Comparison of temperature-dependent calibration methods of an instrument to measure OH and HO₂ radicals using laser-induced fluorescence spectroscopy

Laser-induced fluorescence (LIF) spectroscopy has been widely applied to fieldwork measurements of OH radicals and HO2, following conversion to OH, over a wide variety of conditions, on different platforms and in simulation chambers. Conventional calibration of HOx (OH + HO2) instruments has mainly relied on a single method, generating known concentrations of HOx from H2O vapour photolysis in a flow of zero air impinging just outside the sample inlet (SHOx = CHOx . [HOx ], where SHOx is the observed signal and CHOx is the calibration factor). The fluorescence assay by gaseous expansion (FAGE) apparatus designed for HOx measurements in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC) at the University of Leeds has been used to examine the sensitivity of FAGE to external gas temperatures (266–348 K). The conventional calibration methods give the temperature dependence of COH (relative to the value at 293 K) of (0.0059±0.0015) K−1 and CHO2 of (0.014±0.013) K−1. Errors are 2σ . COH was also determined by observing the decay of hydrocarbons (typically cyclohexane) caused by OH reactions giving COH (again, relative to the value at 293 K) of (0.0038 ± 0.0007) K−1. Additionally, CHO2 was determined based on the second-order kinetics of HO2 recombination with the temperature dependence of CHO2 , relative to 293 K being (0.0064 ± 0.0034) K−1. The temperature dependence of CHOx depends on the HOx number density, quenching, the relative population of the probed OH rotational level and HOx transmission from the inlet to the detection axis. The first three terms can be calculated and, in combination with the measured values of CHOx, show that HOx transmission increases with temperature. Comparisons with other instruments and the implications of this work are discussed

A brief review of the use of environmental chambers for gas phase studies of kinetics, chemical mechanisms and characterisation of field instruments

This introductory review considers the role of environmental chambers in atmospheric chemistry, emphasising the importance of being able to carry out studies in controlled conditions. The advantages and disadvantages of different types of chambers are discussed and compared. Examples of the use of chambers for kinetic and mechanistic studies are presented. The final section of this brief review considers the use of chambers in providing a well defined environment for calibrating and investigating the performance of field instruments

Rate Constants and Branching Ratios for the Reaction of CH Radicals with NH3 : A Combined Experimental and Theoretical Study

International audienceRate Constants and Branching Ratios for the Reaction of CH Radicals with NH3 : A Combined Experimental and Theoretical Stud

Kinetics of the Gas-Phase Reactions of syn- and anti-CH3CHOO Criegee Intermediate Conformers with SO2 as a Function of Temperature and Pressure

Kinetics of reactions between SO2 and CH3CHOO Criegee intermediate conformers have been measured at temperatures between 242 and 353 K and pressures between 10 and 600 Torr using laser flash photolysis of CH3CHI2/O2/N2/SO2 gas mixtures coupled with time-resolved broadband UV absorption spectroscopy. The kinetics of syn-CH3CHOO + SO2 are pressure-dependent and exhibit a negative temperature dependence, with the observed pressure dependence reconciling apparent discrepancies between previous measurements performed at ∼298 K. Results indicate a rate coefficient of (4.80 ± 0.46) × 10–11 cm3 s–1 for the reaction of syn-CH3CHOO with SO2 at 298 K and 760 Torr. In contrast to the behavior of the syn-conformer, the kinetics of anti-CH3CHOO + SO2 display no significant dependence on temperature or pressure over the ranges investigated, with a mean rate coefficient of (1.18 ± 0.21) × 10–10 cm3 s–1 over all conditions studied in this work. Results indicate that the reaction of syn-CH3CHOO with SO2 competes with unimolecular decomposition and reaction with water vapor in areas with high SO2 concentration and low humidity, particularly at lower temperatures

Ambient isoprene and monoterpene concentrations in a Greek fir (Abies Borisii-regis) forest. Reconciliation with emissions measurements and effects on measured OH concentrations

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Isoprene and its degradation products methyl vinyl ketone, methacrolein and formaldehyde in a eucalyptus forest during the FIELDVOC'94 campaign in Portugal

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