Stable Isotope Evidence for Abiotic Ammonium Production in the Hydrothermal Vent Fluids from the Mid-Cayman Rise

The Mid-Cayman Rise hosts the world's deepest (up to 4,987 meters) hydrothermal vent field, Piccard. Under the tremendous pressure, the vent fluid from Piccard can be as hot as 398°C. Here, the concentration of ammonium (35 μmol/kg) is much higher than that of the bottom water nitrate (22 μmol/kg). The undetectable nitrate in the vent fluid suggests that nitrate is completely reduced to ammonium in the reaction zone and there has to be an additional source for ammonium production. Because Piccard is unsedimented (i.e., lacking significant sedimentary organic matter), the other possible source of ammonium is the reduction of nitrogen gas (N2). We demonstrated that the isotopic composition of ammonium (δ15N-NH4+) for the Piccard vent fluid end-member (3.4 ± 0.1 ‰) supports the mixing between two ammonium sources: the reduction of nitrate and the reduction of N2. However, at Von Damm, shallower depth (up to 2,300 meters) causes the vent fluid to be relatively cooler (138°C) compared to Piccard and it is very likely that the reduction of nitrate is the only source of ammonium in the vent fluid. Studying the vent fluids from these sites where the temperatures are well above the upper limit for life can be useful in assessing the conditions and abiotic processes that might have given rise to the ammonium production in the early prebiotic ocean.