Tocopherols and associated derivatives track the phytoplanktonic response to evolving pelagic redox conditions spanning Oceanic Anoxic Event 2

Tocopherols serve a critical role as antioxidants inhibiting lipid peroxidation in photosynthetic organisms, yet are seldom used in geobiological investigations. The ubiquity of tocopherols in all photosynthetic lifeforms is often cited as an impediment to any diagnostic paleoenvironmental potential, while the inability to readily analyze these compounds via conventional methods, such as gas chromatography-mass spectrometry, further diminishes the capacity to serve as useful 'biomarkers'. Here, we analyzed an exceptionally preserved black shale sequence from the Demerara Rise that spans Oceanic Anoxic Event 2 (OAE-2) to reexamine the significance of tocopherols and associated derivatives (i.e. tocol derivatives) in ancient sediments. Tocol derivatives were analyzed via liquid chromatography-quadrupole time-of-flight-mass spectrometry and included tocopherols, a methyltrimethyltridecylchroman, and the first reported detection of tocopherol quinones and methylphytylbenzoquinones in the geologic record. Strong correlations between tocol derivatives were observed over the studied interval. Tocol derivative concentrations and ratios, which normalized tocopherols to potential derivatives, revealed absolute and relative increases in tocopherols as exclusive features of OAE-2 that can be explained by two possible mechanisms related to tocopherol production and preservation. The development of photic zone euxinia during OAE-2 likely forced an upward migration of oxygenic photoautotrophs, increasing oxidative stress that elicited heightened tocopherol biosynthesis. However, shoaling euxinic conditions may have simultaneously acted to enhance tocopherol preservation given the relatively high lability of tocopherols in the water column. Both scenarios could produce the observed stratigraphic distribution of tocol derivatives in this study, although the elevated tocopherol concentrations that define OAE-2 at the Demerara Rise are primarily attributed to enhanced tocopherol production by shoaling phytoplanktonic communities. Thus, the occurrence of tocopherols and associated derivatives in sediments and rocks of marine origin is likely indicative of shallow-water anoxia, tracking the phytoplanktonic response to the abiotic stresses associated with vertical fluctuations in pelagic redox.