Journal article
Chemical Amplification - Cavity Attenuated Phase Shift Spectroscopy Measurements of Atmospheric Peroxy Radicals
Analytical chemistry (Washington), v 86(20), pp 10266-10273
21 Oct 2014
PMID: 25260158
Featured in Collection : UN Sustainable Development Goals @ Drexel
Abstract
We describe a new instrument for the quantification of atmospheric peroxy radicals (Hc, CH3O2, C2H5O2, etc.) using the chemical amplification method. Peroxy radicals are mixed with high concentrations of NO and CO, causing a chain reaction that produces a measurable increase in NO2 which is quantified by cavity attenuated phase shift (CAPS) spectroscopy, a highly sensitive spectroscopic detection technique. The instrument utilizes two identical reaction chambers, each with a dedicated CAPS NO2 sensor. Similar to all dual-channel chemical amplifiers, one reaction chamber operates in amplification or "ROx" mode and the other in background or "Ox" mode. The peroxy radical mixing ratio is determined by the difference between the two channels' NO2 readings divided by a laboratory-determined chain length. Each reaction chamber alternates between ROx and Ox mode on an anti-synchronized schedule, eliminating the effect of CAPS baseline offsets on the calculated peroxy radical concentrations. The chain length is determined by a new calibration method: peroxyacetyl and methyl peroxy radicals are produced by the photolysis of acetone and quantified as NO2 following reaction with excess NO. We demonstrate the performance of the instrument with results from ambient sampling in Amherst and several diagnostics of its precision. The detection limit while sampling ambient air at a relative humidity (RH) of 40% is 0.6 ppt (1 min average, signal-to-noise ratio =2), with an estimated accuracy of 25% (2s).
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Details
- Title
- Chemical Amplification - Cavity Attenuated Phase Shift Spectroscopy Measurements of Atmospheric Peroxy Radicals
- Creators
- Ezra C. Wood - University of Massachusetts AmherstJohn R. Charest - University of Massachusetts Amherst
- Publication Details
- Analytical chemistry (Washington), v 86(20), pp 10266-10273
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 8
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemistry
- Web of Science ID
- WOS:000343639800039
- Scopus ID
- 2-s2.0-84910617354
- Other Identifier
- 991020902976904721
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InCites Highlights
Data related to this publication, from InCites Benchmarking & Analytics tool:
- Web of Science research areas
- Chemistry, Analytical