United States Environmental Protection Agency Industrial Environmental Research Laboratory Cincinnati OH 45268 Research and Development EPA-600/S2-82-063 Sept. 1982 Project Summary Chemical Stabilizers for the Control of Fugitive Asbestos Emissions from Open Sources Paul K. Ase, Roger Koch, and George Yamate Quarried serpentinite, recently found to contain asbestos, is used as aggregate for surfacing secondary roads. Emission concentrations of 0.6 x 106 to 8 x 10* fibers/m3 were collected 20m downwind from a serpentinite surfaced roadway. These levels correspond to emission factors of 34x1010 to 370x1010 fibers/km- vehicle at vehicular traffic speed of 13.4 m/sec (30 mph). Chemical treatments were tested for controlling these asbestos emis- sions. Laboratory tests were developed for screening 51 candidate commer- cial materials. Four of the most promising were field tested. Asbestos emission reductions of up to 90% were achieved with chemical treat- ments at application rates ranging from $0.08/m2 to $0.25/m2. Similar emission reductions were observed with traffic speeds reduced to 6.7 m/sec (15 mph). This Project Summary was devel- oped by EPA's Industrial Environ- mental Research Laboratory, Cincin- nati. OH. to announce key findings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). Introduction Quarried serpentinite crushed stone is the major source of crushed stone where it is readily available and in localities where access to limestone is limited. Limestone is preferred because it is a sedimentary material, and therefore has better weathering prop- erties. Serpentinite is used as road aggregate material for parking lots, driveways, and country roads. It is also used as base course for highways, as concrete aggregate, and as binder filler for asphalt paving. Serpentinite rock formations occur at or near the earth's surface in many regions of eastern United States. Belts of serpentinite extend from Maine to Alabama, covering much of the Appalachian Moutains. Serpentinite is native to extensive regions of the western United States also. The bulk of serpentinite quarried in the United States for crushed stone is made up of antigorite. However, chryso- tile, tremolite, deweylite, talc, antho- phyllite, and other silicate minerals have been reported to occur in serpen- tinite. Dustfall collected along roads and trails in a western recreational area located over a serpentinite massif contained 90 percent chrysotile. On the other hand, the average concentrations of asbestos in quarried serpentinite crushed stone ranged from 10 * 1010 fibers/g to 100 * 10'° fibers/g, repre- senting roughly 0.1 to 1% by weight asbestos in the quarried stone. The erosive action of vehicular passage is much more intensive than the action of wind alone. The large dust plume in the wake of an automobile on a dirt road gives visible demonstration to the intense dust generating forces that accompany vehicular traffic on unpaved ------- roadways (See Figure 1). The mechan- ical action of the tires on the road surface kicks up dust particles and places them directly into suspension. The simultaneous turbulence of vehic- ular movement adds more suspension in the wake. Large dust plumes are formed which are easily dispersed by the faintest air currents. On unpaved crushed stone roadways, the pressure of vehicular tires on the road surface applies an intense grinding action on the unbound rock which replenishes the fines lost to suspension. Since the effect of vehicular traffic is much more severe than the action of wind alone, the amount of stabilizer material needed to control roadway emissions is also much greater than that required to control wind erosion. The present program was undertaken to determine the extent to which dust control agents might provide control over asbestos emissions from the use of crushed serpentinite rock on unpaved roadways. Laboratory tests were devel- oped to screen control agents and levels of their application. In all, 69 materials were considered. Of these, 51 were screened in the laboratory tests. Three levels of application, based on cost of control agents, were tested. Transmis- sion electron microscope (TEM) analysis of air samples collected near the roadway were used to evaluate the effectiveness of four of the most promising control agents in field appli- cations. Conclusions Serpentinite is native to many parts of eastern and western United States. Serpentinite rock in some of these regions is quarried and is used locally as aggregate for surfacing material on secondary roads. The quarried ser- pentinite is known to contain asbestos. Chemical stabilizers were tested for controlling asbestos emission from unpaved roadways surfaced with crushed serpentinite. Significant asbestos emis- sions over background levels were measured on the untreated roadway. Emission factors of 34 x 1010 to 370 x 1010 fibers/km-vehicle were reached for a vehicular traffic speed of 13.4 m/sec (30 mph). These emission generation levels corresponded to ambient concentrations of 0.6 x 106 to 8 x 106 f/m3 at 20 m downwind from the road. Fiber emission reductions of 80 to 90 percent were achieved with chemical treatment. Similar reductions were Figure 1. Large dust plume in the wake of an automobile on a serpentinite crushed stone road. achieved with reduction in traffic speed to 6.7 m/sec (15 mph). The asbestos emissions were essen- tially all chrysotile asbestos. The observed fibers were all in the respirable range and averaged <0.1 fjm indiameter and <2 //m in length. The emission fibers were classified in terms of four structural forms: individual fibers, matrices, bundles, and clusters. The fiber structures found in the roadway emissions were mostly either single fibers or fibers attached to rock matrix material. Very few bundles or clusters of fibers were found. Fiber structures found in the emission from the untreated roadway section and the treated roadway sections were indistinguishable. Respirable emission levels were much lower than projected from the concentration of asbestos fibers in the dust from fresh quarry crushed aggre- gates. This may be due, in part, to the manner in which the serpentinite tends to break up along asbestos-containing seams during crushing. It may also be due, in part, to the presence of larger aggregates in which the fibers are still bound and not released. The field-tested treatments showed that they were each capable of control- ling asbestos emissions. The treatment choice would depend on a number of factors including: availability of treat- ment, equipment on hand, and local climatic conditions. More extensive testing could be used to refine application strategies. These should be tailored to the physical nature of the individual treatments and anticipated local condi- tions. Under the most severe weather conditions, traffic controls could also be used to hold down emissions. Alterna- tively, significant emissions reductions might be achieved by removing the initial fines from the freshly produced aggregates. Methodology There is no data on the comparative effectiveness of stabilizers for the present application, i. e., to control emission of asbestos from crushed stone roadways. Stabilizers were se- lected from those which showed prom- ise in other applications such as soil stabilizers, as palliatives for treatment of unpaved roadways, and for application on asbestos waste piles, as well as other more recent commercial materials. Of 69 chemical agents originally selected, 51 were laboratory tested. A number of desirable properties for chemical agents are needed for them to act as effective stabilizers including low application cost, water solubility, high bondability to the particles, long life and stability, resistant to heat and cold, nonphytotoxicity, biodegradability, no drainage water pollution problems, ease of cleaning from application devices, and effectiveness at low dilutions. In addition, for roadway use it would be useful for the chemical agents to have a regenerative capacity in order to maintain control action in spite of the continual generation of fresh particu- lates from the pulverization of surface materials. The stabilizer cost was used as a basis for comparing stabilizer effectiveness in the laboratory tests. Application rates of $0.01/m2, $0.05/m2, and $0.25/m2 were selected. These rates were based on bulk material prices and the amount of each material required for a 1 m2 x 2.54 cm (1 in.) deep application. Laboratory Tests In the laboratory screening tests, the main emphasis was placed on the measurements of treatment control effectiveness. Ball milling was selected to simulate the wear action of vehicular traffic over crushed stone road beds, and the fine fractions, measured by sieve analysis, were used to determine stabilizer effectiveness. The overall laboratory test procedure used a series of six consecutive steps: 1. Sample Preparation — Weighing and Drying, 2. Initial Sieve Analysis, 3. Treatment Application, 4. Rain Cycling, 5. Traffic Simulation, and 6. Final Sieve Analysis. The treatment effectiveness of each stabilizer treatment was calculated as the weight fraction of fines <140 mesh found in each sample after the traffic simulation compared to the weight ------- fraction of fines <140 mesh found initially in each sample. The treatment effectiveness is referred to here as the Treatment Score (TS): TS _ Final Wt % <140 mesh Initial Wt % <140 mesh where the Wt % is based on the total dry sample weight. The treatment effec- tiveness, TS (treatment), is further normalized by comparison with the treatment effectiveness of the control, TS (control), treated with water only. The value for the normalized treatment effectiveness is referred to as Relative Treatment Score (RTS): TS (treatment) Wind TS (control) The RTS is the ratio of the treatment effectiveness for a particular stabilizer at a selected treatment level (e.g., $0.01 /m2, $0.25m2) compared to the effectiveness with only water (control). The value for TS (control) was calculated from the average of randomly selected control samples. Field Tests Four of the most highly ranked laboratory treatments were selected for field testing: Coherex (oil byproduct emulsion), SS-1H (asphalt emulsion), Liquidow (aqueous calcium chloride), and Orzan GL-50 (ammonium liquo- sulfonate). These treatments were applied on the roadway and upwind and downwind high volume air sampling stations were positioned to collect emissions. The collected high volume filter samples were analyzed by trans- mission electron microscope (TEM) methods for ambient air asbestos. A public secondary road in Maryland, surfaced with crushed serpentinite, was selected for field testing. The crushed serpentinite rock used on the road was produced locally. This aggre- gate material is used on approximately 60 miles of unpaved secondary roads throughout the country. Fresh crushed serpentinite, crusher No. 6 (~<7.5 cm) was applied during the summer along a 5OO-m field test section. The field treatments were applied in the fall. A section of roadway was prepared for each of the four treatments and a fifth was used as a control section with no treatment, as shown in Figure 2. Applications were made with readily available road working equipment: a water sprinkler truck and a road grader. The grader was used to serape the road surface to a depth of 2.5 cm (1 in.), and this was done just before each treatment UpwindSamp/ing Sites D- --D 6 N t 5. -+ j I\|\\\N t, Test Sections 4. 3. \v\\N_- Holy Cross Road Ammonium Coherex Lignosulfonate 20m twnwind Sampling Sites d 5 -D-- 30m 2. -i\\\\TLi\\\\s/ _ QJI Calcium EmulsionChloride --D D-- 432 1. fs ^ x \ \N Control --D ' Weather O ' < Station Figure 2. Field test sections on crushed serpentinite roadway, each 5.5m x 67.5m. Table 1. Comparison of Laboratory and Field Application Rates. Application Rate Laboratory Treatment Coherex (oil byproduct emulsion) SS-1H (asphalt emulsion) Liquidow (calcium chloride) Orzan GL-50 (lignosulfonate) 1/m2 1.8 2.3 7.2 7.2 (gal. /yd2) (0.4) (0.5) (1.6) (1.6) Field 1/m2* 1.5 2.3 2.3 2.3 (gal. /yd2) (0.33) (0.5) (0.5) (0.5) *Treatments were diluted for ease of application and applied at the rate of 4.5 1/m2 (1 gal./yd2) of the diluted treatment. application. The treatment and their application rates are shown in Table 1. The test sections, each 67.5 m (220ft) long and 5.6 m (18.5 ft) wide, were separated by 23 m (75 ft) long inhibited sections on which the emulsion oil was applied to minimize "cross talk" between the sections. (Figure 3.) All treatments, except the SS-1H, emulsion oil, were applied from the water truck. All treatments were made as single applications. The amount needed for a 2.5 cm (1 inch) depth was mixed for each test area in the sprinkler truck and applied through a sprinkler bar. Between 6 to 10 passes of each treatment were used to get uniform application and to permit the treatments to soak in. (Figure 4). After each treatment application, the grader was used to mix the treatment into surface layer by blading. (Figure 5). In this operation the wetted, treated aggregates were bladed to the center of the road from each side. Then the central pile was spread out and a crown formed in the middle of the road. (Figure 6). This procedure was used to provide intimate mixing of the aggregates with the treatment. Several additional passes Figure 4. Application of a treatment were then made by the grader to roll out from the water truck to a test the surface. section. Figure 3. Emulsion oil application to minimize "cross talk" between test sections. ------- Figure 5. Grader used to mix the treat- ment into surface layer by blading. Figure 6. Central pile spread out to provide intimate mixing of the aggregates with the treatment. Upwind/downwind air samples were collected immediately after application of treatments and six months later, in the spring. These ambient air samples were collected with high volume sam- plers on 20.3 cm x 25.4 cm membrane filters. The downwind high volume samplers were located 20 m downwind of the road centerline and aligned with the average wind direction through the middle of each roadway test section. Two upwind stations were located 30 m upwind of the roadway, 150 m apart. At the beginning and end of each run high volume sampler flow rates were verified with a magnehelic gauge calibrated with a high volume air sample calibrator. Meterological information was obtained continuously from a recording weather station which was located in an open field 40 m south of the control section. The instrument readout was used to align the sampling stations with the test sites and the current average wind direction. Tests were conducted only when the average wind direction was perpendicular to the roadway. Ambient air samples were collected on membrane filters. The bulk of the samples were collected on 0.4 /um pore diameter polycarbonate membrane filters. In addition, 0.8 fjm pore size cellulose mixed ester membrane filters were used to collect emission from the control section in parallel with the polycarbonate filter samplers. A What- man 41 cellulose filter was used as a backup support filter for each membrane filter. At the end of each run, filter sections were stored in 150 mm petri dishes and returned to the laboratory for analysis. The filter samples were prepared and analyzed in accordance with EPA's provisional methodology for ambient air asbestos. The EM grid samples were examined with a JEOL 100C analytical electron microscope in the Transmission Electron Microscope (TEM) mode. Grid samples were screened initially under low magnification by TEM to determine suitability for further examination. In this inspection the grid was examined for loading, uniformity, lack of processing contamination, adequacy of clearing, and damage. Inadequate grids were either reprocessed or discarded and reprepared from another filter section. Acceptable prepared samples were examined at a 20.000X magnification for chrysotile and amphibole asbestos fibers. Fibers with length to width ratios of greater than 3:1 and substantially parallel sides were recorded. The fibers were classified as: • chrysotile asbestos • amphibole asbestos • ambiguous (incomplete spot pat- tern) • non-asbestos (definitely some other mineral) • no pattern (unknown, no spot pattern). Fibers were classified based on mor- phology and recognition of selected area electron diffraction (SAED) pattern. TEM morphology and SAED patterns from standard samples were used as guides for fiber identification. Fibers showing the tubular structure of chry- sotile are tentatively classified as chrysotile but morphological features alone are not sufficient to distinguish chrysotile and amphibole from other fibrous minerals. A recognizable SAED pattern is used to confirm identification. Pattern recognition is not always easy for ambient air samples which can include interference from nearby part- icles and attached aggregates. Due to the very light fiber loading encountered in the field samples, the procedures for counting at low loading levels were followed. The entire grid opening was scanned and the entire grid openinc was considered as a single field. Each grid opening was scanned in a series ol parallel scans across the grid until a total of 10 grid openings or 100 total fibers were counted, whichever occurred first. In the roadway emission samples, fibers were identified in several contexts with other particulates, not currently considered under the provisional meth- odology. These were characterized as asbestos structures. The effective concentration and desposition pattern in the respiratory system will be affected by the asbestos content and on the aerodynamic size of individual asbestos structures. The individual "fiber" is a form of asbestos structure which is isolated from all other particulates. The other structural forms are "bundles", "clusters", and "matrices", by themselves or in com- binations. A bundle is a single entity composed of fibers in a parallel ar- rangement with each fiber closer together than one fiber diameter. A cluster is a single entity composed of numerous fibers in random orientation with all other fibers intermixed in a single group. A matrix is a fiber with one end free and the other end embedded in some other material. Each of these asbestos structures were included as single asbestos entities in the analysis for asbestos fibers, provided it met the test for asbestos by morphology and SAED pattern. Results The transmission electron microscope was used as the principal analytical tool for the field sample measurements. In general, the filter loadings were all very light. The asbestos fiber concentrations on a count basis were mainly all chrysotile. The overall amphibole fiber concentration was <3 percent. While the amphiboles found were all single fibers, chrysotile occurred about equally as single fibers and as matrix fibers. Bundles and clusters were only occa- sionally observed. The asbestos emissions concentra- tions from the road were determined as the difference between upwind and downwind concentrations based on the TEM fiber counts. These observed levels of asbestos concentrations were used to estimate emission factors. In the control section, the emission factor (f/km- vehicle) varied from 32 x 10'° to 370 x 1010 fibers/km-vehicle corresponding to net emission concentrations of 0.6 x ------- 10e to 7.7 x io» fibers/m2. The lowest levels were collected in mid-fall just after treatment application while the highest levels were collected during the following spring. With chemical treat- ment, overall fiber emission reductions of 80 to 90 percent were achieved. Two stabilizer mechanisms for asbes- tos emission control were identified: 1) Stabilizer which forms a solid, water resistant surface coating and binds road aggregates togeth- er — This type is represented by SS-1H and Coherex, both of which are petroleum byproducts. After 6 months, they still retained better than 80 percent emission reduction when applied at the level of $0.20/m2 to $0.25/m2. 2) Stabilizer which forms a water soluble surface matrix which binds surface particles together — This type may not control aggregate wear as well as the first, but is able to rewet new particulates and repair worn surfaces to minimize emission. This type is represented by Liquidow (calcium chloride) and Orzan GL-50 (ligno-sulfonate). The first is hygroscopic and main- tains a high moisture presence in the road surface. The second fills the voids and can be redispersed by precipitation. These showed little emission control after 6 months when applied at the rate of $0.08/m2, but periodic reapplica- tion can be used to maintain emission control. Essentially all of the asbestos found in the downwind air samples were within the respirable range, (<3.5 /urn in aerodynamic diameter). A large fraction of the fibers were still attached to matrix particulates. This suggests that the fibers in serpentinite, which occur in thin veins and bundles, are in intimate association with the matrix rock but are easily separated into small, thin fibers which are then emitted. However, the concentration of asbes- tos collected from the control section emissions were much lower than expected based on the level of fines in the road surface aggregates and the on average concentration of asbestos found in fresh quarried crushed stone. Several factors may contribute to this reduced level of asbestos emissions found. When fresh aggregate is laid on the road, the fiber release may be relatively high. However, the original free fibers may soon be depleted by being emitted into the air or by being washed away. When subsequent grinding of the larger aggregates replaces the original fines with others which contain reduced concentrations of asbestos, the long- term asbestos emissions from the road will be reduced correspondingly. Those fibers buried in the aggregates could not be identified and were not counted. Thus, the presence of these fibers would not be evident under EM analysis. Also, much of the fugitive dust ejected from an unpaved road are large particulates, which deposit close to the edge of the road. Fibers bound in such large particles did not reach the samplers and thus were also excluded from analysis. Paul K. Ase, Roger Koch, and George Yamate are with IIT Research Institute. Chicago, IL 60616. Mary K. Stinson is the EPA Project Officer (see below). The complete report, entitled "Chemical Stabilizers for the Control of Fugitive Asbestos Emissions from Open Sources," (Order No. PB 82-249 905; Cost: $9.00. subject to change) wilt be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Industrial Pollution Control Division Industrial Environmental Research Laboratory—Cincinnati U.S. Environmental Protection Agency Edison, NJ 08837 . S. GOVERNMENT PRINTING OFFICE: 1982/659-095/539 ------- United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Postage and Fees Paid Environmental Protection Agency EPA 335 Official Business Penalty for Private Use $300 RETURN POSTAGE GUARANTEED Third-Class Bulk Rate ------- |