Carbonyl Compounds In Air Research Articles

Simple Ozone Scrubber Using a Glass Fiber Filter Impregnated with Hydroquinone for the Quantitative Analysis of Ambient Air Samples.

As a standard method for measuring the concentration of carbonyl compounds in air, 2,4-dinitrophenylhydrazine (DNPH) derivatization followed by high-performance liquid chromatography (HPLC) is widely used. However, the method is often plagued by interference issues related to the ozone content in ambient air samples. Although the use of a potassium iodide (KI) scrubber circumvents these problems, the combination of a DNPH-coated silica cartridge and KI scrubber often performs poorly, particularly in high humidity. The KI in the scrubber becomes wet under these conditions, trapping the carbonyl compounds under investigation before they can reach the DNPH cartridge; this ultimately results in inaccurate readings. In this study, a new type of ozone scrubber consisting of a glass fiber filter coated with hydroquinone (HQF) was developed. The HQF scrubber was placed in front of the DNPH-coated silica cartridge, allowing airborne carbonyl compounds to pass unimpeded through the HQF section before being trapped by the DNPH-coated silica. The subsequent reaction of the trapped carbonyls with DNPH produced carbonyl 2,4-DNPhydrazone derivative that is used as the basis for the quantitative and qualitative analyses of ambient air samples. The hydroquinone in HQF reacts with ozone to form benzoquinone with an efficiency of more than 95% under wide relative humidity range (8 - 95%). The performance of our novel HQF scrubber was compared with those of potassium iodide (KI) and our previously developed trans-1,2-bis(2-pyridyl)ethylene (BPE)-coated silica scrubbers using ambient air samples, and the results showed that both HQF-DNPH and BPE-DNPH cartridges detected carbonyl compounds in the same concentration levels. The proposed method is superior to the KI-based and BPE-based technique for ozone removal because the HQF is very small and can be easily attached to any commercially available DNPH cartridge.

Monitoring of Air-Dispersed Formaldehyde and Carbonyl Compounds as Vapors and Adsorbed on Particulate Matter by Denuder-Filter Sampling and Gas Chromatographic Analysis.

Carbonyl compounds (CCs) are products present both as vapors and as condensed species adsorbed on the carbonaceous particle matter dispersed in the air of urban areas, due to vehicular traffic and human activities. Chronic exposure to CCs is a potential health risk given the toxicity of these chemicals. The present study reports on the measurement of the concentrations of 14 CCs in air as vapors and 2.5 µm fraction PM by the ENVINT GAS08/16 gas/aerosol sampler, a serial sampler that uses annular denuder, as sampling device. The 14 CCs were derivatized during sampling prior to gas-chromatographic separation and multiple detection by mass spectrometry, nitrogen-phosphorus thermionic, electron capture detection. Outdoor air multiple samples were collected in four locations in the urban area of Florence. The results evidenced that formaldehyde, acetaldehyde, and acetone were the more abundant CCs in the studied areas. The data collected was discussed considering the particle to vapor ratio of each CC found. The CCs pollution picture obtained was tentatively related to the nature and intensity of the traffic transiting by the sampling sites. This approach allowed to determine 14 CCs in both concentrated and diluted samples and is proposed as a tool for investigating outdoor and indoor pollution.

Development of a paper-based approach for the detection of carbonyl compounds in indoor air samples

This study contributes to the development of a method to measure the level of airborne carbonyl compounds. Carbonyl compounds (CC) are very common indoor air pollutants which are widely used in building and home furnishing industries. Most CC off-gas or vaporize even at normal room temperatures, which results in an increase in the indoor volatile organic carbon levels. Acute and chronic exposure to formaldehyde can result in respiratory symptoms and eye, nose, and throat irritation in humans. Because of these adverse health effects and the increased levels of CC in indoor air and residential areas, there has been a considerable attention toward the development of sensitive methods to monitor indoor CC levels. Most methods available for monitoring indoor CC levels are indirect and time consuming. This paper describes a novel, portable, on site, low-cost and green method for regular monitoring of CC in air. In this method, the derivatization reagent, 2,4-dinitrophenylhydrazine (2,4-DNPH) was used to capture the airborne CC. Formaldehyde was used as the CC for this study. A novel paper-based platform soaked with 2,4 DNPH was used for the quantification of air born CC. Derivatives of CC were formed on a paper-based platform which were then directly analyzed using FTIR or an image scanner. The FTIR response for the carbonyl derivatives, which correlates with the levels of airborne CC, was used to quantify the levels of airborne CC. The same was scanned using a high resolution image scanner to obtain the RGB values and the yellow color intensity was calculated. Based on the RGB values, the produced yellow color intensity and the levels of CC produced a linear relationship. The use of an image scanner to quantify the levels of CC makes this method a portable, sensitive and on-site CC detection method. This newly developed paperbased FTIR method is agreeable with the stranded HPLC method at 95% confidence limit.

Levels and Health Risk of Carbonyl Compounds in Air of the Library in Guangzhou, South China

ABSTRACTThe concentrations of 18 carbonyl compounds and their health risks for people were investigated in indoor and outdoor air of three different rooms of a library in Guangzhou, South China. Indoor air samples were collected during normal activities of staff and students, and carbonyl compounds were analyzed by high-performance liquid chromatography. The results show that the total concentrations of 18 carbonyls ranged from 8.8 to 73.9 µg m–3 with a mean value of 24.7 µg m–3. Acetone was the most abundant species with a mean value of 10.8 µg m–3 in indoor air, followed by formaldehyde and acetaldehyde. The levels of carbonyls in this study were relatively lower than most of other microenvironments in the literature. The average total concentration of carbonyls in the electronic reading room was higher than those in stack room and compact stack room. Diurnal variation in carbonyl concentrations was not distinct in the three rooms. The indoor/outdoor ratios and Spearman correlation coefficients demonstrated that endogenous emission sources contributed significantly to most of indoor carbonyls, while outdoor infiltration might be one of the main sources for acetaldehyde. The personal exposure, lifetime cancer risk, and non-cancer chronic health impacts through inhalation associated with formaldehyde and acetaldehyde were estimated and discussed.

Derivatization techniques for determination of carbonyls in air

Abstract This review critically assesses the derivatization techniques employed in sampling and detection of carbonyl compounds in air. We explore the most common techniques reported for the collection of vapor- phase carbonyl compounds by focusing on the hydrazine-derivatization techniques developed with the aid of diverse sorptive media [solution (e.g., in impingers), solid sorbents, solid-phase extraction, solid-phase microextraction, and denuder, or other approaches]. We discuss the advantages and the disadvantages of each sampling and pretreatment option for key carbonyl compounds with reference to measurement data obtained under laboratory and field conditions.

Ozone removal in the collection of carbonyl compounds in air

The most widely used method for measuring carbonyl compounds in air is 2,4-dinitrophenylhydrazine (DNPH) derivatization followed by high-performance liquid chromatography (HPLC). However, substantial negative interference caused by the presence of ozone in air has been reported. To avoid the influences of ozone, a potassium iodide scrubber (KI-scrubber) is commonly used. However, when air sampling using a DNPH-cartridge and a KI-scrubber is performed under conditions of high humidity, moist potassium iodide in the KI-scrubber traps carbonyls before they reach the DNPH-cartridge. Moreover, wet KI reacts with I2 to form KI3 and this oxidative reagent moves to the DNPH-cartridge and destroys the DNPH and DNPhydrazone derivatives. In order to alleviate these problems, new ozone scrubbers (BPE-scrubber, HQ-scrubber) have been developed. BPE-scrubber and HQ-scrubber consist of silica gel particles impregnated with trans-1,2-bis-(2-pyridyl) ethylene (BPE) and hydroquinone (HQ), respectively. BPE reacts with ozone to form pyridine aldehyde and HQ reacts with ozone to form benzoquinone. The amounts of reducing agent in silica gel (130mg) for ozone scrubber are 1% (w/w) for BPE-cartridge; 0.2% (w/w) for HQ-scrubber. These scrubbers can be used in air containing 140μg/m3 of ozone for 24h at a flow rate of 200mL/min. When the relative humidity exceeded 80%, KI in the KI-scrubber was gradually moistened and changed to yellow in color. Peak abundance of formaldehyde, acetaldehyde and acetone DNPhydrazones was diminished to 25%, 15%, and 2%, respectively, compared with the BPE-scrubber or HQ-scrubber. When using a BPE-scrubber or HQ-scrubber, decomposition of DNPH and DNPhydrazones was not observed at a wide range of relative humidities (3–97%).

A Prototype of Electrochemical Sensor for Measurements of Carbonyl Compounds in Air

AbstractThe paper presents the results of investigation on a prototype sensor for measurements of benzaldehyde and formaldehyde in air. Sensitivity, limit of quantification and coefficient of selectivity of the sensor have been determined as a function of membrane thickness and electrode type using square wave voltammetry (SWV) technique. The working and counter electrodes were made of platinum and gold. Ionic liquids 1‐hexyl, 3‐methylimidazolium bis(trifluoromethanesulfonyl)imide constituted an internal electrolyte. Polydimethylsiloxane (PDMS) membrane separated gaseous medium from the electrolyte.

A chemical potential driven micro-membrane sampler and its application for the determination of trace carbonyl compounds in air

A chemical potential driven micro-membrane sampler for enrichment of trace gaseous carbonyl compounds has been developed. The sampler is composed of exposed parts with membrane and analysis parts with polypropylene tube. The membrane acts as a barrier, through which the analytes dynamically diffuse and transfer from absorbents present outside to extract solvent inside through the difference of chemical potential. Formaldehyde and acetic acid were selected as verification samples. Quantification is achieved through high performance liquid chromatography (HPLC) analysis. The mass of analytes determined shows a linear correlation with concentration of the gaseous analytes. The limits of detection of formaldehyde and acetic acid after 8 h sampling were 3.32 and 0.76 μg m −3.

Nickel Complexes of N/O‐Functionalized N‐Heterocyclic Carbenes as Precatalysts for Michael Reactions in Air at Room Temperature Under the Much Preferred Base‐Free Conditions

AbstractA series of several new nickel precatalysts supported overN/O‐functionalized N‐heterocyclic carbenes (NHC) for the Michael reactions of β‐dicarbonyl, β‐keto ester, β‐diester, and α‐cyano ester compounds with α,β‐unsaturated carbonyl compounds in air at ambient temperature under the much preferred base‐free conditions are reported. Specifically, the nickel complexes, [1‐(R1‐aminocarbonylmethyl)‐3‐R2‐imidazol‐2‐ylidene]2Ni [R1 = 2‐C6H4(OMe); R2 = Me (1b), iPr (2b), CH2Ph (3b) and R1 = 2‐CH2C4H3O; R2 = Me (4b), CH2Ph (5b)] carried out the highly convenient base‐free Michael addition of the activated C–H compounds across α,β‐unsaturated carbonyl compounds in air at room temperature. The complexes 1b–5b were synthesized by the direct reaction of the respective imidazolium chloride salt with NiCl2·6H2O in CH3CN in the presence of K2CO3 as a base. The exceptional stability of 1b–5b has been attributed to the deeply buried nickel–NHC σ‐bonding molecular orbitals as evidenced from the density functional theory (DFT) studies. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Low cost selective sensor for carbonyl compounds in air based on a novel conductive poly( p-xylylene) derivative

A novel poly( p-xylylene), PPX, derivative bearing phenyl side groups was electrochemically synthesized in 85% yield. The polymer, poly(2-phenyl- p-xylylene) (PPPX), presented a major fraction (88%) soluble in common organic solvents. It showed to be thermally resistant up to 140 °C. UV–VIS analysis revealed an Egap of ~ 3.0 eV. Gas sensors made from thin films of CSA doped PPPX deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five carbonyl compounds: acetaldehyde, propionaldehyde, benzaldehyde, acetone and butanone. Three-dimensional plots of relative response vs. time of half-response vs. time of half-recovery showed good discrimination between the five carbonyl compounds tested.

DNPH捕集管-HPLC法を用いた家庭用冷蔵庫内のアルデヒド・ケトン類の測定

DNPH捕集管-HPLC法を用いた家庭用冷蔵庫内のアルデヒド・ケトン類の測定

Experimental choices for the determination of carbonyl compounds in air

The analysis of carbonyls in ambient air has received a great deal of scientific attention with the advancement of analytical techniques and increased demand for the build-up of its data base. In this review article, we have attempted to provide some insight into the relative performance of different instrumental approaches available for the analysis of ambient carbonyls with a major emphasis on high performance liquid chromatographic and gas chromatographic methods. Reported in several international standard procedures, derivatization of carbonyls with 2,4-dinitrophenylhydrazine (2,4-DNPH) with either an impinger or cartridges is the most commonly used method of HPLC detection. In this respect, a number of alternative hydrazine reagents have also been discussed for use with HPLC. In contrast, GC methods based on the combined application of adsorptive enrichment on solid sorbents and thermal desorption are examined with regard to their suitability for carbonyl analysis in air. Particular emphasis has been directed towards the advantages and drawbacks of these different instrumental techniques for ambient carbonyls. Based on this comparative approach, we discuss the suitability for each method for carbonyl analysis.

Investigation of carbonyl compounds in air from various industrial emission sources

The emission concentrations of carbonyl compounds in air were quantified from a total of 195 man-made source units within 77 individual companies at a large industrial complex in Korea. The measurement data were evaluated both by absolute magnitude of concentration and by their relative contribution to malodor formation such as malodor degree (MD) derived from empirical formula. It was found that formaldehyde exhibited the highest mean concentration of 323 ppb with a median value of 28.2 ppb, while butyraldehyde recorded the highest contribution to odor formation with an MD value of 3.5 (186 (mean) and 9.8 ppb (median)). The relative intensity of carbonyl emission, when compared by the sum of MD, showed the highest source strength from the food and beverage (industry sector) and scrubber (source unit). A comprehensive evaluation of the carbonyl data from diverse industrial facilities thus allowed us to describe the fundamental patterns of their emission.

Pollution survey of carbonyl compounds in train air

The methods for sampling and analyzing 10 carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, crotonaldehyde, butyraldehyde, benzaldehyde, cyclohexanone, valeraldehyde in indoor air were proposed with the sampling efficiency, recovery and detection limit being 92% - 100%, 91% - 104%, 0.26ng/m3 - 0.82ng/m3, respectively. Pollution survey of 10 carbonyl compounds in air of 6 trains was conducted. It was indicated that the total concentrations of carbonyl compounds were 0. 1591 mg/m3 - 0.2828 mg/m3 with the average concentration of 0.2330 mg/m3, the average concentrations of formaldehyde, acetaldehyde and acetone were 0.0922 mg/m3, 0.0499 mg/m3 and 0.0580 mg/m3, accounted for 42.6%, 21.4%, 24.9% of the total carbonyl compounds' concentrations, respectively. The carbonyl compounds probably came from woodwork and tobacco. The intake of carbonyl compounds for the passengers was approximately 0.043 mg/h - 0.076 mg/h.

Determination of carbonyl compounds in air and cancer risk assessment in an academic institute in Fortaleza, Brazil

Carbonyl compounds (CCs) were measured in outdoor and indoor air of libraries, classrooms, laboratories, and offices at the Universidade Federal do Ceará, Fortaleza, Brazil, from 5 November to 20 December 2004. Indoor air was sampled during normal activities of personnel and students. The results showed that acetone was the most abundant carbonyl compound in outdoor and indoor air, with an average concentration of 52.48 μg m −3, followed by formaldehyde (12.42 μg m −3), acetaldehyde (2.90 μg m −3), benzaldehyde (2.35 μg m −3), butyraldehyde (2.31 μg m −3), and acrolein (2.02 μg m −3). Acetone was the main compounds in research laboratories and offices, whereas formaldehyde was predominantly present in the libraries, student laboratories, and classrooms. The indoor/outdoor (I/O) ratio indicated that levels of CCs in indoor air are more elevated than in outdoor air. Ratios were 11.20 for acetone in research laboratories, 8.48 for acetaldehyde in offices, and 8.37 for formaldehyde in student laboratories. The cancer risk for professionals was 5–30-fold higher than that for students, while the risk was even higher in some libraries and offices when compared to particular laboratories. For women, the estimated cancer risk is 4% higher than that calculated for men.

Evaluation of a diffusive sampler for measurement of carbonyl compounds in air

Abstract A diffusive sampling device (DSD-DNPH) has been developed for collection of ppb levels of 21 carbonyl compounds in indoor air. It is comprised of silica gel coated with 2,4-dinitrophenylhydrazine (DNPH) as the absorbent, a porous sintered polyethylene tube (PSP-diffusion filter) which acts as a diffusive membrane, and a small polypropylene syringe (PP-reservoir) which is used for the elution of the analytes from the absorbent. As the diffusive membrane comprises the entire cylindrical surface of the tube, it allows ‘radial’ exposure from all sides. A side-by-side comparison was made with active samplers, demonstrating good correlation (formaldehyde r 2 =0.992). The sampling rate (71.9 ml min −1 ) of formaldehyde was determined from comparison with an active sampling method and the sampling rates of other carbonyl compounds were calculated from their diffusion coefficients. These calculated sampling rates agreed with the experimental values. Little influence of wind velocity on the sampler was observed. The relative standard deviations for formaldehyde and acetaldehyde concentrations were 5.5% and 8.6%, respectively, with face velocity from 0 to 5.0 m/s. The DSD-DNPH enables the estimation of time-weighted average concentration of carbonyl compounds. Concentrations of formaldehyde estimated by the 7-day sampling method were nearly equal to the mean value calculated from the 24-hour sampling method measured over 7 days. This confirmed that the concentration of formaldehyde could be precisely monitored by 7-day continuous sampling.

Measurement of acid-catalyzed isomerization of unsaturated aldehyde-2,4-dinitrophenylhydrazone derivatives by high-performance liquid chromatography analysis

Aldehyde-2,4-dinitrophenylhydrazones exist as ( E)- and ( Z)-geometrical isomers, and adventitious isomerization during sample preparation can cause analytical errors. Purified alkenal-2,4-dinitrophenylhydrazone derivatives comprise only the ( E)-isomer. However, partial isomerization to the ( Z)-isomer occurs upon addition of acid to attain an equilibrium isomer ratio. The UV–visible spectral properties of the isomers differ; the ( Z)-isomer exhibiting a 6–10 nm lower absorption maximum compared to the ( E)-isomer. Alkenal-2,4-dinitrophenylhydrazones having a C C double bond at the 2- or 3-position of the alkenal exhibited similar absorption maxima with an equilibrium isomer ratio (0.035) that was much lower than those of other alkenals. The C C double bond at the 3-position migrates to a position of conjugation with the C N double bond during hydrazone synthesis to form a stabilized molecular structure. Alkenal-2,4-dinitrophenylhydrazones having a double bond at the 4-position or greater exhibited a similar absorption maxima equilibrium isomer ratio (0.14) to alkanal-2,4-dinitrophenylhydrazones. The quantitative analysis of carbonyl compounds in air or water using DNPH is usually conducted in the presence of an acid catalyst. Consequently, the solution of the direct extract prepared for HPLC or GC analysis contains both ( E)- and ( Z)-isomers.

Carbonyl levels in indoor and outdoor air in Mexico City and Xalapa, Mexico

Carbonyl compounds in air were measured at two houses, three museums, and two offices. All sites lacked air-conditioning systems. Although indoor and outdoor air was measured simultaneously at each site, the sites themselves were sampled in different dates. Mean concentrations were higher in indoor air. Outdoor means concentrations of acetone were the highest in all sites, ranging from 12 to 60 μg m −3. In general, formaldehyde and acetaldehyde had similar mean concentrations, ranging from 4 to 32 and 6 to 28 μg m −3, respectively. Formaldehyde and acetone mean indoor concentrations were the highest, ranging from 11 to 97 and 17 to 89 μg m −3, respectively, followed by acetaldehyde with 5 to 47 μg m −3. Formaldehyde and acetaldehyde had the highest mean concentration in the offices where there were smokers. Propionaldehyde and butyraldehyde concentrations did not show definite differences between indoor and outdoor air. In general, the highest outdoor and indoor hourly concentrations were observed from 10:00 to 15:00 h. Mean indoor/outdoor ratios of carbonyls exceeded 1. Formaldehyde and acetaldehyde risks were higher in smoking environments.

ChemInform Abstract: Rhodium‐Catalyzed Conjugated Addition of Aryllead Reagents to α,β‐Unsaturated Carbonyl Compounds in Air and Water.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Pressure dependence of the photooxidation of selected carbonyl compounds in air: n-butanal and n-pentanal

Dilute mixtures of n-butanal and n-pentanal in synthetic air (up to 100ppm) were photolyzed with fluorescent UV lamps (275–380nm) in air at 298K. The main photooxidation products, identified and quantitatively analyzed by FT-IR spectroscopy, were ethene (n-butanal) or propene (n-pentanal), CO, vinylalcohol and ethanal. The photolysis rates and the absolute quantum yields Φ of both compounds were found to be slightly dependent on the total pressure. At 100Torr, in the photolysis of n-butanal and n-pentanal Φ100=0.48±0.02 and 0.40±0.04, whereas at 700Torr, the total quantum yields were Φ700=0.38±0.02 and 0.32±0.01, respectively. These results could be explained by the collisional deactivation of photoexcited molecules. Two decomposition channels were identified in both cases: the radical channel RCHO→R+HCO, and the molecular channel CxHyCHO→Cx−1Hy−3+CH2CHOH, having the relative yields of 68±3 and 32±3% (n-butanal), and 20±4 and 80±4% (n-pentanal) at 700Torr. The product, CH2CHOH, tautomerizes to ethanal. UV absorption cross-sections were measured prior to photolysis. For the comparison, the products were also analyzed after photolysis of both compounds in teflon bags using direct sunlight.