Determination of Room Temperature OH Rate Constants for Acetylene,Ethylene Dichloride,Ethylene Dibromide,p-Dichlorobenzene and Carbon Disulfide

A relative rate procedure was used to measure hydroxyl rate constants at room temperature in the presence of oxygen. The photolysis of methyl nitrite in the presence of nitric oxide was used to generate OH radicals. The rate of loss of the test compounds was measured relative to that of ethane (k_OH = 2.74 × 10^-13 cm³ molec^-1 s^-1). The rates obtained at 297 ± 2 K are: acetylene = (7.8 ± 1.6) × 10^-13 cm³ molec^-1 s^-1,1,2-dichloroethane (2.8 ± Q.6) × 10^-13 cm³ molec^-1 s^-1, 1,2-dibromoethane (2.4 ± 0.5) × 10^-13 cm³ molec^-1 s^-1, p-dichlorobenzene (4.3 ± 0.9) × 10^-13 cm³ molec^-1 s^-1 and carbon disulfide (29 ± 6) × 10^-13 cm³ molec^-1 s^-1. Under a proposed EPA rule, this OH rate determination procedure could be used to determine if a given volatile organic will be subject to control for reduction of photochemical ozone.     

Photochemical ozone creation potentials for oxygenated volatile organic compounds: sensitivity to variations in kinetic and mechanistic parameters

The sensitivity of Photochemical Ozone Creation Potentials (POCP) to a series of systematic variations in the rates and products of reactions of radical intermediates and oxygenated products is investigated for the C₄ alcohols, 1-butanol (n-butanol) and 2-methyl-1-propanol (i-butanol), using the recently developed Master Chemical Mechanism (MCM) as the base case. The POCP values are determined from the calculated formation of ozone in the boundary layer over a period of approximately five days along an idealised straight line trajectory, using a photochemical trajectory model and methodology described in detail previously. The results allow the relative impacts on calculated ozone formation of various classes of chemical reaction within the degradation chemistry to be assessed. The calculated POCP is found to be very insensitive to many of the changes investigated. However, it is found to be sensitive to variations in the rate coefficient for the initiating reaction with OH (k_OH), although the sensitivity decreases with increasing k_OH. The POCP appears to vary approximately linearly with k_OH at low values (i.e. k_OH less than ca. 4×10^-13 cm³ molecule^-1 s^-1), whereas at high reactivities (i.e. k_OH greater than ca. 4×10^-11 cm³ molecule^-1 s^-1), the calculated POCP value is comparatively insensitive to the precise value of k_OH. The POCP is also very sensitive to mechanistic changes which influence the yields of unreactive oxygenated products (i.e. those with OH reactivities below ca. 10^-12 cm³ molecule^-1 s^-1), for example acetone. The propensity of the organic compound to produce organic nitrates (which act as comparatively unreactive reservoirs for free radicals and NO_x) also appears to have a notable influence on the calculated POCP. Recently reported information relevant to the degradation of oxygenated VOCs is then used to update the chemical schemes for the 17 alcohols and glycols, 10 ethers and glycol ethers, and 8 esters included in the MCM, and new schemes are incorporated for dimethoxy methane (CH₃OCH₂OCH₃) and dimethyl carbonate (CH₃OC(O)OCH₃), which are proposed fuel additives. New or updated POCP values are calculated for all 37 oxygenated VOCs and, where applicable, these are compared with the previous POCP values and reported Maximum Incremental Reactivity (MIR) values.     

Evaluation of atmospheric sources of PCDD/Fs, PCBs and PBDEs around a steel industrial complex in northeast China using passive air samplers

The concern about emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) from steel industrial parks has increased in the past decades. In this study, polyurethane foam (PUF)-disk based passive air samples were collected in and around a big steel industrial park of Anshan, Northeast China from June 2008 to March 2009. The levels, seasonal variations and potential sources of PCDD/Fs, PCBs and PBDEs in the atmosphere around the steel industrial complex were investigated, and potential contribution of these three groups of persistent organic pollutants (POPs) from iron and steel production was also assessed. The air concentrations of ∑₁₇PCDD/Fs (summer: 0.02-2.77 pg m⁻³; winter: 0.20-9.79 pg m⁻³), ∑₁₉PCBs (summer: 23.5-155.8 pg m⁻³; winter: 14.6-81.3 pg m⁻³) and ∑₁₃PBDEs (summer: 2.91-10.7 pg m⁻³; winter: 1.10-3.89 pg m⁻³) in this targeted industrial park were relatively low in comparison to other studies, which implied that the industrial activities of iron and steel had not resulted in serious contamination to the ambient air in this area. On the whole, the air concentrations of PCDD/Fs in winter were higher than those of summer, whereas the concentrations of PCBs and PBDEs showed opposite trends. The result from principal component analysis indicated that coal combustion might be the main contributor of PCDD/F sources in this area.     

Influence of temperature on the chemical removal of 3-methylbutanal,trans-2-methyl-2-butenal,and 3-methyl-2-butenal by OH radicals in the troposphere

Absolute rate coefficients for the gas-phase reactions of OH radical with 3-methylbutanal (k₁), trans-2-methyl-2-butenal (k₂), and 3-methyl-2-butenal (k₃) have been obtained with the pulsed laser photolysis/laser-induced fluorescence technique. Gas-phase concentration of aldehydes was measured by UV absorption spectroscopy at 185 nm. Experiments were performed over the temperature range of 263–353 K at total pressures of helium between 46.2 and 100 Torr. No pressure dependence of all k_i (i = 1–3) was observed at all temperatures. In contrast, a negative temperature dependence of k_i (i.e., k_i increases when temperature decreases) was observed in that T range. The resulting Arrhenius expressions (±2σ) are: k₁(T) = (5.8 ± 1.7)×10^?12 exp{(499 ± 94)/T} cm³ molecule^?1 s^?1, k₂(T)=(6.9 ± 0.9)×10^?12 exp{(526 ± 42)/T} cm³ molecule^?1 s^?1, k₃(T)=(5.6 ± 1.2)×10^?12 exp{(666 ± 54)/T} cm³ molecule^?1 s^?1.The tropospheric lifetimes derived from the above OH-reactivity trend are estimated to be higher for 3-methylbutanal than those for the unsaturated aldehydes. A comparison of the tropospheric removal of these aldehydes by OH radicals with other homogeneous degradation routes leads to the conclusion that this reaction can be the main homogeneous removal pathway. However, photolysis of these aldehydes in the actinic region (λ > 290 nm) could play an important role along the troposphere, particularly for 3-methyl-2-butenal. This process could compete with the OH reaction for 3-methylbutanal or be negligible for trans-2-methyl-2-butenal in the troposphere.     

Levels and distribution of Dechlorane Plus in coastal sediments of the Yellow Sea, North China

Dechlorane Plus (DP) has been determined in surface sediments from three Chinese coastal bays, e.g. Jiaozhou, Sishili and Taozi Bay in North China. DP concentrations ranged from <1.2 to 187 pg g⁻¹ dry weight (dw) (mean: 24.7 pg g⁻¹ dw) in Jiaozhou Bay, <1.2 to 135 pg g⁻¹ dw (mean 69.9 pg g⁻¹ dw) in Sishili Bay and <1.2 to 66.7 pg g⁻¹ dw (mean: 40.4 pg g⁻¹ dw) in Taozi Bay, respectively. Additionally, two dechlorinated species were quantified, which accounted for 0.6-5.1% of the ∑DP concentration.The f_syn values (syn-isomer/(syn- + anti-isomer)) in sediments from Jiaozhou Bay (mean 0.29) were close to the technical DP mixture (0.2-0.4), probably indicating local inputs of DP. In contrast, sediments in Sishili and Taozi Bay showed much lower f_syn values (mean 0.16). During transportation the DP isomers are subject to stereo selective degradation which partly resulted in the relative enrichment of anti-DP in coastal sediments.     

Kinetics of the gas-phase reactions of NO3 radicals with ethyl acrylate,n-butyl acrylate,methyl methacrylate and ethyl methacrylate

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO₃ radicals with a series of acrylate esters: ethyl acrylate (k₁), n-butyl acrylate (k₂), methyl methacrylate (k₃) and ethyl methacrylate (k₄) at 298 ± 1 K and 760 Torr. The obtained rate constants are k₁ = (1.8 ± 0.25) × 10^?16 cm³ molecule^?1 s^?1, k₂ = (2.1 ± 0.33) × 10^?16 cm³ molecule^?1 s^?1, k₃ = (3.6 ± 1.2) × 10^?15 cm³ molecule^?1 s^?1, k₄ = (4.9 ± 1.7) × 10^?15 cm³ molecule^?1 s^?1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO₃ radicals. In addition, the atmospheric lifetimes of the compound against NO₃ attack are estimated and the results show that NO₃ reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.     

Organochlorine pesticides in soils of Mexico and the potential for soil-air exchange

The spatial distribution of organochlorine pesticides (OCs) in soils and their potential for soil-air exchange was examined. The most prominent OCs were the DDTs (Geometric Mean, GM = 1.6 ng g⁻¹), endosulfans (0.16 ng g⁻¹), and toxaphenes (0.64 ng g⁻¹). DDTs in soils of southern Mexico showed fresher signatures with higher F_DDTe = p,p′-DDT/(p,p′-DDT + p,p′-DDE) and more racemic o,p′-DDT, while the signatures in the central and northern part of Mexico were more indicative of aged residues. Soil-air fugacity fractions showed that some soils are net recipients of DDTs from the atmosphere, while other soils are net sources. Toxaphene profiles in soils and air showed depletion of Parlar 39 and 42 which suggests that soil is the source to the atmosphere. Endosulfan was undergoing net deposition at most sites as it is a currently used pesticide. Other OCs showed wide variability in fugacity, suggesting a mix of net deposition and volatilization.     

Levels and profiles of long-chain perfluorinated carboxylic acids in human breast milk and infant formulas in East Asia

In this study, 90 human breast milk samples collected from Japan, Korea, and China were analyzed for perfluorooctanoic acid (PFOA) (C8), perfluorononanoic acid (PFNA) (C9), perfluorodecanoic acid (PFDA) (C10), perfluoroundecanoic acid (PFUnDA) (C11), perfluorododecanoic acid (PFDoDA) (C12), and perfluorotridecanoic acid (PFTrDA) (C13). In addition, infant formulas (n = 9) obtained from retail stores in China and Japan were analyzed. PFOA was the predominant compound and was detected in more than 60% of samples in all three countries. The PFOA, PFNA, PFDA, and PFUnDA levels in Japan were significantly higher than those in Korea and China (p < 0.05). The PFTrDA level was highest in Korea (p < 0.05). The median PFOA concentrations were 89 pg mL⁻¹ (48% of total perfluorinated carboxylic acids (PFCAs) (C8-C13)) in Japan, 62 pg mL⁻¹ (54%) in Korea, and 51 pg mL⁻¹ (61%) in China. The remaining ∑PFCAs (C9-C13) were 95 pg mL⁻¹ in Japan, 52 pg mL⁻¹ in Korea, and 33 pg mL⁻¹ in China. Among the long-chain PFCAs, odd-numbered PFCAs were more frequently detected than even-numbered PFCAs, except for PFDA in Japan. There were no evident correlations between the mother’s demographic factors and the PFCA concentrations. PFOA, PFNA, and PFDA were frequently detected in both Japan and China, but there were no significant differences between the two countries. The total PFCA concentrations in the infant formulas were lower than those in the breast milk samples in Japan (p < 0.05), but not in China (p > 0.05). In conclusion, various PFCAs were detected in human breast milk samples from East Asian countries.     

Extent of H-atom abstraction from OH + p-cymene and upper limits to the formation of cresols from OH + m-xylene and OH + p-cymene

Aromatic hydrocarbons are important constituents of vehicle exhaust and of non-methane volatile organic compounds in ambient air in urban areas. It has recently been proposed that dealkylation is a significant pathway for the OH radical-initiated reactions, leading to the formation of phenolic compounds and/or oxepins (Noda, J., Volkamer, R., Molina, M.J., 2009. Dealkylation of alkylbenzenes: a significant pathway in the toluene, o-, m-, and p-xylene + OH reaction. Journal of Physical Chemistry A 113, 9658–9666.). We have investigated the formation of cresols from the reactions of OH radicals with m-xylene and p-cymene, and obtain upper limits of <1% for formation of each cresol isomer from OH + m-xylene and <2% for formation of each cresol isomer from OH + p-cymene. In addition, we have measured the formation yield of 4-methylacetophenone (the major product formed subsequent to H-atom abstraction from the CH(CH₃)₂ group) in the OH + p-cymene reaction to be 14.8 ± 3.2%, and estimate that H-atom abstraction from the CH₃ and CH(CH₃)₂ groups in p-cymene accounts for 20 ± 4% of the overall OH radical reaction. We also used a relative rate technique to measure the rate constant for the reaction of OH radicals with 4-methylacetophenone to be (4.50 ± 0.43) × 10^?12 cm³ molecule^?1 s^?1 at 297 ± 2 K.     

Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate,methyl acrylate and butyl methacrylate at atmospheric pressure

Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH₂C(CH₃)C(O)OCH₃ (MMA), CH₂CHC(O)OCH₃ (MAC) and CH₂C(CH₃)C(O)O(CH₂)₃CH₃ (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10^?10 cm³ molecule^?1 s^?1) as follows: k_(Cl+MMA) = 2.82 ± 0.93, k_(Cl+MAC) = 2.04 ± 0.54 and k_(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287–313 K were used to derive the following Arrhenius expressions (in units of cm³ molecule^?1 s^?1): k_(Cl+MMA) = (13.9 ± 7.8) × 10^?15 exp[(2904 ± 420)/T], k_(Cl+MAC) = (0.4 ± 0.2) × 10^?15 exp[(3884 ± 879)/T], k_(Cl+BMA) = (0.98 ± 0.42) × 10^?15 exp[(3779 ± 850)/T]. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above.An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log k_OH = 1.09 log k_Cl ? 0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed.     

Degradation kinetics of anthracene by ozone on mineral oxides

To further understand the role of substrates on the heterogeneous reactions of polycyclic aromatic hydrocarbons, the reactions of ozone with anthracene adsorbed on different mineral oxides (SiO₂, α-Al₂O₃ and α-Fe₂O₃) and on Teflon disc were investigated in dark at 20 °C. No reaction between ozone and anthracene on Teflon disc was observed when the ozone concentration was ～1.18 × 10¹⁴ molecules cm^?3. The reactions on mineral oxides exhibited pseudo-first-order kinetics for anthracene loss, and the pseudo-first-order rate constant (k_1,obs) displayed a Langmuir–Hinshelwood dependence on the gas-phase ozone concentration. The adsorption equilibrium constants for ozone (K_O3) on SiO₂-1, SiO₂-2, α-Al₂O₃ and α-Fe₂O₃ were (0.81 ± 0.26) × 10^?15 cm³, (2.83 ± 1.17) × 10^?15 cm³, (2.48 ± 0.77) × 10^?15 cm³ and (1.66 ± 0.45) × 10^?15 cm³, respectively; and the maximum pseudo-first-order rate constant (k_1,max) on these oxides were (0.385 ± 0.058) s^?1, (0.101 ± 0.0138) s^?1, (0.0676 ± 0.0086) s^?1 and (0.0457 ± 0.004) s^?1, respectively. Anthraquinone was identified as the main surface product of anthracene reacted with ozone. Comparison with previous research and the results obtained in this study suggest that the reactivity of anthracene with ozone and the lifetimes of anthracene adsorbed on mineral dust in the atmosphere are determined by the nature of the substrate.     

Dry deposition and soil-air gas exchange of polychlorinated biphenyls (PCBs) in an industrial area

Ambient air and dry deposition, and soil samples were collected at the Aliaga industrial site in Izmir, Turkey. Atmospheric total (particle + gas) ∑₄₁-PCB concentrations were higher in summer (3370 ± 1617 pg m⁻³, average + SD) than in winter (1164 ± 618 pg m⁻³), probably due to increased volatilization with temperature. Average particulate ∑₄₁-PCBs dry deposition fluxes were 349 ± 183 and 469 ± 328 ng m⁻² day⁻¹ in summer and winter, respectively. Overall average particulate deposition velocity was 5.5 ± 3.5 cm s⁻¹. The spatial distribution of ∑₄₁-PCB soil concentrations (n = 48) showed that the iron-steel plants, ship dismantling facilities, refinery and petrochemicals complex are the major sources in the area. Calculated air-soil exchange fluxes indicated that the contaminated soil is a secondary source to the atmosphere for lighter PCBs and as a sink for heavier ones. Comparable magnitude of gas exchange and dry particle deposition fluxes indicated that both mechanisms are equally important for PCB movement between air and soil in Aliaga.     

Kinetic studies of O3 reactions with 3-bromopropene and 3-iodopropene in the temperature range 288–328 K

The kinetics of the reactions of O₃ with 3-bromopropene and 3-iodopropene has been studied over the temperature range of 288–328 K at atmospheric pressure. The results obtained for the room temperature rate constants are (1.88 ± 0.22) × 10^?18 and (3.52 ± 0.43) × 10^?18 cm³ molecule^?1 s^?1, and the proposed Arrhenius expressions are k = (3.47 ± 1.28) × 10^?15 exp[(?2233 ± 110)/T] and k = (8.17 ± 2.12) × 10^?14 exp[(?2991 ± 80)/T] cm³ molecule^?1 s^?1 for 3-bromopropene and 3-iodopropene, respectively. The atmospheric chemical lifetimes of these two compounds with O₃ were also estimated from these values.     

The impact of production type and region on polychlorinated biphenyl (PCB), polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in Canadian chicken egg yolks

Chicken eggs from five different production types (conventional, omega-3 enriched, free range, organic and free run) were collected, when available, from three regions (west, central and east) of Canada to determine persistent organic pollutant (POP) concentrations. Total polychlorinated biphenyl (PCB) concentrations (∑37 congeners) in yolks from the eggs ranged from 0.162 ng g⁻¹ lipid to 24.8 ng g⁻¹ lipid (median 1.25 ng g⁻¹ lipid) while the concentration of the sum of the 6 indicator PCBs ranged from 0.100 ng g⁻¹ lipid to 9.33 ng g⁻¹ lipid (median 0.495 ng g⁻¹ lipid). Total polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) concentrations ranged from 2.37 pg g⁻¹ lipid to 382 pg g⁻¹ lipid (median 9.53 pg g⁻¹ lipid). The 2005 WHO toxic equivalency (TEQ) ranged from 0.089 pg TEQ_{PCDD/F+dioxin-like[DL]-PCB} g⁻¹ lipid to 12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid (median 0.342 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). PCB and PCDD/F concentrations were significantly different (p < 0.001) in egg yolks from different regions of collection. In contrast to observations in Europe, PCB and PCDD/F concentrations in Canadian egg yolks were not impacted solely by the production type (e.g., conventional, free range, organic, etc.) used to maintain the laying chickens. Additionally, only one Canadian free range yolk from western Canada (12.8 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid) exceeded the European toxic equivalent concentration limits for eggs (5 pg TEQ_{PCDD/F+DL-PCB} g⁻¹ lipid). This differs from observations in Europe where free range/home produced eggs frequently have higher POP concentrations than eggs from other production types. Median PCB dietary intake estimates based on consumption of eggs were less than 10 ng d⁻¹ while median PCDD/F intakes were less than 45 pg d⁻¹.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

Direct measurements and parameterisation of aerosol flux,concentration and emission velocity above a city

Articles have recently been published on aerosol size distributions and number concentrations in cities, however there have been no studies on transport of these particles. Eddy covariance measurements of vertical transport of aerosol in the size range 11 nm<D_p<3 μm are presented here. The analysis shows that typical average aerosol number fluxes in this size range vary between 9000 and 90,000 cm⁻² s⁻¹. With concentrations between 3000 and 20,000 cm⁻³ this leads to estimates of particle emission velocity between 20 and 75 mm s⁻¹. The relationships between number flux and traffic activity, along with emission velocity and boundary layer stability are demonstrated and parameterised. These are used to derive an empirical parameterisation for aerosol concentration in terms of traffic activity and stability. The main processes determining urban aerosol fluxes and concentrations are discussed and quantified where possible. The difficulties in parameterising urban activity are discussed.     

Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants in air and seawater of the European Arctic

The spatial distribution of polybrominated diphenyl ethers (PBDEs) and several alternative non-PBDE, non-regulated brominated flame retardants (BFRs) in air and seawater and the air-seawater exchange was investigated in East Greenland Sea using high-volume air and water samples. Total PBDE concentrations (Ó₁₀PBDEs) ranged from 0.09 to 1.8 pg m⁻³ in the atmosphere and from 0.03 to 0.64 pg L⁻¹ in seawater. Two alternative BFRs, Hexabromobenzene (HBB) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), showed similar concentrations and spatial trends as PBDEs. The air-seawater gas exchange was dominated by deposition with fluxes up to −492 and −1044 pg m⁻² day⁻¹ for BDE-47 and DPTE, respectively. This study shows the first occurrence of HBB, DPTE and other alternative flame retardants (e.g., pentabromotoluene (PBT)) in the Arctic atmosphere and seawater indicating that they have a similar long-range atmospheric transport potential (LRAT) as the banned PBDEs.     

A PLP–LIF kinetic study of the atmospheric reactivity of a series of C4–C7 saturated and unsaturated aliphatic aldehydes with OH

Absolute rate coefficients for the reaction of OH radical with a series of saturated and unsaturated aliphatic aldehydes were measured with the pulsed laser photolysis/laser-induced fluorescence technique at room temperature and as a function of total pressure (p_T=100–400 Torr). No pressure dependence of the rate coefficients was observed. The weighted average values obtained, k_OH±2σ, in units of 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, were 2.88±0.26 for n-butanal, 2.48±0.24 for n-pentanal, 2.60±0.21 for n-hexanal, 2.96±0.23 for n-heptanal, 3.51±0.71 for crotonaldehyde, 2.35±0.32 for trans-2-pentenal, 2.95±0.45 for trans-2-hexenal and 2.45±0.30 for trans-2-heptenal, respectively. The results are compared with previous data when available and with the corresponding coefficients for the reactions with NO₃ and O₃. The dominant tropospheric chemical loss process for these aliphatic aldehydes is the daytime reaction with OH, except in the case of trans-2-heptenal where the estimated lifetime for the reaction with NO₃ radical is smaller than the corresponding value for the OH reaction.     

Distribution of polychlorinated dibenzo-p-dioxins and dibenzofurans in ambient air of different regions in China

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in fourteen ambient air samples collected in twelve cities of five provinces and one large municipality in China. The PCDD/F concentrations varied from 2.6 to 120 pg m⁻³ (or from 0.04 to 1.93 pg I-TEQ m⁻³). Generally, TCDF was the dominant homologue group and as a rule the homologue concentration of PCDF decreased with rising chlorine substitution number of PCDF. In all cases 2,3,4,7,8-PeCDF was the most important contributor to the I-TEQ value, accounting for 35–57% of the total I-TEQ value. Higher PCDD/F levels in ambient air were found during winter. The highest PCDD/F levels were found in Chengdu, Sichuan Province. In general, the PCDD/F levels in this study were in the same range as in other studies in China.