Ethane-Based Chemical Amplification Measurement Technique for Atmospheric Peroxy Radicals

Peroxy radicals play important roles in the atmospheric oxidation of organic compounds and the formation of ozone and secondary organic aerosol. There are few peroxy radical measurement techniques; the most common, chemical amplification using CO and NO, requires the use of toxic reagents, and its calibration factor is very sensitive to relative humidity. We present a new method for quantifying atmospheric peroxy radicals, ECHAMP (Ethane CHemical AMPlifier). Sampled air is mixed with NO and C₂H₆ (rather than CO), effecting a series of reactions that ultimately produces 25 molecules of NO₂ per sampled peroxy radical under dry conditions. This “amplification” factor decreases to 17 at a relative humidity of 50%, yielding a 1σ precision for 90 s average measurements of 0.8–2.5 ppt depending on the atmospheric variability of ozone. We demonstrated the utility of the new technique with measurements in Bloomington, IN, in July 2015

Evaluation of a New Vocus Reagent-Ion Source and Focusing Ion-Molecule Reactor for use in Proton-Transfer-Reaction Mass Spectrometry

<div>We evaluate the performance of a new chemical ionization source called Vocus, consisting of a discharge reagent-ion source and focusing ion-molecule reactor (FIMR) for use in protontransfer-reaction time-of-flight mass spectrometry (PTR-TOF) measurements of volatile organic compounds (VOCs) in air. The reagent ion source uses a low-pressure discharge. The FIMR consists of a glass tube with a resistive coating, mounted inside a radio-frequency (RF) quadrupole. The axial electric field is used to enhance ion collision energies and limit cluster ion formation. The RF field focuses ions to the central axis of the reactor and improves the detection efficiency of product ions. Ion trajectory calculations demonstrate the mass-dependent focusing of ions and enhancement of the ion collision energy by the RF field, in particular for the lighter ions. Product ion signals are increased by a factor of 10 when the RF field is applied (5,000-18,000 cps ppbv^-1), improving measurement precision and detection limits while operating at very similar reaction conditions as traditional PTR instruments. Due to the high water mixing ratio in the FIMR, we observe no dependence of the sensitivity on ambient sample humidity. In this work, the Vocus is interfaced to a TOF mass analyzer with a mass resolving power up to 14,000, which allows clear separation of isobaric ions, observed at nearly every nominal mass when measuring ambient air. Measurement response times are determined for a range of ketones with saturation vapor concentrations down to 5×10⁴ μg m^-3 and compare favorably with previously published results for a PTR-MS instrument.</div