concawe report nr. 7/78 atmospheric sulphates: occurrence, formation, fate and measurement- a critical review by Dr. P.C, Blokker NOTE ‘The disconinuity of the page numbering is due to some blank pages that had ‘been normally numbered in the original hard copy but left out of the scanned file in order to reduce the digital file size This report does not necessarily represent the views of any company participating in CONCAWE: Reproduction permitted with due acknowledgement @concawe Den Haag December 1978CONTENTS SOURCES OF SULPHATES AND NITRATES IN THE ATMOSPHERE CONCENTRATION PATTERNS OF SULPHATES IN THE ATNOSPHERE SIZE DISTRIBUTION AND CHEMICAL COMPOSITION OF ‘SULPHATES IN THE A’ SIZE DISTRIBUTION CHEMICAL COMPOSITION ESTIMATED CONCENTRATION OP CAR EXHAUST SULPHATES IN AIR FROM AND PHYSICAL AND PHOTOCHEMICAL OXIDATION OF SULPHUR DIOXIDE OXIDATION OF SO, IN WATER DROPLETS OXIDATION OF SO, ADSORBED TO SOLID PARTICLES OXIDATION OF SO, IN STACK GAS PLUMES NGE TRANSPORT AND REMOVAL OF SULPHUR DIOXIDE FE AEROSOLS INTRODUCTION DISPERSION AND RENOVAL OF SULPHUR DIOXIDE AND AEROSOLS DURING LONG-PANGE TRANSPORT EVIDENCE TOR LONG-RANSE TRANSPORT CONCLUDING REMARKS ANALYSIS OF ATMOSPHERIC SULPHATES TOTAL AEROSOL SULPHU DETERMINATION X-ray fluorescence Reduction and determination as H,S Electron Spectroscopy for Chemical Analysis (BSCA) Direct flame photometric determination page 13 13 14 19 21 31 a1 32 37 39 39 40 40 40 4cone 2 Wy 8.3 oe ew ew TOTAL SOLUBLE SULPHATE DBT! HINATION Gravimetric Wet chemical methods Jon exchange chromatography DETERIINATION OF DIFFERENT SPECIES (SPECIATION) OF ATMOSPHERIC SULPHATES Thermal volatilization Solvent extraction Gas-phase ammonia titration Electrical mobility determination of sulphuric acid by using different humidities Infra-red analysis Complexation-spectrometry for sulphuric acid Electron microscony and related techniques Acid-base indicators Ring-oven technique Field desorption mass spectrometry ‘Thermometric method to determine sulphite and sulphate Gas-chromatographic determination of sulphuric acid after methylation Auxiliary methods to supplement the determination of different sulphate species Oxidation state differentiation of aerosol sulphate by electron spectroscopy (ESCA) Total titratable acidity Ammonium ion determination SIZE DISTRIBUTION MEASUREMENT Multi-stage imnactors Virtual impactor Centrifugal separation Automatic methods for measuring size distribution in situ Light-scattering of visible light Light-scattering of laser light Scintillation - spectral analysis Electrical aerosol analysers Diffusion battery Condensation nuclei counter LITERATURE REFERENCES: page 41 41 41 42 42 43 43 44 44 44 45 45 45 45 45 46 46 47 48 48 48 49 53concawe SUMMARY AND CONCLUSIONS The report reviews published literature on the occurrence, formation, fate and measurement of atmospheric sulphate acrosols. These aerosols may contain considerable amounts of nitrates. Ecological or health effects are not dealt with, In the first sections the sources, concentration pattern, size distribution and chemical composition of airborne sulphates in urban and non-urban areas are reviewed. A separate section deals with estimated local concentration of sulphates from exhaust gases emitted by motor cars equipped with catalytic afterburners. In section 6 the formation of sulphate aerosols in ambient air is discussed. In section 7 a review of long-range transport and natural removal of sulphate aerosols is given. Finally, section 8 reviews the methods of analysis of total sulphates and for different species of sulphates, as well as the methods for determining the particle size distribution of aerosols. Sources of sulphates and nitrates The main sources of sulphates are oxidation of anthropogenic sulphur dioxide and natural hydrogen sulphide, whilst nitrates are formed fron anthropogenic and natural nitrogen oxides (0x). In urban areas anthropogenic sources will generally be by far the most important. The main anthropogenic emissions of sulphur dioxide are from the combustion of coal/residual oil, and smelting the main sources of nitrogen oxides are combustion of coal and petroleum products. The main information on the concentration pattern of airborne sulphates is from the USA. Although urban sulphur dioxide concentrations have generally decreased during the last decade, the urban sulphate concentrations have remained more or less constant, presumably because total sulphur dioxide emissions have increased and the life-time of sulphates is greater than that of sulphur dioxide, Sulphate aerosol formation from sulphur dioxide present in exhaust gases of cars equipped with catalytic afterburners is a new field. The sulphate aerosol concentrations are very low if no catalytic equipment is used, but the percentage of sulphur dioxide oxidized to sulphuric acid may be high if catalytic afterburners are used. Because car exhaust is a low level source, in the first instance not sufficient natural annonia (the ubiquitous gas normally available in the global atmosphere for neutralisation) is available to neutralise sulphuric acid to less harmful sulphate.This has caused some concern, mainly in the USA, because it is possible that in future most cars may be equipped with catalytic exhaust converters intended for emission control of carbon monoxide and hydrocarbons. However, preliminary expertimental results on the sulphate increase in tunnels are reassuring. Size distribution nd, These properties are very important for a good understanding of the formation, transport, transformation and removal processes, and for the evaluation of health effects, Data on the size distribution of sulphate aerosols have gradually become available in recent years, but data on chemical compositions are scarce mainly because of analytical difficulties, The mass median diameter of sulphate aerosols is mostly in the neighbourhood of 0.3 jm, The aerosols are usually a mixture of sulphuric acid, anmonium bisulphate and ammonium sulphate, For the formation of sulphates in the atmosphere two main processes are responsible: photochemical oxidation of sulphur dioxide and oxidation of sulphur dioxide in aqueous droplets in clouds, Limited information is available on the actual rates of oxidation via these routes. Direct photo-oxidation of sulphur dioxide is mostly considered not to be a major factor. Nevertheless, oxidation rates up to about 0.5% per hour have been found in laboratory experiments. Most investigators are of the opinion that in photo-oxidation of sulphur dioxide nitrogen oxides and reactive (generally unsaturated) hydrocarbons play an important role (indirect photo-oxidation of sulphur dioxide), Oxidation rates up to 3% per hour have been found in laboratory experiments, Accordingly, one would expect that a reduction in the emission levels of nitrogen oxides and unsaturated hydrocarbons would also result in a reduction of atmospheric sulphates, but lack of information on the quantitative aspects in the real atmosphere makes any prediction very difficult. In periods with little sunshine and high humidities, particularly with fog and mist, the oxidation of sulphur dioxide in aqueous droplets is considered to be the main process, The oxidation of sulphur dioxide stops when the pi decreases below 2. If sufficient ammonia stemming from biological decay is present in the air, the ammonia will continue to neutralise the sulphuric acid formed, and the oxidation of sulphur dioxide will proceed, Moreover,high humidities, low temperature and the presence of catalytic metal ions (mainly ferric ions) cause a great increase in the oxidation rate.A third possible route for oxidation of SO, may be adsorption of S0z to solid particles followed by formatién of sulphurous acid in the presence of water and partly neutralisation to sulphites, Subsequently, oxidation to sulphates may occur, Little is known of the importance of this route in ambient air. In the plumes of power stations oxidation rates as high as 5% per hour and more have been noted under exceptional weather conditions, such as high humidities and presence of catalytic metal salts. The complicated nature of the reaction mechanism and the great influence of factors, such as humidity, temperature, presence of sunlight and catalysts, make it extremely difficult to make any predictions in actual cases on the rate of oxidation of sulphur dioxide and on the precise nature of the reactio! products forned, Moreover, analytical difficulties in determining the reaction products have hampered progress. In the author's opinion collecting more data is needed on the composition of atmospheric sulphate aerosols under various atmospheric conditions, and of various concentrations of sulphur dioxide, nitrogen oxides and reactive hydrocarbons, to gain a better insight in sulphate formation so as to improve the capability of prediction, Such a phenomenological, statistical approach would, for the time being, be more fruitful than sophisticated studies of the complex reaction mechanisms involved, Long-range transport and removal Conversion of sulphur dioxide to sulphate aerosols has an important influence on long-range transport because the residence time of sulphate aerosols is greater, especially in summer, than that of sulphur dioxide. Moreover, the aerosols are more or less acid, The available information shows considerable evidence of the existence of substantial long-range transport of sulphur compounds, However, the quanitative aspects are not very reliable, For the dispersion and scavenging processes of sulphur dioxide and sulphates reasonable calculations and models are available, but the resulting estimates for long-range transport have a low accuracy. Therefore, the ratio of the annual amount of sulphur deposition in a region caused by "import" and originating from the region itself is uncertain, Analysis An important difficulty in the analysis of airborne sulphate in its various forms is the lack of methods for in situ analysis at ambient concentrations because collection of particles on filters or impactor surfaces has serious limitations.concaw ‘The available analytical techniques, mostly applied to collected samples, are summarize: - For the determination of total sulphates X-ray fluorescence and direct flame photometry are the most attractive methods. The latter is an in situ method, but is still in the development stage. - For total water soluble components many methods exist. The most promising may be flash pyrolysis followed by flame photometric detection. - The determination of different species of sulphate (speciation) is still in the development stage. A short description is given of speciation techniques by thermal volatilisation, solvent extraction, gas phase ammonia titration, electric mobility determination, infrared analysis, electron microscopy, acid-base indicators, ring oven, mass spectometry and a thermometric— and gaschromatographic method. - Finally, auxillary methods to supplement the determination of different sulphate species (state of oxidation of sulphur dioxide, acidity, ammonium ion) and methods for the determination of size distribution are reviewed.concawe INTRODUCTION Atmospheric sulphates have been of growing interest in recent years partly because studies have given preliminary indications that health effects previously associated with sulphur dioxide and particulates were related more strongly to sulphuric acid aerosols and certain other sulphates, and partly because rainfall may sometimes have an acidity, mainly caused by acid sulphate formation, that may produce adverse ecological consequences in vulnerable areas. In this report, the occurrence, formation, long-range transport, physical and chemical properties, and measurement of atmospheric sulphate aerosols will be discussed based on literature information. Effects on human health and ecology, and methods to diminish sulpnate levels in the atmosphere are not dealt with. Atmospheric sulphates are always present in the form of aerosols, defined as suspended solid or liquid particles contained in the atmosphere, The term "suspended" means that the particles are too small in size to have an appreciable falling velocity and may therefore persist in the atmosphere for lengthy periods. Sulphates can include sulphuric acid, acid sulphates (ammonium or metallic bisulphates), ammonium sulphate (also having an acid character), zine ammonium sulphates and neutral metallic sulphates either dissolved in small water droplets or adsorbed to solid particles like soot. In this report atmospheric sulphates will also include sulphites, and moreover sulphur dioxide or sulphur trioxide adsorbed to solid particles, These definitions also include many sulphate compounds which are harmless, such as sodium, potassium, calcium and magnesium sulphates, e.g. present in seaspray. But their presence may seriously interfere with identification and measurement of acid sulphates in the atmosphere, Therefore, in most surveys on ambient air concentrations only sulphate concentrations are given, and in interpreting results it is assumed that sulphate values stem from oxidation of sulphur dioxide or sulphides in the atmosphere, This assumption will be correct if presence of sea drift can be excluded. Furthermore, it should be mentioned that atmospheric sulphates always contain nitrates; sometimes the nitrate concentration is low but at other times 20-50% (expressed on equivalent basis) of the aerosol consists of nitrates.concawe 7 SOURCE OF SULPHATES AND NITRATES IN THE ‘The main sources of sulphates are by oxidation of anthropogenic SO, and of natural H,S. The nitrates which are always present, coe from anthropogenic and natural nitrogenoxides, Robinson and Robbins (1971) made estimates (Table 1) for sulphate and nitrate aerosol production, Similar estimates are reviewed by Rasmussen et al (1975), Table 2 Global sulphate and nitrate aerosol production estimates for the mid-1960's. Source Production 10° tons/year Anthropogenic source sulphate from $0, a7 nitrate from NO/N 30 Natural sources: sulphate from HS 204 nitrate from NO/NO, 432 sulphate from sea salt (our estimate) 140 * Robinson and Robbins estimgted the sea salt aerosol production to be 1900 x 10” tons/year. We assume that 14% of this is sulphate, Only about 10% of the sea salt aerosol will be found on land; moreover, it is harmless because it is neutral. ‘The above division between anthropogenic and natural sources is valid on a global basis. However, in any given area local source conditions, either anthropogenic or natural, will probably dominate, In urban areas anthropogenic sources will generally be by far the most important, However, Hitchcock (1976) shows from sulphate measurements at coastal and inland non-urban sites and urban sites in the Northeastern states of the USA that in summer and fall biogenic sulphate sources contribute most of the sulphate observed in the cities; in some cities this is also the case during other seasons, These,biogenic sources were estimated to contribute up to 6 yg/m or more to the annual geometric mean,The data in Table 1 for anthropogenic sulphates and nitrates stem from the following estimates for 1965: SO, production of 146 x 10° tons/year, of which 70% is cofverted to sulphate. 6 NO/NO, production of 53 x 10° tons/year, of which 42% is conveFted to nitrate. The remaining 30% of SO, and 58% of NO, are estimated to be scavenged from the atmosphere by gaseous absorption, especially by vegetation. Robinson and Robbins (1968, 1969) made estimates (Table 2) for the origin of these anthropogenic emissions: Table 2 World-wide annual emission estimates of sulphur dioxide and nitrogen oxides (as NO,) for the mid-1960's, Source 80, emission | NO, emission 10® tons/yr | 108 tons/yr Coal combustion 102 26.9 Petroleum product: gasoline combustion 0.3 7.5 kerosene combustion 0.2 1.3 distillate oi1 combustion 2.0 3.6 residual 011 combustion 20,3 9.2 petroleum ref, operations 5.7 0.7 Natural gas 2.1 Smetting or others 15.7 1.6 146.2 52.9 The Table shows that SO, from combustion of motor gasoline may be considered as a sulphur source of minor importance, although in areas with a high car density it is giving some concern (section 5).CONCENTRATION PATTERNS OF SULPHATES IN THE ATMOSPHERE Most data in any significant number are available only for total sulphates; therefore, until very recently little reliable information was available on the partition between sulphate salts and sulphuric acid. This is an important drawback in assessing possible air pollution impacts of airborne sulphates. In the natural or unpolluted atmosphere sulphate is a common constituent, These natural sulphates are formed as a result of oxidation processes acting on biological emissions of hydrogen sulphides or organic sulphides. In marine or coastal areas sulphate aerosols are moreover formed by seaspray. Data quoted by Altshuller (1973) from the Air Quality Data from National Air Surveillance Networks in the USA indicate that at Western non-urban stations the annual average sulphate 3 concentrations for the years 1965-1968 ranged from 0.5-5.3 ye/m? and averaged 2.6 ug/m? overall. For Eastern non-urban sites the annual averages ranged from 5.3-14.1 yjg/m? and averaged 8.1 ug/m? overall. In urban areas the annual average concentrations for the years 1964-1968 ranged from 2.4~49 ug/m*, with an overall average of 11.4 g/m?. For Western urban sites the overall average was 6.4 ug/m3 and for Eastern urban sites 13,5 ug/m?, The average annual urban concentrations for the years 1968-1970 (US EPA 1973) ranged from 3-26 ug/m®, with 9-26 g/m? for the Northeastern section of the USA. It is remarkable that in some urban areas concentrations are not higher than concentrations in non-urban areas. Hore detailed recent information on sulphate concentrations in Los Angeles and New York is given by Hidy et al (1978). Urban SO, concentrations in the USA have generally decreased from 1964 to 1970 by between 45 and 55%, while total SO, emissions have increased about 40%. The reason is that the emission data are determined on the basis of national fuel consumption and industrial emissions; hence without any influence of the location of the sources, while the SO, concentration measurements are identified, for the most part, with central urban areas where a consistent decrease of SO, emissions has occurred due to the removal of sources to rural areas as well as by switching to low-sulphur fuels and processes (US EPA 1973). The urban sulphate concentrations in contrast to the 80. concentrations have remained more or less constant durifig the above period although at individual sites and in earlier data from the EPA national monitoring network, good correlations were found between sulphate and SO, concentrations. Altshuller and the EPA have given two possible explanations for this lack of correlation between sulphate and S0, concentrations.The first explanation is that it is assumed that significant amounts of sulphate formed by oxidation of non-urban SO, such as from large power stations, were transported into an urban area The essence of this explanation is that the life-time of sulphates is much higher than that of 80,. The second explanation is tha at the earlier high S0, concentration levels the sulphate concentration had reached a saturation level because of diminished oxidation of S0, to sulphate, This diminished oxidation might be due to two factors: firstly, the presence of an insufficient amount of naturally occurring ammonia and of other alkaline substances in liquid droplets to keep the pil high enough for continued oxidation and, secondly, the presence of insufficient catalytically active solid substances to provide sufficient active area to oxidize adsorbed S0,. These arguments may be better understood after reading the se¢tion on formation of sulphate aerosols. Data on sulphate concentrations in Europe are available from the OECD Study on Long-Range Transport of Air Pollutants (LRTAP summarized by Ottar (1978). Annual mean aerosol sulphate concentrations range from about 10 yg/m3 in rural areas in the Federal Republic of Germany, the Netherlands and the United Kingdom, to 0.5 yg/m? or lower in the remote areas of Northern and Western Europe. More detailed information, including some very limited information from Asia and Africa, is given by Mészdros (1978) Brosset has reported on sulphate concentrations in Sweden during episodes with high concentrations (Brosset 1976 and 1978). The data showed that the total mean sulphate concentration in a rural area was dependent on the wind direction, In the period February ; May 1973 the mean sulphate concentration varied from 9-51 g/m®; during February - March 1975 the highest daily value was about 120 ug/m®, The normal values in this rural area are between 3-13 ug/m?, nence somewhat higher than in Western non- urban stations in the USA, Moreover, data on amounts of sulphates in rain-water in Europe are available, mainly measured by Egnér and Erickson, and Meethan, and sunmarized by de Bary and Junge (1963), The highest concentrations of the so-called excess sulphates (obtained by subtracting the amount of sea salt sulphate from total sulphate were found over the British Isles and in Central Europe. Before 1959 the monthly average concentrations of excess sulphate in precipitation in winter was about 6-7.6 mg/l. In South Scandinavia the excess was about 1,4-2.4 mg/l. The lowest values were found in North Scandinavia (0,.9-2.4 mg/l). Recently data for the mean weighted concentrations of sulphate in precipitation in Norway were published (Semb 1976) for the year: 1972-1974, The average concentration during the year 1973 varied from about 3.5 in the South of Norway to 0.8 in the North, Ottar (1976 and 1978) has given data derived from the OECD programme for the Study of Long-Range Transport of Air Pollution 10The data refer to precipitated sulphate in Southern Norway during two weeks in January 1974, and to the estimated dry deposition pattern for sulphur dioxide and the estimated wet deposition pattern for sulphate for the period December 1973 to March 1975 in Europe, 5 The highest of the latter values were about 4 g/m” {calculated as S0,) for Southern Norway and Scotland, and 6 g/m” for Switzérland. rTcor G2 iGa we SIZE DISTRIBUTION AND CHEMICAL COMPOSITION OF SULPHATES IN THE ATMOSPHERE SIZE DISTRIBUTION ‘The first data on the size distribution of sulphate aerosols were reported by Roesler et al (1965) and Wagman et al (1967), They used Anderson cascade impactors for fractionation in sizes, Median mass diameters of about 0.4 um were found in several urban and suburban areas, The diameters were found to increase with relative humidity, These investigations gave only a rough indication because cascade impactors are not very suitable for size discrimination in the size range below 1 um, the most interesting range from the health and visibility points of view. Ludwig and Robinson (1968) used the Goetz aerosol analyser (see section 8.4.3) for determining the size distribution, an instrument more suitable for determining smaller diameter size distributions than most other instruments available in this period. With this instrument five size fractions ranging from a mean diameter of 9,27 to 1. um were obtained, and an after- filter was used to collect particles with a diameter less than 0.2 um, The mass median diameters for sulphate-containing particles at various sampling sites on the West Coast of the USA varied from 0.2 to 0.4 um (except 1,0 um at a site near the ocean). Tt was found that the diameter increased with relative humidity as can be seen from Table 3. Table 3 Mass median equivalent diameters of sulphur-compound aerosols at different humidities (Ludwig and Robinson 1968) Relative humidity Unweighted average mass median equivalent diameter um 12.5 ~ o.14 27.5 - 0.32 42.5 - 0.27 87.5 - 0.40 72.5 - 0.76 Average mass median equivalent dianete 50% of the sampled mass of sulphur compounds is associated with particles whose equivalent diameters are less than the mass median equivalent diameter.concawe Data on the number size distribution of aerosols in the urban area of Mainz (not necessarily sulphate aerosols) are given by Heintzenberg (1974). The measurements were made with an integrating nephelometer, with the Royco Optical Particle Counter and with a condensation nuclei counter, The number size distributions showed a maximum at about 0.07 um. Whitby et al (1972) and Whitby (1978) discovered that most of the atmospheric aerosol mass of Los Angeles smog is distributed bimodally; the lower mass mode being in the size range 0,1-1,0 yim(geometric mean diameter about 0,3 um), while the upper mode was between 7 and 10 um. The saddle point between the two mass (or volume) modes was between 0.8 and 3 um. Brosset (1976) found a similar distribution in South Sweden with a Royco Particle Counter (section 8.4.4). Whitby and Cantrell (1975) ascribe the coarse particles mainly to natural sources such as soil dust, sea spray, volcanos and plant particles, and the fine particles to anthrozogenic sources. A group of still finer particles (with a particle diameter of about 0.01 wm or smaller, hence in the Aitken nuclei or transient nuclei range) stem from photochemical nucleation, condensation and coagulation processes (Husar et al 1972). The size spectrum determination of these very tine particles has become possible only recently, viz. with the electrical aerosol analyser in the diameter range from about 0.004 to 9.5 ym and the diffusion battery in the range of 0.002 to 0.1 um. The concentrations in both cases are measured with a condensation nuclei counter. 4.2 CHENICAL COMPOSITION In the past only data were available for the total amount of aerosol sulphate, the total amount of soluble sulphate and the acidity. For ecological and human health effects the acidity and composition of sulphates are considered to be of much more importance than the mere amounts of total sulphates. The main data on the composition of sulphate aerosols are from Brosset (1975 and 1978) in Sweden. He found that the coarse particles in South Sweden were always neutral or alkaline, and the fine particles neutral or acid. Some of the results obtained are given in Tables 4 and 5 for different episodes. Black episodes involve an increase of fine black narticles, white episodes of colourless particles 14concawe Table 4 Observed mean concentrations of fine and coarse particles and of black particles expressed as ug/m? (Febru; Sampling: impactors. ary - May 1973) Mean concentrat Normal Black White Episode Episode Episode e 7-13 29 48 particles Coarse 15-31 12 24 particles Black 2 16 3 particles Table 5 ns of some ions expressed as equivalent fractions (%) in the water soluble part of fine and coarse particles in samples from Onsala (March - May 1973). Sampling: impactors. Normal Black White Episode Episode Episode 87-82 75 88 3-12 22 2 Fine cr 7-41 4 10 particles fae ° a ° ca 4 8 14 mn,” 46-48 69 65 so" 7-45 29 25 a %0, 2-15 36 18 eet cl 37-91 27 982 ou” o- 3 8 5 a ° 0 ° Hy 5-32 21 15 Later when sampling was improved and counting was carried out by a Royco counter the results summarized in Table 6 were obtained. 18concawe Table 6 Comparison of particle composition during white and black episodes at Onsala, 1975 and 1976 (mean values). Sampling: on FALP filter (Millipore Corporation) Counting: Royeo 220 counter. Black White White Episode Episode | Episode «© ay @) Number of 8 5 13 observations 2 80, 162, 1s2 141 cone. 4 in een? 0, au <2 <2 n mole/ni x “ 54 a mi," 341 243 167 nat oa 24 48 1.9 Cone. Soot 34 8 8 in 3 be/m un 0.034 0.009 o.o11 () and (£) are western and eastern wind respectively. (C) = Continental air, Some of the conclusions of the author can be summarized as follows: - During black and white episodes the concentrations of fine particles are increased. - Black episodes are accompanied by increased concentrations of nitrate, dark components and metals, It is assumed that the Sulphate is formed by catalytic oxidation of 80,, and accompanied by the uptake of Nil. = White episodes are accompanied by increased acidity and low concentrations of nitrate, darx components and metals. It is assumed that the sulphate is formed by homogenous (e.g. photochemical) oxidation of S0,. For conclusions from the author dealing with the source of these episodes (long-range transport), we refer to section 7.3. 16CONG Eggleton (1969) has given data on the chemical composition of aerosols in the Tees area (England) in summer during days of poor visibility. He found during these days averages of 1.4, 13.9 and 4.8 ug/m3 for particulate acid (as H,S0,), sulphate ion and ammonium ion, respectively; or expressed in fanoequiv./m? 29, 290 and 266, respectively. On a typical misty day very high concentrations were found: 2710 nanoequiv./m of sulphate ion and 1830 nanoequivalent of ammonium ion, Eggleton believes that most of the visibility loss on this day could be ascribed to ammonium sulphate. The precipitation chemistry data from the LRTAP Programme (Ottar 1978) have shown that sulphuric acid is the main acid component in precipitation, However, a relative contribution of 20 to 50% from nitric acid (on an equivalent basis) is often observed. A parameter connected with acidity of sulphate aerosols is the pH of rainwater, several figures having been published on this subject. The lowest values in the period 1962-1966 in Europe were found in the Netherlands, Germany, Belgium, Denmark and South Sweden, ranging from 3.9 - 4.2 (Odén 1976), During this period the minimum pH in Great Britain was 4.9, The acidity problem is amply discussed by Odén; pH maps for Europe between 1965 and 1966 are given. For six stations (two in Norway, four inSweden) the trend of pH is given for the period 1955-19 During this period the pH dropped from about 5.6 - 5.8, with many irregularities, to about 4.5. A correlation between pH and excess sulphates is not always present. A drawback of pH for assessing acidity is that it depends on the buffering capacity of rainwater, Titration of acidity gives much more information, but these data are scarce and only gradually becoming available. Likens (1976) showed that the contribution of sulphate to the ambient acidity of precipitation at Hubbard Brook Forest in New Hampshire (USA) dropped from 83% in 1964-65 to 66% in 1973-74, but the nitrate contribution increased from 15% to 30%, During this period the mean annual pi of precipitation remained about constant at 4,1 but the annual input of hydrogen ion (i" concentration times amount of precipitation) increased 36%, mainly due to the increased amounts of nitric acid. Hydrochloric acid and organic acids were of minor importance, Likens and Borman (1974) remarked that before 1970 much of the SO, was fixed as neutralised sulphate on soot and fly-ash commonly emitted by coal combustion in those years, and precipitated to the land near the combustion source. More recently, with increasing combustion of oil, the heightening of stacks and the installation of particle removing devices, S0, is dispersed over wide areas, and in the absence of sufficfent amount of alkaline substance in the atmosphere, appreciable quantities of SO, are converted to acid leading to low p's or precipitation fa® away from the emission sources. 17ESTIMATED CONCENTRATION OF SULPHATES IN AIR FROM CAR EXHAUST The information given summarizes a review of Robinson (1975). ‘The small amounts of sulphur in gasoline have for a long time not been considered a significant source of urban sulphur oxides. In the USA the total S02 emission in 1970 was estimated as 34 x 106 tons and the S02 emission from gasoline as 0.17 x 10% tons. Hence even in the USA with its high car density the gasoline contribution was only 0.5%, Even in Los Angeles where $0, emissions from stationary sources are relatively low, car-exhaust S02 is only about 14% of the overall community total S0, emissions (Los Angeles County Air Pollution Control District 1971). ‘The above opinion has changed in the USA since 1973 because it was discovered that catalytic exhaust control systems (for reduction of hydrocarbon and CO emissions) convert exhaust gas S80, into the more toxic sulphuric acid aerosols at an appreciable rate, and because of the increased concern about urban sulphate aerosols in general. It is generally believed that part of the 50, oxidized to sulphate aerosol is in the form of HS0,, although thé available analytical techniques allowed only the“determination of total soluble sulphate (eltzer et al 1974, Burkart et al 1974). Hence it can for instance not be excluded that part of the $0, is present as a sulphite aerosol which subsequently may be oxidized on the filter of the sampling instrument, for instance under influence of other particles collected on the filter In non-catalyst systems the sulphate emission is very low (less than 2% of the fuel sulphur is converted to sulphate; Beltzer et al 1974), In catalyst systems the conversion is related to the type of catalyst used and the nature of the vehicle driving cycle, In pelletised oxidation catalytic systems the conversion was found to be between 3 and 11% under 1975 Federal test procedure conditions, and may be between 26 and 36% at a speed of 100 km/h, In monolithic oxidation catalytic equipment the conversion was between 21 and 40% under 1972 Federal test procedure, No experiments were carried out at 100 km/h. Because the sulphate contribution from catalyst=equipped vehicles to ambient sulphate concentrations cannot be measured if the number of cars with such equipment is low, estimates based on models have been made by Robinson (1975) and by Roberts and Friedlander (1974), Robinson uses the APRAC-1A urban diffusion model for CO for heavy traffic conditions in towns and calculations based on lead measurements for Los Angeles freeway conditions, For particulars we refer to Robinson's publication. Robinson assumes that in catalyst-equipped vehicles the conversion of 80, to HyS04 is 30%, that lead-free gasoline contains 0,025% Sulphur and that 25% of the cars is equipped with a catalyst unit. 19Con 1Ge He calculates that under unfavourable wind conditions (wind speed 2m/s) the highest sulphate concentration inside a car is 6.0 vg 80, /m3, For Los Angeles freeway driving during rush hours an average of about 4 ug SO,/m® was calculated. For area- wide average sulphates in Pasadena (Southern California) the sulphate increment due to car-exhaust would be 0.2 yjg/m® at a level of 20 ug/m? without conversion. Calculations by Roberts and Friedlander (1974) give an increment of 4 yig/m*, but they use a conversion of 50%, sulphur content of 0.075% and 100% converter-equipped cars, Robinson remarks that peak- or short- time levels have not been estimated because any sulphate hazard is more likely to be a chronic situation from repeated exposure, The author states that under calm conditions an increase in concentration by a factor of 5 is possible. Recently Pierson et al (1978) have investigated sulphate emissions from vehicles in two tunnels. It was estimated that in 1976, 28% of the gasoline consumed was by catalyst-equipped automobiles. The sulphate contributed by vehicles even in the tunnels was found to be generally modest relative to rural ambient sulphate levels, Sulphate emission from automobiles was far less than that from Diesel trucks.FORWATION OF SULPHATE AEROSOLS ARACTERISTICS AND PHYSICAL AND CHEMICAL Little detailed knowledge is available on the oxidation of SO, to sulphates in the atmosphere. This makes it difficult to predict the rate of sulphate formation in practice, and the physical and chemical characteristics of the sulphates formed. This in turn hampers the assessment of health and ecological effects which are dependent on properties such as acidity and particle size. ‘Three major types of sulphate formation by oxidation of SO, may be distinguished, viz. a, photochemical oxidation (gas phase) b. oxidation of S0, dissolved in water droplets (gas-liquid) ©. oxidation of 80, adsorbed to solid particles (gas-solid) The complicated nature of these reaction mechanisms and the great influence of many factors on one or more of these reactions (such as humidity, temperature, sunlight, presence of various compounds, including catalysts) make it.extremely difficult to ascertain the contribution of each of these factors to the formation of an aerosol that has been collected, or to predict the way and rate of formation in the atmosphere, The difficulties in analysing an aerosol once formed in detail (often called "speciation") has moreover hampered thorough investigations in most cases, Until very recently almost all the sulphate data in existence were for the anion alone, while important properties of sulphates - such as water solubility, particle size distribution, acidity and toxicity - depend on the molecular composition and not on the anion alone. Even if the aerosols are analysed in detail, the changes in the aerosol that may occur when they are collected on filters (reaction with filter material, oxidation) may give a wrong picture. Determination of airborne sulphate in situ, hence without collection by filter or impaction, is not yet practical due to insufficient selectivity or sensitivity (or both) of existing methods. There is a clear need for improved sulphate speciation because it can lead not only to a better knowledge of important properties mentioned above but also to a better understanding of generation, transportation and removal processes which determine the identity and concentration in the atmosphere, The present situation is that in relatively simple models for reaction mechanisms (Beilke et al 1975) large discrepancies, up to two ordersof magnitude, occur and therefore the statement of Beilke for homogeneous systems that there is little hope of being able to predict the complicated formation of sulphate in the real atmosphere with any reasonable success is a very realistic one, Of course, studies of actual kinetics of sulphur reactions are very interesting and needed from the academic point of view and basic information has already been obtained from it. a1Conca Wwe However, for the practical purpose of being able to predict sulphate formation in specific cases, it seems more fruitful for the time being to follow a different route. This route could be to ascertain how much and what kind of sulphates (composition size distribution) are formed under various atmospheric conditions and how dispersion takes place. For such a phenomenological, statistical approach much more data should be made available because of the great number of parameters that may influence aerosol formation such as temperature, humidity, light intensity, type and amounts of catalysts (metals, ammonia) source and amount of SO, emission (exhaust from oil- or coa: burning, car-exhaust, natural sources). It may be mentioned here that from OECD S0,-enission data for Europe and measured SO, and sulphate concéntrations at several sampling sites, the estimated rate of transformation of $0, to sulphate varied between 0.3 - 1.7% per hour, with a mean of 0.8% per hour. This is an order Of magnitude smaller than the estimated rate of decay of $0, (mainly by dry deposition) which varied from 2.6 - 14% per hour with a mean of 7.9%, corresponding to a residence time (time of conversion by 50%) of about half a day (Eliassen and Saltbones 1975). Alkezweeny and Powell (1977) have reviewed oxidation rates mainly based on EPA reports from Levy et al (1976). They imply that the transformation rate of $0, to sulphate can be anywhere from 2 ~ 20% per hour. a It was mentioned before that sulphate aerosols always contain nitrates, Harker et al (1977) disclose that data from two stud the Aerosol Characterisation Study by Hidy in 1974 and a power station plume study by Richardson in 1975, showed that in a number of instances there was an inverse relationship between the levels of sulphate and nitrate in particulate samples. For this reason Harker et al carried out experiments on the levels of these constituents in aerosols photochemically formed in an irradiation chamber, It was observed that sulphate formation in the presence of $0, decreased the anount of nitrates formed in the aerosol significantly below that observed in the absence of S0,. According to the investigators, these and other observations indicate that the sulphuric acid formed releases NO, from the surface of the aerosol particles, probably in the form of nitric acid. Although a rather pessimistic view is taken here on the value of detailed study of kinetics for the near future, a brief survey will be given on the main knowledge of the different types of sulphate formation mentioned before. PHOTOCHEMICAL OXIDATION OF SULPHUR DIOXIDE In several laboratory experiments it has been demonstrated that aerosols can be formed by irradiation of mixtures of higher molecular weight hydrocarbons (especially unsaturated ones) and nitrogen oxides. 22we Originally, it was assumed that the well-known smog formation in California was due to this mechanism, Although it can not be ruled out that this mechanism plays some role, it is now generally believed that SO, is a main factor in aerosol formation. Direct photo-oxidation of SO, in sunlight to S0,, followed by formation of a sulphuric acid aerosol in the présence of water vapour, does not seem to be a major factor because in laboratory experiments with very pure air conversion rates of only abt. 0.1% per hour were found (Renzetti and Doyle 1960, Urone et al 1968, Mészdros 1973), In later experiments Smith and Urone (1974) found rates of 0.25 - 0.55%/n, Sidebottom et al (1972) estimated the theoretical maximum rate at 1.9%/n. Cox and Penkett (1970) found conversion rates up to 0.65%/h in laboratory experiments, but they do not exclude the influence of trace impurities such as nitrogen oxides and olefinic hydrocarbons. Later experiments (Cox and Penkett 1971a) gave experimental evidence that low concentrations of nitric oxide and olefinic hydrocarbons can strongly influence the rate of photo-oxidation of S0g (indirect photo-oxidation) .They conclude that the reaction rate of 0.65% per hour is more appropriate to the atmospheric situation than the earlier generally accepted values of 0.1 - 0.2% per hour They even calculate that in the atmosphere of London in cases where the concentration of nitrogen oxide would be 0.03 nom and the concentration of reactive hydrocarbons 0.1 ppm, an oxidation rate of 80, of 10% per hour could be expected. Further, it may be mentioned that Becker et al (1973) found SO. removal rates by homogeneous gas phase oxidation of 0.1 - 3% pér hour in laboratory experiments and that Clark et al (1976) found rates ranging from 0.55 - 1.3% per hour in ambient air near a freeway in California, The nature of the oxidant(s) responsible for the oxidation of 80, was not established by Cox and Penkett, At low concentrations ozone does not react rapidly with 80,, but such species as peroxy radicals or peroxy acyl nitrates forfied by complex reactions between ozone, NO and olefins presumably are the oxidants that oxidize $0,. It is interesting that in later experiments by Cox amd Penkett (971b) large amounts of aerosol were produced when SO, was added to a mixture of ozone and olefins (hence without irradiation). The formation pattern was similar to aerosols produced photochemically from NO and olefins. Also, Nészdros (1973) says, basing his opinion on atmospheric analysis and literature data, that in addition to NO, and 0 further atmospheric trace constituents are necessary@tor thé explanation of photochemical sulphate formation in the atmosphere. 23conceal He refers to Cadle (1972) who proposes that these constituents are reactive hydrocarbons, especially olefins, which play an important part not only in photochemical smogs but also in the free atmosphere, These hydrocarbons might be, for example, terpenes and a-pinene formed by the exhalation of plants. Eggleton and Cox (1978) have reviewed the work on homogeneous oxidation carried out under the European COST Project 61A (Research into the physico-chemical behaviour of 80, in the atmosphere) just completed, It is concluded that homogeneous oxidation of SO, by photochemically initiated free radical reactions is significant for conversion of 80, to sulphate in the lower atmosphere. In the Western Europeai summer, SO, oxidation rates are expected to be between 0.5 and 5% per hour depending on the degree of pollution of the atmosphere, with the lower figure relating to clean air. In winter time, rates in sunlight are expected to be a factor of 2 lower, and due to the reduced hours of sunlight, the overall removal rate of SO by photochemical reactions is lower by an even greater amount. Further a theoretical evaluation of existing kinetic data related to the homogeneous reactions of $0, within the troposphere is given by Calvert et al (1978). From the above it is clear that nitrogen oxides and reactive hydrocarbons have a significant impact on photochemical oxidation of sulphur dioxide. Accordingly, one would expect that a reduction in the emission levels of these two precursors would also result in a reduction of atmospheric sulphates, but the lack of information on the quantitative aspects in the real atmosphere makes it extremely difficult to make any predictions on the effect of such reductions. Collection of data on sulphate acrosol formation during sunny periods in regions with relatively high sulphur dioxide concentrations but with different concentrations of nitrogen oxides and reactive hydrocarbons, might provide more quantitative information. Tae physical aspects of acrosol formation, such as nuclei generation and growth of aerosols, has been the subject of severa theoretical and experimental investigations, Based on laboratory and field measurements, Husar et al (1972), and Husar and Whitby (1973) assume that the photochemical reaction produces first a great number of nuclei. Then coagulation and condensation occurs while the process of generation of new nuclei continues. In the initial stages the aerosol formed consists of 80, which may be partially neutralised by atmospheric NH, and sofid‘alkaline particles if present. Junge and Abel (1965) carried out calculations of the change in aerosol size distribution as a result of coagulation processes, They predict that the concentration of particles larger than 0,1 jim change very little whereas particles less than 0,01 um radius disappear almost completely in 12 hours. A summary of the results of the calculations is given by Robinson and Robbins (1971).ve Conca Goetz and Pueschl (1967) are of the opinion, based on laboratory experiments, that particle formation occurs largely by chemical reactions at the surfaces of previously existing airborne particles serving as reaction centres. Other theoretical and experimental investigations on nuclear generation and growth of mainly sulphuric acid aerosols that may be mentioned are from Coutarel et al (1967), Wadden et al (1974), Smith et al (1975), Takahaski et al (1975), Nair and Vohra (1975), Carabine and Maddock (1976), Middleton and Kiang (1978), Friedlander (1978). These papers will not be discussed here as they seem, for the time being, to contribute little to the practical aspects of aerosol formation in the atmosphere. 6.2 OXIDATION OF SO, IN WATER DROPLETS In the atmosphere this process involves dissolving of SO, in water droplets which may be present in clouds or fog, followed by the formation of sulphite which is oxidized by air and partly neutralised by ammonia or metal oxides In several investigations the oxidation of $0, in pure water and the influence of NH, and heavy metal ions on’this process have been studied becausé these compounds are commonly found in the atmosphere. Nearly all these investigations suffer from the fact that because of experimental difficulties systems were studied that differ greatly from actual atmospheric conditions such as - one-phase systems instead of the two-phase system water droplets/airje.g. Brimblecombe and Spedding (1974); - two-phase systems but with air as the disperse phase, hence an air-water transfer different from that in the real atmosphere; e.g. Junge and Ryan (1958); - two-phase systems with water droplets, hence more realistic, but with concentrations of SO, and metal ions that are orders of magnitude higher than normally found in clouds; e.g. Johnstone and Coughanowr (1958). Therefore, Barrie and Georgii (1976) tried to improve this situation by exposing droplets (diam. ca. 2 mm) containing cloud- like concentrations (<10-4 M) of heavy metal ions to cloud-like concentrations (0.01-1 ppm) of SO, in air, and measuring the conversion of S0, to sulphate, It was found in agreement with former investigations that janganese and iron ions are effective catalysts for $0, oxidation in acidic solutions but copper ions not, in contradictYon to the results obtained by Junge and Ryan (1958), In agreement with all former investigators Barrie and Georgii found that the rate of 80, oxidation decreased with decreasing pitconcawe They made the following quantitative estimate of the rate of SO, oxidation in a typical urban cloud. Calculation rate of 80, remoyal (% h”')_, by a cloud of liquid water content 071 gm ‘and SO, conéentration 20 ppb and 1000 ppb as a function of tempeature and cloud water composition Cloud water composition 5s sinca + Temperature 20 UM Meh ° 5 ey 107° ner, 20 ppb 1000 ppb 25 0.81 0.26 2.2 0.88 8 0.81 0.026 2.2 0.88 The above concentrations of dissolved manganese- and iron salts correspond roughly with commonly, found amounts in urban aerosols (abt 0.2 ug Mn and 1 ug Fe per m3) (Lee and von Lehmden 1973, Georgii et al 1974). ‘The rates of sulphate formation for the MnCl, + FeCl, composition and the SO, concentrations,in the above Tablé are eqilivalent to 18 and 350°ug SO," per cm per hour for 20 and 1000 ppb of S0,, respectively, If*these rates are compared with actual concentrations in cloud water in polluted air in the USSR, viz. 20 - 150 jig SO, per cn®, it would mean that these concentrations could be achieved in 1-8 hours in an urban air cloud and in 3-26 min, in very polluted air near a source, Other parameters in catalytic oxidation of SO, in clouds are Ni concentration, temperature and humidity. he influence of NH, was studied by Junge and Ryan (1958), Nearly all atmospheric NH, stems from biological decay. The amounts are so great that*in the long run sufficient NH, is available in the ambient atmosphere to neutralise most af the sulphuric acid formed by oxidation of $0,. Robinson and Robbins (1968, 1969) give the following estimates for global emissions of pollutants that are of interest for acid aerosols: tgs + natura, + 100 x 208 tons, anthropogente : 3 x 10% tons Nig : natural :1160 x 10° tons, anthropogenic : 8 x 106 tons O°: natural £430 % 10 tons, anthropogente / 53 x 10° tons) No (NO, included) 2: natural ; 658 x 10° tons. 26COnGcalwe ‘The estimated atmospheric background concentrations are: NH: 6-20 ppb; SO,: 0.2 ppb; NO: 0,2-2 ppb; NO, : 0.5-4 ppb. However NH, concentrations are very variable in both space and time, Marifime air at altitudes above 1 km may contain very low NH, concentrations and this may explain the existence of acid subphates as a dominant atmospheric aerosol (Ngar-Cheung Lau and Charison R.J. 1977). After the investigations by Junge and Ryan, the influence of Ni on sulphate formation has been studied by many investigators such as Van den Heuvel and Mason (1963), Robinson and Robbins (1969), MeKay (1971), Miller and de Pena (1972), Beilke et al (1975), Freiberg (1976a). It is generally accepted that at low pli's (below pl ca. 2.0 80, is practically not oxidized notwithstanding the presence of metal catalysts, but that atmospheric NH, keeps the pil of the water droplets sufficiently high during the formation of 4,80, from $0, to allow $0, oxidation to continue The limiting steps in the oxidation are considered to be mainly solubility effects due to the pH and the reaction rate between NH, and 5 gas phase, , and not diffusion and transport processes in the Beilke et al (1975) and Beilke and Gravenhorst (1978) found that the oxidation rate of 80, in water in the absence of metal catalysts was approximately inversely proportional to the square of the hydrogen ion concentration. They estimated that for typical atmospheric clouds (cloud liquid water content in the order of 1 g/m3) the empirical results lead to oxidation rates varying from 10-> to 15% as the pH of the droplets vary from 3 to 6, Therefore, they state that unless the pH of the droplets is unusually high, excessively long times are expected to be necessary for effective oxidation in the absence of catalysts. They find it more likely that the large amount of Sulphate found in the atmosphere is a result of reactions of SO, with oxygen in the presence of catalysts or with other more strongly oxidizing agents such as dissolved ozone. Also Larson and Harrison (1977) are of the opinion that ozone may contribute importantly to the production of acid sulphates. in the atmosphere, With respect to the influence of temperature, the authors found that the influence of temperature on the rate of conversion of SO, to sulphate could be neglected. However, in a discussion paper Freiberg (1976b) points out that because the experiments were carried out in buffered solutions of Na citrate - NaOH or Na citrate - HCl, this conclusion needs not to be valid for the more real ammonia buffered droplets in the atmosphere, 27conca They state that the solubility of NH3 is highly sensitive to ‘the temperature and that on the basis of the presented results one would expect in the atmosphere an oxidation rate inversely proportional to the temperature (also see Freiberg 1974). Beilke et al in the discussion paper agree with this, and mention that a negative temperature coefficient has been confirmed empirically. Haury et al (1978) found little influence of the temperature in laboratory experiments with initial concentrations of 3-5 ng S0g/m% in the presence of up to 15 mg/m? of aerosols made from 0.01 molar MnSO4. However, the experiments were carried out at a constant relative humidity. They further found that the oxidation rate increases with humidity. OXIDATION OF S0g ADSORBED TO SOLID PARTICLES In this process it is assumed that the first step is the adsorption of $0, to solid particles followed by the formation of sulphurous acid in the presence of water, where partly neutralisation to sulphites may occur, and that subsequent oxidation to sulphuric acid and sulphates takes place. It is hot easy to distinguish this pathway from the foregoing category, dissolving of S02 in water immediately followed by oxidation. Only by the new techniques of X-ray photoelectron spectroscopy applied to samples collected with an impactor it was possible to prove the existence of sulphites (Craig et al 1974, Novakov et al 1972). These investigators have shown that sulphite is a significant part of the particulate sulphur fraction of aerosols, especially in the size range of 0.6 to 2 microns. In photochenically active parts of the day in Pasadena, California, it was found by Novakov et al (1972) that the sulphate/sulphite ratio varied between 0.32 and 1.27 for the size class of 0.6-2 \m, and between 1.49 and 1.85 for the size class of 2-5 jim.That S0g adsorption is the dominant initial route is not proven, but it is according to Novakov the most likely process. Part of the adsorbed SO) is then converted to anmoniun sulphate; sometimes it is likely that $0, reacts with calcitin sulphate or gypsum if these are present. Suantitative determination of the importance of various gas- particle reactions in the urban atmosphere must await the collection of more data;moreover, it is very desirable that particles smaller than 0.6 ym are included in the studies. Liberty et al (1978) carried out adsorption and desorption experiments with S02 and different types of dust. Considerable adsorption was found but conversion with urban atmospheric dusts to sulphate at room temperature did not take place to a considerable extent. However high conversion rates were found with alkaline dusts from certain industrial emissions. 28con Cawe Eatough et al (1978) studied the composition of aerosol samples collected from the flue line or stacks of smelters, coal- and oil-fired power plants or collected in New York City. It was found that stable sulphite species may form in aerosols from each of these sources. Oxidation to sulphate was extremely slow. Newnan et al (1975) conclude from their experiments on oxidation of S0, in the plumes of oil and coal-fired stations that the surface area of solid particles plays an important role in the oxidation of $0). Whether sulphite formation occurs was not measured, however. With respect to this section on solid particles, many uncertainties are present. It is not known how much of the solid constituents can dissolve in the aqueous droplets or are converted to soluble salts by means of the sulphuric acid formed. Also little is known on the influence of chemical compositions and particle size distributions on the oxidations of adsorbed S0p in actual practice. OXIDATION OF SO, IN STACK GAS PLUMES With respect to the oxidation mechanism of S0z also the oxidation of SO, in stack gas plunes is of considerable interest. Current US EPA Studies (USEP 1975) and observations by Davis et al (1974) suggest the possibility of homogeneous gas phase reactions in power plant plumes involving nitrogen oxides, It is suggested that S0, oxidation rates are initially inhibited by high concentrations of NO, which is preferentially oxidized, but increase considerably with distance as more ambient air mixes with the plume. However high S0g oxidation rates in field studies of stack plumes have often been attributed to heterogeneous reactions at high relative humidities in either water droplets or film surrounding particles, and in the Presence of certain catalytic metal salts. Gartrell et al (1963), and Stephens and NcCaldin(1971) found that high relative humidity Promotes the oxidation of 50). Over a time period of 1-2 hours the extent of oxidation in Gartrell's experiments was 3% at 70% humidity, 30% at 70% humidity and 60% under mist conditions. In the experiments of Stephens and McCaldin no oxidation was observed at relative humidities below 35%, At a humidity of 40-55% an oxidation rate was noticed of about 15% per hour over a time period of 1-3 hours, and at a humidity of 79% a rate of about 35% over a period of 1 hour. However, analytical difficulties make these results questionable. Further stack plumes contain solid particulates mainly iron oxides, that may partly dissolve as salts in water droplets or may partly be converted to soluble salts by means of sulphuric acid formed. Calculations made by Foster (1969) show that the rates of S0, oxidation observed may be accounted for by the catalytic qualities of the iron present. 29conceal we He suggests that also other oxides present in the effluent dust play an important part in that they react with the sulphuric acid as it is formed, thus keeping the droplets in a neutral condition in which the iron and manganese catalysts are most active. In this way the high reaction rates found by Gartrel et al (1963) could well be explained. From laboratory experiments Barbaray et al (1977) conclude that V,05 contribute: little to the production of atmospheric sulphuric acid below 150°C, but carbon particles do, The latter might be due to the third reaction mechanism, discussed before (section 6.3). Newman et al (1975) have conducted experiments on the oxidation of S0, in the plumes of oil- and coal-fired stations 4 32g /34 using the change of the isotopic ratio 92s/34s during oxidation of S0g to S03. The average conversions found were about 6-14% for the oil-fired plumes and 3-4% for the coal-fired ones, and no correlation with distance, temperature or meteorological conditions, including relative humidity, were noticed. Wilson (1978) however considers the sulphur isotope technique used for part of the experiments to be erroneous and concludes that no difference has been established between oil- and coal- fired plumes and that, depending on conditions, conversion rates of substantially greater than 1% per hour are possible but that accurate measurements of the conversion rate could not be obtained. Based on the recent EPA study, Project MISTT (itidwest Interstate Sulfur Transformation and Transport), Wilson (1978) and Gillani et al (1978) report that the rate of conversion of S02 to sulphate aerosol in power plant plumes is low near the point of emission, but increases to several percent per hour as ambient air mixes with the plume, The rate of conversion varied from 4% to 5% per hour.The major pathway is a honogencous reaction depending on sunlight intensity, humidity, background ozone levels and mixing of the plume with air, Heterogeneous reactions may be important at night, in clouds or other conditions under which liquid droplets exist. There are several quantitative indications that under proper conditions the conversion rates due to heterogencous reactions may be significantly greater than 5% per hour. Lusis and Wiebe (1976) present results of experiments on the rate of formation of sulphates from $0) in the plume of a stack at a nickel smelter, Oxidation rates were generally less than 3% per hour (average about 1% per hour). No temperature or humidity effects could be detected. 30a We LONG-RANGE TRANSPORT AND REMOVAL OF SULPHUR DIOXIDE AND SULPHATE AEROSOL INTRODUCTION In the 1960's, measurements indicated that the precipitation in Europe was becoming increasingly more acid. The yearly dispersion patterns for acidity in precipitation indicated that the pollutants might be carried by air currents over long distances from the heavily industrialised areas of central Europe towards outskirt areas, Over land in polluted areas 80-90% of total sulphur is estimated to be present as S0, (Robinson and Robbins 1968), but in the global atmosphere about 65% is estimated to be present as sulphate aerosols because of the relative high conversion rate of SO, to sulphates according to the processes discussed, The conversion rate has a considerable influence on long-range transport because the residence time of sulphate aerosols is greater, especially in summer, than that of SO, which was estimated by Robinson and Robbins at 2-4 days;"Nordo (1973) derives residence times (time for convergion by 50%) or & days for initial SO, concentrations of 1 ug/m?, 3 days for 10 ug/m? and 10 hours fér 100 ug/m?, Moreover, these aerosols are more or less acid, resulting in acid precipitation over large areas. For these reasons long-range transport and removal processes will be discussed in this survey. During the last decade the interest in the subject of long-range drift, mainly of sulphur dioxide and sulphate aerosols, and the ecological consequences such as impact on forests and freshwater organisms, has grown enormously. A great number of publications and programmes for international cooperation have appeared, In the context of this revort only a condensed review will be given on phenomena related to long-range transport, transformation during transport, and removal of S0, and sulphate aerosols. An earlier review has been given by Blokker (1970). After this publication, the subject has been dealt with in several publications such as Rodhe (1972), Rodhe et al (1972), Holt-Jensen (1973), Smith and Jeffrey (1974), Bolin and Persson (1975), Fisher (1975), Scriven and Fisher (1975), Eliassen and Saltbones (1975), Eliassen (1978), Brosset (1976), Dovland et al (1976), Benarie (1976), Rodhe (1978), In 1971 a case study of Sweden on the impact on the environment of sulphur in air and precipitation was presented at the UN Conference on the Human Environment in 1971 (Royal Ministry of Foreign Affairs and Royal Ministry of Agriculture 1971). In 1972 a programme was started under the auspices of the OECD, coordinated by the Norwegian Institute for Air Research. Daily sampling sites have been set up in Burope and a survey of SO, emission throughout Europe has been made; this is used in conjiinction with a simple transport model to calculate the annual deposition, 31Rodhe (1972) points out that the situation of possible harmful effects caused by the acidity of precipitation is quite different from that of 80, because in the former case the deposition is not so markedly conéentrated in the close surroundings of a source but is distributed more uniformly over large areas and has moreover a cumulative effect. He mentions that the reason why the deposition of sulphates does not show such a pronounced maximum in the closest surrounding of sulphur source as does the concentration of 80,, seems to be the following: = The sulphates that are deposited though precipitation originate to a large extent from the rain producing layers (1-5 km), where the concentration is much less influenced by local emissions than in the surface air. - A large part of the SO, probably not deposited until after it has become oxidized to form sulphate aerosols. The sulphate aerosols are created gradually in the air and the concentration is not very much higher near the sources than in remote areas within a given region. DISPERSION AND REMOVAL OF SULPHUR DIOXIDE AND AEROSOLS DURING LONG-RANGE TRANSPORT Long-range transport of sulphur dioxide from a large area source is controlled by two main processes: dispersion and removal. Dispersion of plumes from stacks has been the subject of many well known surveys with the object of calculating ground level concentrations, neglecting removal processes. In studying long- range transport the main interest is in the total flux and the total deposition of sulphur dioxide per annum, where source height effects can be ignored. Scriven and Fisher (1975) have used a model for calculating the deposition of sulphur dioxide by absorption in dry conditions (the so called dry deposition). One of the assumptions is that vertical dispersion is limited by an elevated inversion whose height lies in the range 0.5-2 km. It was calculated that in the absence of rain and chemical reactions, and in taking inversion heights of about 1 km, $0, life-times of about 14 day and decay distances in the order of”700 km are obtained. (Calculations by Eliassen and Saltbones 1975, referred to in section 6, give a residence time of about } day). When conversion to sulphate aerosol takes place, again under the assumption that rainfall is absent, the corresponding life-times and decay distances are increased by an order of magnitude. The reason is that the deposition velocity in the 0,1-1 um range is between 10-3 and 10"? cm/s, while that of SO, is about 0.8 cm/s (Chamberlain 1966, US Environ. Proteétion Agency 1975). 32Removal of S occur either or sulphate aerosols by wet deposition can yy wash-out (removal of pollutants by the falling precipitation below the cloud) and rain-out (removal by incorporation of pollutants into cloud droplets within the cloud and subsequent deposition in rain), Scriven and Fisher (1975) state on the basis of estimates by Chamberlain (1960) that when moderate rainfall (1 mm/h) is present wash-out dominates by far the removal of sulphur dioxide, resulting in a reduction of life time by an order of magnitude. However, on an annual average basis wash-out and dry deposition are comparable removal mechanisms for 80, in the UK. For sulphate aerosols it is mentioned that wash-out is the dominating process on both the short and long time basis. The rain-out process is much more difficult to evaluate. Rodhe and Grandell (1972) believe on basis of former data that except in areas where the aerosols are concentrated in the lowest layers of the atmosphere or where a considerable part of the particles is larger than about 1 um, the wash-out process is less effective than the rain-out process Calculations by these investigators, based on this concept and on a Statistical investigation of the distribution of dry and precipitation periods, give expected lengths of life for aerosols in the order of 1}-3 days in winter and 4-12 days in summer in Western Europe, In subtropical regions the expected life may be much greater and the relative importance of dry deposition may consequently be much larger. A useful summary on dry and wet removal of sulphur from the atmosphere has been given by Garland (1978), From a simplified model he suggests that about half the SO, emitted to the atmosphere is removed by dry deposition, the remainder is oxidized to sulphate and removed in precipitation, probably mainly by rain-out, Several investigators have approached the problem of spatia dispersion in a way different from that of Scriven and Fisher by looking at the end points of a large number of air trajectories released at different times from the source determined by geostropic wind measurenents. Rodhe (1978) used this method to investigate the sulphur budget for the atmosphere over Northern Europe and in addition allows for the finite life times of the sulphur. For European conditions the residence (turn-over) times of $0,, sulphate and total sulphur are roughly 25, 80 and 50 hours respectively, The residence time with respect to the different removal and transformation processes are generally somewhat more uncertain, For $0, dry deposition, wet deposition and transformation to sulphate“corressond to residence times of about 60, 100 and 30 hours respectively for sulphate the residence time for dry deposition is very large for wet deposition estimated at 80 hours, These figures would imply that about 30% of the SO, is transformed to sulphate before being deposited. These fime scales may of course not be applied to seasons or other climatic conditions 33Results from the OECD study on Long-range Transport concerning transport and deposition of sulphur compounds, and the acidification of precipitation, are summarised by Ottar (1978). The study has shown that considerable quantities of sulphur dioxide produced by burning of fossil fuels are transferred from the major source areas to remote regions. Further, that emission data together with atmospheric dispersion models and wind trajectories can be used to determine the movement of pollutants over a large region containing major emission source areas. The results presented in Ottar's article are based on a Langrangian model presented by Eliassen (1978). The transmission of the pollutants was calculated by estimating the concentration of sulphur dioxide in air parcels which moved with the wind along air trajectories passing over grid elements of 127 x 127 km. The rate of emission and the time used to pass a grid element were taken into account, as was the loss by chemical transformation and deposition. It was assumed that main transport took place in the lowest two kilometres of the atmosphere, Concentration fields computed on this basis were used to estimate the dry deposition of sulphur dioxide and the wet deposition of sulphate for each grid element (dry deposition of aerosol sulphate was less than 10% of the sulphur dioxide deposition), For the period December 1973 to March 1975 the most pronounced maxima appeared in areas exposed to a combination of polluted air masses and heavy precipitation; they amounted to about 4 g/m (calculated as S0,) in Southern Norway, Switzerland and Scotland. A trajectory model is also applied by Nordo (1976) who also gives an extensive survey of the long-range transport problem in Europe. EVIDENCE FOR LONG-RAN ‘TRANSPORT There are a number of investigations attempting to quantity long-range transport of sulphur compounds, These investigations are partly based on experimental data, partly on the use of models and budget calculations. A review of the most important investigations is given below. - In the Northeast of the USA a clear increase of non-urban sulphate levels has been measured for 1965 to 1972 (US EPA 1975), For this and other reasons the EPA believes that long-range transport plays a major role in high sulphate levels and "acid" rain in the Northeastern parts of the USA, The Science Advisory Board of the EPA (SAB) suggests that the impact of non-urban sources on urban areas is likely to be minor, because the SAB assumes that dilution and removal would reduce sulphates to negligible levels during transport, The SAB believes that the available evidence is insufficient to confirm the validity of their assumption or any of the explanations offered to date for the observed sulphate trends. 34CONG We - In Burope mainly long-range transport from Western Europe to Scandinavia has been studied. Little information is available on the long-term trend of dry deposition on the ground, hence absorption of SO, and impingement of sulphate aerosol. Much more information”is available on wet deposition. It was found (summarized by Dovland et al 1976) that an area of highly acid precipitation in Central Europe has expanded considerably to Southern Norway and Sweden from 1955 to 1973. In Southern Scandinavia there is a significant decrease in the mean pH, and an increase in the mean sulphate and nitrate concentrations within this period. The distribution of wet deposition in Norway reveals a maximum zone of acid precipitation along the Southern coast, where the annual mean pH is about 4.3 and, the annual mean deposition of excess sulphate about 4 g¢ S0,/m?. The excess sulphate is obtained by subtracting the amount of sea salt sulphate from total sulphate. Most of this Aeposition occurs with precipitation during limited periods or “episodes” when the air has passed over areas in Europe with large S0, emissions, - At a station on the Onsala peninsula, on the Southwest coast of Sweden, far from local pollution, it was found (Brosset et a 1975) that the air occasionally receives contributions of black or colourless particles which are more or less acid (section 4.2), Brosset concludes that during black episodes the aerosols, containing black, slightly acid particles (carbonaceous material), originate from the Southwest/East- Southeast sector, hence from the Continent and South and Middle England, During white episodes the aerosols, containing acid and colourless particles, possibly originate from the North Sea area, including Northern England. Brosset menticns thet there ig reascn te assume that the black episodes actively contribute to the acidification problems experienced in Sweden. Although these data form strong arguments for long-range drift, quantitative evaluation of this contribution is very difficult. = Rodhe (1978) has made estimates (based on the model discussed in section 7,2) of the anthropogenic emissions of sulphur compounds for a number of countries in Northwest Europe (OECD figures) and of the deposition of sulphur compounds in Southern and Northern Sweden, taking into account the different deposition processes. He comes to the conclusion that there must be a considerable net outflow of anthropogenic sulphur through a circle of about 1000 km radius which encloses the large anthropogenic sources in the UK and Northern Central Europe. A rather speculative calculation results in a contribution ratio for Southern Sweden from natural, Swedish anthropogenic and foreign anthropogenic sources of approximately 30:20:50, respectiygly. The tota deposition is estimated at 0.87 g sulphur/n’/y in 1965 for Southern Sweden and 0.56 g sulphur /n”/y for Northern Sweden.In this connection it was interesting to hear unofficially a a recent congress in Géteborg that some USA investigators are convinced that an important part of the sulphate aerosols in Norway and Sweden originates from North America through transport via the western "jetstrean". Benarie (1976) has attempted to establish a "source oriented" sulphur balance and to define which proportion of the total sulphur emitted is actually involved in long-range transport either as sulphate or as unconverted S0,. The emission data used are from the Paris region:; ground@level data for SO, and sulphate aerosol mainly from a station 37 km south ofthe centre of the Paris district (the data are mainly from the OECD project). It was concluded that somewhat less than half of the total sulphur seems to be transported beyond the 37 km radius limit, Gaseous and particular dry deposition are considered to be mainly responsible for the deposition within the 37 kn radius circle, Also, some data for a station at a distance of 320 km were used. In applying the decay constant for $0, recently obtained by Eliassen and Saltbones (1975) from OBCD data, and extending the whole procedure for the emissions of France, Great Britain and the Federal Republic of Germany, Benarie arrives to a maximum amount of sulphur deposited in a circular area within 1000 and 3000 km limits corresponding to maximum 0,6 ¢ S0,/n*/year. This is estimated at being less than half of the gldbal background. Applied to Sweden a good agreement was obtained with the estimates of Rodhe (1972). Fisher (1975) has carried out similar calculations based on a model developed by Scriven and Fisher (1975) (discussed in section 7.2) and on estimates of the percentage SO, leaving the United Kingdom on particular days by using aircraft data from Smith and Jeffrey (1975), These data showed that in dry conditions about 30% of the emitted SO, was lost by dry deposition before reaching the aircraft tracks. It was further estimated that 50-60% left the country as $0, and 10-20% as sulphate. From these data Fisher made the following estimates for sulphur deposition over Sweden bry and wet deposition over Southern Sweden, calculated as $0, 2 in g/m /y Fron natural sources ca, 0.5 (Rodhe 1972 From British sources ca. 0.2 From Swedish sources ca, 9.4 From all European ca, 2 It may be mentioned that the average deposition over England from British sources was estimated at ca, 5g/m?/y and this is imereased by inclusion of other European sources to ca. 6g¢/m2/y.oOncawe 7.4 CONCLUDING REMARKS ‘The information summarized in this section shows considerable evidence for the existence of substantial long-range transport of sulphur compounds in the atmosphere, However, the quantitative aspects are not very reliable, The many inaccurate factors and assumptions made in calculations of dispersion and scavenging processes, the uncertainty of the natural background and the use of simplified models undoubtedly result in estimates of low accuracy. Therefore, the ratio of the annual amount of sulphur deposition in a region caused by "import" and originating from the region itself is uncertain, 37con Caw ANALYSIS OF ATMOSPHERIC SULPHATES In the past only total aerosol sulphate and total water soluble sulphate was measured. Recently progress has been made with new techniques to determine different species of airborne sulphate containing particles. This is of great importance for a better understanding of the generation, transport, transportation and removal processes of sulphates, health effects and control strategies, An excellent critical review of the analytical methodology for sulphate in airborne particles has recently been given by Tanner and Newman (1976), containing more than 100 references. For this reason, only a condensed survey of methods and only the most recent references, for an important part based on the above review, are given here in this report. It is stated that the physical and chemical nature of airborne sulphates, such as the size distribution and the type of cations associated with individual sulphate ions, is largely unknown. Size distribution information is limited mostly to impactor or virtual impactor data, hence is discriminative only for particles > 0.3 um diameter. Determination of different species is mainly focussed on specific methods for sulphuric acid. Attempts to deduce the in situ chemical nature of airborne sulphates by collection on filters are seriously hampered by the following problems: - neutralisation reactions of acidic sulphates with basic materials collected on filter surfaces and with basic gases, mainly ammonia, during collection; - catalytic oxidation of SO, by filter material or by particles collected theredn. In the atmosphere itself, reactions with airborne particles may proceed much slower than in the concentrated form on filters or impactors, where the opportunity of interparticle, collision-induced interaction is much greater; - less than 100% collection efficiency of some filter materials for particles in some size ranges. Determination in situ, hence without filter collection is seldom practical, due to insufficient selectivity and/or sensitivity of existing methods. TOTAL AEROSOL SULPHUR DETERMINATION Nost, but not all the aerosol sulphur in airborne particulate matter is present as sulphate, but in the published data it is mostly assumed that all sulphur is present as sulphate, 39