Interferences of nitrogen dioxide in the determination of aldehydes and ketones by sampling on 2,4-dinitrophenylhydrazine-coated solid sorbent

Kärst, Uwe; Binding, Norbert; Cammann, Karl; Witting, U.

doi:10.1007/bf00323325

Cited by 64 publications

(65 citation statements)

References 14 publications

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“…Nitrogen dioxide can react with the DNPH solution during the aldehyde collection, 29,30 and the products formed can interfere with the formaldehyde peak. The analytical method used enabled us to separate these two products.…”

Section: Methodsmentioning

confidence: 99%

The Influence of Gasoline Formulation on Specific Pollutant Emissions

Zervas

Montagne

Lahaye

1999

Journal of the Air & Waste Management Association

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Many recent works have dealt with the influence of fuel composition on regulated and specific pollutant emissions from spark ignition engines. While many qualitative correlations have been already proposed, only a few quantitative ones are known (benzene remains an exception).This paper describes qualitative and quantitative correlations between fuel composition and specific pollutant emissions (individual hydrocarbons, aldehydes, ketones, alcohols, and organic acids) of a spark ignition engine. The aim of this work was to find the precursors of the main specific pollutants. Then, for each of them, a multilinear equation has been calculated, illustrating the correlation between its concentration in exhaust gases and its content in the fuel. The results of these calculations point out which initial compound favors the formation of a determined pollutant. As lean conditions are probably going to be used in future commercial engines, the fuel effect has been studied for a broad range of equivalence ratios (from 0.8 to 1.2).Two fuel matrixes were designed. The first one was obtained by introducing eight pure hydrocarbons (nC 6 , nC 8 , isoC 8 , 1-hexene, cyclohexane, toluene, o-xylene, and IMPLICATIONSThe topic of this paper strongly interests both refiners and car manufacturers. Besides being of scientific interest, knowing precisely which compound induces which pollutant, could enable refiners to determine which gasoline formulations provide better control of pollutant emissions, especially toxic compounds and ozone precursors. Car manufacturers could use this information to optimize engine tunings and catalyst use to reduce those emissions. Further, these works are of scientific interest, helping to improve understanding of the possible impact of regulation changes on pollutant emissions, helping refiners to improve fuel formulations, and helping all parties concerned by helping to improve air quality. ethylbenzene) in an alkylate base. The second one was formulated to test the behavior of four oxygenated compounds (methanol, ethanol, isopropanol, and methyl tertio-butyl ether [MTBE]).Individual unburned hydrocarbons, aldehydes, alcohols, and organic acids were analyzed according to accurate methods developed in our laboratory.Results show that benzene exhaust is mainly emitted from benzene fuel, the substituted aromatics, and, to a lesser degree, from cyclohexane; 1,3-butadiene is produced from 1-hexene or cyclohexane; and isobutene is a product of isooctane and MTBE. Exhaust toluene comes mainly from toluene fuel, but also from o-xylene and ethylbenzene fuels. Isopropylbenzene exhaust seems to be produced only from ethylbenzene fuel. Exhaust concentrations of acetaldehyde and acetone showed a strong correlation with, respectively, ethanol and isopropanol fuel contents. Methacroleine exhaust concentration was strongly correlated with the fuel's isooctane content. Benzaldehyde was produced by the aromatic fuels. Methanol was found in the exhaust gases of all the oxygenated fuels. High quantities of hexane...

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Section: Methodsmentioning

confidence: 99%

The Influence of Gasoline Formulation on Specific Pollutant Emissions

Zervas

Montagne

Lahaye

1999

Journal of the Air & Waste Management Association

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“…Nonetheless, its potential shortcomings in measurement have been reported in published studies. Nitrogen dioxide (NO 2 ) can react with DNPH to form 2,4-dinitrophenylazide (DNPA) which has chromatographic properties similar to those of formaldehyde-DNP-hydrazone (or co-called formaldehyde-DNPH derivative), leading to co-elution problems (Grömping et al, 1993;Karst et al, 1993;Grömping and Cammann, 1996;Ban-Weiss et al, 2008). Tang et al (2004) further suggested that ambient nitrogen monoxide (NO) can oxidize to NO 2 while an ozone scrubber is installed upstream.…”

Section: Introductionmentioning

confidence: 99%

Technical Note: Concerns on the Use of Ozone Scrubbers for Gaseous Carbonyl Measurement by DNPH-Coated Silica Gel Cartridge

Ip²,

et al. 2013

Aerosol Air Qual. Res.

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ABSTRACT2,4-Dinitrophenylhydrazine (DNPH) is a typical derivatizing agent coated on sorbent cartridges for detection of carbonyl compounds at ambient levels. However, airborne oxidant of ozone (O 3 ) can react with DNPH to form side products that can interfere with the accurate detection of carbonyls. It is the most critical interferer degrading carbonyl-DNP-hydrazone formed on the cartridge during sampling, resulting in underestimation of carbonyl concentrations; this strong oxidant can be removed by installing a denuder or scrubber coated or filled with potassium iodide (KI) upstream. The purpose of this study is to demonstrate and discuss the usage of novel KI-filled ozone traps in affecting carbonyl collection efficiency of DNPH-coated silica gel cartridges in field and laboratory settings. Results of the study showed that measured carbonyls concentrations were 4.9-13.5% lower in samples collected without any ozone traps compared to those collected with a commercially available ozone scrubber or KI denuder. Although ozone can be reduced efficiently by KI, both environmental relative humidity (RH) and byproducts formed from the oxidation of KI with ozone, namely iodine (I 2 ) and hydroxyl ion (OH -), can inhibit derivatization kinetics and contribute to degradation of the carbonyl-DNP-hydrazones formed during sampling. Placement of an acid-permeated polyethylene filter between the ozone scrubbers and the DNPH-coated cartridge notably improved carbonyl collection efficiency by neutralizing the byproduct OH -. End-users of the DNPH method should consider these findings and evaluate the performance of ozone scrubbers accordingly during sampling events.

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“…These studies examined only a limited number of fuels, and the method used in those studies to quantify carbonyl emissions is now known to be prone to interferences (Karst et al, 1993;Achatz et al, 1999). The reported emissions of glyoxal and methylglyoxal from those studies are contradicted by field measurements from aircraft that find significantly 5 less glyoxal but more methylglyoxal in fresh biomass burning plumes than was measured in the lab (Zarzana et al, 2017).…”

Section: Introductionmentioning

confidence: 39%

“…In those studies, carbonyls were detected through derivatization followed by separation using high performance liquid chromatography and detection by ultraviolet absorption measurements. It is now known that measurements of formaldehyde using this method have interferences from unrelated species such as NO 2 that react with the derivatizing 30 agent to form products with similar retention times and absorbances (Karst et al, 1993). ACES also measures NO 2 , and the NO 2 concentrations were comparable to those of formaldehyde for many burns.…”

Section: Glyoxal Emission Ratios and Factorsmentioning

confidence: 88%

Primary emissions of glyoxal and methylglyoxal from laboratory measurements of open biomass burning

Zarzana¹,

Selimovic²,

Koss³

et al. 2018

Preprint

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Abstract. We report the emissions of glyoxal and methylglyoxal from the open burning of biomass during the NOAA-led 2016 FIREX intensive at the Fire Sciences Laboratory in Missoula, MT. Both compounds were measured using cavity enhanced spectroscopy, which is both more sensitive and more selective than methods previously used to determine emissions of these two compounds. A total of 75 burns were conducted, using 33 different fuels in 8 different categories, providing a far more comprehensive dataset for emissions than was previously available. Measurements of methylglyoxal using our instrument 5 suffer from spectral interferences from several other species, but methylglyoxal emissions could be constrained within roughly a factor of 2. Methylglyoxal emissions were 2-3 times higher than glyoxal emissions on a molar basis, in contrast to previous studies that report methylglyoxal emissions lower than glyoxal emissions. Methylglyoxal emission ratios for all fuels averaged 3.6±2.4 ppbv methylglyoxal/ppmv CO, while emission factors averaged 0.66±0.50 g methylglyoxal/kg fuel burned. Primary emissions of glyoxal from biomass burning were much lower than previous laboratory measurements, but consistent with 10 recent measurements from aircraft. Glyoxal emission ratios for all fuels averaged 1.4±0.7 ppbv glyoxal/ppmv CO, while emission factors averaged 0.20±0.12 g glyoxal/kg fuel burned, values that are at least a factor of 4 lower than assumed in previous estimates of the global glyoxal budget. While there was significant variability in the glyoxal emission ratios and factors between the different fuel groups, glyoxal and formaldehyde were highly correlated during the course of any given fire, and the ratio of glyoxal to formaldehyde, R GF , was consistent across many different fuel types, with an average value 15 of 0.068±0.018. While R GF values for fresh emissions were consistent across many fuel types, further work is required to determine how this value changes as the emissions age.1 Atmos. Chem. Phys. Discuss., https://doi

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Interferences of nitrogen dioxide in the determination of aldehydes and ketones by sampling on 2,4-dinitrophenylhydrazine-coated solid sorbent

Cited by 64 publications

References 14 publications

The Influence of Gasoline Formulation on Specific Pollutant Emissions

The Influence of Gasoline Formulation on Specific Pollutant Emissions

Technical Note: Concerns on the Use of Ozone Scrubbers for Gaseous Carbonyl Measurement by DNPH-Coated Silica Gel Cartridge

Primary emissions of glyoxal and methylglyoxal from laboratory measurements of open biomass burning

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