Methane in the Atmosphere

Methane is present in the troposphere with a volume concentration of about 1.5 ppm. Estimates of Koyama (1963) indicate a predominantly biological origin with a total production rate of about 2.7 × 10¹⁴ g CH₄/yr. From that he estimated the atmospheric lifetime of methane to be around 20 years. Measurements of the C-l4 in methane by Libby and later by Bainbridge, et al. (1961 ) gave a C-l4 content of 75% of recent wood and, therefore, confirm the predominant biological origin, the addition of inactive CH; from industrial sources being only about 25%. Much less is known about sinks of CH₄. Cadle (1966) reported fairly high destruction rates by atomic O, a reaction which should be important at high altitude. Bainbridge (1966) indeed reports a decrease in the measured methane concentration above the tropopause. He, however, considers this decrease too small to account for the destruction rate of 20 years estimated by Koyama. Our measurements on air samples collected on aircraft flights at various altitudes show a high variability of the CH₄ content both with time and altitude.     

Alkyl sulfonic acids in the atmosphere

A gas Chromatographie technique, based on methylation with diazomethane and specific sulfur detection (FDP), is proposed for the on-filter speciation of add aerosol constituents. First results indicate, that apart from sulfuric acid (and/or acid sulfate) the atmospheric aerosol may contain sulfurous acid (and/or acid sulfite) and sulfonic acid. The latter are postulated to be products from the atmospheric oxidation of sulfides, disulfides and mercaptans.     

Chiral organochlorine pesticides in the atmosphere

We measured the enantiomeric fractions (EF) of various organochlorine pesticides in air samples from Indiana, Arkansas, and Louisiana collected in 2002–2003. Enantiomeric fractions for o,p′-DDD are reported here for the first time, and they suggest preferential depletion of one enantiomer over the other, with a mean value of 0.44. For the chlordanes, the EFs followed the same trends as reported in previous studies. EF values for trans-chlordane (TC) were slightly below 0.5, and values for cis-chlordane (CC) were slightly above 0.5. For cis-heptachlor epoxide (HEPX), the EF values averaged 0.65, indicating a clear preferential depletion of the (−)-enantiomer. For TC and CC, no clear distinction could be made between the values measured among the three sites, suggesting that it is not possible to use these EF values as “source signatures”. For HEPX, the Indiana site had significantly higher EF values than did the Arkansas site; this difference may reflect differences in the historic use of heptachlor in these two regions.     

Transfer of visible radiation in the atmosphere

The problem of the transfer of visible radiation in the terrestrial atmosphere is addressed from the visual-air-quality point-of-view. Attention is therefore focused on computations of the luminance, dominant wavelength, and spectral purity of the sky radiation requiring radiance values for a number of wavelengths in the 0.38–0.78 μm interval of the electromagnetic spectrum. These colorimetric parameters are determined, for five different plane-parallel atmospheric models, from values of the radiances at 23 unequally spaced wavelengths. The diffuse radiation is evaluated after taking into account all orders of scattering, but after neglecting the polarization aspects of the scattered radiation. The atmospheric models studied are for average, cloudfree, mid-latitude summer conditions, and vary from an aerosol-free, absorption-free model at one end to a model with a very large amount of aerosols and absorption by ozone, water vapor and oxygen at the other. These models are assumed to rest on a ground obeying Lambert's law of reflection.Discussion of results is confined to variations of the aforementioned colorimetric parameters as a function of the zenith angle of observation in a vertical plane passing through the sun and the observer, but for several positions of the sun, and for several atmospheric conditions. For a few selected cases, results obtained after including all orders of scattering are compared with those obtained after consideration of the first scattering of the incoming solar, and outgoing ground-reflected radiation.The main features of the sunlit sky for various cloud free atmospheric conditions and for various sun's positions are, qualitatively speaking, well-reproduced by the model calculations. Attention is drawn to the need for a detailed comparison of the colorimetric measurements taken simultaneously with the observations of various atmospheric parameters of crucial importance, and computations carried out with the input parameters representative of the experimental conditions; and also to the need for including absorption by other gases and sphericity of the earth-atmosphere system in future modeling studies.     

Smoke concentration in the greater Cairo atmosphere

A study of smoke content of the atmosphere over the Greater Cairo area was conducted during the 12 months from June 1977 to May 1978. Smoke samples were taken continuously over two-hour periods at two sites, one in Shubra El-Kheima industrial sector on the northern boundary of the study area and the other in a purely residential district about 15 km south-south-west of the first site.A comparison was made between the averaged concentrations at both sites. It was found that the industrial area was considerably higher in smoke contamination and that industrial activity is the principal source of smoke in the Cairo atmosphere.Daily and yearly cycles of smoke concentration were also studied and discussed in terms of man-made source activities and meteorological conditions. Concentrations were found to be much higher in the cold months. The daily cycle rhythm was the same at the two sites, having two well developed maxima in the morning and late evening and a pronounced minimum in the mid-afternoon. Daily maxima were almost of the same order of magnitude in each site. The morning maximum seemed to be formed by fumigation just after sunrise in the industrial sector and appeared two hours later in the downwind residential district.No significant difference was found between smoke concentrations during weekdays and weekends.     

Ubiquity of bisphenol A in the atmosphere

Bisphenol A (BPA) is a suspected endocrine disruptor in the environment. However, little is known about its distribution and transport in the atmosphere. Here, the concentrations of BPA in the atmospheric aerosols from urban, rural, marine, and the polar regions were measured using solvent extraction/derivatization and gas chromatography/mass spectrometry technique. The concentrations of BPA (1-17,400 pg m⁻³) ranged over 4 orders of magnitude in the world with a declining trend from the continent (except for the Antarctica) to remote sites. A positive correlation was found between BPA and 1,3,5-triphenylbenzene, a tracer for plastic burning, in urban regions, indicating that the open burning of plastics in domestic waste should be a significant emission source of atmospheric BPA. Our results suggest that the ubiquity of BPA in the atmosphere may raise a requirement for the evaluation of health effects of BPA in order to control its emission sources, for example, from plastic burning.     

Sampling of carbonaceous particles in the atmosphere

A method for measurement of atmospheric carbonaceous particulate matter is proposed and evaluated. A diffusion denuder, placed ahead of a filter, is used to exclude vapor-phase organic compounds which might be retained by adsorption on the filter. The carbonaceous material lost by volatilization from the filter after collection is retained with a fluidized bed of powdered Al₂O₃. The efficiencies of the denuder and Al₂O₃ were evaluated with vapor phase phenanthrene and octadecane. Atmospheric sampling was done at two urban and one background site in California using the proposed technique in parallel with conventional hi-vol and dichotomous samplers. Hi-vol samples appear to have lost up to half of the particle phase carbon during sampling. About half this error could be eliminated by sampling at low face velocity. The effects of face velocity appear to distort the proportions of fine and coarse particulate carbon obtained with a dichotomous sampler.     

Volatile organic compounds in the atmosphere of forests

The procedure of sampling and gas chromatographic-mass spectrometric analysis of air containing volatile emissions from living plants has been elaborated. The qualitative composition of volatile organic compounds (VOC) produced by 22 species of plants which are characteristic for Northern hemisphere forests has been studied. The emission rate of isoprene and terpenes for some of them has been determined. Terpene concentrations in coniferous forests of different regions of the U.S.S.R. have been also determined. The list of compounds identified includes more than 70 substances of different classes. Total terpene concentrations in the coniferous forests air usually vary from 3.5 to 35 μg⁻³. Strong influence of meteorological conditions on the emission rate and terpene concentrations in the air under the forest canopy has been noted.     

Ammonia and ammonium concentrations in the antarctic atmosphere

Concentrations of gaseous ammonia and particulate ammonium ion were determined at the South Pole and near Lake Vanda in the Wright Valley, Victoria Land, during November–December 1980. Ammonia gas concentrations which ranged from less than 0.01 to ~ 0.03 μg m ⁻³ (S.T.P.) represented a small fraction of the total (gas plus partiulate) ammonia. At the South Pole the particulate sulphate was apparently nearly fully neutralized by ammonium whereas in the Wright Valley there was evidence of a greater maritime component and a smaller fraction of ammonium in the aerosol. The presence of ammonia in the South Polar atmosphere indicates tropospheric transport of particles observed at the South Pole in the southern summer.     

Evolution of vehicle exhaust particles in the atmosphere

Aerosol mass spectrometer (AMS) measurements are used to characterize the evolution of exhaust particulate matter (PM) properties near and downwind of vehicle sources. The AMS provides time-resolved chemically speciated mass loadings and mass-weighted size distributions of nonrefractory PM smaller than 1 microm (NRPM1). Source measurements of aircraft PM show that black carbon particles inhibit nucleation by serving as condensation sinks for the volatile and semi-volatile exhaust gases. Real-world source measurements of ground vehicle PM are obtained by deploying an AMS aboard a mobile laboratory. Characteristic features of the exhaust PM chemical composition and size distribution are discussed. PM mass and number concentrations are used with above-background gas-phase carbon dioxide (CO2) concentrations to calculate on-road emission factors for individual vehicles. Highly variable ratios between particle number and mass concentrations are observed for individual vehicles. NRPM1 mass emission factors measured for on-road diesel vehicles are approximately 50% lower than those from dynamometer studies. Factor analysis of AMS data (FA-AMS) is applied for the first time to map variations in exhaust PM mass downwind of a highway. In this study, above-background vehicle PM concentrations are highest close to the highway and decrease by a factor of 2 by 200 m away from the highway. Comparison with the gas-phase CO2 concentrations indicates that these vehicle PM mass gradients are largely driven by dilution. Secondary aerosol species do not show a similar gradient in absolute mass concentrations; thus, their relative contribution to total ambient PM mass concentrations increases as a function of distance from the highway. FA-AMS of single particle and ensemble data at an urban receptor site shows that condensation of these secondary aerosol species onto vehicle exhaust particles results in spatial and temporal evolution of the size and composition of vehicle exhaust PM on urban and regional scales.     

Temperature dependence of PCBs in the UK atmosphere

A thermodynamic approach was taken to assess the state of equilibrium between air and the Earth’s surface for PCBs at a variety of sites located in urban and rural areas. The Clausius–Clapeyron equation was applied to atmospheric PCB data, relating PCB partial vapour pressure (ln P) to inverse temperature (1/K); essentially representing the temperature controlled transition between condensed phases and the atmospheric gas phase. The slopes of the resulting plots ranged from −3100 to −8272 for a range of congeners at two city sites, significantly steeper than those generated at two rural locations, where there was little or no correlation between ln P and temperature. It was inferred that advection and variable meteorological conditions mask any localised, temperature dependent, air–surface exchange at these rural locations when weekly or two weekly integrated samples were taken. At a third rural site, close to Lancaster University, an intensive highly time-resolved sampling regime, carried out during very stable meteorological conditions resulted in highly correlated plots (r²>0.6), with slopes ranging from −7151 to −14 148 for different congeners. By reducing meteorological variables in this manner localised temperature controlled air–surface exchange became evident. Enthalpies of phase change generated from the temperature coefficients were similar to literature values for the enthalpy of vapourisation and the enthalpy of phase change from octanol to air. This suggests that, under these stable conditions, equilibrium was achieved as a function of either vapour pressure (P^°_L) or the octanol–air partition coefficient (K_OA).     

Measurement of methyl halides in the marine atmosphere

An analytical method for measuring atmospheric methyl halides was established based on canister sampling and capillary GC/MS. Stability tests for air samples collected in two kinds of canisters (electro-chemical buffing and fused-silica lined) with smooth inner surfaces, showed that both provided stable storage for CH₃Cl, CH₃Br, and CH₃I. The method was applied to the measurement of methyl halides at a remote island (Okinawa, Japan) in August 1996, where nocturnal ozone depletion had been observed in summer. We found that atmospheric CH₃Cl increased during stable nights and was negatively correlated with surface ozone concentration. The highest CH₃Cl concentration amounted to as high as 1400 pptv and indicated that CH₃Cl emitted from the surrounding coastal areas had accumulated in the boundary layer under a stable atmosphere at that time. A positive correlation was observed between CH₃Br and CH₃I, suggesting a common source in the area.     

Secondary organic aerosol importance in the future atmosphere

In order to investigate the secondary organic aerosol (SOA) response to changes in biogenic volatile organic compounds (VOC) emissions in the future atmosphere and how important will SOA be relative to the major anthropogenic aerosol component (sulfate), the global three-dimensional chemistry/transport model TM3 has been used. Emission estimates of biogenic VOC (BVOC) and anthropogenic gases and particles from the literature for the year 2100 have been adopted.According to our present-day model simulations, isoprene oxidation produces 4.6 Tg SOA yr⁻¹, that is less than half of the 12.2 Tg SOA yr⁻¹ formed by the oxidation of other BVOC. In the future, nitrate radicals and ozone become more important than nowadays, but remain minor oxidants for both isoprene and aromatics. SOA produced by isoprene is estimated to almost triple, whereas the production from other BVOC more than triples. The calculated future SOA burden change, from 0.8 Tg at present to 2.0 Tg in the future, is driven by changes in emissions, oxidant levels and pre-existing particles. The non-linearity in SOA formation and the involved chemical and physical feedbacks prohibit the quantitative attribution of the computed changes to the above-mentioned individual factors. In 2100, SOA burden is calculated to exceed that of sulfate, indicating that SOA might become more important than nowadays. These results critically depend on the biogenic emissions and thus are subject to the high uncertainty associated with these emissions estimated due to the insufficient knowledge on plant response to carbon dioxide changes. Nevertheless, they clearly indicate that the change in oxidants and primary aerosol caused by human activities can contribute as much as the change in BVOC emissions to the increase of the biogenic SOA production in the future atmosphere.     

Homogeneous oxidation of sulphur compounds in the atmosphere

Work carried out under the European COST 61a Project on the homogeneous oxidation of sulphur compounds in the atmosphere is briefly reviewed. Mechanisms for sulphur dioxide can be divided into three classes;

• 1.(a) oxidation by free radicals generated photochemically,
• 2.(b) oxidation by intermediates produced in thermal reactions, and
• 3.(c) direct photo-oxidation.

Only (a) makes a substantial contribution to SO₂ oxidation with calculated maximum rates of between 2 and 6% h⁻¹ in sunlight irradiated urban air during summer months and 1–2% h⁻¹ in unpolluted air. Most of the oxidation is brought about by the attack of the OH radical on SO₂ but the contribution of RO₂ radical attack is not well determined due to uncertainties in RO₂ rate constants. H₂S, CH₃SH and (CH₃)₂S react with OH radicals giving atmospheric life-times about 1 day.     

空气中多环芳烃的研究进展

介绍了国内对大气中气态,颗粒态ＰＡＨｓ的研究概况,室内外空气中ＰＡＨｓ污染与城市交通间的相关性,ＰＡＨｓ总量代表物,硝基ＰＡＨｓ及人体接触ＰＡＨｓ的生物指标。