Gas chromatographic determination of peroxyacetyl nitrate: Two convenient calibration techniques

Meyrahn, H.; Helas, G.; Warneck, Peter

doi:10.1007/bf00113903

Cited by 18 publications

(13 citation statements)

References 18 publications

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“…respectively, than those at 10 • C, and the decay rates after the maximum signals were slower at 25 • C than at 10 • C. This phenomenon was contrary to the thermal decomposition behavior of PAN and PPN, but was in good agreement with the results of Meyrahn et al [37] in a glass container and Helmig et al [29] in a Tedlar bag, who explained such phenomena as the strong wall-catalysis/absorption at low temperature. Therefore, the GC-ECD was calibrated in this study via the volatilization of the PAN and PPN solutions for 30 min at 25 • C. The RSD of the GC peak area for PAN from repetitions of volatilization (n = 7) was 10.4% ( 2 ).…”

Section: Preparing Calibration Gaseous Mixturessupporting

confidence: 88%

“…The large excess of acetone relative to NO in the mixture favored the complete conversion of NO x to PAN [37]. Both PAN and NO 2 have been verified to be efficiently converted (∼98%) to NO in a molybdenum-containing catalytic converter of NO x analyzer at 325 • C, and can be detected by the NO x analyzer [20].…”

Section: Gc Calibration With In Situ Photochemical Formationmentioning

confidence: 93%

“…To ensure the reliability of the calibration, another method was also performed to further calibrate the PAN signal in the GC-ECD; this method was the in situ formation of PAN via the photochemical reaction of a gaseous mixture containing excess acetone with NO (the ratio of acetone to NO was ∼200:1) in a 150 L Teflon bag irradiated using low-pressure mercury lamps which have a principal emission wavelength of 253.7 nm. NO can be completely converted to PAN in the presence of excess acetone after 5 min of irradiation [37]. The exact NO x concentration in the gaseous mixture was quantified using a Model 42i NO x Analyzer (Thermo Scientific, USA), and the formed PAN was simultaneously detected using GC-ECD.…”

Section: Gc Calibrationmentioning

confidence: 99%

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Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection

Zhang

Liu

et al. 2012

Journal of Chromatography A

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a b s t r a c tGas chromatography equipped with electron capture detector (GC-ECD) has been widely used for detecting atmospheric peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN). However, to the best of our knowledge, only a few capillary columns have been adopted for separation to achieve the direct and simultaneous analysis of the two atmospheric pollutants. This paper demonstrates a novel method for directly and simultaneously measuring atmospheric carbon tetrachloride (CCl 4 ), PAN, and PPN using GC-ECD with a DB-1 separation column. The responses of the GC-ECD to PAN, PPN, and CCl 4 were individually calibrated by using gas mixtures prepared via volatilization of synthesized solutions of PAN and PPN or high-purity CCl 4 reagent in a Teflon Bag. The concentrations of PAN and PPN in the synthesized solutions were quantified by ion chromatography (IC). Further calibration of the GC-ECD for PAN was conducted by in situ photochemical formation of gaseous PAN which was quantified by a NO x analyzer. The two calibration methods agreed well with each other, and the overall uncertainties for measuring atmospheric PAN were estimated to be ±13% and ±15% based on the calibrations of IC and NO x , respectively. The detection limits (three times the signal to noise ratio) for PAN, PPN, and CCl 4 were estimated to be 22, 36, and 5 pptv (parts per trillion by volume), respectively. The atmospheric concentrations of these compounds were measured for several days in August in Beijing, and the values obtained in this study were found to be in good agreement with the data reported in the literature for Beijing using other GC-ECD methods.

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Section: Preparing Calibration Gaseous Mixturessupporting

confidence: 88%

Section: Gc Calibration With In Situ Photochemical Formationmentioning

confidence: 93%

Section: Gc Calibrationmentioning

confidence: 99%

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Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection

Zhang

Liu

et al. 2012

Journal of Chromatography A

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“…In order to test the sensitivity of the instrument to peroxyacetyl nitrate (PAN) interferences, it was prepared by means of the photolysis of acetone and NO in air as described by (Meyrahn et al, 1987) and later by (Warneck and Zerbach, 1992;Flocke et al, 2005). Reactions (R9)-(R13) show the reaction sequence by which PAN is formed by acetone photolysis (Singh et al, 1995).…”

Section: Pan Preparationmentioning

confidence: 99%

Interferences in photolytic NO<sub>2</sub> measurements: explanation for an apparent missing oxidant?

et al. 2016

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Abstract. Measurement of NO 2 at low concentrations (tens of ppts) is non-trivial. A variety of techniques exist, with the conversion of NO 2 into NO followed by chemiluminescent detection of NO being prevalent. Historically this conversion has used a catalytic approach (molybdenum); however, this has been plagued with interferences. More recently, photolytic conversion based on UV-LED irradiation of a reaction cell has been used. Although this appears to be robust there have been a range of observations in low-NO x environments which have measured higher NO 2 concentrations than might be expected from steady-state analysis of simultaneously measured NO, O 3 , j NO 2 , etc. A range of explanations exist in the literature, most of which focus on an unknown and unmeasured "compound X" that is able to convert NO to NO 2 selectively. Here we explore in the laboratory the interference on the photolytic NO 2 measurements from the thermal decomposition of peroxyacetyl nitrate (PAN) within the photolysis cell. We find that approximately 5 % of the PAN decomposes within the instrument, providing a potentially significant interference. We parameterize the decomposition in terms of the temperature of the light source, the ambient temperature, and a mixing timescale (∼ 0.4 s for our instrument) and expand the parametric analysis to other atmospheric compounds that decompose readily to NO 2 (HO 2 NO 2 , N 2 O 5 , CH 3 O 2 NO 2 , IONO 2 , BrONO 2 , higher PANs). We apply these parameters to the output of a global atmospheric model (GEOS-Chem) to investigate the global impact of this interference on (1) the NO 2 measurements and (2) the NO 2 : NO ratio, i.e. the Leighton relationship. We find that there are significant interferences in cold regions with low NO x concentrations such as the Antarctic, the remote Southern Hemisphere, and the upper troposphere. Although this interference is likely instrument-specific, the thermal decomposition to NO 2 within the instrument's photolysis cell could give an at least partial explanation for the anomalously high NO 2 that has been reported in remote regions. The interference can be minimized by better instrument characterization, coupled to instrumental designs which reduce the heating within the cell, thus simplifying interpretation of data from remote locations.

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“…Peroxyacetyl radicals and PAN were made in the laboratory from the photolysis of acetone in the presence of oxygen and subsequent reaction with N0 2 as implemented by Meyrahn et al (1987). Acetone was carried into a l-L glass bulb by a stream of nitrogen at approximately 12 Lmin-1 .…”

Section: Pan and Ch 1 Co·0mentioning

confidence: 99%

Evaluation of the Salicylic Acid–Liquid Phase Scrubbing Technique to Monitor Atmospheric Hydroxyl Radicals

Salmon

Schiller

Harris

2004

Journal of Atmospheric Chemistry

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Abstract. A novel method has been examined for monitoring tropospheric hydroxyl radicals (OH), the most important oxidant in tropospheric chemistry. Aqueous phase salicylic acid reacts with atmospheric OH to produce 2,5-dihydroxy benzoic acid (2,5-DHBA) and other products. High Performance Liquid Chromatography (HPLC) is used to separate the post-reaction solution and the products are quantified using fluorescence detection. Unlike other methods, it has been reported to be inexpensive, portable and relatively simple. Although the sensitivity was sufficient to measure typical daytime OH concentrations of 0.04--0.4 ppt., the method was hindered by numerous interferences. Successive identification and elimination of these still resulted in a signal that was much larger than expected. Tests showed that this was not likely to be due to ozone, H0 2 , NOx, H 2 0 2 , aerosols, light or bacteria. Experimental and numerical studies suggest that the interference could be due to methyl peroxy radicals. The effect of many other components in the atmosphere, both individual and combined, must also be tested before the method can be used reliably in the field. The validity of previous reports of ambient hydroxyl measurements using this technique is therefore brought into question.

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Gas chromatographic determination of peroxyacetyl nitrate: Two convenient calibration techniques

Cited by 18 publications

References 18 publications

Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection

Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection

Interferences in photolytic NO<sub>2</sub> measurements: explanation for an apparent missing oxidant?

Evaluation of the Salicylic Acid–Liquid Phase Scrubbing Technique to Monitor Atmospheric Hydroxyl Radicals

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Gas chromatographic determination of peroxyacetyl nitrate: Two convenient calibration techniques

Cited by 18 publications

References 18 publications

Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection

Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection

Interferences in photolytic NO&lt;sub&gt;2&lt;/sub&gt; measurements: explanation for an apparent missing oxidant?

Evaluation of the Salicylic Acid–Liquid Phase Scrubbing Technique to Monitor Atmospheric Hydroxyl Radicals

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Interferences in photolytic NO<sub>2</sub> measurements: explanation for an apparent missing oxidant?