Origin and palaeoenvironmental significance of C₂₅ and C₂₇ n-alk-1-enes in a 25,000-year lake-sedimentary record from equatorial East Africa

We studied the distribution of long-chain alkenes (n-C₂₃ to n-C₃₁) in well-dated sediments from Lake Challa, a deep crater lake near Mt. Kilimanjaro in equatorial East Africa, to reveal signatures of palaeo-environmental and palaeo-climatic changes affecting the production of these compounds during the last 25 kyr. The apolar fractions of organic sediment extracts dated to the last 16 kyr showed an unusual dominance of δ¹³C-depleted n-C_25:1 and n-C_27:1 alk-1-enes. These alkenes were not detected in soil and litter from near the shoreline and from the inner rim of the crater, pointing to an autochthonous, aquaticsource. Analysis of suspended particulate matter indicated that the n-alk-1-enes are produced in the well-oxygenated upper 30 m of the water column, indicating a phytoplanktonic origin. Sedimenting particles collected monthly from December 2006 to November 2007 showed increased fluxes of n-alk-1-enes following the locally prominent short rain season in November–December. Green algae and/or cyanobacteria were identified as candidate sources of these alkenes. Production of the n-C_25:1 and n-C_27:1 alkenes in Lake Challa was much reduced during the Last Glacial Maximum and early late-glacial period, suggesting a temperature or CO₂ effect on habitat suitability. We explored the potential of n-alk-1-ene accumulation rates, and of a derived Alkene Index [n-C_27:1]/([n-C_25:1] + [n-C_27:1]), to record longer-term climatic changes. The Alkene Index record of Lake Challa over the past 25 kyr shows clear periodicity with a dominant frequency of 2.3 kyr, potentially indicative of monsoon variability directly or indirectly forced by variation in solar radiation.