Hurley SJ, FJ Elling, M Könneke, C Buchwald, SD Wankel, AE Santoro, JS Lipp, K-U Hinrichs and A Pearson. 2016. Nitrification rate is a fundamental control on archaeal lipid composition and the TEX86 proxy. Proceedings of the National Academy of Sciences of the United States of America. 113:7762-7767.
Date Published:
June 30, 2016
A Pearson, AE Santoro, C Buchwald, FJ Elling, JS Lipp, KU Hinrichs, M Könneke, SD Wankel, SJ Hurely,

Membrane lipids of marine Archaea – known as GDGTs – are the basis of the TEX86 sea surface temperature (SST) paleoproxy. GDGTs are ubiquitous in marine sediments, and their broad distribution and high preservation potential have led to an ever-increasing use of TEX86. The planktonic Thaumarchaeota that are believed to be the major sources of GDGTs to marine sediments are autotrophic nitrifiers, assimilating carbon directly from dissolved CO2. Therefore the δ13C values of GDGTs additionally provide information about the DIC system and paleoproductivity. However, as for all biological proxies, understanding the physiology and biochemistry of the responsible organisms is essential to understanding how the proxies work. From this perspective, the TEX86-SST proxy is uniquely perplexing: How is it possible that multiple approaches to calibration show a good correlation between TEX86 and SSTs, when maximum activity of Thaumarchaeota is near and below the base of the photic zone? Here we show data from two studies that help address this question. Analyses of GDGT δ13C values show that the dominant GDGT flux to sediments is not from the sea surface. The data are measured on intact GDGTs purified by orthogonal dimensions of HPLC, followed by measurement of δ13C values on a Spooling Wire Microcombustion (SWiM)-IRMS with 1σ precision of ±0.2‰ and accuracy of ±0.3‰. Using this approach, we confirm that GDGTs, generally around ‑19.0‰ to ‑18.5‰, are isotopically “heavy” compared to other marine lipids, and that crenarchaeol in particular is a good tracer of water column GDGT export. In parallel, we investigated the mechanistic underpinning of the TEX86 proxy using isothermal culture studies of the ammonia-oxidizing thaumarchaeonNitrosopumilus maritimus SCM1 to explore the relationship between TEX86 and growth conditions. Evidence suggests that growth rate and electron donor supply are important controls on GDGT ratios and that TEX86scales with the in-situ rate of nitrification. Constraining the physiological basis of the TEX86 proxy and the mechanism by which this signal is transported to the sedimentary record is crucial to the proxy’s application to ancient environments.