Fast-turnaround alkyl nitrate measurements during the PROPHET 1998 summer intensive

TitleFast-turnaround alkyl nitrate measurements during the PROPHET 1998 summer intensive
Publication TypeJournal Article
Year of Publication2001
AuthorsOstling K, Kelly B, Bird S, Bertman SB, Pippin MR, Thornberry TDean, Carroll MAnne
JournalJournal of Geophysical Research
Volume106
IssueD20
Pagination24,439-24,449
KeywordsVOLATILE ORGANIC COMPOUNDS
Abstract

An automated gas chromatographic system for making fast-turnaround measurements of alkyl nitrates was developed and tested. Every 30 min, samples were automatically acquired on a 1/16-inch OD Tenax trap made from fused silica-lined stainless steel tubing and injected by thermal desorption into the gas chromatograph. The system exhibited good chromatographic resolution, minimal breakthrough, and on-trap stability for C3-C5 nitrates. The detection limit of the instrument was <0.1 parts per trillion by volume for C3-C5 nitrates with an overall uncertainty of 30% for isopropyl nitrate and 50% for all other quantified compounds. Overall uncertainty of the method was limited by calibration precision rather than by sampling method or chromatography. The system was deployed in the field as part of the Program for Research on Oxidants: Photochemistry, Emissions, and Transport intensive held at UMBS in northern Michigan during the summer of 1998 from July 15 to August 22. Ambient results show a significant dynamic range with absolute levels affected by air mass history and pollution sources. The sum of measured C3-C5 alkyl nitrates obtained during this intensive ranged from 3.45 to 65.8 pptv, with a mean of 18.6 pptv and contributed 1% on average to total NOy, with a range of 0.5% to 3%. Differences in the contribution to NOy are found when the data are filtered according to air mass origin. A positive relationship between n-propyl nitrate and peroxypropionyl nitrate was observed over the course of the intensive.