Origin and palaeoenvironmental significance of C₂₅ and C₂₇n-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 d13C-depleted n-C25:1 and n-C27:1 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, aquatic source. 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-C25:1 and n-C27:1 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-C27:1]/([n-C25:1] + [n-C27:1]), 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

Seasonal variability in the abundance and stable carbon-isotopic composition of lipid biomarkers in suspended particulate matter from a stratified equatorial lake (Lake Chala, Kenya/Tanzania): Implications for the sedimentary record

We studied the distribution and stable carbon-isotopic (δ13C) composition of various lipid biomarkers in suspended particulate matter (SPM) from the water column of Lake Chala, a permanently stratified crater lake in equatorial East Africa, to evaluate their capacity to reflect seasonality in water-column processes and associated changes in the lake's phytoplankton community. This lake has large seasonal variation in water-column dynamics (stratified during wet seasons and mixing during dry seasons) with associated phytoplankton succession. We analyzed lipid biomarkers in SPM collected monthly at 5 depths (0–80 m) from September 2013 to January 2015. Seasonal variation in total phytoplankton biovolume is strongly reflected in the concentration of phytadienes, a derivative of the general photosynthetic pigment chlorophyll. The wax and wane of several specific biomarker lipids between June and December 2014 reflect pronounced phytoplankton succession after deep mixing, starting with a long and sustained chlorophyte bloom (reflected by C23:1, C25:1 and Cn-alkenes, and C21 and C23n-alkanes), followed by a peak in diatoms between July and October (loliolide and isololiolide), and then eustigmatophytes (C30 and C32 1,15 diols) once stratification resumes in October. Peak abundance of the C19:1n-alkene during shallow mixing of the water column in January–February 2014 can be tentatively linked to the seasonal distribution of cyanobacteria. The concentration, seasonal variability, and low δ13C values of the C28 fatty acid in the SPM suggest that this biomarker is produced in the water column of Lake Chala instead of having the typically assumed vascular plant origin. The δ13C signature of particulate carbon and all aquatic biomarkers become increasingly more negative (by up to 16‰) during mixing-induced episodes of high productivity, whereas enrichment would be expected during such blooms. This reversed fractionation may be attributed to chemically enhanced diffusion, which generates depleted HCO3− under high pH (>9) conditions, as occur in the epilimnion of Lake Chala during periods of high productivity. The influence of this process can potentially explain previously observed 13C-depleted carbon signatures in the paleorecord of Lake Chala, and should be considered prior to paleorecord interpretation of organic-matter δ13C values derived (partially) from aquatic organisms in high-pH, i.e. alkaline, lake

Origin, formation and environmental significance of des-A-arborenes in the sediments of an East African crater lake

Non-hopanoid pentacyclic triterpenoids occur widely in lake sediments, but their biological sources and diagenetic pathways are not fully resolved. We tentatively identified a number of des-A-arborene isomers occurring in relatively high abundance in the 25,000 year (25 kyr) sedimentary record of Lake Chala, a deep crater lake in tropical East Africa. The mono-, di- and tri-unsaturated des-A-arborenes are transformation products of isoarborinol/arborinone. These precursors have an aquatic source and are most likely biosynthesized by algae or aerobic bacteria in the epilimnion. The relatively depleted δ13C values (on average −32.3‰ ± 1.3‰) of des-A-arbor-9(11)-ene are consistent with an aquatic source (algae or aerobic bacteria). In general, isoarborinol and its microbially induced transformation products are found in present and ancient tropical lacustrine settings (typically crater lakes) with permanently anoxic bottom waters and sediments. Based on molecular mechanics calculations of des-A-arborenes, it is clear that these transformation products are not in thermodynamic equilibrium, strongly indicating that their formation is microbially mediated. Subtle temporal and spatial differences in the microbial community might therefore not only dictate the variable relative contributions of different des-A-arborenes found in the sediments of Lake Chala over the last 25 kyr, but also explain the distribution of arborane derivatives in comparable crater-lake settings elsewhere

Origin, formation and environmental significance of des-A-arborenes in the sediments of an East African crater lake

Non-hopanoid pentacyclic triterpenoids occur widely in lake sediments, but their biological sources and diagenetic pathways are not fully resolved. We tentatively identified a number of des-A-arborene isomers occurring in relatively high abundance in the 25,000 year (25 kyr) sedimentary record of Lake Chala, a deep crater lake in tropical East Africa. The mono-, di- and tri-unsaturated des-A-arborenes are transformation products of isoarborinol/arborinone. These precursors have an aquatic source and are most likely biosynthesized by algae or aerobic bacteria in the epilimnion. The relatively depleted δ13C values (on average −32.3‰ ± 1.3‰) of des-A-arbor-9(11)-ene are consistent with an aquatic source (algae or aerobic bacteria). In general, isoarborinol and its microbially induced transformation products are found in present and ancient tropical lacustrine settings (typically crater lakes) with permanently anoxic bottom waters and sediments. Based on molecular mechanics calculations of des-A-arborenes, it is clear that these transformation products are not in thermodynamic equilibrium, strongly indicating that their formation is microbially mediated. Subtle temporal and spatial differences in the microbial community might therefore not only dictate the variable relative contributions of different des-A-arborenes found in the sediments of Lake Chala over the last 25 kyr, but also explain the distribution of arborane derivatives in comparable crater-lake settings elsewhere

Seasonal variability in the abundance and stable carbon-isotopic composition of lipid biomarkers in suspended particulate matter from a stratified equatorial lake (Lake Chala, Kenya/Tanzania) : Implications for the sedimentary record

We studied the distribution and stable carbon-isotopic (δ13C) composition of various lipid biomarkers in suspended particulate matter (SPM) from the water column of Lake Chala, a permanently stratified crater lake in equatorial East Africa, to evaluate their capacity to reflect seasonality in water-column processes and associated changes in the lake's phytoplankton community. This lake has large seasonal variation in water-column dynamics (stratified during wet seasons and mixing during dry seasons) with associated phytoplankton succession. We analyzed lipid biomarkers in SPM collected monthly at 5 depths (0–80 m) from September 2013 to January 2015. Seasonal variation in total phytoplankton biovolume is strongly reflected in the concentration of phytadienes, a derivative of the general photosynthetic pigment chlorophyll. The wax and wane of several specific biomarker lipids between June and December 2014 reflect pronounced phytoplankton succession after deep mixing, starting with a long and sustained chlorophyte bloom (reflected by C23:1, C25:1 and C27:1 n-alkenes, and C21 and C23 n-alkanes), followed by a peak in diatoms between July and October (loliolide and isololiolide), and then eustigmatophytes (C30 and C32 1,15 diols) once stratification resumes in October. Peak abundance of the C19:1 n-alkene during shallow mixing of the water column in January–February 2014 can be tentatively linked to the seasonal distribution of cyanobacteria. The concentration, seasonal variability, and low δ13C values of the C28 fatty acid in the SPM suggest that this biomarker is produced in the water column of Lake Chala instead of having the typically assumed vascular plant origin. The δ13C signature of particulate carbon and all aquatic biomarkers become increasingly more negative (by up to 16‰) during mixing-induced episodes of high productivity, whereas enrichment would be expected during such blooms. This reversed fractionation may be attributed to chemically enhanced diffusion, which generates depleted HCO3− under high pH (>9) conditions, as occur in the epilimnion of Lake Chala during periods of high productivity. The influence of this process can potentially explain previously observed 13C-depleted carbon signatures in the paleorecord of Lake Chala, and should be considered prior to paleorecord interpretation of organic-matter δ13C values derived (partially) from aquatic organisms in high-pH, i.e. alkaline, lakes

Seasonal and multi-annual variation in the abundance of isoprenoid GDGT membrane lipids and their producers in the water column of a meromictic equatorial crater lake (Lake Chala, East Africa)

Isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs) are membrane lipids of Archaea. Organic biomarker proxies associated with these lipids, such as the TEX 86 paleothermometer and Branched and Isoprenoid Tetraether (BIT) index, are often used in paleoenvironmental reconstructions for the marine environment, but their general applicability in lacustrine settings is hampered by limited understanding of the biological sources and environmental drivers influencing isoGDGT production. To validate the use of isoGDGT proxies in lakes, we studied the occurrence of isoGDGTs in Lake Chala, a permanently stratified (meromictic) crater lake in equatorial East Africa. We analyzed the abundance and distribution of isoGDGTs in 17 depth profiles of suspended particulate matter (SPM) collected monthly between September 2013 and January 2015, and compared this with the abundance and composition of archaea based on 16S rRNA gene and quantitative PCR analysis. Both isoGDGTs and archaeal abundance in the SPM were exceptionally low throughout the study period. In the oxygenated part of the water column, higher fractional abundances of crenarchaeol are matched by a predominance of the ammonia-oxidizing Thaumarchaeota I.1b that are known to produce this GDGT, whereas deep anoxic water layers are characterized by high fractional abundances of GDGT-0 as well as the anaerobic heterotrophic Group C3 MCG Bathyarchaea and specific euryarchaeotal methanogens. Analysis of intact polar lipid (IPL) isoGDGTs using SPM depth profiles from three months representing distinct seasons during the study period revealed the presence of several IPLs of GDGT-0 in the anoxic lower water column, which are rarely found in natural settings. IPL GDGT-0 with a phosphatidylglycerol (PG-), monohexosephosphatidylglycerol (MH-PG-) and dihexose-phosphatidylglycerol (DH-PG-) head-group was typically only present just above the lake bottom at 90 m depth and probably reflect specific communities of anaerobic archaea. We also determined the flux and distribution of isoGDGTs in settling particles collected monthly between November 2006 and January 2015 from a sediment trap suspended at 35 m water depth to assess seasonal and inter-annual variability in surface-water isoGDGT production, and compared this with the temporal distribution of isoGDGTs in the 25,000-year long sediment record from Lake Chala. Monthly variation of isoGDGTs in the 98-month settling-particles record did not show a strong annual pattern related to seasonal water-column mixing and stratification, likely because the oxycline was regularly situated below sediment-trap depth. Episodes of high GDGT-0 concentrations relative to crenarchaeol in the settling particles can therefore be linked to periods of exceptionally shallow oxycline depth, which suppresses the thaumarchaeotal bloom. During such intervals, TEX86 based paleotemperatures are not reliable because isoGDGT input from other archaeal sources disproportionally influences TEX86 values and creates a cold-temperature bias. Additionally, the abundance of the crenarchaeol isomer relative to crenarchaeol (f[CREN]) gradually increases during such episodes of high GDGT-0/crenarchaeol ratio, suggesting increasing dominance of Group I.1b over Group I.1a Thaumarchaeota, and might prove a good marker for prolonged shallow-oxycline conditions. Most importantly, the associated near-absence of crenarchaeol during times of strong upper-water-column stratification results in high BIT-index values. We propose that this suppression mechanism may be the principal driver of BIT-index variation in the sediment record of Lake Chala, and the main source of observed congruence between the BIT index and climate-driven lake-level variation on long time scales. (C) 2021 The Authors. Published by Elsevier Ltd

Seasonal and multi-annual variation in the abundance of isoprenoid GDGT membrane lipids and their producers in the water column of a meromictic equatorial crater lake (Lake Chala, East Africa)

Isoprenoid glycerol dialkyl glycerol tetraethers (isoGDGTs) are membrane lipids of Archaea. Organic biomarker proxies associated with these lipids, such as the TEX86 paleothermometer and Branched and Isoprenoid Tetraether (BIT) index, are often used in paleoenvironmental reconstructions for the marine environment, but their general applicability in lacustrine settings is hampered by limited understanding of the biological sources and environmental drivers influencing isoGDGT production. To validate the use of isoGDGT proxies in lakes, we studied the occurrence of isoGDGTs in Lake Chala, a permanently stratified (meromictic) crater lake in equatorial East Africa. We analyzed the abundance and distribution of isoGDGTs in 17 depth profiles of suspended particulate matter (SPM) collected monthly between September 2013 and January 2015, and compared this with the abundance and composition of archaea based on 16S rRNA gene and quantitative PCR analysis. Both isoGDGTs and archaeal abundance in the SPM were exceptionally low throughout the study period. In the oxygenated part of the water column, higher fractional abundances of crenarchaeol are matched by a predominance of the ammonia-oxidizing Thaumarchaeota I.1b that are known to produce this GDGT, whereas deep anoxic water layers are characterized by high fractional abundances of GDGT-0 as well as the anaerobic heterotrophic Group C3 MCG Bathyarchaea and specific euryarchaeotal methanogens. Analysis of intact polar lipid (IPL) isoGDGTs using SPM depth profiles from three months representing distinct seasons during the study period revealed the presence of several IPLs of GDGT-0 in the anoxic lower water column, which are rarely found in natural settings. IPL GDGT-0 with a phosphatidylglycerol (PG-), monohexose-phosphatidylglycerol (MH-PG-) and dihexose-phosphatidylglycerol (DH-PG-) head-group was typically only present just above the lake bottom at 90 m depth and probably reflect specific communities of anaerobic archaea. We also determined the flux and distribution of isoGDGTs in settling particles collected monthly between November 2006 and January 2015 from a sediment trap suspended at 35 m water depth to assess seasonal and inter-annual variability in surface-water isoGDGT production, and compared this with the temporal distribution of isoGDGTs in the 25,000-year long sediment record from Lake Chala. Monthly variation of isoGDGTs in the 98-month settling-particles record did not show a strong annual pattern related to seasonal water-column mixing and stratification, likely because the oxycline was regularly situated below sediment-trap depth. Episodes of high GDGT-0 concentrations relative to crenarchaeol in the settling particles can therefore be linked to periods of exceptionally shallow oxycline depth, which suppresses the thaumarchaeotal bloom. During such intervals, TEX86-based paleotemperatures are not reliable because isoGDGT input from other archaeal sources disproportionally influences TEX86 values and creates a cold-temperature bias. Additionally, the abundance of the crenarchaeol isomer relative to crenarchaeol (f[CREN']) gradually increases during such episodes of high GDGT-0/crenarchaeol ratio, suggesting increasing dominance of Group I.1b over Group I.1a Thaumarchaeota, and might prove a good marker for prolonged shallow-oxycline conditions. Most importantly, the associated near-absence of crenarchaeol during times of strong upper-water-column stratification results in high BIT-index values. We propose that this suppression mechanism may be the principal driver of BIT-index variation in the sediment record of Lake Chala, and the main source of observed congruence between the BIT index and climate-driven lake-level variation on long time scales