Effect of aridity on δ 13 C and δD values of C 3 plant- and C 4 graminoid-derived leaf wax lipids from soils along an environmental gradient in Cameroon (Western Central Africa)

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.