Development and validation of a cryogen-free automatic gas chromatograph system (GC-MS/FID) for online measurements of volatile organic compounds

Wang, Ming; Zeng, Limin; Lü, Sihua; Shao, Min; Liu, Xinglong; Yu, Xiangyao; Chen, Wentai; Yuan, Bin; Zhang, Qian; Hu, Min; Zhang, Zhanyi

doi:10.1039/c4ay01855a

Cited by 118 publications

(75 citation statements)

References 34 publications

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“…The results reported here are similar to many previous intercomparison studies that have reported good quantitative agreement, within ±20 % (R 2 > 0.85), between PTR-MS and GC techniques for the measurement of the sum of the C 8 aromatics (Warneke et al, 2001;Kuster et al, 2004;Jobson et al, 2010;Rogers et al, 2006;de Gouw and Warneke, 2007;Wang et al, 2014;Cui et al, 2016). However, slopes as low as 0.6 (Kato et al, 2004) and as high as 3.2 have been reported with the discrepancy in both cases, which is attributable to calibration inaccuracies.…”

Section: Aromaticssupporting

confidence: 79%

“…2. ) (Warneke et al, 2001;Kuster et al, 2004;de Gouw and Warneke, 2007;Kaser et al, 2013;Wang et al, 2014;Kajos et al, 2015;Cui et al, 2016).…”

Section: Tolueneunclassified

“…Conversely, generally good agreement has been observed between PTR-MS and GC methods and AP-CIMS (atmospheric pressure chemical ionization mass spectrometry) (slopes = 0.97-1.18, intercept = −0.28-0.06, R 2 = 0.77-0.96) (Fig. 3) (Sprung et al, 2001;Kaser et al, 2013;Wang et al, 2014;Kajos et al, 2015).…”

Section: Acetonementioning

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: Aromaticssupporting

confidence: 79%

“…2. ) (Warneke et al, 2001;Kuster et al, 2004;de Gouw and Warneke, 2007;Kaser et al, 2013;Wang et al, 2014;Kajos et al, 2015;Cui et al, 2016).…”

Section: Tolueneunclassified

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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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“…The performances of these instruments were presented in Tables S1 and S2 in the Supplement. VOCs were measured by a cryogen-free online GC-MSD/FID system, developed at Peking University (Yuan et al, 2012;Wang et al, 2014a). The time resolution is 1 h but the sampling time starts from the 5th to 10th minute every hour.…”

Section: Simultaneous Measurementsmentioning

confidence: 99%

How the OH reactivity affects the ozone production efficiency: case studies in Beijing and Heshan, China

et al. 2017

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Abstract. Total OH reactivity measurements were conducted on the Peking University campus (Beijing) in August 2013 and in Heshan (Guangdong province) from October to November 2014. The daily median OH reactivity was 20 ± 11 s −1 in Beijing and 31 ± 20 s −1 in Heshan, respectively. The data in Beijing showed a distinct diurnal pattern with the maxima over 27 s −1 in the early morning and minima below 16 s −1 in the afternoon. The diurnal pattern in Heshan was not as evident as in Beijing. Missing reactivity, defined as the difference between measured and calculated OH reactivity, was observed at both sites, with 21 % missing reactivity in Beijing and 32 % missing reactivity in Heshan. Unmeasured primary species, such as branched alkenes, could contribute to missing reactivity in Beijing, especially during morning rush hours. An observation-based model with the RACM2 (Regional Atmospheric Chemical Mechanism version 2) was used to understand the daytime missing reactivity in Beijing by adding unmeasured oxygenated volatile organic compounds and simulated intermediates of the degradation from primary volatile organic compounds (VOCs). However, the model could not find a convincing explanation for the missing reactivity in Heshan, where the ambient air was found to be more aged, and the missing reactivity was presumably attributed to oxidized species, such as unmeasured aldehydes, acids and dicarbonyls. The ozone production efficiency was 21 % higher in Beijing and 30 % higher in Heshan when the model was constrained by the measured reactivity, compared to the calculations with measured and modeled species included, indicating the importance of quantifying the OH reactivity for better understanding ozone chemistry.

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“…Lau et al (2010) found that 31-48 % of ambient VOCs in Hong Kong were generated by vehicle-and marine-vessel-related sources in [2002][2003], and the percentage increased to 40-54 % in 2006-2007. In order to investigate urban roadside VOCs in Hong Kong, multiple sampling and analytical techniques were used, such as offline 2,4-dinitrophenylhydrazine (DNPH) cartridge sampling followed by high-performance liquid chromatography (HPLC) analysis for oxygenated volatile organic compounds (OVOCs); online gas chromatography (GC) with flame ionization detection (FID); and offline canister sampling followed by GC with mass spectrometer detection (MSD), FID, and electron capture detection (ECD) for VOCs Cheng et al, 2014;Ou et al, 2015). These techniques, however, can be impacted by their relatively low sampling resolution that may lead to the underestimation or overestimation of ambient OVOC and VOC concentration levels (Wisthaler et al, 2008;Jobson et al, 2010;Wang et al, 2014). Moreover, since there is no single technique that can measure all OVOCs and VOCs simultaneously, different kinds of sampling and analytical techniques are usually used to obtain the measurements of these species (Wisthaler et al, 2008;Ambrose et al, 2010;Jobson et al, 2010;Warneke et al, 2011a).…”

Section: Introductionmentioning

confidence: 99%

Measuring OVOCs and VOCs by PTR-MS in an urban roadside microenvironment of Hong Kong: relative humidity and temperature dependence, and field intercomparisons

et al. 2016

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Abstract. Volatile organic compound (VOC) control is an important issue of air quality management in Hong Kong because ozone formation is generally VOC limited. Several oxygenated volatile organic compound (OVOC) and VOC measurement techniques -namely, (1) offline 2,4-dinitrophenylhydrazine (DNPH) cartridge sampling followed by high-performance liquid chromatography (HPLC) analysis; (2) online gas chromatography (GC) with flame ionization detection (FID); and (3) offline canister sampling followed by GC with mass spectrometer detection (MSD), FID, and electron capture detection (ECD) -were applied during this study. For the first time, the proton transfer reaction-mass spectrometry (PTR-MS) technique was also introduced to measured OVOCs and VOCs in an urban roadside area of Hong Kong. The integrated effect of ambient relative humidity (RH) and temperature (T ) on formaldehyde measurements by PTR-MS was explored in this study. A Poly 2-D regression was found to be the best nonlinear surface simulation (r = 0.97) of the experimental reaction rate coefficient ratio, ambient RH, and T for formaldehyde measurement. This correction method was found to be better than correcting formaldehyde concentrations directly via the absolute humidity of inlet sample, based on a 2-year field sampling campaign at Mong Kok (MK) in Hong Kong. For OVOC species, formaldehyde, acetaldehyde, acetone, and MEK showed good agreements between PTR-MS and DNPH-HPLC with slopes of 1.00, 1.10, 0.76, and 0.88, respectively, and correlation coefficients of 0.79, 0.75, Published by Copernicus Publications on behalf of the European Geosciences Union. L. Cui et al.: Measuring OVOCs and VOCs by PTR-MS0.60, and 0.93, respectively. Overall, fair agreements were found between PTR-MS and online GC-FID for benzene (slope = 1.23, r = 0.95), toluene (slope = 1.01, r = 0.96) and C 2 -benzenes (slope = 1.02, r = 0.96) after correcting benzene and C 2 -benzenes levels which could be affected by fragments formed from ethylbenzene. For the intercomparisons between PTR-MS and offline canister measurements by GC-MSD/FID/ECD, benzene showed good agreement, with a slope of 1.05 (r = 0.62), though PTR-MS had lower values for toluene and C 2 -benzenes with slopes of 0.78 (r = 0.96) and 0.67 (r = 0.92), respectively. All in all, the PTR-MS instrument is suitable for OVOC and VOC measurements in urban roadside areas.

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Development and validation of a cryogen-free automatic gas chromatograph system (GC-MS/FID) for online measurements of volatile organic compounds

Abstract: A cryogen-free, automatic gas chromatograph system was developed for online measurements of volatile organic compounds in the atmosphere.

Cited by 118 publications

References 34 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

How the OH reactivity affects the ozone production efficiency: case studies in Beijing and Heshan, China

Measuring OVOCs and VOCs by PTR-MS in an urban roadside microenvironment of Hong Kong: relative humidity and temperature dependence, and field intercomparisons

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