Technical Note: Determination of formaldehyde mixing ratios in air with PTR-MS: laboratory experiments and field measurements

Inomata, Satoshi; Tanimoto, Hiroshi; Kameyama, Sohiko; Tsunogai, Urumu; Irie, Hitoshi; Kanaya, Yugo; Wang, Z.

doi:10.5194/acp-8-273-2008

Cited by 128 publications

(166 citation statements)

References 46 publications

(68 reference statements)

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“…The slope of 1.25 may be a result of contributions to the PTR-MS signal at m/z 31 from compounds other than formaldehyde, including methanol, ethanol, and methyl hydroperoxide (Inomata et al, 2008) and glyoxal (Stonner et al, 2016). The protonated molecular ion signal of ethanol and methyl hydroperoxide cannot be unequivocally identified in the PTR-MS spectra and their concentrations were not determined independently by either the AT-VOC or DNPH method, and consequently their contribution to the m/z 31 signal cannot be determined in this study.…”

Section: Formaldehydementioning

confidence: 99%

“…Interference in the identification and quantification of a target compound in PTR-MS measurements of ambient air can and frequently does occur due to the presence of products from other reaction pathways such as isobaric compounds, fragment ions from other compounds, isotopologues and products of secondary reactions Rogers et al, 2006;Inomata et al, 2008;Dunne et al, 2012;Kaser et al, 2013). When comparing PTR-MS measurements to more selective VOC measurement techniques such as chromatographic methods, the presence of interference in the target ion signal often results in an apparent positive bias in the PTR-MS reported values.…”

Section: Proton-transfer-reaction Mass Spectrometry (Ptr-ms)mentioning

confidence: 99%

“…The measurement of formaldehyde with PTR-MS is complex as its proton transfer chemical ionization reaction with H 3 O + is close to endothermic and loss via back reaction in humid air is non-negligible Inomata et al, 2008). In order to account for the water vapour dependence of the PTR-MS response to formaldehyde, daily instrument background and calibration measurements were made using zero air that had the same mole fractions of H 2 O as the ambient air being sampled.…”

Section: Formaldehydementioning

confidence: 99%

“…Rogers et al, 2006;Inomata et al, 2008;Dunne et al, 2012). Where possible, for the compounds examined in this study, a method was developed to correct the PTR-MS target ion signal for the presence of known and quantifiable interference.…”

Section: Proton-transfer-reaction Mass Spectrometry (Ptr-ms)mentioning

confidence: 99%

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Comparison of VOC measurements made by PTR-MS, adsorbent tubes–GC-FID-MS and DNPH derivatization–HPLC during the Sydney Particle Study, 2012: a contribution to the assessment of uncertainty in routine atmospheric VOC measurements

et al. 2018

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Abstract. Understanding uncertainty is essential for utilizing atmospheric volatile organic compound (VOC) measurements in robust ways to develop atmospheric science. This study describes an inter-comparison of the VOC data, and the derived uncertainty estimates, measured with three independent techniques (PTR-MS, proton-transfer-reaction mass spectrometry; GC-FID-MS, gas chromatography with flameionization and mass spectrometric detection; and DNPH-HPLC, 2,4-dinitrophenylhydrazine derivatization followed by analysis by high-performance liquid chromatography) during routine monitoring as part of the Sydney Particle Study (SPS) campaign in 2012. Benzene, toluene, C 8 aromatics, isoprene, formaldehyde and acetaldehyde were selected for the comparison, based on objective selection criteria from the available data. Bottom-up uncertainty analyses were undertaken for each compound and each measurement system. Top-down uncertainties were quantified via the intercomparisons. In all seven comparisons, the correlations between independent measurement techniques were high with R 2 values with a median of 0.92 (range 0.75-0.98) and small root mean square of the deviations (RMSD) of the observations from the regression line with a median of 0.11 (range 0.04-0.23 ppbv). These results give a high degree of confidence that for each comparison the response of the two independent techniques is dominated by the same constituents. The slope and intercept as determined by reduced major axis (RMA) regression gives a different story. The slopes varied considerably with a median of 1.25 and a range of 1.16-2.01. The intercepts varied with a median of 0.04 and a range of −0.03 to 0.31 ppbv. An ideal comparison would give a slope of 1.00 and an intercept of 0.Some sources of uncertainty that are poorly quantified by the bottom-up uncertainty analysis method were identified, including: contributions of non-target compounds to the measurement of the target compound for benzene, toluene and isoprene by PTR-MS as well as the under-reporting of formaldehyde, acetaldehyde and acetone by the DNPH technique. As well as these, this study has identified a specific interference of liquid water with acetone measurements by the DNPH technique.These relationships reported for Sydney 2012 were incorporated into a larger analysis with 61 similar published inter-comparison studies for the same compounds. Overall, for the light aromatics, isoprene and the C 1 -C 3 carbonyls, the uncertainty in a set of measurements varies by a factor of between 1.5 and 2. These uncertainties (∼ 50 %) are significantly higher than uncertainties estimated using standard propagation of error methods, which in this case were ∼ 22 % or less, and are the result of the presence of poorly understood or neglected processes that affect the measurement and its uncertainty. The uncertainties in VOC measurements identified here should be considered when assessing the reliability of VOC measurements from routine monitoring with individual, stand-alone instruments; when utilizing VOC da...

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Section: Formaldehydementioning

confidence: 99%

Section: Proton-transfer-reaction Mass Spectrometry (Ptr-ms)mentioning

confidence: 99%

Section: Formaldehydementioning

confidence: 99%

Section: Proton-transfer-reaction Mass Spectrometry (Ptr-ms)mentioning

confidence: 99%

See 2 more Smart Citations

Comparison of VOC measurements made by PTR-MS, adsorbent tubes–GC-FID-MS and DNPH derivatization–HPLC during the Sydney Particle Study, 2012: a contribution to the assessment of uncertainty in routine atmospheric VOC measurements

et al. 2018

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“…The concentrations of these individual NMHCs observed in The concentrations of benzene, acetaldehyde, acetone, MVK, and methanol was calibrated by using a ten-VOC premixed standard gas containing toluene (4.98 ppmv), 1,3,5-trimethylbenzene (1.01 ppmv), acetonitrile (4.95 ppmv), acetaldehyde (5.04 ppmv), methanol (5.05 ppmv), benzene (5.01 ppmv), acetone (4.99 ppmv), isoprene (4.99 ppmv), p-xylene (4.99 ppmv), and MVK (5.00 ppmv) balanced with N 2 . Formaldehyde concentrations were determined by using the detection sensitivity reported previously (Inomata et al, 2008). For MEK, the volume mixing ratio was calculated theoretically from the equationobtained signal intensity, rate constant, and reaction time for its protonation reaction (Inomata et al, 2010;Kudo et al, 2014).…”

Section: Observations and Model Simulation Inputsmentioning

confidence: 99%

Diagnosis of Photochemical Ozone Production Rates and Limiting Factors in Continental Outflow Air Masses Reaching Fukue Island, Japan: Ozone-Control Implications

Kanaya

Tanimoto

Yokouchi

et al. 2016

Aerosol Air Qual. Res.

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Asian continental outflow air masses reach western Japan in the springtime, carrying high levels of ozone produced over the Asian continent, and facilitating in-situ production. In this study, in-situ production was highlighted; the rate and limiting factors of net ozone production were diagnosed at Fukue Island, a remote island west of Japan, on 17 days during May-June 2009, when the continental outflow air mass arrived, using an observation-based modeling approach. The average ozone production was estimated to be 6.8 ppb per day. Information on the chemical status of the arriving air mass is important, because it affects how further ozone production in the air mass occurs after precursor addition from Japanese domestic emissions. The main limiting factor of ozone production for such air masses was usually nitrogen oxides (NO x ), suggesting that domestic NO x emission control is important in reducing further ozone production. Volatile organic compounds (VOCs) also increased the ozone production rate, and occasionally (14% of time) became the dominant controlling factor. This analysis implies that the VOC reduction legislation recently enacted by the Japanese government should be effective. VOC-limited conditions occurred particularly when the air mass traveled within 6-8 h, via the Korean Peninsula. The uncertainty in the radical chemistry mechanism governing ozone production had a non-negligible impact, but the main conclusion relevant to policy was not altered. When chain termination was augmented by HO 2 + NO/NO 2 reactions in the presence of H 2 O and by heterogeneous loss of HO 2 on aerosol particle surfaces, as recently verified or hypothesized, the daily ozone production rate decreased by up to 24%, and the fraction of hours when the VOC-limited condition occurred varied from 14% to 13-26%.

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Laboratory measurements of emission factors of nonmethane volatile organic compounds from burning of Chinese crop residues

et al. 2015

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The emission factors (EFs) of nonmethane volatile organic compounds (NMVOCs) emitted during the burning of Chinese crop residue were investigated as a function of modified combustion efficiency in laboratory experiments. NMVOCs, including acetonitrile, aldehydes/ketones, furan, and aromatic hydrocarbons, were monitored by proton-transfer-reaction mass spectrometry. Rape plant was burned in dry conditions and wheat straw was burned in both wet and dry conditions to simulate the possible burning of damp crop residue in regions of high temperature and humidity. We compared the present data to field data reported by Kudo et al. (2014). Good agreement between field and laboratory data was obtained for aromatics under relatively more smoldering combustion of dry samples, but laboratory data were slightly overestimated compared to field data for oxygenated VOC (OVOC). When EFs from the burning of wet samples were investigated, the consistency between the field and laboratory data for OVOCs was stronger than for dry samples. This may be caused by residual moisture in crop residue that has been stockpiled in humid regions. Comparison of the wet laboratory data with field data suggests that Kudo et al. (2014) observed the biomass burning plumes under relatively more smoldering conditions in which approximately a few tens of percentages of burned fuel materials were wet.

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Technical Note: Determination of formaldehyde mixing ratios in air with PTR-MS: laboratory experiments and field measurements

Cited by 128 publications

References 46 publications

Comparison of VOC measurements made by PTR-MS, adsorbent tubes–GC-FID-MS and DNPH derivatization–HPLC during the Sydney Particle Study, 2012: a contribution to the assessment of uncertainty in routine atmospheric VOC measurements

Comparison of VOC measurements made by PTR-MS, adsorbent tubes–GC-FID-MS and DNPH derivatization–HPLC during the Sydney Particle Study, 2012: a contribution to the assessment of uncertainty in routine atmospheric VOC measurements

Diagnosis of Photochemical Ozone Production Rates and Limiting Factors in Continental Outflow Air Masses Reaching Fukue Island, Japan: Ozone-Control Implications

Laboratory measurements of emission factors of nonmethane volatile organic compounds from burning of Chinese crop residues

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