TY - JOUR A1 - Schwab, Valerie F. A1 - Garcin, Yannick A1 - Sachse, Dirk A1 - Todou, Gilbert A1 - Sene, Olivier A1 - Onana, Jean-Michel A1 - Achoundong, Gaston A1 - Gleixner, Gerd T1 - Dinosterol delta D values in stratified tropical lakes (Cameroon) are affected by eutrophication JF - Organic geochemistry : the international journal for rapid publication of current research in organic geochemistry and biochemistry N2 - 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. KW - Hydrogen KW - Isotope KW - Fractionation KW - Biomarkers KW - Dinosterol KW - Lake KW - Redox potential KW - Paleoenvironmental KW - Proxy Y1 - 2015 U6 - https://doi.org/10.1016/j.orggeochem.2015.08.003 SN - 0146-6380 VL - 88 SP - 35 EP - 49 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Schwab, Valerie F. A1 - Garcin, Yannick A1 - Sachse, Dirk A1 - Todou, Gilbert A1 - Sene, Olivier A1 - Onana, Jean-Michel A1 - Achoundong, Gaston A1 - Gleixner, Gerd T1 - 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) JF - Organic geochemistry : the international journal for rapid publication of current research in organic geochemistry and biochemistry N2 - 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. KW - Evapotranspiration KW - D-enrichment KW - Pentacyclic triterpene methyl ethers KW - PTMEs KW - n-Alkane KW - Compound-specific isotope KW - Paleo KW - Climate KW - Proxy Y1 - 2015 U6 - https://doi.org/10.1016/j.orggeochem.2014.09.007 SN - 0146-6380 VL - 78 SP - 99 EP - 109 PB - Elsevier CY - Oxford ER -