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Residential indoor exposure to volatile organic compounds (VOCs) is a major public health concern. However, the relevant pollution sources have not been well characterized in China. In this study, the 24-h integrated concentrations of 55 VOC species in 27 urban residences, Beijing were measured in the summer. The sources were characterized with positive matrix factorization (PMF) and general linear model (GLM). The most abundant species in terms of geometric mean concentration were formaldehyde (55.1 μg/m3), acetaldehyde (18.7 μg/m3), acetone (14.8 μg/m3), toluene (14.1 μg/m3), hexanal (13.8 μg/m3), n-hexadecane (8.9 μg/m3) and n-pentadecane (8.5 μg/m3). PMF generated 7 factors associated with VOC sources, including aldehydes from ozone-initiated secondary reactions, butyraldehyde from hydrolysis of building materials and furniture, wood flooring emission, wooden furniture emission, wall coverings emission, mobile emission and halogenated hydrocarbons of miscellaneous outdoor origin. GLM identified leather sofa as another source of indoor terpenes and formaldehyde. GLM also found composite wood flooring had stronger emission of VOCs than solid wood flooring, except 1,4-dichlorobenzene. A comparison with multiple studies across the world suggested that: (1) more intensive ozone-initiated secondary reactions resulted in the significantly higher indoor carbonyl concentrations in Beijing than in Japan and USA in the summer; (2) the indoor concentrations of benzene and C12-C17 alkanes were much higher in Beijing, due to the traffic conditions and prevalent use of wood flooring varnishing.

This work assessed the effects of biodiesel on carbonyl emissions from diesel trucks. Biodiesel converted from waste cooking oil was employed and mixed with commercial fossil diesel to produce four blends: B0 (pure conventional diesel fuel), B5 (5% v/v biodiesel), B20 (20% v/v biodiesel) and B100 (pure biodiesel). Four diesel trucks were tested under real-world conditions using a portable emissions measurement system, including one China III light-duty diesel truck (LDDT), one China IV LDDT, one China III heavy-duty diesel truck (HDDT) and one China IV HDDT. A driving cycle including highway (HW) and non-highway (NHW) driving conditions was employed and carbonyls were sampled using 2,4-dinitrophenylhydrazine cartridges and analyzed via high performance liquid chromatography. Seven carbonyl compounds were detected, and formaldehyde, acetaldehyde, acetone and butyraldehyde were the primary carbonyls. Total carbonyl emissions from the China III LDDT, China III HDDT and China IV HDDT vehicles with selective catalytic reduction decreased monotonically with increases in the biodiesel proportion, while the China IV LDDT with a particle oxidation catalyst system showed an increasing trend. With increases in the biodiesel proportions, complementary variations were observed in the proportions of formaldehyde and butyraldehyde obtained using the China III LDDT, China IV LDDT and China III HDDT vehicles. However, in the case of the China IV HDDT trials, the formaldehyde and acetaldehyde emissions exhibited complementary variations. Under different driving conditions, the effects of adding biodiesel on carbonyl emission factors were different. In China III LDDT trials, biodiesel reduced carbonyl emissions to a greater extent under HW conditions, but the opposite occurred in China III HDDT tests. Using the China IV LDDT vehicle, the emission factors did not increase as much during HW trials compared with NHW trials when the B5 and B20 fuels were used, but were significantly higher than the NHW values when pure biodiesel was employed. In China III LDDT data, the proportions of formaldehyde, acetaldehyde and butyraldehyde showed opposite variations under the two driving conditions. Using the China IV LDDT vehicle, a significant increase in formaldehyde and decrease in butyraldehyde were found during HW trials, but not NHW trials. Ozone formation potentials were obtained from carbonyls emission factors using the maximum incremental reactivity method and their variations were similar to those of the carbonyl emission factors.

The exhaust gas constituents of light-duty diesel vehicles (LDDVs), including total hydrocarbon (THC), non-methane hydrocarbon (NMHC), carbon monoxide (CO), nitrogen oxide (NOx), and volatile organic compounds (VOCs) were measured by a dynamometer study following federal test procedure-75 (FTP-75) and highway fuel economy cycle. The average fuel consumption of these LDDVs was 0.126 L km−1 for FTP-75, with about 10% fuel consumption savings for highway driving. The average emission factors of NMHC, CO and NOx for light-duty vehicles were 0.158/0.132 (90% of THC), 1.395/1.138, and 1.735/1.907 g km−1 for FTP-75/Highway, respectively. Styrene, n-propylbenzene, n-undecane, o-ethyltoluene, 1,2,4-trimethylbenzene, toluene, o-xylene, isopropylbenzene, m,p-xylene, and ethylbenzene were the dominant VOCs of LDDV exhaust, and the emission factors were about 10–60 mg kg−1. In addition, formaldehyde, acetaldehyde, acetone, butyraldehyde, and m-tolualdehyde were the major carbonyl species from LDDV exhaust, and the emission factors ranged from 1 to 10 mg km−1. The ozone formation potentials of m,p-xylene, o-ethyltoluene, 1,2,4-trimethylbenzene, o-xylene, n-propylbenzene, styrene, and isoprene were >50 mg-O3 km−1. In addition, formaldehyde, acetaldehyde, and butyraldehyde revealed high ozone formation potential of carbonyl species, with values ranging from 10 to 95 mg-O3 km−1. Based on the exhaust constituents and ozone formation potential observed, diesel vehicles could be an important air pollution source for urban and industrial areas.

This study evaluates the relative recovery (RR) of five different carbonyls (CCs) (i.e., acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde) following their reaction as 2, 4-dinitrophenylhydrazine (DNPH) derivatives when using gas phase and liquid phase standards. To this end, relative efficiency of CC-DNPH derivatization is compared between two liquid-phase standards (commercially available vs. lab made mixture) and between liquid and gas-phase standard. If the results are compared in terms of response factors (RF) derived for five carbonyls from all different standard phases, the recovery of gaseous CC standard was distinguished from that of liquid counterparts. The RR of the heavier carbonyls (propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde) was approximately 60% low relative to their liquid counterparts; however, it was not the case for the lighter carbonyls (acetaldehyde) with the RR of ∼92%. This study thus suggests that the quantification of heavy carbonyls in ambient air, unless made by standards of the same matrix (i.e., gas phase) or compensated by the proper correction factor, may be subject to a large bias due to difference in derivatization reaction efficiency between matrix types. Hence, consideration of the matrix effect at the calibration stage is of particular importance to measure CC quantitatively.

The amount of odorants effused from Lake Sihwa during the low tide period was estimated using sediment samples collected from various sites. A wide variety of odorants released from lake sediment were measured such as reduced sulfur compounds (RSCs), aldehydes, nitrogenous compounds, volatile organic compounds (VOCs), and volatile fatty acids (VFAs). A comparison of emission rates (μg m−2 min−1) showed large mean values from such species as NH3 (14,550), toluene (370), and DMS (106), while the lowest values were seen from VFAs and some VOCs. If their emission concentrations are converted into odor intensity (OI), the OI values were dominated by such odorants as NH3 (2.07), H2S (1.65), DMS (1.80), acetaldehyde (1.52), butyric acid (1.59), butyraldehyde (1.28), isovaleric acid (1.15), and valeric acid (0.78). The dilution to threshold (D/T) ratio derived on the basis of the air dilution sensory (ADS) test yielded a mean of 62 (range: 10–173); 19 out of 21 samples were seen to exceed the guideline D/T value of 15. The sum of odor intensities derived from individual odorants exhibited strong compatibilities with the D/T ratio (r2 = 0.87; α = 0.003). The overall results of this study confirm that the sediment can play an important role in the malodor phenomenon in the area surrounding the Lake Sihwa.

With the use of biodiesel in clear growth, it is important to quantify any potential emission benefits or liabilities of this fuel. Several researches are available concerning the regulated emissions of biodiesel/diesel blends, but there is a lack of information about non-regulated emissions. In a previous paper [Correa, S.M., Arbilla, G., 2006. Emissoes de formaldeido e acetaldeido de misturas biodiesel/diesel. Periodico Tche Quimica, 3, 54–68], the emissions of aromatic hydrocarbons were reported. In this work, seven carbonyl emissions (formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde, butyraldehyde, and benzaldehyde) were evaluated by a heavy-duty diesel engine fueled with pure diesel (D) and biodiesel blends (v/v) of 2% (B2), 5% (B5), 10% (B10), and 20% (B20). The tests were conducted using a six cylinder heavy-duty engine, typical of the Brazilian fleet of urban buses, in a steady-state condition under 1000, 1500, and 2000 rpm. The exhaust gases were diluted nearly 20 times and the carbonyls were sampled with SiO2–C18 cartridges, impregnated with acid solution of 2,4-dinitrophenylhydrazine. The chemical analyses were performed by high performance liquid chromatography using UV detection. Using average values for the three modes of operation (1000, 1500, and 2000 rpm) benzaldehyde showed a reduction on the emission (−3.4% for B2, −5.3% for B5, −5.7% for B10, and −6.9% for B20) and all other carbonyls showed a significative increase: 2.6, 7.3, 17.6, and 35.5% for formaldehyde; 1.4, 2.5, 5.4, and 15.8% for acetaldehyde; 2.1, 5.4, 11.1, and 22.0% for acrolein+acetone; 0.8, 2.7, 4.6, and 10.0% for propionaldehyde; 3.3, 7.8, 16.0, and 26.0% for butyraldehyde.

Concentrations of formaldehyde, acetaldehyde, acetone, propionaldehyde and butyraldehyde were measured in a semi-urban coastal site in the Gulf of Campeche, Mexico, during the winter, summer and autumn seasons. Measurements were carried out from 10 February 2004 to 16 November 2004. Carbonyl compound levels showed pronounced diurnal and seasonal variations. Maximum concentrations occurred between 13:00 h and 16:00 h, when vehicular traffic and photochemical activity were intense, and during the summer (when there was greater solar radiation). Only acetone during the first campaign (winter) did not correlate with temperature; it showed an inverse diurnal pattern, with higher concentrations during the night, probably due to a local and temporal source. The low concentrations of the main carbonyls found in this study, compared with the values reported for other urban areas, seem to indicate that air quality is still satisfactory in Carmen City.

The kinetics of OH oxidation of several organic compounds of atmospheric relevance were measured in the aqueous phase. Relative kinetics were performed using various organic references and OH sources. After validation of the protocol, temperature-dependent rate constants for the reactions of OH radical with ethyl ter-butyl ether ( k 297 K = 1.5 ( ± 1.7 ) × 1 0 9 M - 1 s - 1 , E a / R = 580 (±560) K), n-butyl acetate ( k 297 K = 1.8 (±0.4)×109 M−1 s−1, E a / R = 1000 (±200) K), acetone ( k 298 K = 0.11 (±0.05)×109 M−1 s−1, E a / R = 1400 (±500) K), methyl ethyl ketone ( k 298 K = 0.81 ( ± 0.18 ) × 1 0 9 M - 1 s - 1 , E a / R = 1200 (±200) K), methyl iso-butyl ketone ( k 298 K = 2.1 ( ± 0.5 ) × 1 0 9 M - 1 s - 1 , E a / R = 1200 (±300) K) and methylglyoxal ( k 298 K = 0.53 ( ± 0.04 ) × 1 0 9 M - 1 s - 1 , E a / R = 1100 (±300) K) were determined. A non-Arrhenius behavior was found for phenol, in good agreement with the contribution of an OH addition to the mechanism, which also includes H-abstraction by OH radicals. Global rate constants of acetaldehyde, propionaldehyde, butyraldehyde and valeraldehyde were studied at 298 K only, as these compounds partly hydrate in the aqueous phase. All the obtained data (except those of phenol) complemented by literature data were used to investigate three methods to estimate rate constants for H-abstraction reactions of OH radicals in aqueous solutions when measured data were not available: Evans-Polanyi-type correlations, comparisons with gas-phase data, structure activity relationships (SAR). The results show that the SAR method is promising; however, the data set is currently too small to extend this method to temperatures other than 298 K. The atmospheric impact of aqueous phase OH oxidation of water-soluble organic compounds is discussed with the determination of their global atmospheric lifetimes, taking into account both gas- and aqueous-phase reactivities. The results show that atmospheric droplets can act as powerful photoreactors to eliminate soluble organic compounds from the atmosphere.

In this work, glass tube and mist chamber sampling techniques using 2,4-dinitrophenylhydrazine as derivative agent for the analysis of gaseous carbonyl compounds are compared. Trapping efficiencies of formaldehyde, acetaldehyde, propionaldehyde, acetone, acrolein, glyoxal, crotonaldehyde, benzaldehyde, butyraldehyde and valeraldehyde are experimentally determined using a gas-phase generator. In addition to generalise our results to all atmospheric gaseous compounds and derivative agents, theoretical trapping efficiencies and enrichment factors are expressed taking into account mechanisms involved in the two kinds of traps. Theoretical and experimental results show that, as expected, the trapping efficiencies of the glass tube depend mainly on solubility of compounds. The results provide new information and better understanding of phenomena occurring in the mist chamber and the ability of this sampler to concentrate the samples. Hence, the mist chamber is the more convenient sampling method when the trapping is associated to a fast derivatisation of the compounds and the glass tube technique must be used to trap atmospheric compounds without simultaneous derivatisation.