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152 CHAPTER 5. SMALL-SCALE AIR-SEA INTERACTION 5.1.8 Spectroscopic Techniques for Gas-Exchange Measurements Felix Vogel Abstract To evaluate the applicability of different spectroscopic techniques for temporally resolved gas-exchange measurements a Raman spectometer was built and existing UV/Vis systems were improved. Laboratory experiments yielded that Raman spectroscopy is not suitable for dynamic gasexchange measurements due to its insufficient temporal resolution while the applicability of UV/Vis spectroscopy was confirmed. Figure 5.8: Simultaneous measurement of the concentration of anisole in the air and water-bulk during an invasion experiment Background Studying gas-exchange processes contributes to the understanding of our climate system as well as it is fundamental research of turbulent processes in fluids. Accounting for small scale processes to yield an accurate parametrisation of the transfer rate, temporally resolved in-situ measurements of the concentration change have to be performed. Besides classical methods measuring dissolved gases, recently temporally highly resolved spectroscopic techniques with volatile aromatics have been introduced as a new tool for the investigation of the transfer processes [Degreif2006]. Funding None Methods and results Experiments with pure and dissolved aromatics yielded that the newly built Raman setup is not suitable for systemanic gas-exchange measurements. To conduct experiments at the circular wind-wave flume of the University of Heidelberg and the linear wind-wave flume of the University of Hamburg, one waterphase and one air-phase setup was developed. The performance of both UV/Vis spectrometers was evaluated at the Aeolotron laboratory. With an absorption path length of up to 10 metres the temporal resolution of the air-phase spectrometer is of the order of deciseconds. Invasion experiments yielded that the in-situ concentration can be monitored continuously in the range of 30 ppm−0.3 ppm for example for benzaldehyde. For the UV/Vis setup to measure the water-phase concentration an absorption length of one metre and an integration time of 40 ms turned out to be adequate. Outlook/Future work To reduce the uncertainties of the calculated piston velocities, the solubilities of the applied substances should be determined in laboratory experiments, as the values given in the available literature vary largly. The acquistion of concentration gauged spectra is also needed to determine the piston velocities of moderately soluble substances. As their transfer rate is not dominated by the transfer rate of one compartment, both air and water-phase concentration have to be taken into account. Main publications [Vogel, 2006]
5.1. SMALL-SCALE AIR-SEA INTERACTION 153 References Bock, E. J., Hara, T., Frew, N. M., & McGilles, W. R. 1999. Relationship between air-sea gas transfer and short wind waves. J. Gephys. Res., 104, 25 821–25 831. Csanady, G.T. 1990. The role of breaking wavelets in air–sea gas transfer. J. Geophys. Res., 95, 749–759. Degreif, K. A. 2006. Untersuchungen zum Gasaustausch - Entwicklung und Applikation eines zeitlich aufgelsten Massenbilanzverfahrens. PhD Thesis, <strong>Universität</strong> Heidelberg. Falkenroth, A.; Herzog, A.; Jähne B. Visualization of Air Water Gas Exchange using Novel Fluorescent Dyes. ISFV 12, 10- 14 September 2006, Göttingen. Falkenroth, Achim, Degreif, Kai, & Jähne, Bernd. 2007. Visualisation of Oxygen Concentration Fields in the Mass Boundary Layer by Fluorescence Quenching. In: Garbe, C.S., Handler, R.A., & Jähne, B. (eds), Transport at the Air Sea Interface - Measurements, Models and Parameterizations. Springer. Frew, N. M. 1997. The role of organic films in air-sea gas exchange. Pages 121–172 of: Liss, Peter S., & Duce, Robert S. (eds), The Sea Surface and Global Change. Cambridge, UK: Cambridge University Press. Frew, N. M., Bock, E. J., Schimpf, U., Hara, T., Haußecker, H., Edson, J. B., McGillis, W. R., Nelson, R. K., McKeanna, B. M., Uz, B. M., & Jähne, B. 2004. Air-sea gas transfer: its dependence on wind stress, small-scale roughness and surface films Small-Scale Air-Sea Interaction with Thermography. J. Geophys. Res, C8(109). C08S17, doi:10.1029/2003JC002131. Garbe, C. S., Roetmann, K., & Jähne, B. 2006a. An Optical Flow Based Technique for the Non- Invasive Measurement of Microfluidic Flows. Pages 1–10 of: 12TH INTERNATIONAL SYMPO- SIUM ON FLOWVISUALIZATION. Garbe, C. S., Roetmann, K., & Jhne, B. 2006b. An Optical Flow Based Technique for the Non- Invasive Measurement of Microfluidic Flows. Pages 1–10 of: 12th International Symposium on Flow Visualization. Garbe, C. S., Degreif, K., & Jhne, B. 2006c. Viscous stress measurements from active thermography on a free air-water interface. Pages 1–10 of: International Symposium on Transport at the Air-Sea Interface. Garbe, C. S., Handler, R. A., & Jähne, B. 2007. Transport at the Air Sea Interface - Measurements, Models and Parameterizations. Springer. Accepted for publication. Garbe, Christoph S., Spies, Hagen, & Jähne, Bernd. 2003. Estimation of Surface Flow and Net Heat Flux from Infrared Image Sequences. J. Mathematical Imaging and Vision, 19, 159–174. Herzog, A. Tiefenaufgelöste Grenzschichtvisualisierung an freien Oberflächen. Jähne, B. 1980. Zur Parameterisierung des Gasaustausches mit Hilfe von Laborexperimenten. PhD Thesis, <strong>Universität</strong> Heidelberg. D-200. Jähne, B. 2001. Air-Sea Interaction: Gas Exchange. In: Steele, J., Thorpe, S., & Turekian, K. (eds), Encyclopedia of Ocean Sciences. Academic Press, London. Jähne, B. 2007a. Complex Motion. Springer. LNCS 3417. Jähne, B. 2007b. Complex Motion in Environmental Physics and Live Sciences. Pages 92–105 of: Jhne, B. (ed), Complex Motion. Springer. LNCS 3417. Jähne, B., & Haußecker, H. 1998. Air-Water Gas Exchange. Annual Rev. Fluid Mech., 30, 443–468. Jähne, B., Münnich, K. O., Bösinger, R., Dutzi, A., Huber, W., & Libner, P. 1987. On the parameters influencing air/water gas exchange. J. Geophys. Res, 92, 1937–1949. Jähne, B., Libner, P., Fischer, R., Billen, T., & Plate, E. J. 1989. Investigating the transfer processes across the free aqueous viscous boundary layer by the controlled flux method. Tellus, 41B, 177–195.
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