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Rafelski, LE, Paplawsky B, Keeling RF.  2015.  Continuous measurements of dissolved O-2 and oxygen isotopes in the Southern California coastal ocean. Marine Chemistry. 174:94-102.   10.1016/j.marchem.2015.05.011   AbstractWebsite

Dissolved O-2/N-2, O-2/Ar, O-2 saturation and delta O-18 were measured continuously near the surface ocean at the Scripps Institution of Oceanography pier in La Jolla, California, for five weeks. The data showed diurnal cycles, in O-2 and delta O-18, with amplitudes of 19 mmol m(-3) and 1.1%., respectively. The diurnal cycles are well described by a box model that includes photosynthesis, respiration, air-sea gas exchange, and mixing. The timing of the cycles can be explained using a photosynthesis rate proportional to photosynthetically active radiation, and the shapes of the cycles can be explained by mixing with a subsurface layer of water that is supersaturated in O-2. Based on the diurnal cycles in O-2 and delta O-18, the average maximum daily photosynthesis rate was 3.7-4.7 mmol O-2 m(-3) h(-1), which is supported by the light-saturated photosynthesis rate estimated from the measured chlorophyll concentration. In the future, these continuous measurement techniques could be used at different locations and depths to improve the understanding of variability in oceanic primary production. (C) 2015 Elsevier B.V. All rights reserved.

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Rafelski, LE, Paplawsky B, Keeling RF.  2013.  An Equilibrator System to Measure Dissolved Oxygen and Its Isotopes. Journal of Atmospheric and Oceanic Technology. 30:361-377.   10.1175/jtech-d-12-00074.1   AbstractWebsite

An equilibrator is presented that is designed to have a sufficient equilibration time even for insoluble gases, and to minimize artifacts associated with not equilibrating to the total gas tension. A gas tension device was used to balance the pressure inside the equilibrator with the total gas tension. The equilibrator has an e-folding time of 7.36 +/- 0.74 min for oxygen and oxygen isotopes, allowing changes on hourly time scales to be easily resolved. The equilibrator delivers "equilibrated" air at a flow rate of 3 mL min(-1) to an isotope ratio mass spectrometer. The high gas sampling flow rate would allow the equilibrator to be interfaced with many potential devices, but further development may be required for use at sea. This system was tested at the Scripps Institution of Oceanography pier, in La Jolla, California. A mathematical model validated with performance tests was used to assess the sensitivity of the equilibrated air composition to headspace pressure and makeup gas composition. Parameters in this model can be quantified to establish corrections under different operating conditions. For typical observed values, under the operating conditions presented here, the uncertainty in the measurement due to the equilibrator system is 2.2 per mil for delta(O-2/N-2), 1.5 per mil for delta(O-2/Ar), 0.059 per mil for delta O-18, and 0.0030 per mil for Delta O-17.