TY - JOUR A1 - Sachse, Dirk A1 - Kahmen, Ansgar A1 - Gleixner, Gerd T1 - Significant seasonal variation in the hydrogen isotopic composition of leaf-wax lipids for two deciduous tree ecosystems (Fagus sylvativa and Acer pseudoplatanus) N2 - Compound specific hydrogen isotope ratios (delta D) 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 delta D values for two different temperate deciduous forest ecosystems that are dominated by two different tree species, Beech (Fagus sylvatica) and Maple (Acer pseudoplatanus). We found significant seasonal variations for both tree species in n-alkane delta D 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 parts per thousand at the same time when overall n-alkane concentrations were lowest. Since delta D values of soil water at 5 and 10 cm depth, which we assume represent the delta D value of the major water source for the investigated beech trees, were enriched in autumn compared to the spring by 30 parts per thousand, whereas n-alkane delta D values increased only by 10 parts per thousand, we observed variations in the apparent fractionation between beech leaf derived n-alkanes and soil water of up to 20 parts per thousand 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 delta D values over time implies a continuous de nova 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. Y1 - 2009 UR - http://www.sciencedirect.com/science/journal/01466380 U6 - https://doi.org/10.1016/j.orggeochem.2009.02.008 SN - 0146-6380 ER - TY - JOUR A1 - Kahmen, Ansgar A1 - Dawson, Todd E. A1 - Vieth, Andrea A1 - Sachse, Dirk T1 - Leaf wax n-alkane delta D values are determined early in the ontogeny of Populus trichocarpa leaves when grown under controlled environmental conditions JF - Plant, cell & environment : cell physiology, whole-plant physiology, community physiology N2 - The stable hydrogen isotope ratios (delta D) of leaf wax n-alkanes record valuable information on plant and ecosystem water relations. It remains, however, unknown if leaf wax n-alkane delta D values record only environmental variation during the brief period of time of leaf growth or if leaf wax n-alkane delta D values are affected by environmental variability throughout the entire lifespan of a leaf. To resolve these uncertainties, we irrigated Populus trichocarpa trees with a pulse of deuterium-enriched water and used compound-specific stable hydrogen isotope analyses to test if the applied tracer could be recovered from leaf wax n-alkanes of leaves that were at different stages of their development during the tracer application. Our experiment revealed that only leaf wax n-alkanes from leaves that had developed during the time of the tracer application were affected, while leaves that were already fully matured at the time of the tracer application were not. We conclude from our study that under controlled environmental conditions, leaf wax n-alkanes are synthesized only early in the ontogeny of a leaf. Our experiment has implications for the interpretation of leaf wax n-alkane delta D values in an environmental context, as it suggests that these compounds record only a brief period of the environmental variability that a leaf experiences throughout its life. KW - cuticle KW - plant water relations KW - stable isotopes Y1 - 2011 U6 - https://doi.org/10.1111/j.1365-3040.2011.02360.x SN - 0140-7791 VL - 34 IS - 10 SP - 1639 EP - 1651 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Kahmen, Ansgar A1 - Sachse, Dirk A1 - Arndt, Stefan K. A1 - Tu, Kevin P. A1 - Farrington, Heraldo A1 - Vitousek, Peter M. A1 - Dawson, Todd E. T1 - Cellulose delta O-18 is an index of leaf-to-air vapor pressure difference (VPD) in tropical plants JF - Proceedings of the National Academy of Sciences of the United States of America N2 - Cellulose in plants contains oxygen that derives in most cases from precipitation. Because the stable oxygen isotope composition, delta O-18, of precipitation is associated with environmental conditions, cellulose delta O-18 should be as well. However, plant physiological models using delta O-18 suggest that cellulose delta O-18 is influenced by a complex mix of both climatic and physiological drivers. This influence complicates the interpretation of cellulose delta O-18 values in a paleo-context. Here, we combined empirical data analyses with mechanistic model simulations to i) quantify the impacts that the primary climatic drivers humidity (e(a)) and air temperature (T-air) have on cellulose delta O-18 values in different tropical ecosystems and ii) determine which environmental signal is dominating cellulose delta O-18 values. Our results revealed that e(a) and T-air equally influence cellulose delta O-18 values and that distinguishing which of these factors dominates the delta O-18 values of cellulose cannot be accomplished in the absence of additional environmental information. However, the individual impacts of e(a) and T-air on the delta O-18 values of cellulose can be integrated into a single index of plant-experienced atmospheric vapor demand: the leaf-to-air vapor pressure difference (VPD). We found a robust relationship between VPD and cellulose delta O-18 values in both empirical and modeled data in all ecosystems that we investigated. Our analysis revealed therefore that delta O-18 values in plant cellulose can be used as a proxy for VPD in tropical ecosystems. As VPD is an essential variable that determines the biogeochemical dynamics of ecosystems, our study has applications in ecological-, climate-, or forensic-sciences. KW - stable isotopes KW - plant-water relations KW - paleoecology KW - climate change KW - Hawaii Y1 - 2011 U6 - https://doi.org/10.1073/pnas.1018906108 SN - 0027-8424 VL - 108 IS - 5 SP - 1981 EP - 1986 PB - National Acad. of Sciences CY - Washington ER - TY - JOUR A1 - Garcin, Yannick A1 - Schwab, Valerie F. A1 - Gleixner, Gerd A1 - Kahmen, Ansgar A1 - Todou, Gilbert A1 - Sene, Olivier A1 - Onana, Jean-Michel A1 - Achoundong, Gaston A1 - Sachse, Dirk T1 - Hydrogen isotope ratios of lacustrine sedimentary n-alkanes as proxies of tropical African hydrology insights from a calibration transect across Cameroon JF - Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society N2 - Hydrogen isotope values (delta D) of sedimentary aquatic and terrestrial lipid biomarkers, originating from algae, bacteria, and leaf wax, have been used to record isotopic properties of ancient source water (i.e., precipitation and/or lake water) in several mid-and high-latitude lacustrine environments. In the tropics, however, where both processes associated with isotope fractionation in the hydrologic system and vegetation strongly differ from those at higher latitudes, calibration studies for this proxy are not yet available. To close this gap of knowledge, we sampled surface sediments from 11 lakes in Cameroon to identify those hydro-climatological processes and physiological factors that determine the hydrogen isotopic composition of aquatic and terrestrial lipid biomarkers. Here we present a robust framework for the application of compound-specific hydrogen isotopes in tropical Africa. Our results show that the delta D values of the aquatic lipid biomarker n-C(17) alkane were not correlated with the delta D values of lake water. Carbon isotope measurements indicate that the n-C(17) alkane was derived from multiple source organisms that used different hydrogen pools for biosynthesis. We demonstrate that the delta D values of the n-C(29) alkane were correlated with the delta D values of surface water (i.e., river water and groundwater), which, on large spatial scales, reflect the isotopic composition of mean annual precipitation. Such a relationship has been observed at higher latitudes, supporting the robustness of the leaf-wax lipid delta D proxy on a hemispheric spatial scale. In contrast, the delta D values of the n-C(31) alkane did not show such a relationship but instead were correlated with the evaporative lake water delta D values. This result suggests distinct water sources for both leaf-wax lipids, most likely originating from two different groups of plants. These new findings have important implications for the interpretation of long-chain n-alkane delta D records from ancient lake sediments. In particular, a robust interpretation of palaeohydrological data requires knowledge of the vegetation in the catchment area as different plants may utilise different water sources. Our results also suggest that the combination of carbon and hydrogen isotopes does help to differentiate between the metabolic pathway and/or growth form of organisms and therefore, the source of hydrogen used during lipid biosynthesis. Y1 - 2012 U6 - https://doi.org/10.1016/j.gca.2011.11.039 SN - 0016-7037 VL - 79 IS - 4 SP - 106 EP - 126 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Sachse, Dirk A1 - Billault, Isabelle A1 - Bowen, Gabriel J. A1 - Chikaraishi, Yoshito A1 - Dawson, Todd E. A1 - Feakins, Sarah J. A1 - Freeman, Katherine H. A1 - Magill, Clayton R. A1 - McInerney, Francesca A. A1 - van der Meer, Marcel T. J. A1 - Polissar, Pratigya A1 - Robins, Richard J. A1 - Sachs, Julian P. A1 - Schmidt, Hanns-Ludwig A1 - Sessions, Alex L. A1 - White, James W. C. A1 - West, Jason B. A1 - Kahmen, Ansgar ED - Jeanloz, R T1 - Molecular Paleohydrology interpreting the Hydrogen- Isotopic Composition of Lipid Biomarkers from Photosynthesizing Organisms JF - Annual review of earth and planetary sciences JF - Annual Review of Earth and Planetary Sciences N2 - Hydrogen-isotopic abundances of lipid biomarkers are emerging as important proxies in the study of ancient environments and ecosystems. A decade ago, pioneering studies made use of new analytical methods and demonstrated that the hydrogen-isotopic composition of individual lipids from aquatic and terrestrial organisms can be related to the composition of their growth (i.e., environmental) water. Subsequently, compound-specific deuterium/hydrogen (D/H) ratios of sedimentary biomarkers have been increasingly used as paleohydrological proxies over a range of geological timescales. Isotopic fractionation observed between hydrogen in environmental water and hydrogen in lipids, however, is sensitive to biochemical, physiological, and environmental influences on the composition of hydrogen available for biosynthesis in cells. Here we review the factors and processes that are known to influence the hydrogen-isotopic compositions of lipids-especially n-alkanes-from photosynthesizing organisms, and we provide a framework for interpreting their D/H ratios from ancient sediments and identify future research opportunities. KW - paleoclimate KW - paleoclimate proxy KW - deuterium KW - organic geochemistry Y1 - 2012 SN - 978-0-8243-2040-9 U6 - https://doi.org/10.1146/annurev-earth-042711-105535 SN - 0084-6597 VL - 40 IS - 1 SP - 221 EP - 249 PB - Annual Reviews CY - Palo Alto ER - TY - JOUR A1 - Romero-Viana, Lidia A1 - Kienel, Ulrike A1 - Sachse, Dirk T1 - Lipid biomarker signatures in a hypersaline lake on Isabel Island (Eastern Pacific) as a proxy for past rainfall anomaly (1942-2006 AD) JF - Palaeogeography, palaeoclimatology, palaeoecology : an international journal for the geo-sciences N2 - Isabel Lake is a hypersaline crater-lake on Isabel Island, Mexico, situated in the eastern tropical Pacific, an area highly sensitive to hydrological changes. Today, annual rainfall mostly occurs during the wet season, from June to October, when the northern edge of the Intertropical Convergence Zone (ITCZ) extends over the island. In order to evaluate the potential of sedimentary lipid biomarker signatures as a proxy of past hydro-climatic variability we have performed a calibration analysis comparing changes in biomarker distribution in the upper 16 cm of the sediment core with a regional instrumental data set. Annual laminations present in the sediment sequence allow for precise chronological control (1942-2006), More than 80 different lipid compounds were identified in the sediment and could be assigned to three major groups of source organisms: (1) algal populations; (2) a mixed community of ciliates, bacteria and cyanobacteria; and (3) photosynthetic sulfur bacteria. We found that the observed changes in the. relative contribution of the different lipid biomarkers to the sediment record were determined by the regional rainfall variability over the last 65 years. The planktonic community of Isabel Lake was highly sensitive to salinity fluctuations related to rainfall variability; seasonal precipitation results in freshwater input into the lake, driving an annual algal bloom and a relative decrease in the abundance of the more halotolerant populations of (cyano) bacteria and ciliates. Consequently, the concentration ratio between the two most abundant biomarkers in the Isabel Lake sediments, n-alkyl diols and tetrahymanol (which we define as the DiTe index), representing algal and ciliate planktonic populations, respectively, was significantly correlated with the seasonal rainfall anomaly (r = 0.68, p < 0.01). We propose that the DiTe index is a proxy of changes in the aquatic ecosystem of Isabel Lake and, by extension, regional hydrological changes in a sensitive climatic area of the eastern tropical Pacific. KW - Lipid KW - biomarkers KW - Diol KW - Tetrahymanol KW - ENSO KW - Salinity KW - Paleoclimate KW - Mexico Y1 - 2012 U6 - https://doi.org/10.1016/j.palaeo.2012.06.011 SN - 0031-0182 VL - 350 IS - 18 SP - 49 EP - 61 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Kahmen, Ansgar A1 - Schefuss, Enno A1 - Sachse, Dirk T1 - Leaf water deuterium enrichment shapes leaf wax n-alkane delta D values of angiosperm plants I experimental evidence and mechanistic insights JF - Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society N2 - Leaf wax n-alkanes of terrestrial plants are long-chain hydrocarbons that can persist in sedimentary records over geologic timescales. Since meteoric water is the primary source of hydrogen used in leaf wax synthesis, the hydrogen isotope composition (delta D value) of these biomarkers contains information on hydrological processes. Consequently, leaf wax n-alkane delta D values have been advocated as powerful tools for paleohydrological research. The exact kind of hydrological information that is recorded in leaf wax n-alkanes remains, however, unclear because critical processes that determine their delta D values have not yet been resolved. In particular the effects of evaporative deuterium (D)-enrichment of leaf water on the delta D values of leaf wax n-alkanes have not yet been directly assessed and quantified. Here we present the results of a study where we experimentally tested if and by what magnitude evaporative D-enrichment of leaf water affects the delta D of leaf wax n-alkanes in angiosperm C3 and C4 plants. Our study revealed that n-alkane delta D values of all plants that we investigated were affected by evaporative D-enrichment of leaf water. For dicotyledonous plants we found that the full extent of leaf water evaporative D-enrichment is recorded in leaf wax n-alkane delta D values. For monocotyledonous plants we found that between 18% and 68% of the D-enrichment in leaf water was recorded in the delta D values of their n-alkanes. We hypothesize that the different magnitudes by which evaporative D-enrichment of leaf water affects the delta D values of leaf wax n-alkanes in monocotyledonous and dicotyledonous plants is the result of differences in leaf growth and development between these plant groups. Our finding that the evaporative D-enrichment of leaf water affects the delta D values of leaf wax n-alkanes in monocotyledonous and dicotyledonous plants albeit at different magnitudes - has important implications for the interpretation of leaf wax n-alkane delta D values from paleohydrological records. In addition, our finding opens the door to employ delta D values of leaf wax n-alkanes as new ecohydrological proxies for evapotranspiration that can be applied in contemporary plant and ecosystem research. Y1 - 2013 U6 - https://doi.org/10.1016/j.gca.2012.09.003 SN - 0016-7037 VL - 111 SP - 39 EP - 49 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Romero-Viana, Lidia A1 - Kienel, Ulrike A1 - Wilkes, Heinz A1 - Sachse, Dirk T1 - Growth-dependent hydrogen isotopic fractionation of algal lipid biomarkers in hypersaline Isabel Lake (Mexico) JF - Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society N2 - In this study, we evaluated the potential of the hydrogen isotopic composition of algal lipid biomarkers as a proxy for past hydroclimatic variability in hypersaline Isabel Lake, Mexico (Eastern Pacific). We compared rainfall variability recorded in the region over the last 65 years with changes in delta D values of the most abundant compounds preserved in the uppermost 16 cm of lake sediment. Changes in delta D values of the 1,15-C-32 diol (delta D-diol), a specific biomarker of algal populations, were related to rainfall variability; specifically, n-alkyl diols were more deuterium-enriched (depleted) during wetter (drier) periods. Strikingly, neither the magnitude of lipid biomarker isotopic changes over interannual timescales (of up to 70-80 parts per thousand) nor the direction of that variability can be explained by changes in delta D values of the water source or salinity fluctuations (approximately 30 on the practical salinity scale) controlled by seasonal rainfall. However, changes in sedimentary biomarker composition, higher total organic carbon content and less negative delta C-13 values of the 1,15-C-32 diol indicate enhanced algal growth during wetter periods. We find that these conditions result in less negative delta D values of n-alkyl diols. We hypothesize that due to higher lipid demand during enhanced algal growth, an increasing proportion of hydrogen for lipid synthesis is derived from the cytosol via oxidation of polysaccharides, which may cause a deuterium enrichment of the acetogenic compounds. This study has significant implications for paleohydrological reconstructions using algal lipid delta D values, particularly in highly seasonal environments such as Isabel Lake. In such environments, delta D values of specific algal lipid biomarkers may not record the full seasonal cycle in source water delta D but appear to be mainly controlled by the physiological state of algal populations. Our data provide the first evidence that changes in D/H fractionation due to algal growth conditions can be recorded in sediments. For paleoclimate reconstructions in such environments, algal growth conditions should be constrained with additional proxy data (delta C-13 values of the same biomarkers), as the net D/H fractionation between water and lipids may not have been constant over time. Y1 - 2013 U6 - https://doi.org/10.1016/j.gca.2012.12.017 SN - 0016-7037 VL - 106 IS - 4 SP - 490 EP - 500 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Hoffmann, Bernd A1 - Kahmen, Ansgar A1 - Cernusak, Lucas A. A1 - Arndt, Stefan K. A1 - Sachse, Dirk T1 - Abundance and distribution of leaf wax n-alkanes in leaves of Acacia and Eucalyptus trees along a strong humidity gradient in northern Australia JF - Organic geochemistry : the international journal for rapid publication of current research in organic geochemistry and biochemistry N2 - Environmental parameters such as rainfall, temperature and relative humidity can affect the composition of higher plant leaf wax. The abundance and distribution of leaf wax biomarkers, such as long chain n-alkanes, in sedimentary archives have therefore been proposed as proxies reflecting climate change. However, a robust palaeoclimatic interpretation requires a thorough understanding of how environmental changes affect leaf wax n-alkane distributions in living plants. We have analysed the concentration and chain length distribution of leaf wax n-alkanes in Acacia and Eucalyptus species along a 1500 km climatic gradient in northern Australia that ranges from subtropical to arid. We show that aridity affected the concentration and distribution of n-alkanes for plants in both genera. For both Acacia and Eucalyptus n-alkane concentration increased by a factor of ten to the dry centre of Australia, reflecting the purpose of the wax in preventing water loss from the leaf. Furthermore, Acacian-alkanes decreased in average chain length (ACL) towards the arid centre of Australia, whereas Eucalyptus ACL increased under arid conditions. Our observations demonstrate that n-alkane concentration and distribution in leaf wax are sensitive to hydroclimatic conditions. These parameters could therefore potentially be employed in palaeorecords to estimate past environmental change. However, our finding of a distinct response of n-alkane ACL values to hydrological changes in different taxa also implies that the often assumed increase in ACL under drier conditions is not a robust feature for all plant species and genera and as such additional information about the prevalent vegetation are required when ACL values are used as a palaeoclimate proxy. Y1 - 2013 U6 - https://doi.org/10.1016/j.orggeochem.2013.07.003 SN - 0146-6380 VL - 62 IS - 9 SP - 62 EP - 67 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Garcin, Yannick A1 - Schefuss, Enno A1 - Schwab, Valerie F. A1 - Garreta, Vincent A1 - Gleixner, Gerd A1 - Vincens, Annie A1 - Todou, Gilbert A1 - Sene, Olivier A1 - Onana, Jean-Michel A1 - Achoundong, Gaston A1 - Sachse, Dirk T1 - Reconstructing C-3 and C-4 vegetation cover using n-alkane carbon isotope ratios in recent lake sediments from Cameroon, Western Central Africa JF - Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society N2 - Trees and shrubs in tropical Africa use the C-3 cycle as a carbon fixation pathway during photosynthesis, while grasses and sedges mostly use the C-4 cycle. Leaf-wax lipids from sedimentary archives such as the long-chain n-alkanes (e.g., n-C-27 to n-C-33) inherit carbon isotope ratios that are representative of the carbon fixation pathway. Therefore, n-alkane delta C-13 values are often used to reconstruct past C-3/C-4 composition of vegetation, assuming that the relative proportions of C-3 and C-4 leaf waxes reflect the relative proportions of C-3 and C-4 plants. We have compared the delta C-13 values of n-alkanes from modern C-3 and C-4 plants with previously published values from recent lake sediments and provide a framework for estimating the fractional contribution (areal-based) of C-3 vegetation cover (f(C3)) represented by these sedimentary archives. Samples were collected in Cameroon, across a latitudinal transect that accommodates a wide range of climate zones and vegetation types, as reflected in the progressive northward replacement of C-3-dominated rain forest by C-4-dominated savanna. The C-3 plants analysed were characterised by substantially higher abundances of n-C-29 alkanes and by substantially lower abundances of n-C-33 alkanes than the C-4 plants. Furthermore, the sedimentary delta C-13 values of n-C-29 and n-C-31 alkanes from recent lake sediments in Cameroon (-37.4%) to 26.5%) were generally within the range of delta C-13 values for C-3 plants, even when from sites where C-4 plants dominated the catchment vegetation. In such cases simple linear mixing models fail to accurately reconstruct the relative proportions of C-3 and C-4 vegetation cover when using the delta C-13 values of sedimentary n-alkanes, overestimating the proportion of C-3 vegetation, likely as a consequence of the differences in plant wax production, preservation, transport, and/or deposition between C-3 and C-4 plants. We therefore tested a set of non-linear binary mixing models using delta C-13 values from both C-3 and C-4 vegetation as end-members. The non-linear models included a sigmoid function (sine-squared) that describes small variations in the f(C3) values as the minimum and maximum delta C-13 values are approached, and a hyperbolic function that takes into account the differences between C-3 and C-4 plants discussed above. Model fitting and the estimation of uncertainties were completed using the Monte Carlo algorithm and can be improved by future data addition. Models that provided the best fit with the observed delta C-13 values of sedimentary n-alkanes were either hyperbolic functions or a combination of hyperbolic and sine-squared functions. Such non-linear models may be used to convert delta C-13 measurements on sedimentary n-alkanes directly into reconstructions of C-3 vegetation cover. (C) 2014 Elsevier Ltd. All rights reserved. Y1 - 2014 U6 - https://doi.org/10.1016/j.gca.2014.07.004 SN - 0016-7037 SN - 1872-9533 VL - 142 SP - 482 EP - 500 PB - Elsevier CY - Oxford ER -