Modeling of multiphase atmospheric aerosols

This paper presents a mathematical model that describes the chemical composition and growth rate of atmospheric aerosols containing sulfate and nitrate, and that is applicable over the entire range of relative humidities. The model describes aerosols as consisting of an insoluble core, a soluble solid shell and an aqueous film. The chemical composition of the solid and aqueous aerosol phases in this model is governed by the following processes:

• 1.(1) the chemical equilibria between the ambient gas and the aerosol liquid phases and between the aerosol liquid and the soluble solid phases;
• 2.(2) the diffusion-limited condensation of H₂SO₄ and
• 3.(3) the liquid-phase chemical reaction of SO₂. At low humidities the liquid phase may not be thermodynamically viable, in which case the model then treats the solid-phase/gas-phase equilibrium.

Model simulations were conducted to study the effect of ambient relative humidity and gas-phase concentrations on the aerosol chemical composition and growth rate. Results indicate that

• 1.(1) precipitation of (NH₄)₂SO₄ occurs at its point of deliquescence (i.e. at a relative humidity of close to 80%) even in the presence of other electrolytes;
• 2.(2) within the uncertainty of the thermodynamic data, the saturation products of NH₃ and HNO₃ for a liquid-coated aerosol and a dry aerosol are in agreement with each other;
• 3.(3) the aerosol concentrations correspond closely to (NH₄) ₂SO₄ and NH₄NO₃ for both liquid and solid phases, i.e. NH₄HSO₄ is predicted to exist in negligible amounts under most conditions and
• 4.(4) the assumption of either an ideal internal mixture or an external mixture for dry sulfates and nitrate aerosols has little effect on model predictions.

     

Background levels of air and precipitation quality for Europe

This paper is intended to be used by specialists engaged in air and precipitation quality management on regional and continental scales. Major goals are to establish definition, methodology and specific values of background air and precipitation quality for sulfur (S) and nitrogen (N) species to be used in practical applications of air resources management. Major findings are the following:

• 1.(a) 69% of SO₂ and 63 % of NO₂ concentration over Europe originate from continental scale anthropogenic sources,
• 2.(b) 15% of precipitation sulfate and 11% of precipitation nitrate over Europe are contributed by hemispheric background,
• 3.(c) hemispheric background pollution values for Europe were found as 1.25 μg (SO₂-S)m⁻³, 0.80 μg (SO₄²⁻-S)m⁻³, 0.157 mg (SO₄²⁻-S)l⁻¹ and 0.04 mg (NO₃⁻-N)ℓ⁻¹.

     

Development of a MnO2-coated,cylindrical denuder for removing NO2 from atmospheric samples

In order to develop a diffusion denuder for the removal of NO₂ from ambient atmospheric samples, a number of materials were screened for their ability to adsorb NO₂:

• 1.(1) MgO;
• 2.(2) MnO₂ on alpha-Al₂O₃;
• 3.(3) water-treated MnO₂ on alpha-Al₂O₃; and
• 4.(4) MnO₂ (activated).

A simple cylindrical denuder coated with MnO₂ (activated) was very effective in the removal of NO₂ from a feedgas of NO₂ in air at ambient temperature and pressure. The other materials were unsatisfactory. The strong oxidizing properties, along with the hydrated surface of the MnO₂ (activated), appear to be important for the sorption of NO₂, as suggested in applications elsewhere. Quantification of denuder sorption efficiencies indicates that MnO2 (activated) is nearly a perfect sorbent for NO₂. The diffusion coefficient of NO₂ in air was found to be 10.8 ± 0.3 cm² min⁻¹ at 22–23°C, which compares favourably with a theoretical estimate. Although MnO₂ (activated)-coated denuders were also found to adsorb SO₂, interference with NO₂ sorption was not sufficient to impair ambient applications.     

Five years of air chemistry observations in the Canadian Arctic

Arctic air chemistry observations made in Canada between 1979 and 1984 are discussed. The weekly average concentration of 25 aerosol constituents has been measured routinely at three locations. Anthropogenic pollution typified by SO₄²⁻ and V has a persistent seasonal cycle. SO₄²⁻ concentrations are similar at all three locations, although they tend to be somewhat higher at Alert than at Mould Bay and Igloolik. The seasonal variation of an aerosol constituent depends on its source. There are four distinctive seasonal variations for:

• 1.(i) anthropogenic constituents Cr, Cu, Mn, Ni, Pb, Sr, V, Zn, H⁺, NH₄⁺, SO₄²⁻, NO₃⁻,
• 2.(ii) halogens (excepting Cl) Br, I, F,
• 3.(iii) sea salt elements Na, Mg, Cl and
• 4.(iv) soil constituents Al, Ba, Ca, Fe and Ti. In the Arctic winter, the mean concentrations of anthropogenic aerosol constituents, except SO₄²⁻, are 2–4 times lower than annual mean concentrations in southern Sweden near a major source region. SO₄²⁻ concentrations are only 30% lower mainly because of production from SO₂. Light scattering (b_scat) and SO₄²⁻ observations indicate that the SO₄²⁻ fraction of the fine particle mass fluctuates between 3 and 65% during the polluted winter months. Daily mean b_sact, at Mould Bay that exceeds 50 × 10⁻⁶m⁻¹ is associated with air originating from the northwest. The soluble major ion composition of aerosols during winter varies markedly with particle size. H⁺, NH₄⁺ and SO₄²⁻ dominate submicrometre particles while sea-salt ions Mg²⁺, Na⁺ and Cl⁻ predominate in supermicrometre particles. Winter SO₂ concentrations at Mould Bay and Igloolik ranged from 0.2 to 1.5 ppb
• 5.(v). The fraction of airborne S as SO₂ ranged from 20 to 90% and peaked in late December-early January. The concentration of total NO₃⁻ (0.025–0.090 ppb(v)) is much lower than that of SO₄²⁻ (0.3–1.2 ppb (v)).

     

Uncertainties in historical aspects of acid precipitation: Getting it straight

Precipitation chemistry data in North America and their associated uncertainties were reviewed by Hansen and Hidy (1982).¹ Critical comments and corrections of that review are presented here, along with data which indicate that

• 1.(1) acid precipitation may not have been widespread in the eastern United States prior to 1930 and
• 2.(2) precipitation has become more acidified, especially in the midwestern and southeastern U.S. between the 1950s and the present.

The methods used by Hansen and Hidy to assess ‘old alkalinity titrations’ are questionable and they omit data which substantiate the claim that early precipitation samples, although of debatable integrity, generally had pH values greater than 5.6.Analyzing acidity maps for 1955–1956, Hansen and Hidy attribute false assumptions to our methodology of map construction and derive a statistical uncertainty for predicted pH values using an inappropriate set of data. Many of their criticisms of the 1965–1966 map of precipitation acidity by Cogbill and Likens (1974) do not apply to updated versions (Likens and Butler, 1981), which show the same general acidity patterns. We present a new map incorporating wet-only data for 1960–1966 which again supports the general pattern of previously published 1965–1966 maps. Our wet-only and bulk precipitation acidity maps for the 1970s are consistent with more recent wet-only maps using data from NADP and CANSAP networks.Statistical uncertainty of acidity values is assessed, including

• 1.(1) the accuracy of the yearly volume-weighted mean,
• 2.(2) regional among-site variability and
• 3.(3) temporal, among-year variability. For high quality samples, the pooled estimate for these three sources of variability is < 22 μeq ℓ⁻¹ at the 95 % confidence interval. This value represents a convenient test for significant differences temporally or spatially in a region. Given the historical data available, many areas of the eastern U.S. show an increase in acidity of > 22 μeq ℓ⁻¹ during the last three decades.

     

Analysis of observations relevant to long-range transport and deposition of pollutants

Observations of annual wet deposition of sulfur made during 1980 at 62 stations in northeastern America are interpreted using a statistical long-range transport model. This work is meant to demonstrate the role of an empirical model in the analysis of observations. Our analysis points to the following conclusions:

• 1.(1) The parameters that represent the conversion of SO₂ to SO₄ and the wet and dry removal of sulfur are insensitive to concentration levels,
• 2.(2) the variation of the wet deposition field is closely related to the distribution of sulfur emissions and
• 3.(3) observations demand efficient wet scavenging of SO₂.

     

Co-occurrence patterns of gaseous air pollutant pairs at different minimum concentrations in the United States

The frequency of co-occurrences for SO₂NO₂, SO₂/O₃ and O₃/NO₂ at rural and remote monitoring sites in the United States was characterized for the months of May-September for the years 1978–1982. Minimum hourly concentrations of 0.03 and 0.05 ppm of each gas were used as the criteria for defining a ‘co-occurrence’. The objectives of this study were to:

• 1.(1) identify the types of co-occurrence patterns and their frequency;
• 2.(2) identify whether the frequency of hourly simultaneous co-occurrences increased substantially when the minimum concentration was lowered (e.g. from 0.05 to 0.03 ppm) for each pollutant; and
• 3.(3) determine whether the frequency of co-occurrences showed large year-to-year variation.

For all pollutant pairs and co-occurrence thresholds (i.e. 0.03 and 0.05 ppm), the frequency of daily and hourly co-occurrences was low for most sites. Year-to-year variability was found to be insignificant; most of the monitoring sites experienced co-occurrences of any type less than 12% of the 153 days. Based on our observations, researchers attempting to assess the potential effects of SO₂/NO₂, SO₂/O₃ and O₃/NO₂ in the United States should construct simulated exposure regimes so that

• 1.(1) hourly simultaneous and daily simultaneous-only co-occurrences are fairly rare and
• 2.(2) when co-occurrences are present, complex-sequential and sequential-only co-occurrence patterns predominate.

     

Discussion of a lagrangian trajectory model describing long-range transport of oxides of nitrogen,the incorporation of pan in the chemical mechanism,and supporting measurements of pan and nitrate species at rural sites in Ontario,Canada

The derivation of a highly simplified parameterization of NO_x chemistry for use with the AES Lagrangian trajectory model is described. Two versions, both employing essentially independent first-order kinetics are discussed:

• 1.(1) a one step mechanism: NO₂→ inorganic nitrate and
• 2.(2) a somewhat more involved reaction scheme including PAN chemistry.

Evaluation of model performance is attempted with data from the Canadian Air and Precipitation Monitoring Network (APN). It is shown that both model versions are able to reproduce trends of annual and monthly average atmospheric nitrate concentrations, although the models tend to suggest transport over larger distances than is apparent from the field data. The inclusion of PAN chemistry appears to improve the model performance. However, the model predicts a winter maximum and a summer minimum for the annual profile of PAN, and this is in direct contradiction with field measurements of PAN elsewhere. Initial results from a PAN measurement program conducted at three sites in Ontario are also reported and compared with the second model version. Observations for summer 1982 are predicted quite well, but data collected during March 1983 are substantially overpredicted. It is indicated that during periods of rain, PAN constitutes the major oxidized NO_x component. The suggestion is made that this observation is due to a much more efficient precipitation scavenging of nitrate species than of PAN.     

A study of atmospheric acid formation in different environments

The mathematical model presented in this paper describes in detail the gas-phase chemistry (80 reactions), gas-phase/liquid-phase equilibrium (12 equilibria) and liquid-phase chemistry (27 reactions and equilibria) of acid formation. The model is used to simulate acid formation under various conditions:

• 1.(1) nonprecipitating clouds in the Adirondacks,
• 2.(2) raining clouds in the Ohio River valley,
• 3.(3) night-time fog in the Los Angeles basin and
• 4.(4) night-time nonprecipitating clouds in the Los Angeles basin. Model calculations are compared with observed values of sulfate and nitrate formation. The model is used to analyze the relative importance of sulfate and nitrate formation pathways under these various conditions.

     

Total SO2 emission control strategies for the management of air pollution in ulsan industrial complex

Since emission regulations in Korea concentrate mainly on the limitation of pollutant concentration in the stack gas, it is difficult to achieve a desirable air quality in a heavily industralized city like Ulsan. To ensure a suitable air quality in the future, a total emission control method is proposed with a stack height formula of H = 10.6 q^0.5, where H is the stack height (m) and q is the SO₂ emission rate (m³ h⁻¹ reduced to 0°C). The total emission permitted can be allocated to industries

• 1.(1) at an uniform reduction rate,
• 2.(2) by the formula Q = aQ_o^0.925, where Q is the emission allowed (g s⁻¹), a is a constant, and Q_o is the emission before control (g s⁻¹), or
• 3.(3) by using a linear programming technique.

The above three approaches were evaluated using the TCM 2 air quality model. In order to achieve the air quality goal set for the area, the first approach requires 38.7 % reduction of SO₂ emission from industries, the second 53.3 %, and the third 4.3 %. The linear programming method is found to be very economical, but there are some administrative difficulties in enforcement.     

Evidence of ozone injury to a crop plant in India

Evidence is presented to show that a serious leaf spot disease of potato which appeared each year in the Punjab since 1978 is primarily due to ozone:

• 1.(i) The symptoms of the leaf spot were similar to the ozone stipple of potato reported in the U.S.A.
• 2.(ii) Activated charcoal and ethylenediurea effectively controlled the spots.
• 3.(iii) Elevated ozone in the atmosphere was detected with the bioindicators Nicotiana tabacum var. Bel-W3 and potato variety Cherokee. This is the first report of ozone injury to a crop plant in India.

     

Influence of selected fixed parameters on pulse-jet fabric filter operation

The effect of (a) fixing the time interval between cleaning pulses or (b) fixing the maximum pressure drop at which cleaning is started, on the performance of the fabric filter was investigated.A maximum pressure drop value of 2500 Pa:

• 1.(a) minimized the effect of the filter medium resistance;
• 2.(b) reduced the energy consumption by the filter;
• 3.(c) minimized the dust emission from the fabric filter to the surrounding atmosphere.

     

Results from the Total Exposure Assessment Methodology (TEAM) study in selected communities in Northern and Southern California

Volatile organic compound levels (VOCs) in breath, personal air, fixed outdoor air and drinking water samples were measured and compared for a probability sample of individuals in Los Angeles and Antioch/Pittsburg, California during 1984. In addition, comparisons were made between seasons (winter vs spring) in Los Angeles for individuals sampled in both seasons. The statistics presented to compare the sites and seasons were primarily percent measurable and concentration levels (e.g. sample medians). For most comparisons, 13 VOC levels were examined for breath, personal and outdoor air samples and four VOCs for water samples.In addition to the results for VOC levels, the paper also briefly describes

• 1.(i) the sampling procedures used to obtain the study participants
• 2.(ii) the collection of air, breath and water samples
• 3.(iii) selected results from the quality assurance procedures used in this study.

For most chemicals, the percent measurable and concentration levels were

• 1.(i) higher in personal air samples than in breath or outdoor air samples,
• 2.(ii) higher in Los Angeles in the winter for air and breath than in the, spring,
• 3.(iii) higher in Los Angeles for air and breath than in Antioch/Pittsburg,
• 4.(iv) quite different for water as compared with air and breath.

Ubiquitous compounds in water were chloroform, bromodichloromethane, dibromochloromethane and bromoform while in air and breath they were 1,1,1-trichloroethane, benzene, tetrachloroethylene, ethylbenzene and the xylenes.Concentrations were higher in

• 1.(i) outdoor air vs breath in the winter in Los Angeles (where outdoor air levels were much higher than in the spring),
• 2.(ii) in personal air vs outdoor air in the upper tails of the concentration distribution (90th percentile) compared to the 50th percentile. For the water samples, relatively high concentrations were noted for chloroform, bromodichloromethane and dibromochloromethane.

In most cases, water concentrations were higher for Los Angeles in the spring. Five VOCs known to be in tobacco smoke (benzene, styrene, ethylbenzene and the xylenes) had significantly higher levels in the breath of smokers.     

On the nature of nitrate particles in a coastal urban area

Application of micro spot and electron microscopy techniques to individual particles in a coastal urban site revealed the following:

• 1.(a) sulfate particles, some of them mixed, dominated the sub-μm (0.3–0.8 μm) size range;
• 2.(b) nitrates were found mostly in the μm size range, in the form of NaNO₃.

The latter was verified by X-ray analysis of individual nitrates. Apparently the NaNO₃ particles were formed through heterogeneous reaction of gaseous HNO₃ with sea salt particles.     

Effects of air pollutants on agriculture and forestry

Historically, studies of the effects of the main phytotoxic gases (SO₂, O₃, NO_x and HF) have focused on determining the threshold for onset of visible foliar injury. The current U.S.A. air quality standards to protect vegetation (500 ppb SO₂ for 3 h and 120 ppb O₃ for l h not to be exceeded more than once per annum) are good examples of the use of this information in the regulatory process. More recently, research has focused on determining the thresholds for effects on economically important yield parameters irrespective of foliar injury. The implication is that long-term seasonal or annual standards may be required to prevent yield losses particularly for the primary pollutants in diffuse-source regions and for secondary pollutants. This paper reviews the literature on thresholds for yield effects of SO₂ and O₃ and concludes that

• 1.(a) the current EEC standard for SO₂ is adequate to protect most crops and trees and
• 2.(b) more work is required to determine whether the U.S.A. threshold for O₃ effects are applicable to the climate and crops of Europe.

Recent results suggest that yield responses vary so much with climatic factors that broad regional standards may not be acceptable. In addition, the effect of one phytotoxic gas must now be assessed against the background of the other gases.Future research on effects of SO₂ and O₃ in particular, will be increasingly influenced by the use of cost-benefit analysis in the regulating process and the consequent demand for dose-response relationships. This approach is fraught with difficulty and particular problems arise

• 1.(a) when ‘hypothetical’ relationships are assumed in the absence of good data and
• 2.(b) when the linearity of dose-response relationships are presumed to justify the extrapolation from effects at high concentrations to lower ambient concentrations.

The evidence for nutritional effects of low levels of SO₂ and NO_x abrogates this assumption and suggests that for some gases at least, there should be a threshold below which no detrimental effects occur. This paper reviews the recent work aimed at producing dose-response relationships for economically important yield parameters.     

A method for developing ozone exposures that mimic ambient conditions in agricultural areas

Ozone fumigations that mimic ambient ozone distributions facilitate the development of links between

• 1.(1) vegetative effects results that are generated in the laboratory and the field and
• 2.(2) predictive effects models that depend upon ambient air quality data.

Experimental exposure profiles were constructed from a readily available ambient air quality data base (i.e. EPA SAROAD). Air quality data from selected monitoring sites were characterized over the 5-month growing season by identifying

• 1.(a) the number of occurrences of hourly ozone concentrations equal to or above 0.07 ppm,
• 2.(b) the number of days of each episode,
• 3.(c) the number of days between episodes and
• 4.(d) the rate of rise and decline of the daily ozone concentrations.

An episodic profile was constructed incorporating the information into a representative 30-day ozone exposure pattern in which the concentration was changed on an hourly basis. In order to compare treatments having equivalent exposures (sum of hourly ozone concentrations equal to or above a minimum value) but dissimilar temporal distributions of hourly concentrations, a second profile was created. This profile was characterized by a repeated daily incremental rise and decline in ozone concentration that had the same hourly maximum concentration each day. The use of experimental exposure profiles mimicking ambient air quality characteristics and applied under controlled experimental conditions permits the examination of important exposure parameters on plant response.     

Report on a British Council specialist tour to India

This Report describes a tour from 2 to 14 January 1986 in Delhi and New Delhi. The principal objectives were:

• 1.(1) To participate in the Indian Science Congress Meeting.
• 2.(2) To present a paper in the section on ‘Recent advances in numerical modelling of the disperion of atmospheric pollutants’ and make an appraisal of the value of the meeting and suggestions for future meetings.
• 3.(3) Discuss the research programme of the Centre for Advanced Studies in Atmospheric and Fluid Sciences of the Indian Institute of Technology with staff and research students and make recommendations for the future direction and development of this programme.
• 4.(4) Participate in seminars and discussions at the Centre. A general impression of the Indian air pollution scene is also given, and its relationship to past and present situations in other parts of the world is discussed.

     

Condensation of flue gas vapours in ducts and chimneys

The growth of a single dust particle by vapour condensation is derived from Fick's diffusion equation after considering the conditions under which it may be used. The treatment is then extended to a polydisperse dust cloud, allowing for

• 1.(1) a constant cooling rate
• 2.(2) the depletion of the vapour by condensation
• 3.(3) the dependence of droplet vapour pressure on curvature and
• 4.(4) the variation of the diffusion coefficient with droplet size.

The general expression obtained for the radial growth of aerosol particles is suitable for numerical integration by computer, and has been applied to the flue gas of an oil-fired power station in the case when the sulphuric acid dewpoint is reached within the chimney. It is shown that, under typical power station operating conditions, the rate of condensation by heterogeneous nucleation is sufficiently fast to maintain the flue gas in the chimney at a low degree of supersaturation, for which condensation by self-nucleation is unlikely.     

An investigation of the assumptions of linear chemistry and superposition in LRTAP models

Most current LRTAP models assume a linear relationship between sulphur emissions and predicted acidic concentrations, as well as the ability to superpose concentrations from different emission sources. This paper uses a non-linear chemistry model and control scenarios of 50% reductions in S, N and hydrocarbon (HC) emissions to examine the validity of these two assumptions at various downwind receptors. The model predicts that a 50% reduction in S emissions will lead to a 60–65% reduction in SO₂ concentrations and a 25–40% reduction in H₂SO₄ concentrations, depending upon whether or not NO_x and/or HC emissions are reduced by 50% at the same time. The non-linearities in the model predictions are due to complex interactions between NO_x, HC, OH and HO₂. Even when there was non-linearity in the individual S species (SO₂ and SO₄), there was little non-linearity in total airborne S. Adding the results of independent model predictions for different sources (superposition) might introduce errors due to

• 1.(1) chemical interactions between the emissions from the various sources
• 2.(2) overestimates of physical processes such as mixing in of ambient air.

The model was also used to examine trends in regional air quality in eastern North Amierica.     

Precursor relationships,ozone formation and midday meteorology in Sydney

Precursor concentration distributions and the derived relationships which characterize the spatial distribution of emission sources in the Sydney airshed in 1975/6/7 are compared with precursor data obtained during the 1981/2 summer. The 1981/2 data shows that:

• 1.(i) NMHC point sources no longer dominate the character of Sydney's moring time urban air parcels and
• 2.(ii) morning time meteorology and/or overall 6:00–10:00 a.m. mass emission rates have changed, resulting in an increase in the frequency of occurrrence of moderate to high NHMC and NO_x concentration events.

The absence of dominant morning time NMHC point sources balances the increased precursor concentrations and gives rise to a predicted ozone concentration distribution for 1981/2 which is similar to that reported elsewhere for 1975/6/7. The marked reduction in the monitored frequency of occurrence of high ozone events since 1975/6/7 cannot be explained by changes in the characteristics of morningtime air parcels and it is suggested that the observed reduction may be due to a change in the midday (10:00 a.m.–4:00 p.m.) meteorology since 1975/6/7.