@article{GarcinSchwabGleixneretal.2012, author = {Garcin, Yannick and Schwab, Valerie F. and Gleixner, Gerd and Kahmen, Ansgar and Todou, Gilbert and Sene, Olivier and Onana, Jean-Michel and Achoundong, Gaston and Sachse, Dirk}, title = {Hydrogen isotope ratios of lacustrine sedimentary n-alkanes as proxies of tropical African hydrology insights from a calibration transect across Cameroon}, series = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society}, volume = {79}, journal = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society}, number = {4}, publisher = {Elsevier}, address = {Oxford}, issn = {0016-7037}, doi = {10.1016/j.gca.2011.11.039}, pages = {106 -- 126}, year = {2012}, abstract = {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.}, language = {en} } @article{GarcinSchefussSchwabetal.2014, author = {Garcin, Yannick and Schefuss, Enno and Schwab, Valerie F. and Garreta, Vincent and Gleixner, Gerd and Vincens, Annie and Todou, Gilbert and Sene, Olivier and Onana, Jean-Michel and Achoundong, Gaston and Sachse, Dirk}, title = {Reconstructing C-3 and C-4 vegetation cover using n-alkane carbon isotope ratios in recent lake sediments from Cameroon, Western Central Africa}, series = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society}, volume = {142}, journal = {Geochimica et cosmochimica acta : journal of the Geochemical Society and the Meteoritical Society}, publisher = {Elsevier}, address = {Oxford}, issn = {0016-7037}, doi = {10.1016/j.gca.2014.07.004}, pages = {482 -- 500}, year = {2014}, abstract = {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.}, language = {en} } @article{SchwabGarcinSachseetal.2015, author = {Schwab, Valerie F. and Garcin, Yannick and Sachse, Dirk and Todou, Gilbert and Sene, Olivier and Onana, Jean-Michel and Achoundong, Gaston and Gleixner, Gerd}, title = {Dinosterol delta D values in stratified tropical lakes (Cameroon) are affected by eutrophication}, series = {Organic geochemistry : the international journal for rapid publication of current research in organic geochemistry and biochemistry}, volume = {88}, journal = {Organic geochemistry : the international journal for rapid publication of current research in organic geochemistry and biochemistry}, publisher = {Elsevier}, address = {Oxford}, issn = {0146-6380}, doi = {10.1016/j.orggeochem.2015.08.003}, pages = {35 -- 49}, year = {2015}, abstract = {In freshwater settings, dinosterol (4 alpha,23,24-trimethyl-5 alpha-cholest-22E-en-3 beta-ol) is produced primarily by dinoflagellates, which encompass various species including autotrophs, mixotrophs and heterotrophs. Due to its source specificity and occurrence in lake and marine sediments, its presence and hydrogen isotopic composition (delta D) should be valuable proxies for paleohydrological reconstruction. However, because the purity required for hydrogen isotope measurements is difficult to achieve using standard wet chemical purification methods, their potential as a paleohydrological proxy is rarely exploited. In this study, we tested delta D values of dinosterol in both particulate organic matter (POM) and sediments of stratified tropical freshwater lakes (from Cameroon) as a paleohydrological proxy, the lakes being characterized by variable degrees of eutrophication. In POM and sediment samples, the delta D values of dinosterol correlated with lake water delta D values, confirming a first order influence of source water delta D values. However, we observed that sedimentary dinosterol was D enriched from ca. 19 to 54\% compared with POM dinosterol. The enrichment correlated with lake water column conditions, mainly the redox potential at the oxic-anoxic interface (E-h OAI). The observations suggest that paleohydrologic reconstruction from delta D values of dinosterol in the sediments of stratified tropical lakes ought to be sensitive to the depositional environment, in addition to lake water delta D values, with more positive dinosterol delta values potentially reflecting increasing lake eutrophication. Furthermore, in lake sediments, the concentration of partially reduced vs. non-reduced C-34 botryococcenes, stanols vs. stenols, and bacterial (diploptene, diplopterol and beta beta-bishomohopanol) vs. planktonic/terrestrial lipids (cholesterol, campesterol and dinosterol) correlated with Eh OAI. We suggest using such molecular proxies for lake redox conditions in combination with dinosterol delta D values to evaluate the effect of lake trophic status on sedimentary dinosterol delta D values, as a basis for accurately reconstructing tropical lake water delta D values. (C) 2015 Elsevier Ltd. All rights reserved.}, language = {en} } @article{SchwabGarcinSachseetal.2015, author = {Schwab, Valerie F. and Garcin, Yannick and Sachse, Dirk and Todou, Gilbert and Sene, Olivier and Onana, Jean-Michel and Achoundong, Gaston and Gleixner, Gerd}, title = {Effect of aridity on delta C-13 and delta D values of C-3 plant- and C-4 graminoid-derived leaf wax lipids from soils along an environmental gradient in Cameroon (Western Central Africa)}, series = {Organic geochemistry : the international journal for rapid publication of current research in organic geochemistry and biochemistry}, volume = {78}, journal = {Organic geochemistry : the international journal for rapid publication of current research in organic geochemistry and biochemistry}, publisher = {Elsevier}, address = {Oxford}, issn = {0146-6380}, doi = {10.1016/j.orggeochem.2014.09.007}, pages = {99 -- 109}, year = {2015}, abstract = {The observation that the hydrogen isotope composition (delta D) of leaf wax lipids is determined mainly by precipitation delta D values, has resulted in the application of these biomarkers to reconstruct paleoclimate from geological records. However, because the delta D values of leaf wax lipids are additionally affected by vegetation type and ecosystem evapotranspiration, paleoclimatic reconstruction remains at best semi-quantitative. Here, we used published results for the carbon isotope composition (delta C-13) of n-alkanes in common plants along a latitudinal gradient in C-3/C-4 vegetation and relative humidity in Cameroon and demonstrated that pentacyclic triterpene methyl ethers (PTMEs) and n-C-29 and n-C-31 in the same soil, derived mainly from C-4 graminoids (e.g. grass) and C-3 plants (e.g. trees and shrubs), respectively. We found that the delta D values of soil n-C-27, n-C29 and n-C-31, and PTMEs correlated significantly with surface water delta D values, supporting previous observations that leaf wax lipid delta D values are an effective proxy for reconstructing precipitation delta D values even if plant types changed significantly. The apparent fractionation (epsilon(app)) between leaf wax lipid and precipitation delta D values remained relatively constant for C-3-derived long chain n-alkanes, whereas eapp of C-4-derived PTMEs decreased by 20 parts per thousand along the latitudinal gradient encompassing a relative humidity range from 80\% to 45\%. Our results indicate that PTME delta D values derived from C-4 graminoids may be a more reliable paleo-ecohydrological proxy for ecosystem evapotranspiration within tropical and sub-tropical Africa than n-alkane delta D values, the latter being a better proxy for surface water delta D values. We suggest that vegetation changes associated with different plant water sources and/or difference in timing of leaf wax synthesis between C-3 trees of the transitional class and C-3 shrubs of the savanna resulted in a D depletion in soil long chain n-alkanes, thereby counteracting the effect of evapotranspiration D enrichment along the gradient. In contrast, evaporative D enrichment of leaf and soil water was significant enough to be recorded in the delta D values of PTMEs derived from C-4 graminoids, likely because PTMEs recorded the hydrogen isotopic composition of the same vegetation type.}, language = {en} } @article{GarcinDeschampsMenotetal.2018, author = {Garcin, Yannick and Deschamps, Pierre and Menot, Guillemette and de Saulieu, Geoffroy and Schefuss, Enno and Sebag, David and Dupont, Lydie M. and Oslisly, Richard and Brademann, Brian and Mbusnum, Kevin G. and Onana, Jean-Michel and Ako, Andrew A. and Epp, Laura Saskia and Tjallingii, Rik and Strecker, Manfred and Brauer, Achim and Sachse, Dirk}, title = {Early anthropogenic impact on Western Central African rainforests 2,600 y ago}, series = {Proceedings of the National Academy of Sciences of the United States of America}, volume = {115}, journal = {Proceedings of the National Academy of Sciences of the United States of America}, number = {13}, publisher = {National Acad. of Sciences}, address = {Washington}, issn = {0027-8424}, doi = {10.1073/pnas.1715336115}, pages = {3261 -- 3266}, year = {2018}, abstract = {A potential human footprint on Western Central African rainforests before the Common Era has become the focus of an ongoing controversy. Between 3,000 y ago and 2,000 y ago, regional pollen sequences indicate a replacement of mature rainforests by a forest-savannah mosaic including pioneer trees. Although some studies suggested an anthropogenic influence on this forest fragmentation, current interpretations based on pollen data attribute the "rainforest crisis" to climate change toward a drier, more seasonal climate. A rigorous test of this hypothesis, however, requires climate proxies independent of vegetation changes. Here we resolve this controversy through a continuous 10,500-y record of both vegetation and hydrological changes from Lake Barombi in Southwest Cameroon based on changes in carbon and hydrogen isotope compositions of plant waxes. delta C-13-inferred vegetation changes confirm a prominent and abrupt appearance of C-4 plants in the Lake Barombi catchment, at 2,600 calendar years before AD 1950 (cal y BP), followed by an equally sudden return to rainforest vegetation at 2,020 cal y BP. delta D values from the same plant wax compounds, however, show no simultaneous hydrological change. Based on the combination of these data with a comprehensive regional archaeological database we provide evidence that humans triggered the rainforest fragmentation 2,600 y ago. Our findings suggest that technological developments, including agricultural practices and iron metallurgy, possibly related to the large-scale Bantu expansion, significantly impacted the ecosystems before the Common Era.}, language = {en} } @misc{GarcinDeschampsMenotetal.2018, author = {Garcin, Yannick and Deschamps, Pierre and Menot, Guillemette and de Saulieu, Geoffroy and Schefuss, Enno and Sebag, David and Dupont, Lydie M. and Oslisly, Richard and Brademann, Brian and Mbusnum, Kevin G. and Onana, Jean-Michel and Ako, Andrew A. and Epp, Laura Saskia and Tjallingii, Rik and Strecker, Manfred and Brauer, Achim and Sachse, Dirk}, title = {No evidence for climate variability during the late Holocene rainforest crisis in Western Central Africa REPLY}, series = {Proceedings of the National Academy of Sciences of the United States of America}, volume = {115}, journal = {Proceedings of the National Academy of Sciences of the United States of America}, number = {29}, publisher = {National Acad. of Sciences}, address = {Washington}, issn = {0027-8424}, doi = {10.1073/pnas.1808481115}, pages = {E6674 -- E6675}, year = {2018}, language = {en} } @misc{GarcinDeschampsMenotetal.2018, author = {Garcin, Yannick and Deschamps, Pierre and Menot, Guillemette and de Saulieu, Geoffroy and Schefuss, Enno and Sebag, David and Dupont, Lydie M. and Oslisly, Richard and Brademann, Brian and Mbusnum, Kevin G. and Onana, Jean-Michel and Ako, Andrew A. and Epp, Laura Saskia and Tjallingii, Rik and Strecker, Manfred and Brauer, Achim and Sachse, Dirk}, title = {Human activity is the most probable trigger of the late Holocene rainforest crisis in Western Central Africa Reply}, series = {Proceedings of the National Academy of Sciences of the United States of America}, volume = {115}, journal = {Proceedings of the National Academy of Sciences of the United States of America}, number = {21}, publisher = {National Acad. of Sciences}, address = {Washington}, issn = {0027-8424}, doi = {10.1073/pnas.1805582115}, pages = {E4735 -- E4736}, year = {2018}, language = {en} }