Elevated δ¹⁵N linked to inhibited nitrification coupled to ammonia volatilization in sediments of shallow alkaline-hypersaline lakes

Alkaline lakes are among the most bioproductive aquatic ecosystems on Earth. The factors that ultimately limit productivity in these systems can vary, but nitrogen (N) cycling in particular has been shown to be adversely affected by high salinity, evidently due to the inhibition of nitrifying bacteria (i.e., those that convert ammonic species to nitrogen oxides). The coastal plain of Coorong National Park in South Australia, which hosts several alkaline lakes along 130 km of coastline, provides an ideal natural laboratory for examining how fine-scale differences in the geochemistry of such environments can lead to broad variations in nitrogen cycling through time, as manifest in sedimentary δ¹⁵N. Moreover, the lakes provide a gradient of aqueous conditions that allows us to assess the effects of pH, salinity, and carbonate chemistry on the sedimentary record. We report a wide range of δ¹⁵N values (3.8‰–18.6‰) measured in the sediments (0–35 cm depth) of five lakes of the Coorong region. Additional data include major element abundances, carbonate δ¹³C and δ¹⁸O values, and the results of principal component analyses. Stable nitrogen isotopes and wt% sodium (Na) display positive correlation (R² = 0.59, p < 0.001) across all lake systems. Principal component analyses further support the notion that salinity has historically impacted nitrogen cycling. We propose that the inhibition of nitrification at elevated salinity may lead to the accumulation of ammonic species, which, when exposed to the water column, are prone to ammonia volatilization facilitated by intervals of elevated pH. This process is accompanied by a significant isotope fractionation effect, isotopically enriching the nitrogen that remains in the lake water. This nitrogen is eventually buried in the sediments, preserving a record of these combined processes. Analogous enrichments in the rock record may provide important constraints on past chemical conditions and their associated microbial ecologies. Specifically, ancient terrestrial aquatic systems with high δ¹⁵N values attributed to denitrification and thus oxygen deficiency may warrant re-evaluation within the framework of this alternative. Constraints on pH as provided by elevated δ¹⁵N via ammonia volatilization may also inform critical aspects of closed-basin paleoenvironments and their suitability for a de novo origin of life.