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1.
《Organic Geochemistry》2012,42(12):1269-1276
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 δ13Cbulk and δDC31 values with R2 = 0.60 (δ13CC31 and δDC31 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. 相似文献
2.
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. 相似文献
3.
We measured hydrogen isotope compositions (δD) of high-molecular-weight n-alkanes (C27-C33) from grasses grown in greenhouses and collected from the US Great Plains. In both cases, n-alkanes from C4 grasses are enriched in D by more than 20‰ relative to those from C3 grasses. The apparent enrichment factor (εC29-GW) between C29n-alkane and greenhouse water is −165 ± 12‰ for C3 grasses and −140 ± 15‰ for C4 grasses. For samples from the Great Plains, δD values of C29n-alkanes range from −280 to −136‰, with values for C4 grasses ca. 21‰ more positive than those for C3 grasses from the same site. Differences in C3 and C4 grass n-alkane δD values are consistent with the shorter interveinal distance in C4 grass leaves, and greater back-diffusion of enriched water from stomata to veins, than in C3 grass leaves. Great Plains’ grass n-alkane isotopic ratios largely reflect precipitation δD values. However, the offset or apparent fractionation between n-alkanes and precipitation is not uniform and varies with annual precipitation and relative humidity, suggesting climatic controls on lipid δD values. The dryer sites exhibit smaller absolute apparent fractionation indicative of D-enrichment of source waters through transpiration and/or soil evaporation. To explore the relationship between climate and n-alkane δD values, we develop three models. (1) The ‘direct analog’ model estimates δDC29 values simply by applying the apparent enrichment factors, εC29-GW, observed in greenhouse grasses to precipitation δD values from the Great Plains. (2) The ‘leaf-water’ model uses a Craig-Gordon model to estimate transpirational D-enrichment for both greenhouse and field sites. The transpiration-corrected enrichment factors between C29 and bulk leaf-water, εC29-GW, calculated from the greenhouse samples (−181‰ for C3 and −157‰ for C4) are applied to estimate δDC29 values relative to modeled bulk leaf-water δD values. (3) The ‘soil- and leaf-water’ model estimates the combined effects of soil evaporation, modeled by analogy with a flow-through lake, and transpiration on δDC29 values. Predictions improve with the addition of the explicit consideration of transpiration and soil evaporation, indicating that they are both important processes in determining plant lipid δD values. D-enrichment caused by these evaporative processes is controlled by relative humidity, suggesting that important climatic information is recorded in leaf wax n-alkane δD values. Calibration studies such as this one provide a baseline for future studies of plant-water-deuterium systematics and form the foundation for interpretation of plant wax hydrogen isotope ratios as a paleo-aridity proxy. 相似文献
4.
《China Geology》2020,3(4):602-610
Thirty-nine crude oils and twenty-one rock samples from Niger Delta Basin, Nigeria have been characterized based on their isotope compositions by elemental analysis-isotope ratio mass spectrometry and gas chromatography-isotope ratio mass spectrometry. The bulk carbon isotopic values of the whole rock extracts, saturate and aromatic fractions range from –28.7‰ to –26.8‰, –29.2‰ to –27.2 ‰ and –28.5 ‰ to –26.7 ‰, respectively while the bulk carbon isotopic values of the whole oils, saturate and aromatic fractions range from –25.4 ‰ to –27.8 ‰, –25.9 ‰ to –28.4 ‰ and –23.5 ‰ to –26.9 ‰, respectively. The average carbon isotopic compositions of individual alkanes (nC12-nC33) in the rock samples range from –34.9‰ to –28.2‰ whereas the average isotopic values of individual n-alkanes in the oils range from –31.1‰ to –23.8‰. The δ13C isotope ratios of pristane and phytane in the rock samples range from –29.2 ‰ to –28.2 ‰ and –30.2 ‰ to –27.4 ‰ respectively while the pristane and phytane isotopic values range from –32.1‰ to –21.9‰ and –30.5‰ to –26.9‰, respectively. The isotopic values recorded for the samples indicated that the crude oils were formed from the mixed input of terrigenous and marine organic matter and deposited under oxic to sub-oxic condition in lacustrine-fluvial/deltaic environments. The stable carbon isotopic compositions were found to be effective in assessing the origin and depositional environments of crude oils in the Niger Delta Basin. 相似文献
5.
Biodegraded oils are widely distributed in the Liaohe basin, China. In order to develop effective oil-source correlation tools specifically for the biodegraded oils, carbon isotopic compositions of individual n-alkanes from crude oils and their asphaltene pyrolysates have been determined using the gas chromatography–isotope ratio mass spectrometry technique. No significant fractionation in the stable carbon isotopic ratios of n-alkanes in the pyrolysates of oil asphaltenes was found for anhydrous pyrolysis carried out at temperatures below 340°C. This suggests that the stable carbon isotopic distribution of n-alkanes (particularly in the C16–C29 range) in the asphaltene pyrolysates can be used as a correlation tool for severely biodegraded oils from the Liaohe Basin. Comparison of the n-alkane isotopic compositions of the oils with those of asphaltene pyrolysates shows that this is a viable method for the differentiation of organic facies variation and post-generation alterations. 相似文献
6.
《Applied Geochemistry》2003,18(10):1641-1651
Compound-specific H isotope analysis has been used to monitor bioremediation of petroleum hydrocarbons. However, the success of this approach requires a full evaluation of the isotopic effects resulting from evaporation, because light petroleum hydrocarbons undergo both biodegradation and evaporation under natural conditions. The authors determined the H isotope fractionation of common volatile petroleum hydrocarbons, including the C10–C14 n-alkanes, MTBE (tert-butyl methyl ether), and BTEX (benzene, toluene, ethylbenzene, p-xylene and o-xylene) during progressive vaporization under simulated experimental conditions. A decrease in δD values for n-alkanes of up to 33.3‰ and up to 44.5‰ for BTEX compounds when 99% of these substances had evaporated was observed. The results also show that H isotope fractionation increases with n-alkane chain length. Such fractionation patterns are interpreted in terms of competition between the decreased intermolecular binding energy in D-enriched species, and the isotope effect due to the mass difference. In contrast to hydrocarbons, methanol and ethanol show H isotopic enrichment during vaporization, indicating that H-bonding, when present in organic molecules, plays a controlling role on the vapor pressure of different isotope species. 相似文献
7.
The carbon isotope composition (δ13C values) of long chain n-alkanes in lake sediments has been considered a reliable means of tracking changes in the terrigenous contribution of plants with C3 and C4 photosynthetic pathways. A key premise is that long chain leaf wax components used for isotope analysis are derived primarily from terrigenous higher plants. The role of aquatic plants in affecting δ13C values of long chain n-alkanes in lacustrine sediments may, however, have long been underestimated. In this study, we found that a large portion of long chain n-alkanes (C27 and C29) in nearshore sediments of the Lake Qinghai catchment was contributed by submerged aquatic plants, which displayed a relatively positive carbon isotope composition (e.g. −26.7‰ to −15.7‰ for C29) similar to that of terrestrial C4 plants. Thus, the use of δ13C values of sedimentary C27 and C29 n-alkanes for tracing terrigenous vegetation composition may create a bias toward significant overestimation/underestimation of the proportion of terrestrial C4 plants. For sedimentary C31, however, the contribution from submerged plants was minor, so that the δ13C values for C31 n-alkane in surface sediments were in accord with those of the modern terrestrial vegetation in the Lake Qinghai region. Moreover, we found that changes in the δ13C values of sedimentary C27 and C29 n-alkanes were closely related to water depth variation. Downcore analysis further demonstrated the significant influence of endogenous lipids in lake sediments for the interpretation of terrestrial C4 vegetation and associated environment/climate reconstruction. In conclusion, our results suggest that the δ13C values of sedimentary long chain n-alkanes (C27, C29 and C31) may carry different environmental signals. While the δ13C values of C31 were a reliable proxy for C4/C3 terrestrial vegetation composition, the δ13C values of C27 and C29 n-alkanes may have recorded lake ecological conditions and sources of organic carbon, which might be affected by lake water depth. 相似文献
8.
《Applied Geochemistry》2005,20(3):455-464
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. 相似文献
9.
European settlement and drought have significantly impacted the hydrology of the Coorong, a shallow coastal lagoon complex in South Australia, which is part of a terminal wetland at the mouth of the River Murray. An increased salinity associated with lower water levels and progressive isolation from ocean flushes contributed to a severe decline in ecological diversity over the past decades. Here we have conducted a molecular and stable isotopic study of a sedimentary core from the northern Coorong Lagoon spanning more than 5000 years to investigate the recent palaeoenvironmental history of the ecosystem. Major alterations were evident in many biogeochemical parameters in sediments deposited after the 1950s coinciding with the beginning of intensified water regulations. The most prominent shift occurred in δ13C profiles of C21–C33 n-alkanes from average values of −23.5‰ to an average of −28.2‰. Further changes included decreases in carbon preference index (CPI) and average chain length (ACL) of the n-alkane series as well as significant increases in algal (e.g. C20 HBI, long chain alkenes and C29-alkadiene) and bacterial (e.g. 13C depleted short chain n-alkanes and hopanoids, δ13C: −35.9‰ to −30.1‰) derived hydrocarbons. Long chain n-alkanes with a strong odd/even predominance as observed here are typically attributed to terrigenous plants. In the Coorong however, terrigenous input to sedimentary OM is only minor. Therefore changes in the before mentioned parameters were attributed to a source transition from a major contribution of macrophytes towards predominantly microalgae and bacteria.δD values of C21–C33 n-alkanes showed a general trend towards more enriched values in younger sediments, indicating an overall rising salinity. However, the most pronounced positive shift in these profiles again occurred after the 1950s. Altogether this study demonstrates that the recent human induced changes of the Coorong hydrology, compounded by a severe drought led to an increase in salinity and alterations of primary production which have been much more significant than natural variations occurring throughout the Holocene over several thousands of years. 相似文献
10.
Production of n-alkyl lipids in living plants and implications for the geologic past 总被引：2，自引：0，他引：2
Aaron F. Diefendorf Katherine H. Freeman Heather V. Graham 《Geochimica et cosmochimica acta》2011,75(23):7472-7485
Leaf waxes (i.e., n-alkyl lipids or n-alkanes) are land-plant biomarkers widely used to reconstruct changes in climate and the carbon isotopic composition of the atmosphere. There is little information available, however, on how the production of leaf waxes by different kinds of plants might influence the abundance and isotopic composition of n-alkanes in sedimentary archives. This lack of information increases uncertainty in interpreting n-alkyl lipid abundance and δ13C signals in ancient settings. We provide here n-alkyl abundance distributions and carbon isotope fractionation data for deciduous and evergreen angiosperm and gymnosperm leaves from 46 tree species, representing 24 families. n-Alkane abundances are significantly higher in angiosperms than gymnosperms; many of the gymnosperm species investigated did not produce any n-alkanes. On average, deciduous angiosperms produce 200 times more n-alkanes than deciduous gymnosperms. Although differences between angiosperms and gymnosperms dominate the variance in n-alkane abundance, leaf life-span is also important, with higher n-alkane abundances in longer-lived leaves. n-Alkanol abundances covary with n-alkanes, but n-alkanoic acids have similar abundances across all plant groups. Isotopic fractionation between leaf tissue and individual alkanes (εlipid) varies by as much as 10‰ among different chain lengths. Overall, εlipid values are slightly lower (−4.5‰) for angiosperm than for gymnosperm (−2.5‰) n-alkanes. Angiosperms commonly express slightly higher Δleaf (photosynthetic discrimination) relative to gymnosperms under similar growth conditions. As a result, angiosperm n-alkanes are expected to be generally 3-5‰ more depleted in 13C relative to gymnosperm alkanes for the same locality. Differences in n-alkane production indicate the biomarker record will largely (but not exclusively) reflect angiosperms if both groups were present, and also that evergreen plants will likely be overrepresented compared with deciduous ones. We apply our modern lipid abundance patterns and εlipid results to constrain the magnitude of the carbon isotope excursion (CIE) at the onset of the Paleocene-Eocene Thermal Maximum (55.8 Ma). When Bighorn Basin (WY) sediment n-alkanes are interpreted in context of floral changes and modern n-alkane production estimates for angiosperms and gymnosperms, the CIE is greater in magnitude (−5.6‰) by ∼1‰ compared to previous estimates that do not take into account n-alkane production. 相似文献
11.
Yongchun Tang Yongsong Huang Yi Wang Bruno Gillaizeau Qisheng Ma 《Geochimica et cosmochimica acta》2005,69(18):4505-4520
A quantitative kinetic model has been proposed to simulate the large D and 13C isotope enrichments observed in individual n-alkanes (C13-C21) during artificial thermal maturation of a North Sea crude oil under anhydrous, closed-system conditions. Under our experimental conditions, average n-alkane δ13C values increase by ∼4‰ and δD values increase by ∼50‰ at an equivalent vitrinite reflectance value of 1.5%. While the observed 13C-enrichment shows no significant dependence on hydrocarbon chain length, thermally induced D-enrichment increases with increasing n-alkane carbon number. This differential fractionation effect is speculated to be due to the combined effect of the greater extent of thermal cracking of higher molecular weight, n-alkanes compared to lower molecular weight homologues, and the generation of isotopically lighter, lower molecular weight compounds. This carbon-number-linked hydrogen isotopic fractionation behavior could form the basis of a new maturity indicator to quantitatively assess the extent of oil cracking in petroleum reservoirs. Quantum mechanical calculations of the average change in enthalpy (ΔΔH‡) and entropy (ΔΔS‡) as a result of isotopic substitution in n-alkanes undergoing homolytic cleavage of C-C bonds lead to predictions of isotopic fractionation that agree quite well with our experimental results. For n-C20 (n-icosane), the changes in enthalpy are calculated to be ∼1340 J mol-1 (320 cal mol-1) and 230 J mol-1 (55 cal mol-1) for D-H and 13C-12C, respectively. Because the enthalpy term associated with hydrogen isotope fractionation is approximately six times greater than that for carbon, variations in δD values for individual long-chain hydrocarbons provide a highly sensitive measure of the extent of thermal alteration experienced by the oil. Extrapolation of the kinetic model to typical geological heating conditions predicts significant enrichment in 13C and D for n-icosane at equivalent vitrinite reflectance values corresponding to the onset of thermal cracking of normal alkanes. The experimental and theoretical results of this study have significant implications for the use of compound-specific hydrogen isotope data in petroleum geochemical and paleoclimatological studies. However, there are many other geochemical processes that will significantly affect observed hydrogen isotopic compositions (e.g., biodegradation, water washing, isotopic exchange with water and minerals) that must also be taken into consideration. 相似文献
12.
We measured molecular distributions and compound-specific hydrogen (δD) and stable carbon isotopic ratios (δ13C) of mid- and long-chain n-alkanes in forest soils, wetland peats and lake sediments within the Dorokawa watershed, Hokkaido, Japan, to better understand sources and processes associate with delivery of terrestrial organic matter into the lake sediments. δ13C values of odd carbon numbered C23-C33n-alkanes ranged from −37.2‰ to −31.5‰, while δD values of these alkanes showed a large degree of variability that ranged from −244‰ to −180‰. Molecular distributions in combination with stable carbon isotopic compositions indicate a large contribution of C3 trees as the main source of n-alkanes in forested soils whereas n-alkanes in wetland soil are exclusively derived from marsh grass and/or moss. We found that the n-alkane δD values are much higher in forest soils than wetland peat. The higher δD values in forest samples could be explained by the enrichment of deuterium in leaf and soil waters due to increased evapotranspiration in the forest or differences in physiology of source plants between wetland and forest. A δ13C vs. δD diagram of n-alkanes among forest, wetland and lake samples showed that C25-C31n-alkanes deposited in lake sediments are mainly derived from tree leaves due to the preferential transport of the forest soil organic matter over the wetland or an increased contribution of atmospheric input of tree leaf wax in the offshore sites. This study demonstrates that compound-specific δD analysis provides a useful approach for better understanding source and transport of terrestrial biomarkers in a C3 plant-dominated catchment. 相似文献
13.
Moss covered, high latitude wetlands hold large amounts of terrestrial organic matter (OM), which may be vulnerable to expected climate warming. Molecular analysis of fluvially transported material from these regions can distinguish between different sources of terrestrial OM. Sphagnum moss may represent one of the major sources. This study aimed to quantitatively establish a molecular proxy for identifying Sphagnum-derived OM from high latitude peatlands in the sub-Arctic coastal ocean. We collected and analyzed Sphagnum species throughout northern Sweden and Finland. Results show that the C25/(C25 + C29) n-alkane ratio is most suitable for terrestrial OM source apportionment in these coastal regions since, compared to other n-alkane Sphagnum proxies, it shows (i) the least variation between species, (ii) the most constant values for different latitudinal regimes and (iii) the largest dynamic range to the higher plant end member in two-source mixing models. Application of the proxy to surface sediments and suspended particulate matter in the sub-Arctic northern Baltic Sea shows that 68–103% of the terrestrial OM fraction is derived from Sphagnum-rich peatland. We recommend that future studies on terrestrial OM fluxes into (sub-)Arctic regions should apply the C25/(C25 + C29) proxy to improve insight into the contribution of Sphagnum-derived terrestrial OM from climate-vulnerable, high latitude wetlands. 相似文献
14.
D. A. Bushnev N. S. Burdelnaya I. V. Goncharov V. V. Samoylenko M. A. Veklich 《Doklady Earth Sciences》2018,480(1):611-614
The molecular and isotopic composition of an extract from the rocks of the Bazhenov Formation in the southeast part of Western Siberia, oils that are genetically related to this formation, and products of hydrous pyrolysis of the organic matter of oil shale (Middle Volgian) of the East European Platform were studied. Common features and differences in their molecular composition were shown. The carbon isotope composition for C14–C30n-alkanes was determined for the first time; a negative isotope anomaly was revealed for C26n-alkane in all samples studied. It was concluded that in spite of the geographical distance, specific biota was revealed in the Volga Basin. This biota conditioned an isotopic indicator, which is genetically significant. 相似文献
15.
Hydrogen isotopic composition of n-alkanes was measured in sediments from an excavated profile of the Early Cretaceous Yixian Formation in Liaoning Province, NE China, aiming to assess the significance of the δD value of n-alkanes in ancient lacustrine sediments as the indicator for determining the source inputs of organic matters and paleoclimatic conditions. The δD values of n-alkanes are in the range of − 250‰ to − 85‰ and display an obvious three-stage variation pattern through the profile, which is consistent with the distribution of the dominated n-alkanes and the profile of their δ13C values. The δD and δ13C values of n-alkanes suggest that short-chain n-alkanes are primarily derived from photosynthetic bacteria and algae; n-C29 and n-C31 are mainly originated from terrestrial higher plants; n-C28 and n-C30 may be derived from the same precursor but via the different biological mechanism of hydrogen isotopic fractionation; while the source inputs of medium-chain n-alkanes are more complicated, with n-C23 being derived from some specific algae or biosynthesized by various aquatic organisms. The paleoclimatic conditions are reconstructed via two approaches. The reconstructed hydrogen isotopic values of lake water and meteoric water (expressed as δDLW and δDMW, respectively) were at the intervals of − 51.8‰ to 17.0‰ and − 118.1‰ to − 43.5‰, respectively, indicating a general climate transition from semi-arid to arid. The calculated ΔδDLW-MW values vary from 37.0‰ to 89.1‰ and display a similar but a significant large-scale variation trend with the ΔδDC23 ‐ long (− 28.8‰ to 85.0‰; long represents long-chain n-alkanes) and ΔδDmid-long (− 15.4‰ to 43.4‰; mid represents medium-chain n-alkanes) values. The discrepancy may be attributed to the source input overlap for n-alkanes and the uncertainties of εwater/lipid values. The coupling of ΔδDC23 ‐ long, ΔδDmid-long and ΔδDLW-MW values with the paleoclimatic evidence indicates that the δD values of n-alkanes could be more sensitive to the change of paleoclimatic conditions. 相似文献
16.
Michael Zech Nikolai Pedentchouk Katharina Leiber Slobodan B. Markovi? 《Geochimica et cosmochimica acta》2011,75(17):4917-4928
During the last decade, compound-specific hydrogen isotope analysis of plant leaf-wax and sedimentary n-alkyl lipids has become a promising tool for paleohydrological reconstructions. However, with the exception of several previous studies, there is a lack of knowledge regarding possible effects of early diagenesis on the δD values of n-alkanes. We therefore investigated the n-alkane patterns and δD values of long-chain n-alkanes from three different C3 higher plant species (Acer pseudoplatanus L., Fagus sylvatica L. and Sorbus aucuparia L.) that have been degraded in a field leaf litterbag experiment for 27 months.We found that after an initial increase of long-chain n-alkane masses (up to ∼50%), decomposition took place with mean turnover times of 11.7 months. Intermittently, the masses of mid-chain n-alkanes increased significantly during periods of highest total mass losses. Furthermore, initially high odd-over-even predominances (OEP) declined and long-chain n-alkane ratios like n-C31/C27 and n-C31/C29 started to converge to the value of 1. While bulk leaf litter became systematically D-enriched especially during summer seasons (by ∼8‰ on average over 27 months), the δD values of long-chain n-alkanes reveal no systematic overall shifts, but seasonal variations of up to 25‰ (Fagus, n-C27, average ∼13‰).Although a partly contribution by leaf-wax n-alkanes by throughfall cannot be excluded, these findings suggest that a microbial n-alkane pool sensitive to seasonal variations of soil water δD rapidly builds up. We propose a conceptual model based on an isotope mass balance calculation that accounts for the decomposition of plant-derived n-alkanes and the build-up of microbial n-alkanes. Model results are in good agreement with measured n-alkane δD results. Since microbial ‘contamination’ is not necessarily discernible from n-alkane concentration patterns alone, care may have to be taken not to over-interpret δD values of sedimentary n-alkanes. Furthermore, since leaf-water is generally D-enriched compared to soil and lake waters, soil and water microbial n-alkane pools may help explain why soil and sediment n-alkanes are D-depleted compared to leaves. 相似文献
17.
《地学前缘(英文版)》2023,14(2):101501
Comprehensive nitrogen biogeochemical cycle has been reconstructed for representative lacustrine organic-rich sedimentary rock in China, namely the Triassic Yanchang Formation (YF, 199–230 Ma) in Ordos and the Cretaceous Qingshankou Formation (QF, 86–92 Ma) in Songliao basins, by evaluating the organic and inorganic nitrogen isotopic compositions rather than only organic or bulk nitrogen isotopic compositions. The results indicate that the nitrogen isotope values of bulk rock (δ15Nbulk) in the non-metamorphic stage are significantly different from that of kerogen, which challenge the conceptual framework of sedimentary nitrogen isotope interpretation. The δ15Nbulk from the YF and QF were lower than their respective the nitrogen isotope values of kerogen (δ15Nker), with offsets up to ～5.1‰, which have the inverse relationship for the metamorphosed rock. Thermal evolution did not significantly modify the δ15N of bulk rock and kerogen. The δ15N of sediments from the YF (δ15Nbulk, 1.6‰–5.6‰) were lower than that of rock from the QF (δ15Nbulk, 10.2‰–15.3‰). The nitrogen isotope values of silicate incorporated nitrogen (δ15Nsil) were slightly lower than those of the δ15Nker in the YF and obviously lower for the QF. The fact that different nitrogen cycles occur in the YF and QF due to the different depositional redox conditions leads to different isotopic results. The YF water environment dominated by oxic conditions is not conducive to the occurrence of denitrification and anammox, and no abundant N2 loss leads to the relatively light δ15Nbulk. In the stratified water for the QF, redox transition zone promotes denitrification and anammox, resulting in the heavy δ15Nbulk of rock and promotes the DNRA, resulting in heavy δ15Nker and low δ15Nsil. 相似文献
18.
Jonathan Nichols Stephen T. Jackson Yongsong Huang 《Geochimica et cosmochimica acta》2010,74(4):1407-1416
We have developed a new approach to quantitatively reconstruct past changes in evaporation based on compound-specific hydrogen isotope ratios of vascular plant and Sphagnum biomarkers in ombrotrophic peatland sediments. We show that the contrast in H isotopic ratios of water available to living Sphagnum (top 20 cm) and in the rooting zone of peatland vascular plants can be used to estimate “?”—the fraction of water remaining after evaporation. Vascular plant leaf waxes record H isotopic ratios of acrotelm water, which carries the D/H ratio signature of precipitation and is little affected by evaporation, whereas the Sphagnum biomarker, C23n-alkane, records H isotopic ratios of the water inside its cells and between its leaves, which is strongly affected by evaporation at the bog surface. Evaporation changes can then be deduced by comparing H isotopic ratios of the two types of biomarkers. We calibrated D/H ratios of C23n-alkane to source water with lab-grown Sphagnum. We also tested our isotopic model using modern surface samples from 18 ombrotrophic peatlands in the Midwestern United States. Finally, we generated a 3000-year downcore reconstruction from Minden Bog, Michigan, USA. Our new record is consistent with records of other parameters from the same peatland derived from different proxies and allows us to differentiate precipitation supply and evaporative loss. 相似文献
19.
Nikolai Pedentchouk 《Geochimica et cosmochimica acta》2006,70(8):2063-2072
This study investigates the extent of post-depositional alteration of δD values of n-alkyl lipids, isoprenoids, and kerogen isolated from a continuous 450 m core that covers the transition from thermally immature to early mature sediments in the lacustrine Kissenda Formation, Lower Cretaceous, Gabon Basin. Large variations in δD values (up to 40‰ for nC17 and up to 30‰ for nC29 alkanes as well as up to 10‰ for kerogen) in closely spaced samples are evident throughout the core and remain preserved even at the bottom of the section. δD values of individual n-alkanes show a slight overall D-enrichment with depth, and a general trend of increasing δD values with increasing n-alkane chain length characterizes all samples, particularly in those below 600 m depth. Hydrogen isotopic compositions of kerogen samples overlap with those of n-alkanes throughout the section. δD values of pristane and phytane are more negative than those of nC17 alkane by as much as 120‰ at shallow depths but increase dramatically and approach δD values of nC17 alkane in the samples closest to the oil window. Integration of analytical and computational results indicates that: (1) n-alkanes and isoprenoids have the potential to preserve the original biological signal before the onset of oil generation; (2) isomeric and structural rearrangements taking place at the beginning stages of oil generation do not influence significantly the δD values of n-alkanes and kerogen. However, these processes have a major effect on the isotopic composition of isoprenoids, causing isotopic D-enrichment up to 90‰. 相似文献
20.
Francesca A. McInerney Brent R. Helliker Katherine H. Freeman 《Geochimica et cosmochimica acta》2011,75(2):541-554
We analyzed hydrogen isotope ratios of high-molecular weight n-alkanes (δDl) and oxygen isotope ratios of α-cellulose (δ18OC) 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 δDl signatures. In the different relative humidity environments of the growth chambers, we observed clear and predictable effects of leaf-water enrichment on δ18OC 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 δDl values. In field samples, we saw clear evidence of enrichment (correlating with relative humidity of the field sites) in both δ18OC and δDl. 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 δDl, 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 δ18OC values. In contrast, the calculated leaf water hydrogen isotope ratios are more enriched than what is required to predict observed δDl values. These calculations lend support to the conclusion that while δ18OC reflects both soil evaporation and transpiration, δDl 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. 相似文献