Direct measurements of the convective recycling of the upper troposphere.

We present a statistical representation of the aggregate effects of deep convection on the chemistry and dynamics of the upper troposphere (UT) based on direct aircraft observations of the chemical composition of the UT over the eastern United States and Canada during summer. These measurements provide unique observational constraints on the chemistry occurring downwind of convection and the rate at which air in the UT is recycled. These results provide quantitative measures that can be used to evaluate global climate and chemistry models.

Chemical ionization mass spectrometer instrument for the measurement of tropospheric HO2 and RO2.

Laboratory characterizations of the peroxy radical chemical ionization mass spectrometer (PerCIMS) instrument have been performed. The instrument functions by drawing ambient air through a 50-microm-diameter orifice into an inlet held at low pressure. Peroxy radicals (HO2 and RO2) within this air are detected by amplified chemical conversion into a unique ion (HSO4-) via the chemistry initiated by the addition of NO and SO2 to the inlet. HSO4- ions are then quantified by a quadrupole filter mass spectrometer. PerCIMS provides measurements of the sum of peroxy radicals, HO2 + RO2 (HOxROx mode), or the HO2 component only (HO2 mode), achieved through the control of concentration of NO and SO2 added to the instrument. The characterization and response of this instrument have been evaluated through modeling of inlet chemistry and laboratory experiments and have also been demonstrated through successful deployment during field campaigns. The performance of PerCIMS with respect to calibration pressure and relative humidity is reported, as are the sensitivities of the instrument to organic peroxy radicals with different hydrocarbon groups. These data show PerCIMS to be a practical field instrument for the fast and accurate evaluation of the concentration of peroxy radicals over a variety of atmospheric conditions. The estimated accuracy of the derived [HOxROx] concentrations is +/- 35% (at the 95% confidence interval), while [HO2] measurements have accuracies of +/- 41% (at the 95% confidence interval). Typical precision of measurements well above the detection limit is 10%, and typical detection limits are 1 x 10(7) radicals cm(-3) for 15-s averaging times.