Differential metamorphic effects on nitrogen isotopes in kerogen extracts and bulk rocks

This work was financially supported by a NASA Exobiology grant to RB (# NNX16AI37G), an NSF graduate student research fellowship to JZ, and a NASA postdoctoral fellowship to EES.The last decade has seen a steady rise in the number of publications on nitrogen isotopes in sedimentary rocks, which have become an established tool for investigating the evolution of life and environmental conditions. Nitrogen is contained in sedimentary rocks in two different phases: bound to kerogen or substituted in potassic minerals (mostly K-bearing phyllosilicates and feldspars). Isotopic measurements and interpretations typically focus either on kerogen extracts alone or on bulk rocks that include both phases. The community is split about which sample type more accurately captures the original composition of the biomass. To address this question, we combined nitrogen isotopes and carbon-to-nitrogen ratios with carbon-to-hydrogen ratios which act as an independent proxy for metamorphic alteration. Our results reveal that metamorphism drives kerogen-bound nitrogen isotopically lighter while silicate-bound nitrogen becomes heavier. For rocks up to greenschist facies, the isotopic effect of this internal partitioning (up to 3-4‰) is larger than the isotopic effect of metamorphic nitrogen loss from the system (up to 1-2‰). The opposite may be true for higher metamorphic grades. We conclude that for low-grade sedimentary rocks with more than 60% of their total nitrogen residing in the silicate phase the primary isotopic composition of the biomass is best approximated by the bulk rock measurement, whereas for high-grade rocks the kerogen extract may be the more accurate proxy. The isotopic difference between nitrogen phases can thus serve as a rough indicator of the degree of metamorphic alteration.PostprintPeer reviewe

Mercury abundance and isotopic composition indicate subaerial volcanism prior to the end-Archean “whiff” of oxygen

Funding: This study was supported by National Aeronautics and Space Administration Exobiology Grant NNX16AI37G (R.B.) and by the MacArthur Professorship (J.D.B.) at the University of Michigan. M.A.K. acknowledges support from an Agouron Institute postdoctoral fellowship.Earth’s early atmosphere witnessed multiple transient episodes of oxygenation before the Great Oxidation Event 2.4 billion years ago (Ga) [e.g., A. D. Anbar et al., Science 317, 1903–1906 (2007); M. C. Koehler, R. Buick, M. E. Barley, Precambrian Res. 320, 281–290 (2019)], but the triggers for these short-lived events are so far unknown. Here, we use mercury (Hg) abundance and stable isotope composition to investigate atmospheric evolution and its driving mechanisms across the well-studied “whiff” of O2 recorded in the ∼2.5-Ga Mt. McRae Shale from the Pilbara Craton in Western Australia [A. D. Anbar et al., Science 317, 1903–1906 (2007)]. Our data from the oxygenated interval show strong Hg enrichment paired with slightly negative Δ199Hg and near-zero Δ200Hg, suggestive of increased oxidative weathering. In contrast, slightly older beds, which were evidently deposited under an anoxic atmosphere in ferruginous waters [C. T. Reinhard, R. Raiswell, C. Scott, A. D. Anbar, T. W. Lyons, Science 326, 713–716 (2009)], show Hg enrichment coupled with positive Δ199Hg and slightly negative Δ200Hg values. This pattern is consistent with photochemical reactions associated with subaerial volcanism under intense UV radiation. Our results therefore suggest that the whiff of O2 was preceded by subaerial volcanism. The transient interval of O2 accumulation may thus have been triggered by diminished volcanic O2 sinks, followed by enhanced nutrient supply to the ocean from weathering of volcanic rocks causing increased biological productivity.PostprintPeer reviewe