Intercomparison of six ambient [CH<sub>2</sub>O] measurement techniques

Gilpin, Tim; Apel, E. C.; Fried, Alan; Wert, B.; Calvert, Jack G.; Zhang, Genfa; Dasgupta, Purnendu Κ.; Harder, J. W.; Heikes, Brian G.; Hopkins, Brian; Westberg, Hal; Kleindienst, Tad; Lee, Yin Nan; Zhou, Xianliang; Lonneman, William A.; Sewell, Scott

doi:10.1029/97jd01314

Cited by 89 publications

(80 citation statements)

References 39 publications

(11 reference statements)

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“…The line used by the TDLAS has a corrected intensity of 5.44 10 −20 cm −1 /(molecule cm −2 ) at 303 K and differs by 6% compared to the new value of 5.78 10 −20 cm −1 /(molecule cm −2 ) at 303 K of Perrin et al (2009). This difference remains within the systematic uncertainties (12.4% at 2σ level) of the TDLAS estimated through various calibration experiments (Gilpin et al, 1997;Fried et al, 2008aFried et al, , 2002.…”

Section: Aircraft Measurementssupporting

confidence: 54%

Global upper-tropospheric formaldehyde: seasonal cycles observed by the ACE-FTS satellite instrument

et al. 2009

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Abstract. Seasonally-resolved upper tropospheric profiles of formaldehyde (HCHO) observed by the ACE Fourier transform spectrometer (ACE-FTS) on a near-global scale are presented for the time period from March 2004 to November 2006. Large upper tropospheric HCHO mixing ratios (>150 pptv) are observed during the growing season of the terrestrial biosphere in the Northern Hemisphere and during the biomass burning season in the Southern Hemisphere. The total errors estimated for the retrieved mixing ratios range from 30 to 40% in the upper troposphere and increase in the lower stratosphere. The sampled HCHO concentrations are in satisfactory agreement with previous aircraft and satellite observations with a negative bias (<25%) within observation errors. An overview of the seasonal cycle of the upper tropospheric HCHO is given for different latitudes, with a particular focus on mid-to-high latitudes that are well sampled by the observations. A maximum is observed during summer, i.e. during the growing season, in the northern mid-and high latitudes. The influence of biomass burning is visible in HCHO upper tropospheric concentrations during the September-to-October period in the southern tropics and subtropics. Comparisons with two state-of-the-art models (GEOS-Chem and LMDz-INCA) show that the models capture well the seasonal variations observed in the Northern Hemisphere (correlation >0.9). Both models underestimate the summer maximum over Europe and Russia and differences in the emissions used for North America result in a Correspondence to: G. Dufour (dufour@lisa.univ-paris12.fr) good reproduction of the summer maximum by GEOS-Chem but in an underestimate by LMDz-INCA. Globally, GEOSChem reproduces well the observations on average over one year but has some difficulties in reproducing the spatial variability of the observations. LMDz-INCA shows significant bias in the Southern Hemisphere, perhaps related to an underestimation of methane, but better reproduces the temporal and spatial variations. The differences between the models underline the large uncertainties that remain in the emissions of HCHO precursors.

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Section: Aircraft Measurementssupporting

confidence: 54%

Global upper-tropospheric formaldehyde: seasonal cycles observed by the ACE-FTS satellite instrument

et al. 2009

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“…Other studies report DNPH-HPLC values for formaldehyde that were systematically lower than those reported by other analytical methods (DOAS, FTIR, Hantzsch, TDLAS) (Kleindienst et al, 1988;Lawson et al, 1990;Gilpin et al, 1997;Hak et al, 2005;Wisthaler et al, 2006).…”

Section: Formaldehydementioning

confidence: 68%

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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“…29.717639 • /-95.341250 • , 4 km southeast of downtown Houston (see Fig. 1 (Gilpin et al, 1997;Cárdenas et al, 2000;Klemp et al, 2003;Hak et al, 2005;Apel et al, 2008;Wisthaler et al, 2008). The limit of detection for the three HCHO instruments ranged from 50-120 pptv (three times signal-to-noise ratio); the estimated uncertainty was ∼10%.…”

Section: Methodsmentioning

confidence: 99%

Formaldehyde and its relation to CO, PAN, and SO<sub>2</sub> in the Houston-Galveston airshed

et al. 2010

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Abstract. The Houston-Galveston Airshed (HGA) is one of the major metropolitan areas in the US that is classified as a nonattainment area of federal ozone standards. Formaldehyde (HCHO) is a key species in understanding ozone related air pollution; some of the highest HCHO concentrations in North America have been reported for the HGA. We report on HCHO measurements in the HGA from summer 2006. Among several sites, maximum HCHO mixing ratios were observed in the Houston Ship Channel (HSC), a region with a very high density of industrial/petrochemical operations.HCHO levels at the Moody Tower (MT) site close to downtown were dependent on the wind direction: southerly maritime winds brought in background levels (0.5-1 ppbv) while trajectories originating in the HSC resulted in high HCHO (up to 31.5 ppbv). Based on the best multiparametric linear regression model fit, the HCHO levels at the MT site can be accounted for as follows: 38.5±12.3% from primary vehicular emissions (using CO as an index of vehicular emission), 24.1±17.7% formed photochemically (using peroxyacetic nitric anhydride (PAN) as an index of photochemical activity) and 8.9±11.2% from industrial emissions (using SO 2 as an index of industrial emissions). The balance 28.5±12.7% constituted the residual which cannot be easily ascribed to the above categories and/or which is transported into the HGA. The CO related HCHO fraction is dominant during the morning rush hour (06:00-09:00 h, all times are given in CDT); on a carbon basis, HCHO emissions are up to 0.7% of the CO emissions. The SO 2 related HCHO Correspondence to: B. Rappenglück (brappenglueck@uh.edu) fraction is significant between 09:00-12:00 h. After 12:00 h HCHO is largely formed through secondary processes. The HCHO/PAN ratios are dependent on the SO 2 levels. The SO 2 related HCHO fraction at the downtown site originates in the ship channel. Aside from traffic-related primary HCHO emissions, HCHO of industrial origin serves as an appreciable source for OH in the morning.

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Intercomparison of six ambient [CH₂O] measurement techniques

Cited by 89 publications

References 39 publications

Global upper-tropospheric formaldehyde: seasonal cycles observed by the ACE-FTS satellite instrument

Global upper-tropospheric formaldehyde: seasonal cycles observed by the ACE-FTS satellite instrument

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

Formaldehyde and its relation to CO, PAN, and SO<sub>2</sub> in the Houston-Galveston airshed

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Intercomparison of six ambient [CH2O] measurement techniques

Cited by 89 publications

References 39 publications

Global upper-tropospheric formaldehyde: seasonal cycles observed by the ACE-FTS satellite instrument

Global upper-tropospheric formaldehyde: seasonal cycles observed by the ACE-FTS satellite instrument

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

Formaldehyde and its relation to CO, PAN, and SO&lt;sub&gt;2&lt;/sub&gt; in the Houston-Galveston airshed

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Intercomparison of six ambient [CH₂O] measurement techniques

Formaldehyde and its relation to CO, PAN, and SO<sub>2</sub> in the Houston-Galveston airshed