotope analysis was performed to study the processes of distribution of water masses and modification of their salinity in the Russian Arctic seas. A wealth of new isotopic data was obtained for freshwater (river runoff, Novaya Zemlya glaciers) and seawater samples collected along a set of extended 2D profiles in the Barents, Kara, and Laptev Seas. The study presents the first δD values measured for the Northeast Atlantic Deep Water NEADW dominated the water column of the Barents Sea (S = 34.90 ± 0.05, δD = +1.55 ± 0.4‰, δ¹⁸O = +0.26 ± 0.1‰, n = 44). This water mass is present in the Kara Sea and western Laptev Sea. The relationship between δD, δ18О, and salinity data was used to calculate the fractions of waters of different origin, including the fractions of continental runoff in waters of the Barents, Kara, and Laptev Seas. It was shown that the relationships between the isotopic parameters (δD, δ¹⁸О) and salinity in waters of the Kara and Laptev Seas is controlled by the intensity of continental runoff and sea ice processes. Sea ice formation is the main factor controlling the formation of the water column on the Laptev Sea shelf, whereas the surface waters of the middle Kara Sea are dominated by the contribution of river runoff. A very strong stratification in the Kara Sea is caused by the presence of a relatively fresh surface layer mostly contributed by estuarine water inputs from the Ob and Yenisei Rivers. The contribution of river waters reaches 40–60% in the surface layer in the central part of the sea and decreases to a few percent down 100 m water depth. Stratification in the western part of the Laptev Sea is controlled by the contribution of freshwater input from the Lena River and modification of salinity by sea ice formation.     

Dinosterol δD values in stratified tropical lakes (Cameroon) are affected by eutrophication

In freshwater settings, dinosterol (4α,23,24-trimethyl-5α-cholest-22E-en-3β-ol) is produced primarily by dinoflagellates, which encompass various species including autotrophs, mixotrophs and heterotrophs. Due to its source specificity and occurrence in lake and marine sediments, its presence and hydrogen isotopic composition (δD) should be valuable proxies for paleohydrological reconstruction. However, because the purity required for hydrogen isotope measurements is difficult to achieve using standard wet chemical purification methods, their potential as a paleohydrological proxy is rarely exploited. In this study, we tested δD values of dinosterol in both particulate organic matter (POM) and sediments of stratified tropical freshwater lakes (from Cameroon) as a paleohydrological proxy, the lakes being characterized by variable degrees of eutrophication. In POM and sediment samples, the δD values of dinosterol correlated with lake water δD values, confirming a first order influence of source water δD values. However, we observed that sedimentary dinosterol was D enriched from ca. 19 to 54‰ compared with POM dinosterol. The enrichment correlated with lake water column conditions, mainly the redox potential at the oxic–anoxic interface (E_h OAI). The observations suggest that paleohydrologic reconstruction from δD values of dinosterol in the sediments of stratified tropical lakes ought to be sensitive to the depositional environment, in addition to lake water δD values, with more positive dinosterol δD values potentially reflecting increasing lake eutrophication. Furthermore, in lake sediments, the concentration of partially reduced vs. non-reduced C₃₄ botryococcenes, stanols vs. stenols, and bacterial (diploptene, diplopterol and ββ-bishomohopanol) vs. planktonic/terrestrial lipids (cholesterol, campesterol and dinosterol) correlated with E_h OAI. We suggest using such molecular proxies for lake redox conditions in combination with dinosterol δD values to evaluate the effect of lake trophic status on sedimentary dinosterol δD values, as a basis for accurately reconstructing tropical lake water δD values.