Effect of aridity on delta ¹³C and delta D values of C₃ plant- and C₄ graminoid-derived leaf wax lipids from soils along an environmental gradient in Cameroon (Western Central Africa)

The observation that the hydrogen isotope composition (δD) of leaf wax lipids is determined mainly by precipitation δD values, has resulted in the application of these biomarkers to reconstruct paleoclimate from geological records. However, because the δD 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 (δ13C) of n-alkanes in common plants along a latitudinal gradient in C3/C4 vegetation and relative humidity in Cameroon and demonstrated that pentacyclic triterpene methyl ethers (PTMEs) and n-C29 and n-C31 in the same soil, derived mainly from C4 graminoids (e.g. grass) and C3 plants (e.g. trees and shrubs), respectively. We found that the δD values of soil n-C27, n-C29 and n-C31, and PTMEs correlated significantly with surface water δD values, supporting previous observations that leaf wax lipid δD values are an effective proxy for reconstructing precipitation δD values even if plant types changed significantly. The apparent fractionation (εapp) between leaf wax lipid and precipitation δD values remained relatively constant for C3-derived long chain n-alkanes, whereas εapp of C4-derived PTMEs decreased by 20‰ along the latitudinal gradient encompassing a relative humidity range from 80% to 45%. Our results indicate that PTME δD values derived from C4 graminoids may be a more reliable paleo-ecohydrological proxy for ecosystem evapotranspiration within tropical and sub-tropical Africa than n-alkane δD values, the latter being a better proxy for surface water δD values. We suggest that vegetation changes associated with different plant water sources and/or difference in timing of leaf wax synthesis between C3 trees of the transitional class and C3 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 δD values of PTMEs derived from C4 graminoids, likely because PTMEs recorded the hydrogen isotopic composition of the same vegetation type