Project: Clumped Oxygen Isotope Signature of Marine Dissolved Oxygen

NSF Award Abstract:
The balance between photosynthetic production of oxygen and biological consumption of oxygen in the marine environment plays a critical role in regulating the composition of Earth’s atmosphere and the long-term stability of Earth’s climate. The ability to accurately measure the production and consumption of oxygen in the marine environment is central to building an informed understanding of the past, present, and future of oxygen and Earth’s climate. Measurement of the abundance of different oxygen isotopes (i.e. oxygen-16, oxygen-17, and oxygen-18) in dissolved oxygen in seawater is a powerful analytical tool that can be used to determine the magnitude of photosynthesis and biological oxygen consumption. This is possible because biological reactions that produce or consume oxygen tend to preferentially utilize different isotopes of oxygen. This analytical tool has been used for two decades to investigate ocean primary productivity, however, there is still significant uncertainty in how biogeochemical processes such as respiration preferentially select and utilize different oxygen isotopes. To remedy this uncertainty, researchers at Harvard University will perform a lab-based calibration and sea-going field deployment of emerging oxygen isotope analyses that target molecules of oxygen that contain two rare oxygen isotopes inside of one molecule (a.k.a. “clumps”, i.e. 17O18O and 18O18O). This work will quantify the clumped oxygen isotope signatures of several of the most consequential oxygen-involving reactions that occur in the marine ecosystem. These oxygen isotope signatures will be used to refine current methods and assumptions for the measurement of gross oxygen production in the global ocean. This research will also help train the next generation of Earth scientists through the mentorship of one graduate student and two undergraduate students. This project will also facilitate the participation of researchers in content creation for a national science competition for middle and high school students that reaches thousands of students annually.

The application of clumped O2 isotope measurements to dissolved oxygen in seawater is poised to give a greater mechanistic view of gross primary productivity and marine oxygen cycling than previously attainable. To realize the analytical potential of clumped oxygen isotope methods, these researchers will characterize the clumped oxygen isotope effects associated with enzyme-level reactions, whole organisms, and the marine water column. Enzyme-level studies will include isotope characterization of a terminal-O2 reductase and enzymes that metabolize reactive oxygen species such as superoxide and hydrogen peroxide. Organism studies will target common and numerically abundant phototrophs and heterotrophs to explore the expected breadth of isotope signatures and fractionation factors in the marine water column. Marine water column dissolved oxygen samples will be collected during one of multiple candidate cruises and analyzed using both traditional triple oxygen isotope techniques and newly developed clumped oxygen isotope methods. Lastly, they will employ the results of lab-based study of clumped O2 to build a model for the interpretation of environmental data with the aim of improving the accuracy and precision of field measurements of gross primary production.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.