Vertical distributions of COS,CS2, DMS and other sulfur compounds in a loblolly pine forest

Measurements of atmospheric COS, CS₂, DMS, SO₂ and aerosol sulfate and methanesulfonate (MSA) concentrations were conducted in a loblolly pine forest in central Georgia between July and September 1990. The daytime profiles obtained for the reduced sulfur gases (COS, CS₂, DMS) often showed significantly higher concentrations at the canopy level than above the forest canopy, indicating a net emission of these gases from the tree tops. No evidence was found for a net uptake of COS by the canopy during daytime. With one exception, all COS concentrations measured during the day were significantly higher than corresponding nighttime values. These results appear to be in conflict with recent studies suggesting a net uptake of atmospheric COS by plants during photosynthetic activity. Possible explanations for these different findings are discussed. Nighttime profiles indicated no major biosphere-atmosphere exchange of COS, CS₂ or DMS. Nighttime DMS concentrations were significantly higher than corresponding daytime values. A clear inverse relationship between the diel variations of DMS and MSA was observed, consistent with rapid photochemical oxidation of DMS under the given conditions.     

Potential particulate pollution derived from UV-induced degradation of odorous dimethyl sulfide

UV-induced degradation of odorous dimethyl sulfide (DMS) was carried out in a static White cell chamber with UV irradiation. The combination of in situ Fourier transform infrared (FT-IR) spectrometer, gas chromatograph-mass spectrometer (GC-MS), wide-range particle spectrometer (WPS) technique, filter sampling and ion chromatographic (IC) analysis was used to monitor the gaseous and potential particulate products. During 240 min of UV irradiation, the degradation e ciency of DMS attained 20.9%, and partially oxidized sulfur-containing gaseous products, such as sulfur dioxide (SO2), carbonyl sulfide (OCS), dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2) and dimethyl disulfide (DMDS) were identified by in situ FT-IR and GC-MS analysis, respectively. Accompanying with the oxidation of DMS, suspended particles were directly detected to be formed by WPS techniques. These particles were measured mainly in the size range of accumulation mode, and increased their count median diameter throughout the whole removal process. IC analysis of the filter samples revealed that methanesulfonic acid (MSA), sulfuric acid (H2SO4) and other unidentified chemicals accounted for the major non-refractory compositions of these particles. Based on products analysis and possible intermediates formed, the degradation pathways of DMS were proposed as the combination of the O(1D)- and the OH- initiated oxidation mechanisms. A plausible formation mechanism of the suspended particles was also analyzed. It is concluded that UV-induced degradation of odorous DMS is potentially a source of particulate pollutants in the atmosphere.     

The investigation of air quality and acid rain over the Gulf of Mexico

A research cruise was conducted in the summer of 1986 by a group of scientist from the U.S.A. and Mexico to investigate air chemistry over the Gulf of Mexico. Chemical, physical, meteorological and oceanographic measurements were carried out to survey temporal and spatial variations of diverse parameters throughout the Gulf. Emphases were placed on air-sea-land exchange of gases and aerosols, natural air quality, transport of anthropogenic air pollution, and acid rain deposition to the Gulf. Although the prevailing winds were easterly from the sea during the cruise, the air was highly polluted with continental aerosols, probably caused by local shifting winds and the oscillation between sea breeze and land breeze. Aerosol number concentrations were measured from 10⁵ cm⁻³ at ports to 10³ cm⁻³ in the open Gulf. The average aerosol mass concentration was ∼25μg M⁻³, consisting of 60% insoluble crustal particles that contained Si, Al, Fe; 30% seasalt particles that contained Na⁺ and Cl⁻; and 10% anthropogenic sulfate and nitrate particles. Samples of rain water collected near the coast were acidic (pH ∼4). The concentrations of dimethyl sulfide correlated with bio-particle concentrations in surface seawater and could be a significant precursor of atmospheric SO₄²⁻ particles. The life cycles of the aerosols in the Gulf, including sources, transport, transformation, and wet and dry deposition are discussed.     

The near U.V. absorption spectra of dimethyl sulfide,diethyl sulfide and dimethyl disulfide at T=300 K

Absorption cross-sections are reported for dimethyl sulfide (CH₃SCH₃), diethyl sulfide (C₂H₅SC₂H₅), and dimethyl disulfide (CH₃SSCH₃) at wavelengths greater than 200 nm, a temperature of 300 K, and a nominal spectral resolution of 0.10 nm. In general, the results are in good agreement with previous measurements of the spectra of these molecules, but are of higher precision and resolution than past measurements. New features in the spectra, including a previously unobserved vibrational progression for diethyl sulfide, are discussed. Finally, the data are used to calculate a photodissociation lifetime for dimethyl disulfide, the only one of the three molecules that absorbs light in the actinic u.v. region of the spectrum. Loss of dimethyl disulfide by photodissociation is expected to be 5 – 10 times slower than loss due to reaction of the compound with OH under atmospheric conditions.     

Seasonal variation of methanesulfonic acid in precipitation at Amsterdam island in the southern Indian Ocean

A 29-month record of methanesulfonate (MSA) concentration in 103 rainwater samples has been performed at Amsterdam Island in the southern Indian Ocean. Rain water MSA concentrations range from 0.008 to 1.150 μeql⁻¹ with a mean value of 0.187 ± 0.054 μeql⁻¹. A strong seasonal variation in rain water MSA concentration was found with a minimum in winter and a maximum in summer, similar to that observed for atmospheric DMS concentrations measured during the same period. The annual average MSA wet deposition during the studied period was 0.51 μeq m⁻² d⁻¹ which represents roughly 20% of the annual average DMS flux.     

介质阻挡放电降解流动态二甲基二硫废气

采用介质阻挡放电等离子体技术(Dielectric Barrier Discharge,DBD)处理常压下流动态气体中的有机硫恶臭气体二甲基二硫(Dimethyl Disulfide,DMDS).研究了不同停留时间、进气浓度及外施电压条件下DMDS的转化,推导了DBD处理DMDS的动力学模型,并根据傅立叶红外(FT-IR)产物分析探讨了反应机理.研究结果表明,DMDS降解产物主要为CO2、SO2和H2O.在停留时间0.067 s、外施电压7500 V、进气量8.4m3·h-1的条件下,进气浓度为80 mg·m-3 DMDS的降解率达到64.3%,体积降解比量为2.26×10-2L·s-1·W-1,绝对处理量达到430 mg·h-1.     

Microanalysis of the aerosol collected over south-central New Mexico during the alive field experiment,May–December 1989

Thirty-eight size-segregated aerosol samples were collected in the lower troposphere over the high desert of south-central New Mexico, using cascade impactors mounted onboard two research aircraft. Four of these samples were collected in early May, sixteen in mid-July, and the remaining ones in December 1989, during three segments of the ALIVE field initiative. Analytical electron microscope analyses of aerosol deposits and individual particles from these samples were performed to physically and chemically characterize the major particulate species present in the aerosol.Air-mass trajectories arriving at the sampling area in the May program were quite different from those calculated for the July period. In general, the May trajectories showed strong westerly winds, while the July winds were weaker and southerly, consistently passing over or very near the border cities of El Paso, Texas, and Ciudad Juarez, Mexico. Aerosol samples collected during the May period were predominantly fine (0.1–0.5 μm dia.), liquid H₂SO₄ droplets. Samples from the July experiment were comprised mostly of fine, solid (NH₄)₂SO₄ or mostly neutralized sulfate particles. In both sampling periods, numerous other particle classes were observed, including many types with probable terrestrial or anthropogenic sources. The numbers of these particles, however, were small when compared with the sulfates. Composite particle types, including sulfate/crustal and sulfate/carbonaceous, were also found to be present. The major differences in aerosol composition between the May and July samples (i.e. the extensive neutralization of sulfates in the July samples) can be explained by considering the different aerosol transport pathways and the proximity of the July aerosol to the El Paso/Juarez urban plume.Winds during the December experiment were quite variable, and may have contributed to the widely varying aerosol compositions observed in these samples. When the aircraft sampled the El Paso/Juarez urban plume, high concentrations of carbonaceous particles were collected. These C-rich particles were of three distinct types, two of which showed combustion morphologies and the third an irregular morphology. Concurrent aethalometer measurements of aerosol black carbon concentration were well correlated (r = 0.83) with the total carbonaceous particle fraction in the aerosol samples. Carbonaceous particles were not observed in abundance in any of the May or July samples (even when the winds passed over El Paso), and we attribute the high concentrations in December to increased wintertime burning of wood, fossil fuels and other combustibles in the urban area.     

Monsoon cloudwater chemistry on the Arabian Peninsula

The potentially catastrophic environmental consequences of the conflict in Iraq, Kuwait and Saudi Arabia, from mid 1990 to early 1991, have highlighted the need for background atmospheric chemistry measurements for the region. The only known cloudwater chemistry data obtained in the Arabian Peninsula are presented here. The samples were collected near the coast, in the Dhofar region of southern Oman, from 22 to 30 July 1990, immediately prior to the start of the conflict on 2 August. Analysis of the samples for pH, 10 major ion concentrations and 23 trace elements, demonstrates that the cloud water was very clean. Enrichment factor calculations showed the ions have oceanic and crusal origins, whereas trace elements such as B, V, Mn, Ni, Zn, Se, Sr, Mo and Ba have anthropogenic sources. In comparison with three mountain cloudwater sampling sites in eastern North America, the Omani site has higher pH values, higher Na⁺ and Cl⁻ concentrations, and lower SO₄²⁻ and NH₄⁺ concentrations.     

Photochemical production of carbonyl sulfide, carbon disulfide and dimethyl sulfide in a lake water

Photochemical production of carbonyl sulfide(COS),carbon disulfide(CS_2) and dimethyl sulfide(DMS) was intensively studied in the water from the Aohai Lake of Beijing city.The lake water was found to be highly supersaturated with COS,CS_2 and DMS,with their initial concentrations of 0.91 ± 0.073 nmol/L,0.55 ± 0.071 nmol/L and 0.37 ± 0.062 nmol/L,respectively.The evident photochemical production of COS and CS_2 in the lake water under irradiation of 365 nm and 302 nm indicated that photochemical production of them might be the reason for their supersaturation.The similar dependence of wavelength and oxygen for photochemical production of COS,CS_2 and DMS implied that they might be from the same precursors.The water cage effect was found to favor COS production but inhibit CS_2and DMS formation,indicating that COS photochemical production was mainly from direct degradation of the precursors and the formation of CS_2 and DMS needed intermediates via combination of carbon-centered radicals and sulfur-centered radicals.The above assumptions were further confirmed by simulation experiments with addition of carbonyls and amino acids(cysteine and methionine),and the photochemical formation mechanisms for COS,CS_2 and DMS in water were derived from the investigations.     

A diffusion tube survey of NO2 levels in urban areas of the U.K.

A nationwide survey of ambient NO₂ concentrations has been carried out by Warren Spring Laboratory and AEA Technology, Harwell, in urban areas of the U.K. The survey utilised passive diffusion tube samplers, deployed at 363 existing smoke/SO₂ monitoring stations, and ran from July to December 1986.Although undertaken primarily to provide an independent check on the siting of monitoring stations to determine compliance with the European Community NO₂ Directive, the survey provides for the first time a nationwide picture of urban levels of this pollutant. London was found to experience the highest average NO₂ concentrations in the U.K., with these being highest close to busy roads. Concentrations were found to be only moderately higher in winter than in summer.Correlations between measurements of SO₂, smoke and NO₂ were examined. The closest correlation is observed between NO₂ and smoke, indicating traffic to be a dominant source of these pollutants. NO₂ data are also shown to correlate well with disaggregated NO_x emission data for the U.K.     

Studying high ozone concentrations by using the Danish Eulerian model

The long-range transport of air pollutants (LRTAP) over Europe is studied by a mathematical model based on a system of partial differential equations (PDEs). The number of PDEs is equal to the number of species studied and the model contains 35 species at present. Among the species are NO, NO₂, NO₃⁻, HNO₃, NH₃, NH₄⁺, O₃, PAN, SO₂, SO₄²⁻ and may hydrocarbons. Most of the 70 chemical reactions involved in the model are nonlinear (including here many photochemical reactions).The model requires large sets of input data. Emissions of SO₂, NO_x, NH₃ and both natural and anthropogenic volatile organic compounds (VOC) are needed in the model. The meteorological data consist of fields of wind velocities, precipitation, surface temperatures, temperatures of the boundary layer, relative humidities and cloud cover, which are read in the beginning of every 6-h interval. Both daytime and nighttime mixing heights are used in the model.Many of the species in the model vary on a diurnal basis. An investigation of the main mechanisms that determine the diurnal variation of the ozone concentrations is performed. One of the important conditions that is necessary if one wants to represent correctly the diurnal variations of the concentrations is to have access to meteorological data that vary diurnally. This is especially true for the temperature and the mixing height.The use of modern numerical algorithms (which are combined with vectorization of the most time-consuming numerical procedures) allows one to perform long-term runs with the model on several high-speed computers. Results obtained in runs with meteorological data for July 1985 and August–October 1989 are discussed. The computed concentrations and depositions are compared with measurements taken at stations located in different European countries. The agreement between calculated concentrations and measurements is reasonably good.Results obtained with several scenarios, in which the NO_x emission and/or the anthropogenic VOC emissions are varied, are presented. Several main conclusions are drawn by studying the results obtained during the comparisons. Some plans for future development of the models are discussed.     

The spatial distribution and particle size of some inorganic nitrogen,sulphur and chlorine species over the North Sea

The use of filter packs and a cascade impactor during a series of research cruises in the southern area of the North Sea has yielded detailed spatial distribution patterns of aerosol concentrations, Cl⁻, NO₃⁻, SO₄²⁻¹ and NH₄⁺ and gaseous concentrations, HCl, HNO₃ and NH₃. The overall distribution of the atmospheric concentrations closely parallels published modelled results for metallic species. The chemical transformations of these aerosols and gases are investigated together with their interactions with the seasalt aerosol. Aerosol chloride loss is greatest in the more polluted areas, whilst concentrations products of NH₃ with HNO₃ and HCl appear insufficient to sustain the existence of NH₄NO₃ and NH₄Cl. Nitrate is associated predominantly with larger particles and appears to be present substantially as a surface coating on marine aerosol. The total dry deposition input for nitrogen species is calculated for the southern sector with extrapolation to the whole of the North Sea, using particle size weighted deposition velocities of 0.63 and 0.21 cm s⁻¹ for NO₃⁻¹ and NH₄⁺, respectively, and literature-derived values for the gaseous constituents. Finally the use of air-mass back trajectories illustrates the role of source regions in influencing the chemical composition of the North Sea atmosphere.     

Real-time,in situ measurements of atmospheric optical absorption in the visible via photoacoustic spectroscopy—IV. Visibility degradation and aerosol optical properties in Los Angeles

Aerosol light absorption (b_abs) has been measured in real-time in Los Angeles with a validated photoacoustic technique, and its impact on visibility degradation has been examined. These measurements were collected during ten days in the summer of 1987 for the Southern California Air Quality Study (SCAQS). Aerosol b_abs (λ = 514.5 nm) varied from an hourly average value of 7 × 10⁻⁶ m⁻¹ in the 3–4 and 4–5 a.m. periods of 13 July to 9 × 10⁻⁵ m⁻¹ in the 7–8 a.m. period of both 28 August and 3 September. This b_abs, which is due solely to elemental carbon (EC) showed a distinct diurnal pattern with low values at night, increasing around sunrise to higher values through mid-afternoon. Comparison of these data with aerosol light scattering data clearly illustrates that the contribution of aerosol light absorption to visibility degradation increases in importance under less polluted conditions. Other urban and rural studies show similar results.     

臭氧与二甲硫醚和乙烯的反应速率常数测定

在室温和1.01×105 Pa条件下,利用烟雾箱以及气相色谱和臭氧分析仪研究手段,采用绝对方法(准一级反应)获得了臭氧与二甲硫醚(DMS)和乙烯(C2H4)的反应速率常数,分别为:kDMS=(1.48±0.12)×10-20 cm3·molecule-1·s-1;kC2H4=(1.35±0.10)×10-18cm3·molecule-1·s-1.其中,臭氧与乙烯的反应速率常数与文献报道吻合较好,臭氧与DMS的反应速率常数比文献报道的上限值低约两个数量级.     

Proportionality between SO2 emissions and wet SO42− concentrations: The effect of area of averaging

An earlier analysis of empirical associations between SO₂ emissions and wet SO₄²⁻ concentrations in central North America (Hilst and Chapman, 1990, Atmospheric Environment 24A, 1889–1901) showed that local wet SO₄²⁻ concentrations were not proportional to SO₂ emissions averaged over areas up to ∼10⁶ km². Because it is axiomatic that at a global level of averaging a proportionality between total S emissions and S deposition should exist, we have extended these analyses in an attempt to determine whether there is proportionality between S emissions and wet SO₄²⁻ deposition. We have found that for the eastern half of central North America (an area of about 4.3 × 10⁶ km²), the annual average wet SO₄²⁻ concentration exhibits a linear-proportional dependence on anthropogenic SO₂ emissions. However, the internal structure of this association for subareas of the eastern half of central North America suggests the “global” proportionality is achieved by a combination of imported SO₂ from major source areas and an oxidant-limited conversion of SO₂ to SO₄²⁻ within the major source areas. If this inference is even approximately correct, a rollback SO₂ control strategy for the eastern United States and southeast Canada should result in an immediate proportional decrease in wet SO₄²⁻ concentrations in minor SO₂ source areas, but no appreciable reduction of wet SO₄²⁻ concentrations in major SO₂ source areas until the oxidant limitation has been overcome.     

Evaluation of a model for hourly spatial concentration distributions

A time-dependent finite difference model in three levels combined with a puff model to account for subgrid effects close to single sources was used to calculate hour-to-hour concentration distributions. Measurements from several selected stations were used to account from time variation in background concentrations. For each hour, weight was given to observed values in areas that were not influenced by local sources.Results of concentration calculations based on hourly data on emission and dispersion are validated by measured time series of SO₂ and NO_x at five stations. A combination of hourly nephelometer readings and 12-h measurements of small particles at three stations are compared with calculated values.Hourly observed and calculated values from two periods (3 January–15 March 1988 and 18 April–24 June 1988) were used for the evaluation of the model for calculating hourly pollution concentrations in each square kilometre. The results showed that prediction of short-term average concentrations (e.g. hourly data) are usually poorly correlated with observations at the same time and location. Slight displacement errors may cause point-to-point correlation to be poor as a result of errors in input data.The pattern of NO_x concentration variation with time was reproduced well at all stations. A subgrid model taking into account the influence of nearby roads would probably improved the model for NO_x at some stations. For SO₂ and small particles, industrial sources have the dominant influence and the correspondence between observed and calculated values were improved by taking into account spatial uncertainty and an hourly variation in background concentrations.     

Evaluating the influence of air pollution on solar radiation observations over the coastal region of Alicante (Southeastern Spain)

The present study evaluates ground-based downward surface shortwave radiation (R_s) over the coastal region of Alicante (Southeastern Spain). Hourly measurements collected over the eleven-year period 2010-2020 are used. Two weather stations located over the region capital, Alicante, have been selected as representative of urban and suburban typologies. Two additional weather stations far from the city have been selected representing rural typologies. R_s is significantly reduced over the urban station during the morning hours within the winter season compared to the observations recorded over the suburban and rural stations, with a global mean difference of -81 and -120 W/m² at 10 LT, respectively. However, no significant differences are obtained during the midday sun, with a global mean difference of -20 W/m² between the urban and rural stations. With the aim of explaining these differences, the current paper investigates the relationship between R_s and different air pollutants: NO_x, SO₂, and fine particulate matter (PM_2.5 and PM₁₀) as well as the wind field measured at the urban and suburban stations. The results found in this work point towards a close relationship between R_s and NO_x concentrations annual cycles, which are also influenced by the prevailing wind circulations observed over the study area. A global mean NO_x concentration of 107 µg/m³ is observed over the urban station at 10 LT during the winter season. In contrast, these high concentrations are significantly reduced over the suburban station, with global mean value of 40 µg/m³ at 10 LT, for this period of the year.     

Diurnal concentrations of black carbon and some other air pollutants in Ljubljana,Slovenia

We report on measurements from an automated air pollution and meteorological station operating in the city center of Ljubljana, Slovenia. Aerosol black carbon, SO₂, NO and NO₂ were measured continuously on a 30-min timebase. Filter samples integrated over periods of 1–3 days were analysed for total particulate carbon and sulfur species. Large variations of pollutant concentrations were seen, correlating with emission source activity and periods of meteorological stagnation. Correlations between primary (BC) and secondary (S_p) species were seen, suggesting a rapid SO₂ to sulfate conversion mechanism. We discuss the influence of meteorology and primary emission activity on air quality in the city.     

Heterogeneous sulfur conversion in sea-salt aerosol particles: the role of aerosol water content and size distribution

Meteorological and chemical conditions during the July 1988 Bermuda-area sampling appear to have been favorable for conversion of sulfur gases to particulate excess sulfate (XSO₄). Observed average XSO₄ and SO₄ concentrations of 11 and 2.1 nmol m⁻³, respectively, at 15 m a.s.l. in the marine boundary layer (MBL) upwind of Bermuda, indicate that conversion of SO₂ to XSO₄, over and above homogeneous conversion, may be necessary to explain the > 5.0 average molar ratio of XSO₄ to SO₂. Given an observed cloud cover of <15% over the region and the <3 nmol m⁻³ SO₃ concentrations observed by aircraft, heterogeneous conversion mechanisms, in addition to cloud conversion of SO₂, are necessary to explain the observed 11 nmol XSO₄ m⁻³.Aerosol water content, estimated as a function of particle size distribution plus consideration of SO₂ mass transfer for the observed particle size distribution, shows that SO₂ was rapidly transferred to the sea-salt aerosol particles. Assuming that aqueous-phase SO₂ reaction kinetics within the high pH sea-salt aerosol water are controlled by O₃ oxidation, and considering mass-transfer limitations, SO₂ conversion to XSO₄ in the sea-salt aerosol water occurred at rates of approximately 5% h⁻¹ under the low SO₂ concentration, Bermuda-area sampling conditions. All of the 2 nmol XSO₄ m⁻³ associated with sea-salt aerosol particles during low-wind-speed, Bermuda-area sampling can be explained by this conversion mechanism. Higher wind speed, greater aerosol water content and higher SO₂ concentration conditions over the North Atlantic are estimated to generate more than 4 nmol XSO₄ m⁻³ by heterogeneous conversion of SO₂ in sea-salt aerosol particles.     

Infrared absorption spectra and integrated band intensities for gaseous methanesulphonic acid (MSA)

A quantitative analysis of the infrared spectrum of gaseous methanesulphonic acid (MSA, CH₃SO₃H) has been performed in the region of 4100-700 cm⁻¹ using in situ Fourier Transform Infrared Spectroscopy (FTIR). The influence of the temperature and the partial pressure of the diluent gas (N₂) on the measured infrared absorption coefficients and the integrated band intensities was investigated. This study represents the first report of infrared absorption coefficients and integrated band intensities for gaseous MSA.