Improved high-performance liquid chromatographic method for artifact-free measurements of aldehydes in the presence of ozone using 2,4-dinitrophenylhydrazine

Smith, David F.; Kleindienst, Tadeusz E.; Hudgens, Edward

doi:10.1016/s0021-9673(01)93146-2

Cited by 97 publications

(60 citation statements)

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“…These peaks come from 2,4-dinitrophenylhydrazine as it is the major compound. This has been observed by Arnst and Tejada [23], and other authors [24][25]. The 2,4-dinitrophenylhydrazones are transformed by ozone action at various rates.…”

Section: 4-dinitrophenylhydrazone Destruction Testsupporting

confidence: 62%

Comparison between two carbonyl measurement methods in the atmosphere

et al. 1999

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Abstract. Two atmospheric aldehyde sampling techniques, the impinger method in which aldehydes are trapped in a 2,4-dinitrophenylhydrazine acidified acetonitrile solution, and the method in which aldehydes are captured in 2,4-dinitrophenylhydrazine acidified coated cartridges commercialised by the WATERS ® , were compared for blank values, sample preservation, ozone action, and water influence. The two methods were tested in a Paris atmosphere and the influence of a KI ozone scrubber has been evaluated. Except for acetaldehyde and benzaldehyde, the two techniques do not give coherent results. When no ozone scrubber is used, the cartridge technique gives systematically lower values. Bad correlation has been obtained between data with scrubber and data without scrubber for the impinger technique except for acetaldehyde. For the cartridge technique, the correlation is better for all the aldehydes but higher values are found when a scrubber is used, except for formaldehyde. Ozone action leads to 2,4-dinitrophenylhydrazone destruction, but also to formaldehyde 2,4-dinitrophenylhydrazone formation by reaction between airborne volatile organic compounds and ozone on the cartridge surfaces.

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Section: 4-dinitrophenylhydrazone Destruction Testsupporting

confidence: 62%

Comparison between two carbonyl measurement methods in the atmosphere

et al. 1999

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“…19 Nitric acid was collected on 47-mm, 1-µm nylon filters (Gelman Sciences, Inc.). The filters were extracted with 15 mL of 0.01-mM perchloric acid solution, and the nitrate ions were analyzed by ion chromatography (Dionex, Inc.) with electrical conductivity detection.…”

Section: Instrumentation and Samplingmentioning

confidence: 99%

Secondary Organic Aerosol Formation from the Irradiation of Simulated Automobile Exhaust

Kleindienst¹,

Corse²,

Li³

et al. 2002

Journal of the Air & Waste Management Association

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A laboratory study was conducted to evaluate the potential for secondary organic aerosol formation from emissions from automotive exhaust. The goal was to determine to what extent photochemical oxidation products of these hydrocarbons contribute to secondary organic aerosol (SOA) and how well their formation is described by recently developed models for SOA formation. The quality of a surrogate was tested by comparing its reactivity with that from irradiations of authentic automobile exhaust. Experiments for secondary particle formation using the surrogate were conducted in a fixed volume reactor operated in a dynamic mode. The mass concentration of the aerosol was determined from measurements of organic carbon collected on quartz filters and was corrected for the presence of hydrogen, nitrogen, and oxygen atoms in the organic species.A functional group analysis of the aerosol made by Fourier transform infrared (FTIR) spectroscopy indicated that carbonyl groups dominated the aerosol with relatively little aliphatic or aromatic C-H functionality. This result is consistent with the presence of polycarbonyl compounds measured in the aerosol. The hygroscopic potential of the aerosol was determined with the use of a liquid water content analyzer, and the analysis indicated that the aerosol uptake of water was minor at relative humidities less than 70%. The yield for the formation of SOA was found to be 1.8% when measured for an aerosol mass of 7.38 µg/m 3 . These results were compared to an aerosol model developed by Odum and coworkers and suggested that 75-85% of the fine particulate matter was due to reaction products of aromatic precursors. Organic analysis of the collected aerosol from this complex system indicates that the identified oxidation products were identical to those found in the toluene oxidation system.

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“…The most common derivatizing agent for aldehydes and ketones is 2,4-dinitrophenylhydrazine (2,4-DNPH). It has been used extensively for the determination of gas-phase carbonyl species [26][27][28][29][30], but only rarely for the measurement of aldehydes and ketones associated with aerosols [31][32][33].A method utilizing 2,4-DNPH to derivatize particulate-phase carbonyl species is presented here, including all aspects relevant for routine analysis. A description of the process whereby particulate samples collected on filter material are extracted, derivatized with a 2,4-DNPH solution, and analyzed by HPLC/UV absorption is presented.…”

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confidence: 99%

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An optimized method for the determination of volatile and semi-volatile aldehydes and ketones in ambient particulate matter

Liggio

McLaren

2003

International Journal of Environmental Analytical Chemistry

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gas-particle partitioning theory, which is largely based on the vapor pressure of the species in question [10][11][12][13]. However, deviations from partitioning theory are now being reported for volatile and semi-volatile products of toluene [14] and -pinene [15] oxidation.In particular, aldehydes and ketones can contribute significantly to this deviation [14,15]. Recent work has also suggested that the additional partitioning of carbonyls to particulate material may occur via a chemical transformation of the parent carbonyl to low-volatility products in the aerosol [16]. Possible mechanisms for this include hydration, polymerization and acetal/hemiacetal formation, which can be catalyzed in the presence of acid [16]. Heterogeneous reactions of this type, with carbonyls, imply that SOA yields may be significantly larger than those predicted by current partitioning theory, which is especially relevant given that many organic photooxidation products contain carbonyl functionality. With this in mind, there are surprisingly few measurements of carbonyl-containing species in ambient particulate material, and even fewer methods available that are geared specifically to this functional group. Existing ambient measurements are usually limited to dicarbonyls such as glyoxal [17,18], methylglyoxal [17,18] and pinonaldehyde [19][20][21][22] or to aerosols produced during laboratory studies [14,15,[23][24][25]. Detection of carbonyls in particulate material typically utilizes methods that involve several derivatizing agents, resulting in the conversion of many of the functional groups present [17][18][19]23]. The simultaneous derivatization of carbonyl, carboxyl and hydroxyl functional groups can significantly increase the complexity of the resultant chromatograms. Utilizing a more selective derivatizing agent can aid in targeting carbonyl-containing species only. The most common derivatizing agent for aldehydes and ketones is 2,4-dinitrophenylhydrazine (2,4-DNPH). It has been used extensively for the determination of gas-phase carbonyl species [26][27][28][29][30], but only rarely for the measurement of aldehydes and ketones associated with aerosols [31][32][33].A method utilizing 2,4-DNPH to derivatize particulate-phase carbonyl species is presented here, including all aspects relevant for routine analysis. A description of the process whereby particulate samples collected on filter material are extracted, derivatized with a 2,4-DNPH solution, and analyzed by HPLC/UV absorption is presented. The anticipated advantage of this simultaneous approach over conventional post-extraction derivatization methods is that the derivatization reaction likely facilitates the extraction of carbonyls from particulate material. Optimal conditions for this extraction/derivatization, the efficiency thereof, and the analytical uncertainties associated with several aspects of the method are also discussed. Significant advances have been made in the areas of pre-concentration, extraction, and reagent purification, which afford improved detecti...

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Improved high-performance liquid chromatographic method for artifact-free measurements of aldehydes in the presence of ozone using 2,4-dinitrophenylhydrazine

Cited by 97 publications

References 10 publications

Comparison between two carbonyl measurement methods in the atmosphere

Comparison between two carbonyl measurement methods in the atmosphere

Secondary Organic Aerosol Formation from the Irradiation of Simulated Automobile Exhaust

An optimized method for the determination of volatile and semi-volatile aldehydes and ketones in ambient particulate matter

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