UC Santa Cruz

Throughout most of the world’s oceans, the bioavailability of marine dissolved organic nitrogen (DON) acts to limit marine primary production and thus is a key control on marine biogeochemical cycles and carbon sequestration. Understanding the processes that control marine DON cycling and availability, and by extension long-term carbon storage in the ocean, are thus of vital importance. Nevertheless, despite significant research, the mechanisms that lead to the accumulation of refractory DON (RDON) largely remain an enigma. In this thesis, I address this knowledge gap by investigating the source and degradation processes of traditionally studied younger, high molecular weight (HMW) DON and, for the first time, directly isolated older, low molecular weight (LMW) solid phase extracted (SPE) DON. I used a range of novel proxies and analytical approaches, including a new suite of D-amino acids and the first compound-specific specific amino acid measurements across the DON age/size spectrum. These powerful molecular level proxies for proteinaceous marine DON source and cycling allowed me to posit a new theory for bacterial control of RDON production. Finally, I pair these analyses with broader advanced solid state NMR techniques to present new information regarding overall marine DON chemical composition. Together, I use these data to propose a novel theory regarding production of the most refractory nitrogen containing molecules in the ocean, suggesting a fundamental paradigm shift in our understanding of the marine DON pool.