Rhinocerotid tooth enamel 18O/16O variability between 23 and 12 Ma in southwestern France

The relationship between the oxygen isotope ratio of mammal tooth enamel and that of drinking water was used to reconstruct changes in the Miocene oxygen isotope ratio of rainfall (meteoric water ${\delta }^{18}$O_MW). These, in turn, are related to climatic parameters (temperature, precipitation and evaporation rate). ${\delta }^{18}$O values of rhinocerotid teeth from the Aquitaine Basin (southwestern France) suggest a significant climatic change between 17 and 12 Ma, characterized by cooling together with precipitation increase, in agreement with other terrestrial and oceanic records. To cite this article: I. Bentaleb et al., C. R. Geoscience 338 (2006).     

The isotope record of short- and long-term dietary changes in sheep tooth enamel: Implications for quantitative reconstruction of paleodiets

Quantitative reconstruction of paleodiet by means of sequential sampling and carbon isotope analysis in hypsodont tooth enamel requires a precise knowledge of the isotopic enrichment between dietary carbon and carbon from enamel apatite (ε_D-E), as well as of the timing and duration of the enamel mineralization process (amelogenesis). To better constrain these parameters, we performed a series of controlled feeding experiments on sheep ranging in age from 6 to 24 months-old. Twenty-eight lambs and 14 ewes were fed isotopically distinct diets for different periods of time, and then slaughtered, allowing the timing and rate of molar growth to be determined. High resolution sampling and stable carbon isotope analysis of breath CO₂ performed on six individuals following a diet-switch showed that 70-90% of dietary carbon had turned over in less than 24 h. Sequential sampling and carbon isotopic analysis was performed on the first (M₁) and second (M₂) lower molars of four lambs as well as on the third lower molar (M₃) of 11 ewes. The changes in diet were recorded in all molars. We found that the length of enamel matrix apposition is approximately one-quarter of the final tooth length during crown extension, and that enamel maturation spans slightly less than 3 months in M₁, and 4 months in M₂ and M₃. Portions of enamel in equilibrium with dietary carbon were used to calculate ε_D-E values. Animals on grass silage diets had values similar to previous observations, whereas animal switched to pelleted corn diets had values ca. 4‰ lower, a pattern consistent with lower methane production observed for animals fed concentrate diets. The tooth enamel forward model of Passey and Cerling (2002) closely predicted the amplitude of isotope changes recorded in tooth enamel, but slightly underestimated the rate of isotope change, suggesting that the rate of accumulation of carbonate during maturation may not be constant over time. Although stable isotope profiles in tooth enamel represent underdetermined systems, our results demonstrate that they can provide useful information about dietary variability if the mineralization process is taken into account.     

Stable isotopes reflect the ecological stability of two high-elevation mammals from the late Quaternary of Colorado

The vertebrate fossil record of Cement Creek Cave, Colorado, spans from > 45,000 yr ago to the present and represents the richest stratified series of high-elevation (> 2900 m) mammal remains known from the late Quaternary of North America. Stable carbon and oxygen isotope analyses of tooth enamel were used to assess potential ecological responses of two species found commonly throughout the cave, Yellow-bellied marmots (Marmota flaviventris) and Bushy-tailed woodrats (Neotoma cinerea), to late Quaternary climate and environmental changes of the Southern Rocky Mountains. Results indicate that despite such perturbations, the dietary ecologies of both species were maintained across this period. Neither taxon shifted to consuming C₄ taxa or different C₃ functional groups; similarly, no significant shifts in surface water use were detected. Variations in enamel δ¹³C were observed, however, that represent the physiological responses of high-elevation plants to changing levels of late Quaternary atmospheric CO₂. While our findings extend both the geographic and elevational record of this plant CO₂ response, they simultaneously highlight the ecological stability of high-elevation M. flaviventris and N. cinerea during climate changes of late Quaternary magnitude.     

Hydrogen isotope ratios of leaf wax n-alkanes in grasses are insensitive to transpiration

We analyzed hydrogen isotope ratios of high-molecular weight n-alkanes (δD_l) and oxygen isotope ratios of α-cellulose (δ¹⁸O_C) for C₃ and C₄ grasses grown in the field and in controlled-environment growth chambers. The relatively firm understanding of ¹⁸O-enrichment in leaf water and α-cellulose was used to elucidate fractionation patterns of δD_l signatures. In the different relative humidity environments of the growth chambers, we observed clear and predictable effects of leaf-water enrichment on δ¹⁸O_C values. Using a Craig-Gordon model, we demonstrate that leaf water in the growth chamber grasses should have experienced significant D-enriched due to transpiration. Nonetheless, we found no effect of transpirational D-enrichment on the δD_l values. In field samples, we saw clear evidence of enrichment (correlating with relative humidity of the field sites) in both δ¹⁸O_C and δD_l. These seemingly contrasting results could be explained if leaf waxes are synthesized in an environment that is isotopically similar to water entering plant roots due to either temporal or spatial isolation from evaporatively enriched leaf waters. For grasses in the controlled environment, there was no enrichment of source water, whereas enrichment of grass source water via evaporation from soils and/or stems was likely for grass samples grown in the field.Based on these results, evaporation from soils and/or stems appears to affect δD_l, but transpiration from leaves does not. Further evidence for this conclusion is found in modeling expected net evapotranspirational enrichment. A Craig-Gordon model applied to each of the field sites yields leaf water oxygen isotope ratios that can be used to accurately predict the observed δ¹⁸O_C values. In contrast, the calculated leaf water hydrogen isotope ratios are more enriched than what is required to predict observed δD_l values. These calculations lend support to the conclusion that while δ¹⁸O_C reflects both soil evaporation and transpiration, δD_l appears to only record evaporation from soils and/or stems. Therefore, the δD of n-alkanes can likely be used to reconstruct the δD of water entering a leaf, supporting the soil-enrichment model of Smith and Freeman (2006). In both the field and controlled studies, we found significant photosynthetic pathway effects on n-alkane δD suggesting that biochemical pathways or plant phylogeny have a greater effect on leaf wax δD than leaf-water enrichment in grasses.     

High-resolution δC intratooth profiles in bovine enamel: Implications for mineralization pattern and isotopic attenuation

We present the first high-resolution carbon isotope and carbonate content profiles generated through the thickness of enamel from a steer fed C₃- then C₄-dominant food. Carbonate contents decrease by ∼2 wt% from the enamel surface to the innermost enamel layer, and each carbon isotope profile shows a mixture of enamel portions mineralized over several months. Downward and outward increasing contribution of C₄ food to the enamel δ¹³C values reveal two components of the mineralization gradient: a vertical component from the tip of the tooth crown to the neck, and a horizontal component from the enamel-dentine junction to the outer enamel. We use our results to infer mineralization parameters for bovines and to calculate expected isotopic attenuations for an array of environmental inputs and microsampling strategies, using the model developed by Passey and Cerling [Geochim. Cosmochim. Acta. 66 (2002) 3225-3234]. Although it seems unlikely that any strategy will perfectly isolate discrete time slices, sampling the innermost enamel layer might offer the advantage of significantly reducing the isotope damping that would become independent of the structure of the input signal.     

Oxygen isotope compositions of phosphate from arvicoline teeth and Quaternary climatic changes, Gigny, French Jura

Oxygen isotope compositions of biogenic phosphates from mammals are widely used as proxies of the isotopic compositions of meteoric waters that are roughly linearly related to the air temperature at high- and mid-latitudes. An oxygen isotope fractionation equation was determined by using present-day European arvicoline (rodents) tooth phosphate: δ¹⁸O_p = 20.98(±0.59) + 0.572(±0.065) δ¹⁸O_w. This fractionation equation was applied to the Late Pleistocene karstic sequence of Gigny, French Jura. Comparison between the oxygen isotope compositions of arvicoline tooth phosphate and Greenland ice core records suggests to reconsider the previously established hypothetical chronology of the sequence. According to the δ¹⁸O value of meteoric water-mean air temperature relationships, the δ¹⁸O value of arvicoline teeth records variations in mean air temperatures that range from 0° to 15°C.     

Seasonal evolution of the isotopic composition of atmospheric water vapour above a tropical lake: Deuterium excess and implication for water recycling

We present an analysis of the rainfall-evaporation-atmospheric moisture cycle in a semi-arid tropical zone (southwestern Madagascar) to quantify the recycling and mixing processes that occur above an endorheic lake system (Lake Ihotry) during an annual cycle. The study combines an isotope mass balance with a detailed field investigation of the lake system and a previously established daily time-step lake water balance model. The mass balance and Craig-Gordon equations are used to calculate the isotopic composition of the evaporative flux from the lake surface (δ_E) and to derive a daily time series of the ambient atmospheric water vapour composition above the lake (δ_AL) during a 8-month dry season. Calculated δ_AL results from a mixing between regional moisture (δ_AR) and locally evaporated water (δ_E), the latter representing 50% of δ_AL at the end of the dry season. The contribution of recycled moisture to on-lake precipitation during the wet season is estimated to ?16%. We show that, as expected, the deuterium excess is high in recycled precipitation and low in evaporated precipitation, but also that the recycled moisture in an endorheic system may have a low deuterium excess resulting from the low deuterium excess in regional precipitation. In case of a long evaporative season, the atmospheric moisture is not in isotopic equilibrium with the annual composition of precipitation because of the contribution of the recycled vapour to the local atmospheric pool. Our approach demonstrates the importance of water recycling on the atmospheric moisture cycle and precipitation in a tropical semi-arid system, and can be applied to other natural systems, enlarging the potential range of investigation of the atmospheric vapour cycle and rainfall sources in tropical lands. It may also represent a valuable complement to direct water vapour sampling, in yielding the long-term evolution of the atmospheric vapour composition with spatially averaged values and smoothed temporal variations.     

Variation in n-alkane δD values from terrestrial plants at high latitude: Implications for paleoclimate reconstruction

The molecular hydrogen isotope composition (δD) of leaf waxes from terrestrial plants is increasingly used to infer hydrological characteristics of ancient high latitude climates. Analysis of the hydrogen isotope composition of n-alkanes (δD_n-alkane) from a global dataset of individual plants growing at low and middle latitudes indicates that plant ecological life form is an important factor in determining the hydrogen isotope fractionation. However, environmental and biological controls of high latitudinal leaf wax δD values are poorly understood because of a lack of δD records from modern flora in these regions. We previously noticed smaller apparent hydrogen isotope fractionations between n-alkanes and environmental water (ε_alk-water) in deciduous trees growing at high latitudes (>59°N; Liu, W.-G., Yang, H., 2008. Multiple controls for the variability of hydrogen isotopic compositions in higher plant n-alkanes from modern ecosystems. Global Change Biology 14, 2166-2177.) To further examine these issues, we measured δD_n-alkane from a variety of plants that inhabit high latitude environments and added critically needed leaf wax δD data from grass and herbs to the existing global δD_n-alkane database. Inclusion of these new data with the existing global dataset (n = 408) confirms plant ecological life form as an important control for leaf wax δD variation for terrestrial plants living at high latitudes. Our results suggest that, while precipitation δD is captured in these high latitude plants, physiological characters such as leaf area, venation pattern and hydraulic system, that enhance transpiration rate during summer growth, may impart δD_n-alkane differences among plants with different ecological life forms.     

Oxygen isotopes in mammal bone phosphate: A new tool for paleohydrological and paleoclimatological research?

Oxygen isotope analyses of water in blood of humans and domestic pigs indicate that the oxygen isotope fractionation effects between ingested water and body water are the same in all specimens of the same species. The δ¹⁸O of body water has been shown to vary linearly with the mean δ¹⁸O of local meteoric water. This conclusion also holds for the bone phosphate. Thus, δ¹⁸O(PO^3?₄) values of unaltered fossil bones from humans and domestic pigs can be used to reconstruct the δ¹⁸O values of local meteoric waters during the life-times of the mammals. Such data can be used for paleohydrological and paleoclimatological studies both on land and at sea.     

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.     

Isotopic constraints on ice age fluids in active geothermal systems: Reykjanes, Iceland

The Reykjanes geothermal system is located on the landward extension of the Mid-Atlantic Ridge in southwest Iceland, and provides an on-land proxy to high-temperature hydrothermal systems of oceanic spreading centers. Previous studies of elemental composition and salinity have shown that Reykjanes geothermal fluids are likely hydrothermally modified seawater. However, δD values of these fluids are as low as −23‰, which is indicative of a meteoric water component. Here we constrain the origin of Reykjanes hydrothermal solutions by analysis of hydrogen and oxygen isotope compositions of hydrothermal epidote from geothermal drillholes at depths between 1 and 3 km. δD_EPIDOTE values from wells RN-8, -9, -10 and -17 collectively range from −60 to −78‰, and δ¹⁸O_EPIDOTE in these wells are between −3.0 and 2.3‰. The δD values of epidote generally increase along a NE trend through the geothermal field, whereas δ¹⁸O values generally decrease, suggesting a southwest to northeast migration of the geothermal upflow zone with time that is consistent with present-day temperatures and observed hydrothermal mineral zones. For comparative analysis, the meteoric-water dominated Nesjavellir and Krafla geothermal systems, which have a δD_FLUID of ∼ −79‰ and −89‰, respectively, show δD_EPIDOTE values of −115‰ and −125‰. In contrast, δD_EPIDOTE from the mixed meteoric-seawater Svartsengi geothermal system is −68‰; comparable to δD_EPIDOTE from well RN-10 at Reykjanes.Stable isotope compositions of geothermal fluids in isotopic equilibrium with the epidotes at Reykjanes are computed using published temperature dependent hydrogen and oxygen isotope fractionation curves for epidote-water, measured isotope composition of the epidotes and temperatures approximated from the boiling point curve with depth. Calculated δD and δ¹⁸O of geothermal fluids are less than 0‰, suggesting that fluids of meteoric or glacial origin are a significant component of the geothermal solutions. Additionally, δD_FLUID values in equilibrium with geothermal epidote are lower than those of modern-day fluids, whereas calculated δ¹⁸O_FLUID values are within range of the observed fluid isotope composition. We propose that modern δD_EPIDOTE and δD_FLUID values are the result of diffusional exchange between hydrous alteration minerals that precipitated from glacially-derived fluids early in the evolution of the Reykjanes system and modern seawater-derived geothermal fluids. A simplified model of isotope exchange in the Reykjanes geothermal system, in which the average starting δD_ROCK value is −125‰ and the water to rock mass ratio is 0.25, predicts a δD_FLUID composition within 1‰ of average measured values. This model resolves the discrepancy between fluid salinity and isotope composition of Reykjanes geothermal fluids, explains the observed disequilibrium between modern fluids and hydrothermal epidote, and suggests that rock-fluid interaction is the dominant control over the evolution of fluid isotope composition in the hydrothermal system.     

Seasonal variation in kangaroo tooth enamel oxygen and carbon isotopes in southern Australia

Serial sampling of tooth enamel growth increments for carbon and oxygen isotopic analyses of Macropus (kangaroo) teeth was performed to assess the potential for reconstructing paleoseasonality. The carbon isotope composition of tooth enamel apatite carbonate reflects the proportional intake of C₃ and C₄ vegetation. The oxygen isotopic composition of enamel reflects that of ingested and metabolic water. Tooth enamel forms sequentially from the tip of the crown to the base, so dietary and environmental changes during the tooth's formation can be detected. δ¹³C and δ¹⁸O values were determined for a series of enamel samples drilled from the 3rd and 4th molars of kangaroos that were collected along a 900 km north–south transect in southern Australia. The serial sampling method did not yield pronounced seasonal isotopic variation patterns in Macropus enamel. The full extent of dietary isotopic variation may be obscured by attenuation of the isotopic signal during enamel mineralisation. Brachydont (low-crowned) Macropus teeth may be less sensitive to seasonal variation in isotopic composition due to time-averaging during mineralisation. However, geographic variations observed suggest that there may be potential for tracking latitudinal shifts in vegetation zones and seasonal environmental patterns in response to climate change.     

Non-biological fractionation of stable Ca isotopes in soils of the Atacama Desert, Chile

We measured Ca stable isotope ratios (δ^44/40Ca) in an ancient (2 My), hyperarid soil where the primary source of mobile Ca is atmospheric deposition. Most of the Ca in the upper meter of this soil (3.5 kmol m⁻²) is present as sulfates (2.5 kmol m⁻²), and to a lesser extent carbonates (0.4 kmol m⁻²). In aqueous extracts of variably hydrated calcium sulfate minerals, δ^44/40Ca_E values (vs. bulk Earth) increase with depth (1.4 m) from a minimum of −1.91‰ to a maximum of +0.59‰. The trend in carbonate-δ^44/40Ca in the top six horizons resembles that of sulfate-δ^44/40Ca, but with values 0.1-0.6‰ higher. The range of observed Ca isotope values in this soil is about half that of δ^44/40Ca values observed on Earth. Linear correlation among δ^44/40Ca, δ³⁴S and δ¹⁸O values indicates either (a) a simultaneous change in atmospheric input values for all three elements over time, or (b) isotopic fractionation of all three elements during downward transport. We present evidence that the latter is the primary cause of the isotopic variation that we observe. Sulfate-δ³⁴S values are positively correlated with sulfate-δ¹⁸O values (R² = 0.78) and negatively correlated with sulfate δ^44/40Ca_E values (R² = 0.70). If constant fractionation and conservation of mass with downward transport are assumed, these relationships indicate a δ^44/40Ca fractionation factor of −0.4‰ in CaSO₄. The overall depth trend in Ca isotopes is reproduced by a model of isotopic fractionation during downward Ca transport that considers small and infrequent but regularly recurring rainfall events. Near surface low Ca isotope values are reproduced by a Rayleigh model derived from measured Ca concentrations and the Ca fractionation factor predicted by the relationship with S isotopes. This indicates that the primary mechanism of stable isotope fractionation in CaSO₄ is incremental and effectively irreversible removal of an isotopically enriched dissolved phase by downward transport during small rainfall events.     

Stable isotope chemistry of fossil bone as a new paleoclimate indicator

During fossilization, bone is thought to recrystallize and alter chemically on timescales of kyr to a few tens of kyr, i.e., similar to the timescale for formation of soils. Therefore, C- and O-isotope compositions of bone apatite should correlate with trends in soil water composition and aridity, and serve as paleoclimate indicators. This hypothesis was tested by analyzing C- and O-isotope compositions of the CO₃ component of fossil bone apatite from mid-Oligocene through late Pleistocene units in Oregon and western Idaho, including the John Day (19.4-30.0 Ma), Mascall (15.2-15.8 Ma), and Rattlesnake (7.2-7.8 Ma) Formations, whose paleosol sequences have been studied in detail, and the Juntura (10-11 Ma), Hagerman (3.2 Ma), and Fossil Lake (<23-650 ka) fossil localities. Tooth enamel δ¹⁸O values provide a baseline of meteoric water compositions. Stable isotope compositions of bone CO₃ do change in response to broad climatic trends, but show poor correlation with compositions of corresponding paleosol CO₃ at specific horizons. Instead, compositional deviations between bone and paleosol CO₃ correlate with compositional deviations with the next higher paleosol; this suggests that the timescale for fossilization exceeds one paleosol cycle. Based on stratigraphic evidence and simple alteration models, fossilization timescales are estimated at 20-50 kyr, indicating that bone CO₃ will prove most useful for sequences spanning >100 kyr. C-isotopes show negative and strong positive deviations during wet and dry climates respectively, and short-term trends correspond well with changes in aridity within the Mascall and Rattlesnake Formations, as inferred from paleosols. A proposed correction to δ¹⁸O values based on δ¹³C anomalies implies a small, ∼1.5‰ increase in meteoric water δ¹⁸O during the late Oligocene global warming event, consistent with a minimum temperature increase of ∼4 °C. A strong inferred decrease in δ¹⁸O of 4-5‰ after 7 Ma closely parallels compositional changes in tooth enamel, and reflects a doubling in the height of the Cascade Range.     

Variations in the isotopic composition of molybdenum in freshwater lake systems

Variations in molybdenum isotopic composition, spanning the range of ∼ 2.3‰ in the terms of ⁹⁷Mo/⁹⁵Mo ratio, have been measured in sediment cores from three lakes in northern Sweden and north-western Russia. These variations have been produced by both isotopically variable input of Mo into the lakes due to Mo isotopic heterogeneity of bedrock in the drainage basins and fractionation in the lake systems due to temporal variations in limnological conditions. Mo isotope abundances of bedrock in the lake drainage basins have been documented by analysis of Mo isotope ratios of a suite of molybdenite occurrences collected in the studied area and of detrital fractions of the lake sediment cores. The median δ⁹⁷Mo value of the investigated molybdenites is 0.26‰ with standard deviation of 0.43‰ (n = 19), whereas the median δ⁹⁷Mo value of detrital sediment fractions from two lakes is − 0.40‰ with standard deviation of 0.36‰ (n = 15).The isotopic composition of Mo in the sediment cores has been found to be dependent on redox conditions of the water columns and the dominant type of scavenging phases. Hydrous Fe oxides have been shown to be an efficient scavenger of Mo from porewater under oxic conditions. Oxidative precipitation of Fe(II) in the sediments resulted in co-precipitation of Mo and significant authigenic enrichment at the redox boundary. In spite of a pronounced increase in Mo concentration associated with Fe oxides at the redox boundary the isotopic composition of Mo in this zone varies insignificantly, suggesting little or no isotope fractionation during scavenging of Mo by hydrous Fe oxides. In a lake with anoxic bottom water a chironomid-inferred reconstruction of O₂ conditions in the bottom water through the Holocene indicates that increased O₂ concentrations are generally associated with low δ⁹⁷Mo/⁹⁵Mo values of the sediments, whereas lowered O₂ contents of the bottom water are accompanied by relatively high δ⁹⁷Mo/⁹⁵Mo values, thus confirming the potential of Mo isotope data to be a proxy for redox conditions of overlying waters. However, it is pointed out that other processes including input of isotopically heterogeneous Mo and Mn cycling in the redox-stratified water column can be a primary cause of variations in Mo isotopic compositions of lake sediments.     

Fractionation of oxygen isotopes between mammalian bone-phosphate and environmental drinking water

The δ¹⁸O of mammalian bone-phosphate varies linearly with δ¹⁸O of environmental water, but is not in isotopic equilibrium with that water. This situation is explained by a model of δ¹⁸O in body water in which the important fluxes of exchangeable oxygen through the body are taken into account. Fractionation of oxygen isotopes between body and environmental drinking water is dependent on the rates of drinking and respiration. Isotopic fractionation can be estimated from physiological data and the estimates correlate very well with observed fractionation. Species whose water consumption is large relatively to its energy expenditure is sensitive to isotopic ratio changes in environmental water.     

A large epeiric methanogenic Bambuí sea in the core of Gondwana supercontinent?

Carbon isotope compositions of both sedimentary carbonate and organic matter can be used as key proxies of the global carbon cycle and of its evolution through time,as long as they are acquired from waters where the dissolved inorganic carbon(DIC)is in isotope equilibrium with the atmospheric CO2.However,in shallow water platforms and epeiric settings,the influence of local to regional parameters on carbon cycling may lead to DIG isotope variations unrelated to the global carbon cycle.This may be especially true for the terminal Neoproterozoic,when Gondwana assembly isolated waters masses from the global ocean,and extreme positive and negative carbon isotope excursions are recorded,potentially decoupled from global signals.To improve our understanding on the type of information recorded by these excursions,we investigate the pairedδ^13Ccarb andδ^13Corg evolution for an increasingly restricted late Ediacaran-Cambrian foreland system in the West Gondwana interior:the basal Bambui Group.This succession represents a 1~(st)-order sedimentary sequence and records two majorδ^13Ccarb excursions in its two lowermost lower-rank sequences.The basal cap carbonate interval at the base of the first sequence,deposited when the basin was connected to the ocean,hosts antithetical negative and positive excursions forδ^13Ccarb andδ^13Corg,respectively,resulting inΔ^13C values lower than 25‰.From the top of the basal sequence upwards,an extremely positiveδ^13Ccarb excursion is coupled toδ^13Corg,reaching values of+14‰and-14‰,respectively.This positive excursion represents a remarkable basin-wide carbon isotope feature of the Bambui Group that occurs with only minor changes inΔ^13C values,suggesting change in the DIC isotope composition.We argue that this regional isotopic excursion is related to a disconnection between the intrabasinal and the global carbon cycles.This extreme carbon isotope excursion may have been a product of a disequilibria between the basin DIC and atmospheric CO2 induced by an active methanogenesis,favored by the basin restriction.The drawdown of sulfate reservoir by microbial sulfate reduction in a poorly ventilated and dominantly anoxic basin would have triggered methanogenesis and ultimately methane escape to the atmosphere,resulting in a^13C-enriched DIC influenced by methanogenic CO2.Isolated basins in the interior of the Gondwana supercontinent may have represented a significant source of methane inputs to the atmosphere,potentially affecting both the global carbon cycle and the climate.     

Isotopic and geochemical evolution of ground and surface waters in a karst dominated geological setting: a case study from Belize,Central America

Analysis of stable isotopes and major ions in groundwater and surface waters in Belize, Central America was carried out to identify processes that may affect drinking water quality. Belize has a subtropical rainforest/savannah climate with a varied landscape composed predominantly of carbonate rocks and clastic sediments. Stable oxygen (δ¹⁸O) and hydrogen (δD) isotope ratios for surface and groundwater have a similar range and show high d-excess (10–40.8‰). The high d-excess in water samples suggest secondary continental vapor flux mixing with incoming vapor from the Caribbean Sea. Model calculations indicate that moisture derived from continental evaporation contributes 13% to overhead vapor load. In surface and groundwater, concentrations of dissolved inorganic carbon (DIC) ranged from 5.4 to 112.9 mg C/l and δ¹³C_DIC ranged from −7.4 to −17.4‰. SO₄², Ca²⁺ and Mg²⁺ in the water samples ranged from 2–163, 2–6593 and 2–90 mg/l, respectively. The DIC and δ¹³C_DIC indicate both open and closed system carbonate evolution. Combined δ¹³C_DIC and Ca²⁺, Mg²⁺, and SO₄²⁻ suggest additional groundwater evolution by gypsum dissolution and calcite precipitation. The high SO₄²⁻content of some water samples indicates regional geologic control on water quality. Similarity in the range of δ¹⁸O, δD and δ¹³C_DIC for surface waters and groundwater used for drinking water supply is probably due to high hydraulic conductivities of the karstic aquifers. The results of this study indicate rapid recharge of groundwater aquifers, groundwater influence on surface water chemistry and the potential of surface water to impact groundwater quality and vise versa.     

Transfer and early diagenesis of biogenic silica oxygen isotope signals during settling and sedimentation of diatoms in a temperate freshwater lake (Lake Holzmaar, Germany)

We have investigated the transfer of oxygen isotope signals of diatomaceous silica (δ¹⁸O_diatom) from the epilimnion (0-7 m) through the hypolimnion to the lake bottom (∼20 m) in freshwater Lake Holzmaar, Germany. Sediment-traps were deployed in 2001 at depths of 7 and 16 m to harvest fresh diatoms every 28 days. The 7 m trap collected diatoms from the epilimnion being the main zone of primary production, while the 16 m trap collected material already settled through the hypolimnion. Also a bottom sediment sample was taken containing diatom frustules from approximately the last 25 years. The δ¹⁸O_diatom values of the 7 m trap varied from 29.4‰ in spring/autumn to 26.2‰ in summer according to the temperature dependence of oxygen isotope fractionation and represent the initial isotope signal in this study. Remarkably, despite the short settling distance δ¹⁸O_diatom values of the 7 and the 16 m trap were identical only during spring and autumn seasons while from April to September δ¹⁸O_diatom values of the 16 m trap were roughly ∼1.5‰ enriched in ¹⁸O compared to those of the 7 m trap. Isotopic exchange with the isotopically lighter water of the hypolimnion would shift the δ¹⁸O_diatom value to lower values during settling from 7 to 16 m excluding this process as a cause for the deviation. Dissolution of opal during settling with intact organic coatings of the diatom cells and near neutral pH of the water should only cause a minor enrichment of the 16 m values. Nevertheless, opal from the bottom sediment was found to be 2.5‰ enriched in ¹⁸O compared to the weighted average of the opal from the 7 m trap. Thus, resuspension of bottom material must have contributed to the intermediate δ¹⁸O_diatom signal of the 16 m trap during summer. Dissolution experiments allowed further investigation of the cause for the remarkably enriched δ¹⁸O_diatom value of the bottom sediment. Experiments with different fresh diatomaceous materials show an increase of opaline ¹⁸O at high pH values which is remarkably reduced when organic coatings of the cells still exist or at near neutral pH. In contrast, high pH conditions do not affect the δ¹⁸O_diatom values of sub-fossil and even fossil opal. IR analyses show that the ¹⁸O enrichment of the sedimentary silica is associated with a decrease in Si-OH groups and the formation of Si-O-Si linkages. This indicates a silica dehydroxylation process as cause for the isotopic enrichment of the bottom sediment. Silica dissolution and dehydroxylation clearly induce a maturation process of the diatom oxygen isotope signal presumably following an exponential behaviour with a rapid initial phase of signal alteration. The dynamics of this process is of particular importance for the quantitative interpretation of sedimentary δ¹⁸O_diatom values in terms of palaeothermometry.     

Dike intrusions into bituminous coal, Illinois Basin: H, C, N, O isotopic responses to rapid and brief heating

Unlike long-term heating in subsiding sedimentary basins, the near-instantaneous thermal maturation of sedimentary organic matter near magmatic intrusions is comparable to artificial thermal maturation in the laboratory in terms of short duration and limited extent. This study investigates chemical and H, C, N, O isotopic changes in high volatile bituminous coal near two Illinois dike contacts and compares observed patterns and trends with data from other published studies and from artificial maturation experiments. Our study pioneers in quantifying isotopically exchangeable hydrogen and measuring the D/H (i.e., ²H/¹H) ratio of isotopically non-exchangeable organic hydrogen in kerogen near magmatic contacts. Thermal stress in coal caused a reduction of isotopically exchangeable hydrogen in kerogen from 5% to 6% in unaltered coal to 2-3% at contacts, mostly due to elimination of functional groups (e.g., OH, COOH, NH₂). In contrast to all previously published data on D/H in thermally matured organic matter, the more mature kerogen near the two dike contacts is D-depleted, which is attributed to (i) thermal elimination of D-enriched functional groups, and (ii) thermal drying of hydrologically isolated coal prior to the onset of cracking reactions, thereby precluding D-transfer from relatively D-enriched water into kerogen. Maxima in organic nitrogen concentration and in the atomic N/C ratio of kerogen at a distance of ∼2.5 to ∼3.5 m from the thicker dike indicate that reactive N-compounds had been pyrolytically liberated at high temperature closer to the contact, migrated through the coal seam, and recombined with coal kerogen in a zone of lower temperature. The same principle extends to organic carbon, because a strong δ¹³C_kerogen vs. δ¹⁵N_kerogen correlation across 5.5 m of coal adjacent to the thicker dike indicates that coal was functioning as a flow-through reactor along a dynamic thermal gradient facilitating back-reactions between mobile pyrolysis products from the hot zone as they encounter less hot kerogen. Vein and cell filling carbonate is most abundant in highest rank coals where carbonate δ¹³C_VPDB and δ¹⁸O_VSMOW values are consistent with thermal generation of ¹³C-depleted and ¹⁸O-enriched CO₂ from decarboxylation and pyrolysis of organic matter. Lower background concentrations of ¹³C-enriched carbonate in thermally unaffected coal may be linked to ¹³C-enrichment in residual CO₂ in the process of CO₂ reduction via microbial methanogenesis.Our compilation and comparison of available organic H, C, N isotopic findings on magmatic intrusions result in re-assessments of majors factors influencing isotopic shifts in kerogen during magmatic heating. (i) Thermally induced shifts in organic δD values of kerogen are primarily driven by the availability of water or steam. Hydrologic isolation (e.g., near Illinois dikes) results in organic D-depletion in kerogen, whereas more common hydrologic connectivity results in organic D-enrichment. (ii) Shifts in kerogen (or coal) δ¹³C and δ¹⁵N values are typically small and may follow sinusoidal patterns over short distances from magmatic contacts. Laterally limited sampling strategies may thus result in misleading and non-representative data. (iii) Fluid transport of chemically active, mobile carbon and nitrogen species and recombination reactions with kerogen result in isotopic changes in kerogen that are unrelated to the original, autochthonous part of kerogen.