Yannick Garcin, Enno Schefuss, Valerie F. Schwab, Vincent Garreta, Gerd Gleixner, Annie Vincens, Gilbert Todou, Olivier Sene, Jean-Michel Onana, Gaston Achoundong, Dirk Sachse

• 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 northwardTrees 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.…