Development of SPME on-fiber derivatization for the sampling of formaldehyde and other carbonyl compounds in indoor air

Abstract

Solid-phase microextraction on-fiber derivatization applied to carbonyl compounds is known, but application to indoor air is poorly developed and the methods deserve to be complemented and optimized. In this work, two derivatization reagents, pentafluorophenylhydrazine and o-2,3,4,5,6-(pentaflurobenzyl)hydroxylamine (PFBHA), and three fiber coatings were tested in order to select the best combination. As Carboxen-based coatings were proven to induce the formation of by-products during the thermal desorption step, a polydimethylsiloxane-divinylbenzene fiber in association with PFBHA was finally chosen. The study of the derivatization kinetics showed that the reaction of PFBHA with carbonyl compounds was instantaneous, except for acetone. Analyses were performed by gas chromatography coupled with flame ionization detection and mass spectrometry. For 5 min fiber exposure, the limits of detection are below 0.5 μg m(-3) in selected ion monitoring mode, the reproducibility was 15% on average, and the linearity of the calibration curves was satisfactory. For on-site application, the influence of air humidity and the conditions in which the impregnated fibers were stored were studied. It is possible to store the fibers for 3 days before and for at least 2 days after sampling. The relative humidity of air was shown to have no influence on solid-phase microextraction sampling in the range from 0 to 70%. For formaldehyde, the method was compared with sampling on 2,4-dinitrophenylhydrazine cartridges, and the first results showed good agreement. Finally, the method was applied to three different indoor environments to check its feasibility.

Derivatization techniques for determination of carbonyls in air

“…Pawliszyn and co-workers have evaluated the feasibility of SPME fibers coated with derivatization reagents to sample vapor-phase CCs [73][74][75]. SPME on-fiber derivatization was used to sample FA, AA, acetone, and hexanal in air for analysis by GC-FID or GC-MS [52]. Three different fibers (PDMS-CAR-DVB, PDMS-CAR, and PDMS-DVB) and two derivatization reagents (PFPH and PFBHA) were compared.…”

Innovative tools and modeling methodology for impact prediction and assessment of the contribution of materials on indoor air quality

“…A PDMS-DVB SPME fibre (Supelco, Bellafonte, PA, USA) treated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) was especially developed for GC-MS analysis of carbonyl compounds including formaldehyde [10]. As SPME is a passive sampler, the amount of pollutants adsorbed on the fibre is directly proportional to the product of the concentration of the pollutant and the exposure time, product which is called "exposure dose" and expressed in µg m −3 min [11,12].…”

Application of Solid-Phase Microextraction Combined with Derivatization for Polar Compound Sampling in Environmental Analysis

“…Among the existing derivatizing agents, pentafluorobenzaldehyde (PFBAY) is widely used for short-chain aliphatic amines, and the derivatizing reaction can proceed rapidly in aqueous solution at room temperature and provides very good yield. After derivatization, the formed derivatives required further extraction and concentration prior to GC analysis [24,25,27,68,106,[111][112][113][114][115][116][117][118][119][120]. Aliphatic amines derivatization with PFBAY to corresponding pentafluorobenzylimines ( Fig.…”

“…Of these pollutants, formaldehyde is of particular concern as it was recognized as "carcinogenic to humans" (class 1) by the International Agency for Research on Cancer, and it is one of the OQAI's ten priority substances [106]. As to carbonyl compounds such as aldehydes and acetone, target analytes are extracted by the commercial SPME fiber by either DI or HS mode [106,109,[114][115][116][117], and combined by in situ derivatization of either in vial or on fiber with o-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) [78][79][80][81][82] or 2,4-dinitrophenylhydrazine/acetylacetone [109] and then for GC analysis. Moreover, online analysis of carbonyl compounds with derivatization by DNPH in aqueous extracts of atmospheric particulate matters by in-tube SPME coupled to capillary LC was reported [110,154].…”

“…PFPH, TFEH, and DNPH: As to the assay of aldehydes and acetone, many assays are based on reactions with derivatization reagents that usually involve 5,5-dimethyl-1,3-cyclohexanedione, N-methylbenzothiazolon-(2)-hydrazone, pentafluorophenylhydrazine (PFPH), and 2,4-dinitrophenylhydrazine (2,4-DNPH). Otherwise, 2,2,2-trifluoroethylhydrazine (TFEH), a very volatile hydrazine, reacts also with carbonyl compounds to produce volatile hydrazones [105][106][107][108][109][110]. Thus, it is possible to analyze the hydrazone with HS-SPMEGC-MS.…”