Atmospheric chemistry of 1,1,1,2-tetrafluoroethane

A one-dimensional eddy diffusion model was used to investigate the fate of 1,1,1,2-tetrafluoroethane (F-134a) in the atmosphere. The substitution of F-134a for F-12 (CF₂Cl₂) used in mobile air conditioning applications would eliminate the possibility of chlorine-related stratospheric ozone depletion from those applications and would introduce no more, and probably less, hydrogen fluoride (HF) into the stratosphere than the continued use of F-12. Such a substitution would only be possible if a commercial process is developed which can produce F-134a in suitable quantities.     

Atmospheric chemistry of 1-methyl-2-pyrrolidinone

Rate constants for the atmospheric reactions of 1-methyl-2-pyrrolidinone with OH radicals, NO₃ radicals and O₃ have been measured at 296±2 K and atmospheric pressure of air, and the products of the OH radical and NO₃ radical reactions investigated. Using relative rate techniques, rate constants for the gas-phase reactions of OH and NO₃ radicals with 1-methyl-2-pyrrolidinone of (2.15±0.36)×10^-11 cm³ molecule^-1 s^-1 and (1.26±0.40)×10^-13 cm³ molecule^-1 s^-1, respectively, were measured, where the indicated errors include the estimated overall uncertainties in the rate constants for the reference compounds. An upper limit to the rate constant for the O₃ reaction of <1×10^-19 cm³ molecule^-1 s^-1 was also determined. These kinetic data lead to a calculated tropospheric lifetime of 1-methyl-2-pyrrolidinone of a few hours, with both the daytime OH radical reaction and the nighttime NO₃ radical reaction being important loss processes. Products of the OH radical and NO₃ radical reactions were analyzed by gas chromatography with flame ionization detection and combined gas chromatography–mass spectrometry. N-methylsuccinimide and (tentatively) 1-formyl-2-pyrrolidinone were identified as products of both of these reactions. The measured formation yields of N-methylsuccinimide and 1-formyl-2-pyrrolidinone were 44±12% and 41±12%, respectively, from the OH radical reaction and 59±16% and ∼4%, respectively, from the NO₃ radical reaction. Reaction mechanisms consistent with formation of these products are presented.     

Atmospheric pollution transport: the parallelization of a transport & chemistry code

We discuss a model for computing the chemical reactions occurring among air pollutants and predict their dispersion in the atmosphere. We consider a parallel implementation on a CRAY T3D, using up to 128 processors. A regular subdomain decomposition is considered to optimize inter-processor communications, while load balancing – the main technical difficulty to obtain a good efficiency – is achieved by re-assigning temporarily pieces of work to other processors, according to a global strategy. The performance of our implementation is described by an analytical relation whose validity is checked on realistic data sets. A speedup of 100 is obtained with 128 processors.     

Atmospheric transport of emissions over urban area sources

The method of variational imbedding has been applied in reducing the problem of solving the nonlinear partial differential equation governing steady-state, two-dimensional advective-diffusive transport of emissions from ground-based area sources to an equivalent initial value problem in ordinary differential equations. Picard's method has then been used to build up a sequence of successive approximations to density distribution of contaminants for the case when both turbulent diffusivity and mean downwind speed are taken to vary with the vertical distance coordinate according to the empirical power law. Solutions corresponding to a few simpler situations have also been presented in this paper.     

Atmospheric BTEX-concentrations in an area with intensive street traffic

The major threat to clean air in developed and industrializing countries is now posed by traffic emissions. The effects of traffic road modifications on the air quality are, however, rarely reported in the literature. The aim of this study was to determine the influence of the modernization and renovation of a traffic artery in the region of Mortsel (Antwerp, Belgium) on the concentration of volatile organic compounds such as: benzene, toluene, ethylbenzene and m-, p-, o-xylenes (BTEX). The original goal of the reconstruction works was to reduce the traffic lanes of one of the busiest streets in Antwerp, in order to discourage the road traffic and in consequence also to improve the air quality in this region. The average concentrations of BTEX before these works in 2003 were: 1.6, 7.0, 0.9, 2.3, and 0.9 μg/m³, for benzene, toluene, ethylbenzene, m + p xylenes, and o-xylene, respectively. However, after the completion of the works, in 2005, they were slightly higher: 2.5, 9.5, 1.6, 3.4, and 1.3 μg/m³, respectively. The scatter plots of benzene against toluene, ethylbenzene and xylenes in 2003 and 2005 showed very good correlations. This fact indicated that all of the measured compounds originated from the same source, namely the road traffic. Moreover, the data obtained from an air-monitoring station at less than 6 km distance from the sampling site (operated by the Flemish Environment Agency, and located in Borgerhout, Antwerp), confirmed the lack of influence of background concentrations of BTEX. The obtained results led to the conclusion that the reduction of the number of traffic lanes had apparently increased the traffic jams and also increased the emission from cars. Therefore, these modernization works had even a negative impact on the local concentration of traffic-related pollutants as BTEX.     

Field studies of aldehyde chemistry in the Paris area

Measurements of carbonyl compound concentrations at different sites in the Paris area have been carried out. Interpretation of the results made use of the following data: general meteorological conditions, wind field analysis and type of primary pollutant sources. The principal phenomena observed were: a sharp formaldehyde decrease during rainfall; concentration levels of lower aldehydes in rural sites comparable to those found in the literature; an important variation in the ratio of primary aldehydes to secondary aldehydes depending on meteorological conditions; a significant increase in lower aldehyde concentrations downwind from the urban center despite vertical dispersion of the pollutants.     

Atmospheric characteristics conducive to high-ozone days in the Atlanta metropolitan area

The purpose of this paper is to identify the atmospheric conditions associated with elevated ground-level ozone concentrations during June–August of 2000–2007 at 11 ozone-monitoring stations in the Atlanta, GA, USA metropolitan statistical area (MSA). Analyses were confined to high-ozone days (HODs), which had a daily maximum 8-h average ozone concentration in the 95th percentile of all June–August values. Therefore, each station had 36 HODs. The southeastern and far northern portions of the MSA had HODs with the highest and lowest ozone concentrations, respectively. HODs at nearly all Atlanta MSA ozone-monitoring stations were enabled by migratory anticyclones. HODs for most stations were hot, dry, and calm with low morning mixing heights and high afternoon mixing heights. All sets of HODs had daily mean relative humidities and afternoon mixing heights that, respectively, were significantly less than and significantly greater than mean values for the remaining days. Urbanized Atlanta typically was upwind of an ozone-monitoring station on its HODs; therefore, wind direction on HODs varied considerably among the stations. HODs may have been caused partially by NO_x emissions from electric-utility power plants: HODs in the southern portion of the MSA were linked to air-parcel trajectories intersecting a power plant slightly northwest of Atlanta and plants in the Ohio River Valley, while HODs in the northern portion of the MSA were linked to air-parcel trajectories intersecting two large power plants slightly southeast of the Atlanta MSA. Results from this study suggest that future research in the Atlanta MSA should focus on power-plant contributions to ground-level ozone concentrations as well as the identification of non-monitored locations with potentially high ozone concentrations.     

Spatiotemporal dynamics of spring and stream water chemistry in a high-mountain area

The present study deals with the application of the self-organizing map (SOM) technique in the exploration of spatiotemporal dynamics of spring and stream water samples collected in the Chocho?owski Stream Basin located in the Tatra Mountains (Poland). The SOM-based classification helped to uncover relationships between physical and chemical parameters of water samples and factors determining the quality of water in the studied high-mountain area. In the upper part of the Chocho?owski Stream Basin, located on the top of the crystalline core of the Tatras, concentrations of the majority of ionic substances were the lowest due to limited leaching. Significantly higher concentration of ionic substances was detected in spring and stream samples draining sedimentary rocks. The influence of karst-type springs on the quality of stream water was also demonstrated.     

Atmospheric deposition of organochlorine pesticides by precipitation in a coastal area

Wet deposition fluxes of organochlorine pesticides (OCPs) were determined for rain samples collected in a coastal area of Turkey. Seventeen precipitation samples were collected over a 1-year period from 2008 to 2009. Rainwater was accumulated at the beginning of rain events using real time monitoring. Atmospheric concentrations were also measured in parallel with deposition samples. Both atmospheric concentrations and deposition fluxes were determined as particle and gas phases. The particle phase and dissolved phase deposition fluxes were 794.26?±?756.70 ngm^?2 day^?1 and 800.77?±?672.63 ngm^?2 day^?1, respectively. The washout ratios for OCP compounds were calculated separately for the particle and dissolved phases using the atmospheric concentrations and rain concentrations. The minimum washout ratio for the particle phase was 2339.47 for Endrin aldehyde, whereas the maximum washout ratio was 497593.34 for Methoxychlor. The maximum washout ratio for the dissolved phase was 247523.89 for Endosulfan beta, whereas the minimum washout ratio was 10169.69 for p,p′-DDT. The dry deposition velocities ranged from 0.01 to 1.67 cms^?1. The partitioning of wet deposition between the particle and dissolved phases was 50 % in terms of total OCP deposition.     

Atmospheric deposition inputs and effects on lichen chemistry and indicator species in the Columbia River Gorge, USA

Topographic and meteorological conditions make the Columbia River Gorge (CRG) an 'exhaust pipe' for air pollutants generated by the Portland-Vancouver metropolis and Columbia Basin. We sampled fog, bulk precipitation, throughfall, airborne particulates, lichen thalli, and nitrophytic lichen distribution. Throughfall N and S deposition were high, 11.5-25.4 and 3.4-6.7 kg ha(-1) over 4.5 months at all 9 and 4/9 sites, respectively. Deposition and lichen thallus N were highest at eastern- and western-most sites, implicating both agricultural and urban sources. Fog and precipitation pH were frequently as low as 3.7-5.0. Peak NO(x), NH(3), and SO(2) concentrations in the eastern CRG were low, suggesting enhanced N and S inputs were largely from particulate deposition. Lichens indicating nitrogen-enriched environments were abundant and lichen N and S concentrations were 2x higher in the CRG than surrounding national forests. The atmospheric deposition levels detected likely threaten Gorge ecosystems and cultural resources.     

Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.     

Atmospheric polycyclic aromatic hydrocarbons observed over the North Pacific Ocean and the Arctic area: Spatial distribution and source identification

During the 2003 Chinese Arctic Research Expedition from the Bohai Sea to the high Arctic (37–80°N) aboard the icebreaker Xuelong (Snow Dragon), air samples were collected using a modified high-volume sampler that pulls air through a quartz filter and a polyurethane foam plug (PUF). These filters and PUFs were analyzed for particulate phase and gas phase polycyclic aromatic hydrocarbons (PAHs), respectively, in the North Pacific Ocean and adjacent Arctic region. The ∑PAHs (where ∑=15 compounds) ranged from undetectable level to 4380 pg m⁻³ in the particulate phase and 928–92 600 pg m⁻³ in the gas phase, respectively. A decreasing latitudinal trend was observed for gas-phase PAHs, probably resulting from temperature effects, dilution and decomposition processes; particulate-phase PAHs, however, showed poor latitudinal trends, because the effects of temperature, dilution and photochemistry played different roles in different regions from middle-latitude source areas to the high latitudes. The ratios of PAH isomer pairs, either conservative or sensitive to degradation during long-range transport, were employed to interpret sources and chemical aging of PAHs in ocean air. In this present study the fluoranthene/pyrene and indeno[123-cd]pyrene/benzo[ghi]pyrene isomer pairs, whose ratios are conservative to photo-degradation, implies that biomass or coal burning might be the major sources of PAHs observed over the North Pacific Ocean and the Arctic region in the summer. The isomer ratios of 1,7/(1,7+2,6)-DMP (dimethylphenanthrene) and anthracene/phenanthrene, which are sensitive to aging of air masses, not only imply chemical evolving of PAHs over the North Pacific Ocean were different from those over the Arctic, but reveal that PAHs over the Arctic were mainly related to coal burning, and biomass burning might have a larger contribution to the PAHs over the North pacific ocean.     

Atmospheric concentration characteristics and gas-particle partitioning of PCBs in a rural area of eastern Germany

Atmospheric concentrations of polychlorinated biphenyls (PCBs) were measured in 14 successive daytime and nighttime air samples collected from Melpitz, a rural site in eastern Germany. The average total concentration of PCBs was 110+/-80 pg m-3 and they were predominately present in the gas phase (approximately 95%). Composition of individual congeners closely resembled those of Clophen A30 and Aroclor 1232. Partial vapor pressures of PCBs were well correlated with temperature and the steep slopes obtained from Clausius-Clapeyron plots (-4500 to -8000) indicated that evaporation from adjacent land surfaces still controls the atmospheric levels of these pollutants. Particle-gas partitioning coefficients (KP) of PCBs were well correlated with the respective sub-cooled vapor pressures (PLo), but the slopes obtained from logKP versus logPLo plots (-0.16 to -0.59) deviated significantly from the expected value of -1. Overall, gas-particle partitioning of PCBs was better simulated by Junge-Pankow than octanol/air partition coefficient-based model.