Comprehensive laboratory measurements of biomass‐burning emissions: 2. First intercomparison of open‐path FTIR, PTR‐MS, and GC‐MS/FID/ECD

Oxygenated volatile organic compounds (OVOC) can dominate atmospheric organic chemistry, but they are difficult to measure reliably at low levels in complex mixtures. Several techniques that have been used to speciate nonmethane organic compounds (NMOC) including OVOC were codeployed/intercompared in well‐mixed smoke generated by 47 fires in the U.S. Department of Agriculture Forest Service Fire Sciences Combustion Facility. The agreement between proton transfer reaction mass spectrometry (PTR‐MS) and open‐path Fourier transform infrared spectroscopy (OP‐FTIR) was excellent for methanol (PT/FT = 1.04 ± 0.118) and good on average for phenol (0.843 ± 0.845) and acetol (∼0.81). The sum of OP‐FTIR mixing ratios for acetic acid and glycolaldehyde agreed (within experimental uncertainty) with the PTR‐MS mixing ratios for protonated mass 61 (PT/FT = 1.17 ± 0.34), and the sum of OP‐FTIR mixing ratios for furan and isoprene agreed with the PTR‐MS mixing ratios for protonated mass 69 (PT/FT = 0.783 ± 0.465). The sum of OP‐FTIR mixing ratios for acetone and methylvinylether accounted for most of the PTR‐MS protonated mass 59 signal (PT/FT = 1.29 ± 0.81), suggesting that one of these compounds was underestimated by OP‐FTIR or that it failed to detect other compounds that could contribute at mass 59. Canister grab sampling followed by gas chromatography (GC) with mass spectrometry (MS), flame ionization detection (FID), and electron capture detection (ECD) analysis by two different groups agreed well with OP‐FTIR for ethylene, acetylene, and propylene. However, these propylene levels were below those observed by PTR‐MS (PT/FT = 2.33 ± 0.89). Good average agreement between PTR‐MS and GC was obtained for benzene and toluene. At mixing ratios above a few parts per billion the OP‐FTIR had advantages for measuring sticky compounds (e.g., ammonia and formic acid) or compounds with low proton affinity (e.g., hydrogen cyanide and formaldehyde). Even at these levels, only the PTR‐MS measured acetonitrile and acetaldehyde. Below a few ppbv only the PTR‐MS measured a variety of OVOC, but the possibility of fragmentation, interference, and sampling losses must be considered.