Temperature-dependent formaldehyde cross sections in the near-ultraviolet spectral region

Cantrell, C. A.; Davidson, J. A.; McDaniel, Anthony H.; Shetter, R. E.; Calvert, Jack G.

doi:10.1021/j100373a008

Cited by 132 publications

(168 citation statements)

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“…During two experiments HCHO was injected into the clean chamber by thermolysis of well defined amounts of paraformaldehyde reaching mixing rations of 30 ppbV at maximum. The HCHO concentration calculated from the injection and the chamber volume agrees with the BB-DOAS measured value when the absorption cross section of Meller and Moortgat (2000) and the temperature coefficient of Cantrell (1990) were used for data evaluation. In two further experiments we produced HCHO in-situ from the ozone + ethene reaction which was intended to provide an independent way of HCHO calibration through the measurements of ozone and ethene.…”

Section: Introductionsupporting

confidence: 57%

“…When other literature cross sections were used deviations of up to 20% from the good agreement would appear. Since the experiments were performed at different temperatures ( T =20 K) the Cantrell (1990) temperature dependence is supported. Since the cross section changes significantly over the temperature range observed in the atmosphere, the temperature dependence of the HCHO absorption cross section remains an important issue to be resolved.…”

Section: Discussionmentioning

confidence: 99%

“…1) was measured many times at different spectral resolutions (Bass et al, 1980;Cantrell, 1990;Rogers, 1990;Meller and Moortgat, 2000;Bogumil et al, 2003;Pope et al, 2005;Smith et al, 2006;Gratien et al, 2007). A recent analysis of the differences in the HCHO spectra by Hak et al (2005) (Meller and Moortgat, 2000;Cantrell, 1990) convolved to a resolution of 0.2 nm and interpolated to a wavelength grid of 0.04 nm. Lower panel: HCHO absorbance measured by the HR-DOAS at a resolution of 2.7 pm in the narrow range extending over 0.21 nm.…”

Section: Introductionmentioning

confidence: 99%

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Investigation of the formaldehyde differential absorption cross section at high and low spectral resolution in the simulation chamber SAPHIR

Brauers¹,

Bossmeyer²,

Dorn³

et al. 2007

Atmos. Chem. Phys.

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Abstract.The results from a simulation chamber study on the formaldehyde (HCHO) absorption cross section in the UV spectral region are presented. We performed 4 experiments at ambient HCHO concentrations with simultaneous measurements of two DOAS instruments in the atmosphere simulation chamber SAPHIR in Jülich. The two instruments differ in their spectral resolution, one working at 0.2 nm (broad-band, BB-DOAS), the other at 2.7 pm (high-resolution, HR-DOAS). Both instruments use dedicated multi reflection cells to achieve long light path lengths of 960 m and 2240 m, respectively, inside the chamber. During two experiments HCHO was injected into the clean chamber by thermolysis of well defined amounts of paraformaldehyde reaching mixing rations of 30 ppbV at maximum. The HCHO concentration calculated from the injection and the chamber volume agrees with the BB-DOAS measured value when the absorption cross section of Meller and Moortgat (2000) and the temperature coefficient of Cantrell (1990) were used for data evaluation. In two further experiments we produced HCHO in-situ from the ozone + ethene reaction which was intended to provide an independent way of HCHO calibration through the measurements of ozone and ethene. However, we found an unexpected deviation from the current understanding of the ozone + ethene reaction when CO was added to suppress possible oxidation of ethene by OH radicals. The reaction of the Criegee intermediate with CO could be 240 times slower than currently assumed. Based on the BB-DOAS measurements we could deduce a high-resolution cross section for HCHO which was not measured directly so far.

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Section: Introductionsupporting

confidence: 57%

Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Investigation of the formaldehyde differential absorption cross section at high and low spectral resolution in the simulation chamber SAPHIR

Brauers¹,

Bossmeyer²,

Dorn³

et al. 2007

Atmos. Chem. Phys.

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show abstract

“…The FRS and Ring spectra, as well as the absorption cross-sections of HCHO, O3, O4, and NO2 were simultaneously fitted to the measurement spectra using a nonlinear least-squares method [26,28] within the QDOAS software. The HCHO absorption cross-section [29], which is also used in the OMI HCHO operational algorithm [30], was used in this present study. The HCHO cross-section [29] may contain the uncertainty [31].…”

Section: Retrieval Of Hcho and O4 Scdsmentioning

confidence: 99%

“…The HCHO absorption cross-section [29], which is also used in the OMI HCHO operational algorithm [30], was used in this present study. The HCHO cross-section [29] may contain the uncertainty [31]. The BrO absorption cross-section was excluded in the spectral fitting routine due to either no or negligible BrO absorption in the measured spectra.…”

Section: Retrieval Of Hcho and O4 Scdsmentioning

confidence: 99%

Investigations of the Diurnal Variation of Vertical HCHO Profiles Based on MAX-DOAS Measurements in Beijing: Comparisons with OMI Vertical Column Data

et al. 2015

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An investigation into the diurnal characteristics of vertical formaldehyde (HCHO) profiles was conducted based on multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements in Beijing during the CAREBEIJING campaign, covering a month-long period through August and September 2006. Vertical HCHO profiles were retrieved based on a combined differential optical absorption spectroscopy (DOAS) technique and an optimal estimation method (OEM). The HCHO volume-mixing ratio (VMR) was found to be highest in the layer from the surface up to an altitude of 1 km and to decrease with altitude above this layer. In all retrieved profiles, HCHO was not detected in the layer from 3-4 km. Over the diurnal cycle, the HCHO VMR values were generally highest at 15:00 local time (LT) and were lower in the morning and late afternoon. The mean HCHO VMRs were 6.17, 1.82, and 0.80 ppbv for the 0-1, 1-2, and 2-3-km layers, respectively, at 15:00 LT, whereas they were 3.54 (4.79), OPEN ACCESSAtmosphere 2015, 6 1817 1.06 (1.43), and 0.46 (0.63) ppbv for the 0-1, 1-2, and 2-3-km layers, respectively, at 09:00 (17:00) LT. The HCHO VMRs reached their highest values at 15:00 LT on August 19, which were 17.71, 5.20, and 2.31 ppbv for the 0-1, 1-2, and 2-3-km layers, respectively. This diurnal pattern implies that the photo-oxidation of volatile organic compounds (VOCs) was most active at 15:00 LT for several days during the campaign period. In a comparison of the derived HCHO VCDs with those obtained from the Ozone Monitoring Instrument (OMI) measurements, the HCHO vertical column density (VCD) values obtained from the OMI measurements tend to be smaller than those from the MAX-DOAS.

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Quantitative measurements and modeling of industrial formaldehyde emissions in the Greater Houston area during campaigns in 2009 and 2011

et al. 2014

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A sensitive Mobile differential optical absorption spectroscopy (DOAS) system with real-time evaluation capability and HCHO detection limit of 3 ppb over 100 m has been developed. The system was operated together with a Solar Occultation Flux system for large-scale vertical flux measurements of HCHO, NO 2 , SO 2 , and VOCs in the Houston-Galveston-Brazoria area during two studies, in 2009 (Study of Houston Atmospheric Radical Precursors campaign) and in 2011 (Air Quality Research Program study). Both in 2009 and 2011, HCHO plumes from five separate local sources in Texas City, Mont Belvieu, and Houston Ship Channel (HSC) were repeatedly detected using Mobile DOAS with emissions varying between 6 and 40 kg/h. In many cases significant alkene emissions were detected simultaneously with the HCHO plumes. Furthermore, in 2011 two additional sources were observed in Texas City and in HSC, with 10 kg/h and 31 kg/h HCHO, respectively. A plume chemistry model was applied to 13 cases to investigate whether the detected HCHO was emitted directly from the industries or was produced by photochemical degradation of VOCs. The model results showed that on average 90% of the detected HCHO was of primary origin and the photochemical production contributed more than 10% in only three cases. Based on the repeatability, it is likely that the most significant HCHO sources in the area are included in this study with an overall emission of 120 kg/h. On a regional scale, this emission is small compared to the secondary HCHO formed from oxidation of reactive VOCs emitted from the same industries, estimated to be an order of magnitude higher.

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Temperature-dependent formaldehyde cross sections in the near-ultraviolet spectral region

Cited by 132 publications

References 1 publication

Investigation of the formaldehyde differential absorption cross section at high and low spectral resolution in the simulation chamber SAPHIR

Investigation of the formaldehyde differential absorption cross section at high and low spectral resolution in the simulation chamber SAPHIR

Investigations of the Diurnal Variation of Vertical HCHO Profiles Based on MAX-DOAS Measurements in Beijing: Comparisons with OMI Vertical Column Data

Quantitative measurements and modeling of industrial formaldehyde emissions in the Greater Houston area during campaigns in 2009 and 2011

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