Fe-catalyzed sulfide oxidation in hydrothermal plumes is a source of reactive oxygen species to the ocean.

Historically, the production of reactive oxygen species (ROS) in the ocean has been attributed to photochemical and biochemical reactions. However, hydrothermal vents emit globally significant inventories of reduced Fe and S species that should react rapidly with oxygen in bottom water and serve as a heretofore unmeasured source of ROS. Here, we show that the Fe-catalyzed oxidation of reduced sulfur species in hydrothermal vent plumes in the deep oceans supported the abiotic formation of ROS at concentrations 20 to 100 times higher than the average for photoproduced ROS in surface waters. ROS (measured as hydrogen peroxide) were determined in hydrothermal plumes and seeps during a series of Alvin dives at the North East Pacific Rise. Hydrogen peroxide inventories in emerging plumes were maintained at levels proportional to the oxygen introduced by mixing with bottom water. Fenton chemistry predicts the production of hydroxyl radical under plume conditions through the reaction of hydrogen peroxide with the abundant reduced Fe in hydrothermal plumes. A model of the hydroxyl radical fate under plume conditions supports the role of plume ROS in the alteration of refractory organic molecules in seawater. The ocean's volume circulates through hydrothermal plumes on timescales similar to the age of refractory dissolved organic carbon. Thus, plume-generated ROS can initiate reactions that may affect global ocean carbon inventories.

Abiotic synthesis of graphite in hydrothermal vents.

Deciphering the origin, age, and composition of deep marine organic carbon remains a challenge in understanding the dynamics of the marine carbon cycle. In particular, the composition of aged organic carbon and what allows its persistence in the deep ocean and in sediment is unresolved. Here, we observe that both high and low temperature hydrothermal vents at the 9° 50' N; 104° 17.5 W East Pacific Rise (EPR) vent field are a source for (sub)micron-sized graphite particles. We demonstrate that commonly applied analytical techniques for quantification of organic carbon detect graphite. These analyses thereby classify graphite as either dissolved or particulate organic carbon, depending on the particle size and filtration method, and overlook its relevance as a carbon source to the deep ocean. Settling velocity calculations indicate the potential for these (sub)micron particles to become entrained in the buoyant plume and distributed far from the vent fields. Thus, our observations provide direct evidence for hydrothermal vents acting as a source of old carbon to the deep ocean.