Nitrogen isotope evidence for alkaline lakes on late Archean continents

Nitrogen isotope ratios in ancient sedimentary rocks are generally interpreted as a proxy for metabolic nitrogen pathways and the redox state of the water column. Fractionation processes occurring under anoxic, alkaline conditions during the dissociation of NH⁺₄ to H⁺ and volatile NH₃ are frequently overlooked, although this mechanism imparts large isotopic fractionations. Here we propose that NH₃ volatilization is largely responsible for δ¹⁵N values of up to ‰ at high C/N ratios in the late Archean Tumbiana Formation. This sequence of sedimentary rocks represents a system of lakes that formed on subaerial flood basalts and were partly filled by basaltic volcanic ash. Aqueous alteration of volcanic glass followed by evaporative concentration of ions should have led to the development of high alkalinity with a pH of 9 or higher, as in modern analogues. In this sedimentologically unusual setting, nitrogen isotope ratios thus provide indirect evidence for the oldest alkaline lake system in the rock record. These very heavy lacustrine δ¹⁵N values contrast markedly with those of Archean marine sedimentary rocks, making a Precambrian “soda ocean” unlikely. Today, alkaline lakes are among the most productive ecosystems on Earth. Some nutrients, in particular molybdenum, are more soluble at high pH, and certain prebiotic reactions would likely have been favored under alkaline conditions in similar settings earlier in Earth's history. Hence alkaline lakes in the Archean could have been significant for the origin and early evolution of life.