EPA United States Environmental Protection Agency Office of Environmental Sciences Research Research and Laboratory Development Research Triangle Park, North Carolina 27711 EPA-600/7-77-021 March 1977 SULFATES IN THE ATMOSPHERE A Progress Report on Project MISTT Interagency Energy-Environment Research and Development Program Report ------- RESEARCH REPORTING SERIES Research reports of the Office of Research and Development, U.S. Environmental Protection Agency, have been grouped into seven series. These seven broad categories were established to facilitate further development and application of environmental technology. Elimination of traditional grouping was consciously planned to foster technology transfer and a maximum interface in related fields. The seven series * * 1. Environmental Health Effects Research 2. Environmental Protection Technology 3. Ecological Research 4. Environmental Monitoring 5. Socioeconomic Environmental Studies 6. Scientific and Technical Assessment Reports (STAR) 7. Interagency Energy-Environment Research and Development This report has been assigned to the INTERAGENCY ENERGY-ENVIRC RESEARCH AND DEVELOPMENT series. Reports in this series result from the effort funded under the 17-agency Federal Energy/Environment Research and Development Program. These studies relate to EPA's mission to protect the public health and welfare from adverse effects of pollutants associated with energy systems. The goal of the Program is to assure the rapid development of domestic energy supplies in an environmentally—compatible manner by providing the necessary environmental data and control technology. Investigations include analyses of the transport of energy-related pollutants and their health and ecological effects; assessments of, and development of, control technologies for energy systems; and integrated assessments of a wide range of energy-related environmental issues. This document is available to the public through the National Technical Information Service, Springfield, Virginia 22161. ------- EPA-600/7-77-021 March 1977 SULFATES IN THE ATMOSPHERE A Progress Report on Project MISTT (Midwest Interstate Sulfur Transformation and Transport) by William E. Wilson U.S. Environmental Protection Agency Research Triangle Park, NC 27711 Robert J. Charlson University of Washington Seattle, Washington Rudolf B. Husar Washington University St. Louis, Missouri Kenneth T. Whitby University of Minnesota Minneapolis, Minnesota Donald Blumenthal Meteorology Research, Inc. Altadena, California ENVIRONMENTAL SCIENCES RESEARCH LABORATORY OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711 ------- DISCLAIMER This report has been reviewed by the Environmental Sciences Research Laboratory, U.S. Environmental Protection Agency, and approved for publication. Mention of trade names or commercial products does not constitute endorsement of recommendation for use. ------- ABSTRACT The size and sulfate content of atmospheric aerosols and the rate and mechanisms for sulfate formation from sulfur dioxide in power plant plumes are reviewed. Emphasis is given to results from the recent USEPA study, Project MISTT (Midwest Interstate Sulfur Transformation and Transport rate of conversion of sulfur dioxide to sulfate 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. Tall stacks reduce ground- level concentrations of sulfur dioxide, resulting in a reduction of the amount removed by dry deposition. In urban plumes, which are well-mixed to the ground near the source, sulfur dioxide is removed more rapidly by dry deposition. Thus, tall stacks increase the atmospheric residence time of sulfur dioxide, which leads to an increase in atmospheric sulfur forma- tion. These sulfate aerosols may be transported over distances of several hundred kilometers and produce air pollution episodes far from the pollution source. This report covers a period from June 1974 to June 1976 and work was completed as of June 1976. 111 ------- CONTENTS Abstract ............................. Figures ............................. v Tables .............................. vi Acknowledgments ......................... vii 1. Introduction ...................... 1 2. Transformation Mechanisms ............... 3 3. Size Distributions ................... 5 4. Chemical Forms of Sulfate ............... 7 5. Review of Plume Studies ................ 9 6. EPA Plume Studies ................... 10 Program plan ................... 10 Plume mapping program ............... 11 Power plant plume characteristics ......... 13 Urban plumes ................... 18 Sulfate budget .................. 22 Removal processes ................. 24 Effects of tall stacks .............. 24 7. Summary ........................ 26 References ............................ 27 ------- FIGURES Number Page 1 Schematic of a trimodal atmospheric aerosol size distribution showing the principal modes, main sources of mass for each mode, and the principal processes involved in inserting mass and removing mass from each mode 6 2 Profiles of Aitken Nuclei concentration (AN), light scattering aerosol (bscat), sulfur dioxide (SCL) and ozone (CO .... 12 3 Schematic of experimental method for pollutant flow measure- ment in large plumes .................... 12 4 Flight plan of the research aircraft through the plume showing the four altitudes at which passes were made .... 15 5 Volume size distribution of aerosol measured within the Labadie power plant plume and background air on August 14, 1974 .................... 15 6 Aerosol volume flows in the plume as a function of time and distance traveled compared with light scattering and Aitken Nuclei flows ... ..... 17 7 Percentage of sulfur concentration due to aerosol sulfur for several estimated background concentrations of aerosol sulfur 17 8 Ozone concentration and aerosol light-scattering coefficient (b ) downwind of St. Louis on 18 July 1975 ........ 19 scat J 9 Flow rates and related data for St. Louis plume on 18 July 1975 ...... ........... 21 10 A profile of the St. Louis urban plume taken early in the morning of July 30, 1975, after following the plume for 18 hours ...... 21 11 Sulfur budget in urban-industrial plumes 23 12 Sulfur budget in power plant plumes 23 VI ------- TABLES Number Page 1 Mechanisms by which Sulfur Dioxide is Converted to Sulfates (10) 4 2 Known Atmospheric Sulfates 8 3 Aerosol Size Distribution Characteristics 16 4 Plume Aerosol Flow Rates and Calculated Sulfur Conversion, 14 August 1974a 16 VII ------- ACKNOWLEDGMENTS A large number of people, in addition to the authors, made important contributions to EPA's studies of sulfate in the atmosphere. These include the following: Environmental Protection Agency, Jack L. Durham and Thomas G. Ellestad; University of Washington, Allan P- Waggoner and Norman C. Ahlquist; Washington University, Noor V. Gillani, Steven B. Fuller and Janja D. Husar; University of Minnesota, Bruce K. Cantrell; Meteorology Research, Inc., Warren H. White and Jerry Anderson; Environmental Measurements, Inc., William M. Vaughan; Environmental Quality Research, Inc., William P. Dannevik; and Rockwell International, Air Monitoring Center, Al Jones. The authors would also like to thank Stephen J. Gage, Deputy Assistant Administrator, Office of Energy, Minerals, and Industry, for his continuing interest in this program and for providing financial supporth through the Interagency Energy/Environment R&D Program. We would also like to thank Gregory D'Alessio, OEMI, for his administrative assistance. VI11. ------- SECTION 1 INTRODUCTION Sulfate is a pollutant of note, having been linked in epidemiological and laboratory studies with adverse effects on human health (1,2). Epidemio- logical studies have, in fact, indicated that sulfate may be more toxic than sulfur dioxide or total suspended particulates. Sulfates are also known to be major contributors to reductions in visual range caused by atmospheric aerosols (3). Studies of acid precipitation in Scandinavia (4) have impli- cated sulfuric acid in a variety of adverse ecological effects. The known adverse health effects of sulfur dioxide (S0~) led to the control of this pollutant (5). Reduction in urban SO- emissions and concen- trations effected by the mandatory use of low-sulfur fuels, however, were not accompanied by a proportional decrease in urban sulfate (6). The observed lack of a proportional decrease has four possible explana- tions: (1) sulfates can be biogenic in origin, resulting from transformations of hydrogen sulfide, methyl disulfide, and methyl mercaptans, which are natural products; (2) measured sulfate values are not real but anomalous, resulting from conversion of S0« to sulfates on filters used in sampling; (3) observed sulfates are primary pollutants produced from the combustion of high-vanadium oil or from combustion in small, inefficient furnaces; and (4) observed sulfates may be explained by the transformation-transport theory. Reductions in urban SO,., emissions have been accompanied by increases in rural SO,., emissions from new power plants located outside cities. S09 from these power plants may be transformed to sulfate in the atmosphere and trans- ported over long distances to urban areas. The fourth possibility, the transformation-transport theory, is supported by Scandinavian (4) and U.S. studies (7) and could account for the increased sulfate levels observed in rural areas and the static sulfate ------- levels observed in urban areas in the U.S. (6). Early information on the rate of conversion of SCL to sulfate in power plant plumes suggested that the rate of conversion was too low to result in significant formation, and sub- sequent transport, of sulfate (7). However, studies of the flux of sulfur out of various areas, e.g., studies by Smith and Jeffrey (8) and of Waggoner et al. (9), successfully showed that some of the sulfur transported from source areas like the United Kingdom arrived in Scandinavia as sulfates. The transformation-transport theory remains, then, a viable hypothesis for the US and is the subject of this paper. ------- SECTION 2 TRANSFORMATION MECHANISMS Though they are not well understood, the mechanisms by which SO- is oxidized to sulfates are important because they determine the rate of forma- tion and, to some extent, the final form of sulfate. Atmospheric S0_ may be oxidized to sulfur trioxide (SO.,) and converted to sulfuric acid aerosol, or it may form sulfite ions that are then oxidized to sulfate. Subsequent to the oxidation, sulfuric acid or sulfate may interact with other materials to form other sulfate compounds. The most important sulfate formation mechanisms identified to date are summarized in Table 1. ------- TABLE 1. MECHANISMS BY WHICH SULFUR DIOXIDE IS CONVERTED TO SULFATES (10) Mechanism Overall reaction Factors on which sulfate formation primarily depends Direct photo- oxidation. Indirect photo- oxidation. 3. Air oxidation in liquid droplets. 4. Catalyzed oxidation in liquid droplets. 5. Catalyzed oxidation on dry surfaces. SO,, SO,. H2S04 light, oxygen water smog, water, NOX organic, oxidants, hydroxyl radical (OH) liquid water SO, Oxygen ->NH, + SO, 4 4 oxygen, liquid water SO ^ SO, 2 heavy metal ions oxygen, water SO. "carbon, particulate Sulfur dioxide concen- tration, sunlight intensity. Sulfur dioxide concen- tration, organic oxidant concentration, OH, NO . Ammonia concentration. Concentration of heavy metal (Fe, V, Mn) ions. Carbon-particle concen- tration (surface area), ------- SECTION 3 SIZE DISTRIBUTION Studies (11) over the past 5 years of the size distribution of particles in both sulfate aerosols and general atmospheric aerosols have led to impor- tant changes in our understanding of the behavior of aerosols such as sulfates in the ambient atmosphere. A schematic diagram of a typical atmospheric aerosol size distribution is shown in Figure 1. The three principal modes (particle-size ranges), the main sources of mass for each mode, and the principal processes involved in inserting and removing mass from each mode are shown. Particles in the Aitken nuclei mode, 0.005 to 0.05 ym diameter, are formed by condensation of vapors produced either by high temperatures or chemical processes. The accumulation mode, which includes particles from 0.05 to 2 ym in diameter, is formed by coagulation of particles in the nuclei mode and by growth of particles in the nuclei mode through condensation of vapors onto the particles. Coarse particles are formed by mechanical pro- cesses such as grinding or rubbing—for example soil, street dust, and rubber tire wear—and by evaporation of liquid droplets. Accumulation mode particles do not continue to grow into coarse particles, however, because the more abundant small particles have a higher gas-aerosol collision rate and dominate the condensational growth process. Sulfates formed by the conversion of SO,., are found in the accumulation mode; MgSO, from sea salt, Na-SO, from paper pulping, and CaSO, from gypsum are found in the "coarse particle mode." ------- CHEMICAL CONVERSION OF GASES TO LOW VOLATILITY VAPORS .1 12 PARTICLE DIAHETEP, MICROMETER 100 TRANSIENT NUCLEI OR AITKE:: NUCLEI r_-vxcE~ ACCUMULATION ~ RANGE !!ECHANICALLY CEMENTED — AEROSOL RANGE — Figure 1. Schematic of a trimodal atmospheric aerosol size distri- bution showing the principal modes, main sources of mass for each mode, and the principal processes involved in inserting mass and removing mass from each mode. ------- SECTION 4 CHEMICAL FORMS OF SULFATE Several different sulfates are among the molecular forms naturally produced as sulfur is cycled through the atmosphere. Table 2 is a list of sulfate forms known to exist in air, along with some of their more outstanding chemical characteristics. As the table shows, sulfate per se is not a single molecular form, and several sulfates are known to be produced from the oxida- tion of S0«. All seven compounds listed are sensed as "sulfate," but they have radically different chemical properties dictated by their molecular nature. They will also have different sizes, depending largely on their mode of formation. Sulfates in the fine-particle size range are respirable and also reduce visibility. Sulfates are also found in the coarse particle mode. Sulfates are either produced and emitted into the air as such, or they are formed in the atmosphere from gas-particle conversions. The first four substances in Table 2 (H-SO, and its products of neutralization with NH_) seem to be formed from S0? oxidation. The remainder of the sulfates are emitted directly by industrial or by natural sources; that is, they are primary rather than secondary pollutants. The chemical nature of these substances varies from the strongly acid nature of H_SO, and NH.HSO, to the relatively inert salts. Water solubility and hygroscopicity and/or deliquescence vary from extremely high (H~SO,) to quite low (CaSO,). ------- TABLE 2. KNOWN ATMOSPHERIC SULFATES Formula Names Sulfuric acid (oil of H2SO vitrol) NH.HSO. Acid ammonium sulfate 4 4 (NH, ) H(SO )? Triammonium acid disul- fate (Letovicite) Ammonium sulfate (NH,)0SO, (Mascagnite) Sodium sulfate Ka,,SO (Glauber's salt) Calcium sulfate CaSO, (gypsum) Magnesium sulfate MgSO, (Epsom salts) Sources Atmospheric oxidation of SO,,; direct from manufacturing . Oxidation of SO with NH addition. Oxidation of SO,, plus NH3. Oxidation of SO. plus NH3 . Paper pulping by kraft process. (1) Wind-tlown dust. (2) Manufacture of gypsum products. (1) Sea spray. (2) Paper pulping. Notable chemical proper t ies Strong acid, very hygroscopic (drying agent at low RH) . Strong acid, hygroscopic . Acidic, del iquenscent (?) at -v65% RH. Weak acid, water- soluble, deliques- cent at 80% RH. Water-soluble, deliquescent at 84% RH; relatively inert. Low solubility in H,,0; relatively inert Very hugroscopic; relatively inert and non-toxic. Probable Size class by mass particle Diameter, Dp 0.1 - 1.0 urn 0.1 - 1.0 urn 0.1 - 1.0 urn 0.1 - 1.0 vim D > 0.5 un (uncontrolled pulp mill) D > 1 pm F Dp > 1 y3i (sea spray) Dp > 0.5 um ------- SECTION 5 REVIEW OF PLUME STUDIES Information on the rate of conversion of S09 to sulfate in power plant plumes was needed to quantify the contributions of power plants to atmospheric sulfates. A critical review of plume studies (7) revealed no reliable infor- mation on conversion rates, and only two studies that provided information on the amount of S0_ converted to sulfate. The early work of Gartrell et al. (12) indicated little conversion of S0~ to sulfate except at relative humidi- ties greater than 75 percent. However, at high relative humidity, conversion of S0? to sulfate may occur either on the filter surface or within the aerosol particles collected on the filter. Therefore, Gartrell's results cannot be accepted unless verified by other techniques. Investigators at the Brookhaven National Laboratory used two techniques to study sulfate formation in power plant plumes (13,14): the sulfur isotope technique and direct measurements of S0_ and sulfate. The isotope technique is considered erroneous because of the presence of several competing reactions having different isotope effects (7). The direct measurement of S0« and sulfate is considered experimentally valid. The Brookhaven workers measured conversion from 0 to 8.5 percent per hour in coal-fired power plant plumes (13) and 0 to 26 percent per hour in oil-fired power plant plumes (14). The Brookhaven work has previously been interpreted to indicate an average conversion rate in coal-fired plumes of 1 percent per hour or less and a substantially higher rate in oil-fired plumes. However, a careful analysis of the data, after discarding the isotope results, indicates that no dif- ference has been established between oil- and coal-fired plumes and that, depending on conditions, conversion rates of substantially greater than 1 percent per hour are possible (7). The sampling techniques and flight patterns used were such that an accurate measurement of the conversion rate could not be obtained (7). ------- SECTION 6 EPA PLUME STUDIES PROGRAM PLAN In order to obtain a better understanding of the physical and chemical processes occurring in power plant plumes, a new series of field studies were undertaken. During July, August and February of 1975, extensive studies involving three-dimensional mapping of large plumes were carried out in the St. Louis area as part of the Midwest Interstate Sulfur Transport and Trans- formation Study (MISTT). Preliminary studies were conducted during July and August of 1973 and 1974. These plume studies differed from earlier ones in that: (1) more gas and aerosol parameters were measured; (2) horizontal and vertical profiles were measured; (3) data were interpreted in terms of mass flows instead of ratios; (4) the background air mixing with the plume was characterized; (5) the chemical composition and size distribution of the aerosols in the plume were determined; and (6) measurements were made in approximately the same air mass as it moved downwind. In previous studies, the fractional conversion of S0_ to sulfate was calculated from the ratio of S02 to sulfate collected as integrated filter samples while circling in random portions of the plume at various downwind distances. This technique can overestimate conversion if any S0? is removed by dry deposition to ground surfaces. For this reason and because of the need to collect large amounts of S0?, samples were usually collected in cohesive plumes which had undergone minimal dilution with background air. This technique can also lead to errors if conversion varies in different parts of the plume or if conversion is influenced by the extent to which the plume has been diluted by background air. That this can indeed be the case is demonstrated in Figure 2, in which the nuclei formation rate is seen to 10 ------- be much greater at the edges of the plume than in the center. Although such a dramatic difference was not often observed, current interpretation of sulfate formation mechanisms suggests that the conversion rate will be higher in those portions of the plume, such as the edges, in which dilution has led to conversion of plume NO to NO- by background 0» (15). To overcome these problems the EPA plume mapping studies were designed to measure S0~ and sulfate mass flow rates at increasing distances from the source in both cohesive and well-mixed plumes. From the change in flow rate with distance, it is possible to calculate transformation and removal rates for individual pollutants (16,17). In the EPA study, the SO- mass flow rates were determined by a continuous SO- monitor. A two-dimensional plot of S0~ concentrations in a plane perpen- dicular to the plume axis was constructed from the horizontal and vertical profiles. The mass flow of SO- was calculated from the SO- concentration and the wind speed and direction. Since no continuous monitor for sulfate was available, the continuous light-scattering (b ) measurement was used as an SC3.U indication of the sulfate concentration distribution. Sulfate, collected in filter samples during each pass through the plume, was analyzed by the flash vaporization-flame photometric detection method—a new, highly sensitive technique modified for aircraft use (18,19). The sulfate flow was calculated from the b /sulfate concentration ratio, integrated over a pass, and the scat b flow. Similarly, b -to-aerosol volume ratios were used to calculate scat scat an aerosol volume flow. PLUME MAPPING PROGRAM Two instrumented aircraft, an instrumented van, and three mobile single- theodolite pilot-balloon units were used in a coordinated measurement program (Figure 3). The primary sampling platform was a single-engine aircraft (20) equipped for continuous monitoring of the gaseous pollutants (0_, NO, NO , -3 X S07); three aerosol parameters (condensation-nuclei count, light-scattering coefficient, and aerosol charge); several meteorological variables (tempera- ture, relative humidity, dew point, and turbulent dissipation); and naviga- tional parameters. Particulate sulfur samples were gathered by a sequential filter tape sampler equipped with a respirable-particle size separator. An 11 ------- .08 K06 E CL CL .04 oT a o .02 O L0 5 Km 10 Km Figure 2. Profiles of Aitken Nuclei concentration (AN), light scattering aerosol (b ), sulfur dioxide (SO,.) and ozone (()„). scat 2. j PRIMARY AIRCRAFT SCOUT "• L'fig '. SOURCT Q(x)=//c(x,y,zjU(zJdydz plume Figure 3. Schematic experimental method for pollutant flow measurement in large plumes. 12 ------- array of four cascade impactors collected size-differentiated aerosol samples for later chemical and microscopic analyses. An optical counter and an electrical-mobility analyzer provided details of the in situ particle-size distribution of grab samples. An instrumented "scout" aircraft located the plume, laid out the sampling path of the primary aircraft, and directed the three mobile pilot-balloon (pibal) units to their respective positions in the center and at the edges of the plume. Coordinated with the aircraft sampling, a van equipped with a correlation spectrometer (COSPEC) made lateral traverses under the plume and measured the integrated overhead burden of SCL and NCL (21). Data collected aboard the two aircraft and in the van were recorded automatically at 1- to 10-second intervals on magnetic tapes for subsequent computer processing. The operations headquarters coordinated the mobile units by radio communication. The flight pattern of the primary aircraft was designed to enable charac- terization of the plume at discrete distances downwind from the source. At each distance, horizontal traverses were made in the plume perpendicular to the plume axis at three or more elevations. These were supplemented by vertical spirals within and outside the plume. The continuous instruments monitored the distribution of pollutants along each pass, and the sequential filter samples, analyzed later by a sensitive flash-vaporization, flame- photometric technique (17), yielded the average particulate sulfur concentra- tion for each pass. From the three-dimensional pollutant concentration field obtained in this manner, together with the vertical profiles of wind velocity measured every half-hour by the three pibal units, the horizontal flow rates of pollutants at each downwind distance were directly calculated. Under well-defined wind conditions (unidirectional, steady wind field), the reproducibility of the pollutant flow measurement was ± 20 percent. POWER PLANT PLUME CHARACTERISTICS Aerosol Volume (22) An electrical aerosol analyzer and an optical particle counter were used to measure, in each of a number of size ranges, the number of particles per o cm of air. By assuming spherical particles, the volume of aerosol material 33 33 in ym per cm of air may be calculated (volume concentration, ym /cm ). Thus 13 ------- from size distribution measurements made during horizontal passes and from upwind spirals, as shown in Figure 4, and at the distances given in Tables 3 and 4, it was possible to calculate aerosol volume flows. Wind velocities at each distance were measured with pilot balloons. Size distributions were also measured, usually near the plume center, as shown in Figure 4. In contrast to the bi- or tri-modal distributions found at ground level (Figure 2), the size distributions at plume height (Figure 5) were unimodal, nuclei apparently having been removed by coagulation and coarse particles by sedimentation. Therefore, these distributions were characterized by fitting them with a single log-normal distribution. The resulting geometric mean diameters and geometric standard deviations are tabulated in Table 3. These show that, although the mean size increased from 0.24 ym at 10 km to 0.29 ym at 45 km, particle sizes in the plume are not significantly different from the average found in the upwind, background spiral. The flow rates, Q(x), of light-scattering aerosols (b ) and Aitken scat nuclei (AN) were obtained for each plume cross section from the double integral of the concentration (x,y,z), and wind velocity, U(z) (17). Since the aerosol volume concentrations calculated from the size distributions could only be determined at discrete points in the plume, the aerosol volume integrals were estimated using the ratios of aerosol volume to b deter- scat mined at discrete points. The assumption that the aerosol volume integral is proportional to b implies that the aerosol size distribution is S Celt constant along a traverse. This is thought to be an acceptable assumption because of the consistency of the size distribution along the plume as shown in Figure 4 and Table 3. Wind velocities at each distance were calculated from pilot balloon observations. The flow rate for each aerosol parameter is the sum of that due to the background plus that contributed by the plume. The background was measured on both sides of the plume in order to separate the two flow rates. Plume-associated flow rates for b , AN, and aerosol volume measured SC3.L in the Labadie power plant plume on 4 and 14 August 1974 are shown in Figure 6. The volume flows are also given in Table 3. From Figure 6 it is seen 14 ------- UPWIND SPIRAL Aerosol Sample Position Plume Traverse Cross Section Portion of Plume Cross Section Not Sampled PLUME TRAVERSE STATIONS DOWNWIND SPIRAL THROUGH PLUME Power Plant Figure 4. Flight plan of the research aircraft through the plume showing the four altitudes at which passes were made, the upwind and in-plume spirals, and the points at which aerosol size distributions were measured. Only two traverses out of four are shown. Background Spiral 10 Km Traverse a Average 21 632 Km Traverse Figure 5. Volume size distribution of aerosol measured within the Labadie power plant plume and background air on August 14, 1974. 15 ------- TABLE 3. AEROSOL SIZE DISTRIBUTION CHARACTERISTICS Geometric Geometric mean standard Date 8-5 8-5 8-5 8-5 8-14 8-14 8-14 8-14 Location Background (upwind) spiral 2-km traverse 4-km traverse 18-km traverse Background spiral (upwind) 10-km traverse Avg. 21 and 3 2 -km traverse 45-km traverse diameter, urn 0.20 + .04 0.20 + .01 0.22 + .006 0.21 + -001 0.30 + .04 0.24 + .05 0.28 + .04 0.29 + .06 TABLE 4. PLUME AEROSOL FLOW SULFUR CONVERSION, Distance km 0 10 21 32 45 , Time flow hr 0 0.70 1.49 2.29 3.17 Aerosol volume above background, cm /sec 185 388 640 1378 deviat ion 2.09 ± .13 1.95 ± .04 1.93 ± .06 1.90 + .06 2.19 + .2 2.14 + .14 2.31 + .12 2.20 + .19 RATES AND CALCULATED 14 AUGUST 1974a S°2 b converted , % 1.1 2.3 3.7 8.0 Avg. vol . , um3/cm 19.3 ± 5.2 22.1 + 1.6 36.5 + 4.2 42.3 + 7.6 17.9 + 4.6 35.8 + 9.3 38.7 + 9.0 47.0 + 16.7 so2 conversion rate, %/hr 1.5 1.8 4.9 Assuming the aerosol is 1LSO, in equilibrium with water vapor. Based on the average SO,, flow of 4.08 kg/sec and a relative humidity of 75%. 16 ------- 1800- 1600 1400 . 1200 o o en ^ IOOO 6 o i 800 > u_ 600 4OO 200 o> 'g x F, Aersol Volume Flow, Labadie !4-Aug.-74 Fv Aersol Volume Flow, Labadie 5-Aug.'74 F»,| Aitken Nuclei Flow, Labadie !4-Aug.-74 // bSCQ( Integral over plume cross section, Labadie l4-Aug.-74/y I — // /\ *-*••" t(Hr.) 0 10 20 30 40 d(Km) Figure 6. Aerosol volume flows in the plume as a function of time and distance traveled compared with light scattering and Aitken Nuclei flows. Excess aerosol flow due to the plume has increased seven times from 10 to 45 km. Note also the four fold increase in the rate of aerosol formation after 2 hours. 20 1 15 10 cc =3 O CC LABADIE PLUME AUGUST 14,1974 BACKGROUND 2 jug/m3 10 20 30 DISTANCE FROM SOURCE, km 40 50 Figure 7. Percentage of sulfur concentration due to aerosol sulfur for several estimated background concentrations of aerosol sulfur. 17 ------- that on 14 August the growth was two-stage, the growth rate increasing by a factor of 4 after about 2 hours, at a distance of about 30 km. One of the chief objectives of this study was to determine the rate at which S0? is converted to sulfate in plumes. It was assumed that the excess aerosol formed in the plume was sulfuric acid in equilibrium with water vapor at the ambient humidity. The fraction converted and the rate of con- version was determined from the ratio of the calculated sulfur in the aerosol to the total sulfur flow calculated from the S02 measurements and the estimated sulfuric acid. These results, presented in the last two columns of Table 4, show that at 45 km 8 percent of the S02 was converted to aerosol and that the conversion rate varies from 1.5 percent/hr at 10 km to 4.9 percent/hr at 45 km. Sulfate Measurements During these experiments, the concentration of soluble sulfate was also measured with a filter apparatus. These filter samples were integrated from one plume edge to the other during the four passes at each distance. The actual conversion rate determined by the sulfate flow rate method will depend on the sulfate background. Figure 7 shows the pattern for several background concentrations. Adequate background sulfate concentrations were not obtained during this experiment. The drop in percent converted between 10 and 21 km may be due to fall out of large particles which escaped the electrostatic precipitator or it may be due to measurement errors. Measure- ments of SCL in the plume are most difficult nearest the stack because of the high concentration gradients and plume inhomogeniety. URBAN PLUMES Similar techniques were used to map the three-dimensional flow of aerosols and trace gases in the air leaving the St. Louis area. It was found that under certain summer, daytime meteorological conditions the aggregate pollu- tant emissions from metropolitan St. Louis often formed a cohesive, well- defined "urban plume" downwind of the city (16,17,23,24). Such a plume can be identified in Figure 8, which shows ozone concentrations and light- scattering coefficients measured within the mixing layer northeast of St. Louis on 18 July 1975 (24). 18 ------- SCALE, kilometers i—ZOO T-150 SPRINGFIELD •MOO •-,../-^ x - 4 V ILLINOIS T-50 WINDS J-o A POWER PLANT • REFINERY OZONE - ~ bSCAT Figure 8. Ozone concentration and aerosol light-scattering coefficient (bscat) downwind of St. Louis on 18 July 1975. Data is taken from horizontal traverses by instrumented aircraft at altitudes between 460 and 760 m msl. Sampling paths are along graph baselines; note that baseline concentrations are not zero (24). 19 ------- On that day, the St. Louis plume incorporated the emissions of major coal-fired power plants at Labadie (Mo.) and Portage des Sioux (Mo.) and of a refinery complex near Wood River (111.), in addition to emissions from industries and automotive traffic of the St. Louis-East St. Louis urban area itself. The concentrated individual plumes immediately downwind of large combustion sources can be identified in Figure 8 by their ozone "deficits ; the depressed concentrations of 0» in these plumes reflect the high concen- tration of NO in effluents. The width of the plume, approximately 40 km, did not change much along its 150-km-length. Apparently, horizontal diffusion at the boundaries of the urban plume was by means of a rather slow dilution mechanism. It appears likely that the elevated ozone concentrations in this plume and the reduced visibility caused by the plume were exported well beyond Decatur (111.). Unlike the primary pollutants NO and S0?, ozone and light-scattering aerosols attained their maximum concentrations well downwind of St. Louis on 18 July 1975. The ozone and most of the aerosol were not emitted but were products of chemical and physical transformations in the atmosphere; their secondary origin is evident in Figure 9, which shows flow rates of ozone and aerosol in the St. Louis plume increasing with distance from the city. The flow rates in Figure 9 represent only the contribution of the St. Louis plume, and are calculated from the measured winds within the plume and from the difference between pollutant concentrations inside and outside the plume. Based on a number of experiments in 1974 and 1975, the following features of the urban plume were observed to be typical: 1. The St. Louis plume significantly degraded the air quality of communities as far as 150 km from the city. 2. The most conspicuous components of the St. Louis plume 50 km or more downwind of the city were the reaction products formed along the way. 3. Most of the aerosol responsible for the high b and resulting decrease scat ° in visibility within the St. Louis urban plume was formed in the atmosphere. The sulfate concentrations in the 18 July 1975 urban plume attained a maximum of 20 yg/m . This is not an extremely high value. On 29-30 July 1975 the urban plume was followed for 18 hours and measurements were made both in the evening and the following morning. During this experiment sulfate con- 20 ------- - 250 2500 200 g 2000 _c : s. < Hi 50 ,„ 1500 ] 100 , , 1000 1 50 o M O 500 Figure 9. Flow rates and related data for St. Louis plume on 18 July 1975. Values are plotted against distance downwind of the St. Louis Gateway Arch, with equivalent travel times for a constant mean wind speed of 45 km/hr shown for comparison. The mass flow rate of ozone and the flow rate of the aerosol light-scattering coefficient (bscat) are shown. Pf* 125 ST. LOUS URBAN PLUME JULY 28 8 29, 1975 DISTANCE, miles Figure 10. A profile of the St. Louis urban plume taken early in the morning of July 30, 1975, after following the plume for 18 hours. Profiles are shown for ozone (» ) , sulfur dioxide ( --- ), (•""")> an^ aerosol sulfate. 21 ------- o centrations of 60 yg/m were measured, as shown in Figure 10. This set of measurements demonstrates that at least under some conditions sulfate formation can exceed removal and dilution and can lead to the accumulation of very high sulfate concentrations. SULFATE BUDGET By examining the total flow of sulfur—both SC>2 and sulfate—we can draw some interesting conclusions regarding the transformation and removal of S0? in the two classes of plumes, that is, power plant plumes and urban plumes (17). The experimental results representing pollutant flow data for gaseous and particulate sulfur are shown in Figures 11 and 12. Pollutant flow measurements in urban plumes are shown in Figure 11. Data are reported here only for those days in which the wind direction was such that the plumes of the rural power plants (tall stacks, > 700 ft.) were well separated from the urban plume which contained emissions from low stacks (< 350 ft.) and near ground level sources. In such plumes, the total sulfur flow rate (gaseous plus particulate) has been found to decrease with distance. The pollutant flow rate, as determined from both the aircraft-measured concentrations and correlation spectrometer data, shows a decay in excess of the estimated experimental uncertainty of the methods (± 20 percent). Sulfur depletion in the urban plumes appears to be equivalent to an exponential rate of decay with a characteristic (1/e) decay time of 3 to 4 hours. Our results show, therefore, that in such plumes only about one- third of the original emissions are transported beyond a radius of 100 km and that formation of new sulfate aerosol is undetectable up to a distance of 50 km. There is evidence that during the daytime the formation of aerosol, including sulfate in an urban plume, begins after an aging time of 1 or 2 hours. In power plant plumes (Figure 12), total sulfur flow measurements showed no loss of sulfur within the limits of experimental uncertainty. The aerosol fraction of total sulfur flow on 14 August 1974 was 6 percent at 10 km and 13 percent at 40 km from the source. As seen in Figure 10 and 11, most of the particulate sulfur formation occurred between 30 and 50 km from 22 ------- o o> O LU h- CO CO 7.5 5.0 4.0 - 3.0- 2.5 - 2.0 1.5 CO 1.0 T I I I I I I I I URBAN a INDUSTRIAL PLUMES -AEROSOL 20%/HOUR LOSS RATE -s AT IMS m/sec 10 20 30 40 50 60 70 80 90 100 110 120 DOWNWIND DISTANCE, X (km) Figure 11. Sulfur budget in urban-industrial plumes. The shaded area represents the particulate sulfur contributions, the solid lines are gaseous sulfur. -, 4-0 o 0) ^ 3.0 . 2.0 UJ I- o: i.5 o u. CO 1.0 CO 2 cc. U- D CO 0.5 I I I I I I I POWER PLANT PLUMES I I I I 10 20 30 40 50 60 70 80 90 100 110 120 DOWNWIND DISTANCE, X (km) Figure 12. Sulfur budget in power plant plumes. D 8.14.1974; A 8.5.1974; o 7.29.1975 (COSPEC). Note the increase of particulate sulfur between 30 and 50 km on 8.14.1974. 23 ------- the source. The SO flow data for 30 July 1975 were obtained by the correla- tion spectrometer, unaugmented by particulate sulfur measurements. These power plant plume measurements, all performed during daytime conditions, demonstrate that there is little removal of the sulfur emitted from tall stacks within a region of 50 to 100 km from the plant. During these measure- ments, dry deposition was minimal either because the plumes had not touched the ground or because they were very dilute at ground level. REMOVAL PROCESSES It is important to understand that most sulfate aerosol is secondary, i.e., formed by gas-to-particle conversion in the atmosphere after emission, and occurs in the accumulation mode. Particles in this size range have very long lifetimes. Some confusion has existed regarding the relative removal rates for SO and sulfate aerosol by deposition. The deposition velocity of aerosols depends on the particle size and reaches a minimum in the accumula- tion size range of 0.1 to 1.0 ym. The deposition velocity of gaseous S0_ depends on the chemical reactivity of the surface. Both deposition velocities depend on the friction velocity and the surface roughness. However, since the diffusion of accumulation mode aerosols through the surface boundard layer (0.001 to 1 cm) is much slower than the diffusion and surface reaction of an SO,., molecule, the deposition velocity of sulfate aerosol is always significantly smaller than for gaseous S09 (25,26,27). Consequently, though SO,, is removed fairly rapidly by dry deposition on soil, vegetation, and other surfaces, the removal processes become slower once the S0? has been converted to sulfate. Therefore, sulfates can travel long distances before their removal by fallout, rainout, or deposition. EFFECTS OF TALL STACKS These aspects of reaction mechanisms, aerosol size, and deposition rates are critical to an understanding of the possible effects of tall stacks. When S02 is emitted near the ground, as from home heating units, the SO- can be removed by surface removal mechanisms (dry deposition). When S0? is emitted higher in the air, as from the tall stacks of fossil-fuel-fired electric power plants, the SO- is diluted before it reaches the ground, and the surface removal rates are reduced. Emissions may, in fact, be trapped above an 24 ------- inversion layer and remain trapped for hours. Thus, elevated stacks theo- retically permit a longer residence time in the ambient atmosphere for S0~ and promote fine particulate sulfate formation by the mechanisms discussed previously. On the other hand, they provide for increased dilution of the sulfate and SCL and thus reduce the impact of emissions in the vicinity of the source. 25 ------- SECTION 7 SUMMARY Earlier work had shown that the rate of conversion of S0» to sulfate in power plant plumes was slow except at very high relative humidity. In the recent EPA program, consistent conversion of several percent per hour at normal levels of relative humidity has been measured. The conversion of SCL to sulfate aerosol in power plant plumes is slow in the early part of the plume; that is, close to the point of emission. As ambient air mixes with the plume, the rate of conversion increases. Thus tall stacks reduce ground-level concentrations of SCL but increase sulfate aerosol formation by reducing surface losses of SCL and by increasing the atmospheric residence time, which results in increased SCL-to-sulfate conversion. In urban plumes, which are well-mixed to the ground, S0~ may be removed by reaction with plants and by deposition. The SCL dry deposition rates vary with vegetation, with the nature of the surface, and with time of year. Urban plumes have been sampled out to 250 km from their sources and power plant plumes out to 60 km. Sampling at these distances revealed that sulfate, generated from SO- in power plant and urban plumes, and ozone, generated from hydrocarbons and nitrogen oxides in urban plumes, may be transported at least hundreds of km and may cause air pollution episodes and other problems far from the source of pollution. These air pollution problems cannot be controlled by the government entity where the air pollution impact actually occurs. 26 ------- REFERENCES 1. Amdur, M.O., T.R. Lewis, M.P- Fitzhand and K.I. Campbell. Toxicology of Atmospheric Sulfur Dioxide Decay Products. Publication No. AP-111, U.S. Environmental Protection Agency, Research Triangle Park, NC 1972. 47 pp. 2. Health Consequences of Sulfur Oxides: A Report from CHESS 1970-1971. EPA-650/1-74-004, U.S. Environmental Protection Agency, Research Triangle Park, NC, 1974. 428 pp. 3. Waggoner, A.P., A.H. Vanderpol, R.J. Charlson, L. Granat, C. Tragard and S. Laisen. Sulfates as a Cause of Tropospheric Haze. Report AC-33, Dept. of Meteorology, University of Stockholm, Sweden. UDC 551.510 4:535.33, 1975. 4. Air Pollution Across National Boundaries. The Impact on the Environment of Sulfur in Air and Precipitation. Sweden's Case Study for the United Nations Conference on the Human Environment. Bert Bolin, ed. Kungl. Boktryckeriert P.A. Nortsedt & Soner 710396. Stockholm, Sweden, 1971. 5. Air Quality Criteria for Sulfur Oxides. Publication No. AP-50, U.S. Department of Health, Education, and Welfare, Public Health Service, Washington, B.C., 1969. 6. Position Paper on Regulation of Atmospheric Sulfates. EPA-450/2-75-007, U.S. Environmental Protection Agency, Research Triangle Park, NC, 1975. 108 pp. 7. Wilson, W.E. Sulfate Formation in Power Plant Plumes: A Critical Review. Project MISTT Report #2. Submitted for publication. 8. Smith, F.B. and G.H. Jeffrey. Airborne Transport of Sulfur Dioxide from the U.K. Atmospheric Environment, 9:643-659, 1975. 9. Waggoner, A.P., A.H. Vanderpol, R.J. Charlson, L. Granat, C. Tragard and S. Laisen. The Sulfate Light Scattering Ratio: An Index of the Role of Sulfur in Tropospheric Optics. Report AC-33, Dept. of Meteorology, Stockholm University, Sweden. Accepted, Nature. 10. Scientific and Technical Assessment Report on Suspended Sulfates and Sulfuric Acid Aerosols. J.R. Smith, ed. Office of Research and Develop- ment, U.S. Environmental Protection Agency, Washington, D.C. 27 ------- 11. Whitby, K.T. Modeling of Atmospheric Aerosol Size Distribution. Progress Report, EPA Research Grant No. R800971, April 1975. 12. Gartrell, F.E., F.W. Thomas and S.B. Carpenter. Atmospheric Oxidation of SO in Coal-Burning Power Plant Plumes. Am. Ind. Hyg. J., 24:113-120, 1963. 13. Newman, L. , J. Forrest and B. Manowitz. The Application of An Isotopic Ratio Technique to the Study of the Atmospheric Oxidation of Sulfur Dioxide in the Plume From a Oil Fired Power Plant. Atmos. Environ., 9:954, 1975. 14. Newman, L., J. Forrest and B. Manowitz. The Application of An Isotopic Ratio Technique to the Study of the Atmospheric Oxidation of Sulfur Dioxide in the Plume From a Coal Fired Power Plant. Atmos. Environ., 9:969, 1975. 15. Wilson, W.E., R.B. Husar, K.T. Whitby, D.B. Kittleson and W.H. White. Chemical Reactions in Power Plant Plumes. In: Proceedings of the 171st National ACS Meeting, Div. of Environ. Chem., New York, N.Y., April 1976. 16. Husar, R.B., B.L. Blumenthal, J. Anderson and W.E. Wilson. The Urban Plume of St. Louis. In: Proceedings of the 167th National ACS Meeting, Div. of Environ. Chem., Los Angeles, CA, April 1974. 17. Husar, R.B., J.D. Husar, N.V. Gillani, S.B. Fuller, W.H. White, J.A. Anderson, W.M. Vaughan and W.E. Wilson. Pollutant Flow Rate Measurement in Large Plumes: Sulfur Budget in Power Plant and Area Source Plumes in the St. Louis Region. In: Proceedings of the 171st National ACS Meeting, Div. of Environ. Chem., New York, N.Y., April 1976. 18. Husar, J.D., R.B. Husar and P.K. Stubits. Determination of Submicrogram Amounts of Atmospheric Particulate Sulfur. Anal. Chem., 47:2062, 1975. 19. Husar, J.D., R.B. Husar, E.S. Macias, W.E. Wilson, J.L. Durham, W.K. Shepherd and J.A. Anderson. Particulate Sulfur Analysis: Application to High Time Resolution Aircraft Sampling in Plumes. Atmos. Environ., in press. 20. White, W.H., J.A. Anderson, W.R. Knuth, D.L. Blumenthal, J.C. Hsiung and R.B. Husar. Midwest Interstate Sulfur Transformation and Transport Project: Aerial Measurements of Urban and Power Plant Plumes, Summer 1974. EPA-600/3-76-110, U.S. Environmental Protection Agency, Research Triangle Park, NC, 1976. 125 pp. 21. Vaughan, W.M., R.B. Sperling, N.V. Gillani and R.B. Husar. Horizontal S02 Mass Flow Measurements in Plumes: A Comparison of Correlation Spectrometer Data with a Dispersion and Removal Model. Paper # 75-17.2, 68th Annual Meeting of the Air Pollution Control Association, Boston, Mass., 1975. 28 ------- 22. Whitby, K.T., B.C. Cantrell, R.B. Husar, N.V. Gillani, J.A. Anderson, D.L. Blumenthal and W.E. Wilson. Aerosol Formation in a Coal Fired Power Plant Plume. In: Proceedings of the 171st National ACS Meeting, Div. of Environ. Chem., New York, N.Y., April 1976. 23. White, W.H., J.A. Anderson, D.L. Blumenthal, R.B. Husar, N.V. Gillani, S.B. Fuller, K.T. Whitby and W.E. Wilson. Formation of Ozone and Light-Scattering Aerosols in the St. Louis Urban Plume. In: Proceedings of the 171st National ACS Meeting, Div. of Environ. Chem., New York, N.Y., April 1976. 24. White, W.H., J.A. Anderson, D.L. Blumenthal, R.B. Husar, N.V. Gillani, J.D. Husar and W.E. Wilson, Jr. Formation and Transport of Secondary Air Pollutants: Ozone and Aerosols in the St. Louis Urban Plume. Science 194:187-189, 1976. 25. Sehmel, G.A. Particle Diffusivities and Deposition Velocities Over a Horizontal Smooth Surface. J. Colloid Interface. Sci., 37:891-906, 1971. 26. Sehmel, G.A. Particle Eddy Diffusivities and Deposition Velocities for Isothermal Flow and Smooth Surfaces. Aerosol Science, 4:125-138, 1973. 27. Sehmel, G.A. and W.H. Hodgson. Particle and Gaseous Removal in the Atmosphere by Dry Deposition. Battelle Pacific Northwest Laboratories, Richland, WA 99352, BNWL-SA-4941, May 1974. 29 ------- TECHNICAL REPORT DATA (Plecsc read Instructions on the reverse before completing) i. REPORT NO. EPA-600/7-77-021 3. RECIPIENT'S ACCESSI ON-NO. 4. TITLE AND SUBTITLE SULFATES IN THE ATMOSPHERE A Progress Report on Project MISTT 5. REPORT DATE March 1977 6. PERFORMING ORGANIZATION CODE AUTHOR(S) W.E. Wilson, R.J. Charlson, R.B. Husar, K.T. Whitby and D. Blumenthal 8. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORGANIZATION NAME AND ADDRESS Environmental Sciences Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Research Triangle Park, North Carolina 27711 10. PROGRAM ELEMENT NO. 1NE625 11. CONTRACT/GRANT NO. 12. SPONSORING AGENCY NAME AND ADDRESS Environmental Sciences Research Laboratory - RTP, NC Office of Research and Development U.S. Environmental Protection Agency Research Triangle Park, North Carolina 27711 13. TYPE OF REPORT AND PERIOD COVERED Interim 14. SPONSORING AGENCY CODE EPA/600/09 15. SUPPLEMENTARY NOTES 16. ABSTRACT The size and sulfate content of atmospheric aerosols and the rate and mechanisms for sulfate formation from sulfur dioxide in power plant plumes are reviewed. Emphasis is given to results from the recent USEPA study, Project MISTT (Midwest Interstate Sulfur Transformation and Transport). The rate of conversion of sulfur dioxide to sulfate 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. Tall stacks reduce ground-level concentrations of sulfur dioxide, resulting in a reduction of the amount removed by dry deposition. In urban plumes, which are well-mixed to the ground near the source, sulfur dioxide is removed more rapidly by dry deposition. Thus, tall stacks increase the atmospheric residence time of sulfur dioxide, which leads to an increase in atmospheric sulfur formation. These sulfate aerosols may be transported over distances of several hundred kilometers and produce air pollution episodes far from the pollution source. 17. KEY WORDS AND DOCUMENT ANALYSIS DESCRIPTORS b.IDENTIFIERS/OPEN ENDED TERMS c. COS AT I Field/Group *Air pollution '-Aerosols *Sulfate *Sulfur dioxide *Sulfuric acid Electric power plants *Plumes "Conversion Project MISTT 13B 07D 07B 10B 21B 3. DISTRIBUTION STATEMENT RELEASE TO PUBLIC 19. SECURITY CLASS (This Report) UNCLASSIFIED 21. NO. OF PAGES 38 20. SECURITY CLASS (This page) UNCLASSIFIED 22. PRICE EPA Form 2220-1 (9-73) 30 ------- |