Atmospheric measurements of OH, HO2 and NO by laser-induced fluorescence spectroscopy using a compact all solid-state laser system
Abstract
Free-radicals are key intermediates that control the budgets of many trace gases, for example ozone, greenhouse gases and harmful pollutants. Measurement of radicals and comparison with model calculations constitutes an important test of our understanding of the underlying chemistry. There is a greater need for compact and lightweight instruments for the in situ measurement of free-radical species that are suitable for deployment from a number of field-platforms. A new field instrument has been developed that incorporates an all solid-state Nd:YAG pumped titanium sapphire laser that is capable of generating radiation at high pulse-repetition-frequency for the detection of OH, HO_2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF). The system offers advantages of wide wavelength tunability, compactness, low weight, greater long-term stability (fibre-optic delivery) and short warm-up time. The instrument was successfully deployed during 2002 in the NAMBLEX field campaign at Mace Head with detection limits for OH and HO_2 (measured simultaneously with laser operation at 308 nm) of 3.1 x 10^5 molecule cm-3 (0.012 ppt) and 2.6 x 10^6 molecule cm-3 (0.09 pptv) respectively. Diurnal profiles of OH have been recorded over a period of 5 weeks. NO controls the HO_2/OH ratio and is the critical parameter in the production of tropospheric ozone, yet measurements in the boundary layer are restricted to a single indirect technique based on chemiluminescent analysers. Measurements of NO in the atmosphere have been made by LIF using the new instrument operating at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a commercial chemiluminescent analyser. Whilst operating at 445 nm, the instrument has detected the IO radical in the laboratory, with a projected detection limit that is well below previously measured atmospheric concentrations of IO. A second instrument to be deployed on an aircraft platform is currently being developed.
- Publication:
-
EGS - AGU - EUG Joint Assembly
- Pub Date:
- April 2003
- Bibcode:
- 2003EAEJA....10521B