An improved dual channel PERCA instrument for atmospheric measurements of peroxy radicals.

This paper describes a new dual-channel PEroxy RadiCal Amplification (PERCA) instrument, which has been designed to improve the time resolution and signal to noise and to reduce the interference caused by variations in ambient ozone concentrations. The instrument was run at the Weybourne Atmospheric Observatory (WAO), North Norfolk, during WAOWEX (Weybourne Atmospheric Observatory Winter Experiment) in January/February 2002 and INSPECTRO (Influence of clouds on the spectral actinic flux in the lower troposphere) in September 2002. The performance of the instrument is assessed and compared to that of a single channel instrument. In particular, it is shown how the precision is greatly improved in fluctuating background ozone conditions. In addition the improved time response of the instrument allows changes in peroxy radical concentrations to be related to rapid changes in nitric oxide concentrations and the ozone photolysis frequency, j(O(1)D).

Airborne measurements of peroxy radicals using the PERCA technique.

The Peroxy Radical Chemical Amplifier (PERCA) technique is a proven method for measurement of ambient levels of peroxy radicals at ground level, but there are no published instances of the technique being used on an aerial platform. Here we describe deployment of a PERCA on the former UK Meteorological Office C-130 Hercules research aircraft. The instrument uses the established method of chemical amplification and conversion of peroxy radicals to nitrogen dioxide (NO2) by doping the sample air-flow matrix with CO and NO, subsequently measuring the NO2 yield with an improved 'Luminox' LMA-3 NO2 detector. NO2 from the amplification chemistry is distinguished from other sources of NO2 reaching the detector by periodically injecting CO approximately 1 s downstream of the NO injection point (termination mode). Chain lengths (CL's) for the amplification chemistry were typically approximately 260 (ground level) to approximately 200 (7,000 m). This variation with altitude is less than the variation associated with the 'age' of the PFA inlet material where the amplification chemistry occurs; CL's of approximately 200 with old tubing to approximately 300 with new clean tubing were typical (ground level values). The CL determinations were made in-flight using an onboard calibration unit based on the 254 nm photolysis of 7.5 to 10 parts per billion (by volume, ppbv) of CH3I in air, producing CH3O2 in a quantitative manner. The noise-equivalent detection limit for peroxy radicals (HO2 + RO2) is 2 parts per trillion (by volume, pptv) at 3,650 m when the background ambient ozone levels are stable, based on a 5 min average of five 30 s amplification cycles and five 30 s termination cycles. This detection limit is a function of several factors but is most seriously degraded when there is large variability in the ambient ozone concentration. This paper describes the instrument design, considers its performance and proposes design improvements. It concludes that the performance of an airborne PERCA in the free troposphere can be superior to that of ground-based instruments when similar sampling frequencies are compared.