Determination of gas bubble fractionation rates in the deep ocean by laser Raman spectroscopy

Author Posting. © The Authors, 2004. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Marine Chemistry 99 (2006): 12-23, doi:10.1016/j.marchem.2004.10.006.A new deep-sea laser Raman spectrometer (DORISS – Deep Ocean Raman In Situ Spectrometer) is used to observe the preferential dissolution of CO2 into seawater from a 50%-50% CO2-N2 gas mixture in a set of experiments that test a proposed method of CO2 sequestration in the deep ocean. In a first set of experiments performed at 300 m depth, an open-bottomed 1000 cm3 cube was used to contain the gas mixture; and in a second set of experiments a 2.5 cm3 funnel was used to hold a bubble of the gas mixture in front of the sampling optic. By observing the changing ratios of the CO2 and N2 Raman bands we were able to determine the gas flux and the mass transfer coefficient at 300 m depth and compare them to theoretical calculations for air-sea gas exchange. Although each experiment had a different configuration, comparable results were obtained. As expected, the ratio of CO2 to N2 drops off at an exponential rate as CO2 is preferentially dissolved in seawater. In fitting the data with theoretical gas flux calculations, the boundary layer thickness was determined to be ~42 μm for the gas cube, and ~165 μm for the gas funnel reflecting different boundary layer turbulence. The mass transfer coefficients for CO2 are kL = 2.82 x 10- 5 m/s for the gas cube experiment, and kL = 7.98 x 10- 6 m/s for the gas funnel experiment.Funding was provided by a grant to MBARI from the David and Lucile Packard Foundation, and by the U.S. Dept. of Energy Ocean Carbon Sequestration Program (Grants No. DE-FC26-00NT40929 and DE-FC03-01ER6305)