December 1994

Roofing Asphalt and Pitch Fumes: Their Composition and Cycling in the Atmosphere, in particular Polycyclic Aromatic Hydrocarbons
Jane Sorensen GEOG 271/3-AA The Natural Environment 3031284 Term Paper #1

Abstract: The composition of roofing tar condensates were noted and their atmospheric cycling reviewed. Polycyclic aromatic hydrocarbons (PAHs) were compounds of particular interest, because some of them are mutagenic. Roofing asphalt is not a significant source of PAH and other potentially hazardous chemicals when compared with the amount that the everyday motor vehicles emitting volume per urban area, nor with certain point sources such as aluminum smelters and coal furnaces. It has been shown hazardous to the workers, however, particularly coal tar pitch types. Mixtures such as asphalt and coal tar exhibit synergistic and antagonistic effects between components with respect to mutagenicity.

Introduction
Remarking on how unprotected people casually report dizziness, headache and nausea when exposed to hot asphalt fumes, and continuous speculation that roofing asphalt smoke and volatiles are carcinogenic I wanted to find out what this mixture of compounds contained, which was the most toxic component, and how that compound circulated in the atmosphere in general. The most toxic component was found to be, arguably, the polycyclic aromatic hydrocarbons (PAHs).

Discussion
The Canadian Standard Association gives classification under code A123.4-M1979 for the following types of roofing tar: Asphalt types 1-3, graded according to the surface temperature of the finished roof and the slope of the surface, and Coal Tar Pitches type A and B with the same grading. Asphalt no. 2 is air-blown without the use of a catalyst and no. 3 has a catalyst of ferric chloride (Machado et a1, 1993). Coal tar pitch is a solid residue of the fractional distillation of coke oven tar. Asphalts are derived from the oxidation of petroleum hydrocarbons. They are both solid at ambient ~temperature and have high vapour pressures, that is, they are not volatile until softening. The hazardous decomposition products are COx, NO x, SOx, other sulfur compounds, hydrogen sulfide during storage and transport of the hot product, and particulate matter (smoke). We have covered most of these compounds and their atmospheric cycling in class, as for hydrogen sulfide, it is very toxic and the workers must take care in opening the combustion compartment, but it oxidizes rapidly in the atmosphere. The maximum allowable limit of fume composition in air for eight hours is 5 mg per cubic meter (CSA 37-GP-37M). For a review of the above compounds and their biological effects, consult the appendix.

1 of 5

Discussion

Several species of polycyclic aromatic hydrocarbons (PAH) are also found in the fume condensates. PAH are compounds with two or more fused cyclic carbon structures, with hydrogen as the only other chemical constituent. The rings are bound in cluster, linear or angular arrangements (Baek et al., 1991; Singh et al., 1993). The chemical species found in asphalt and coal tar fume condensates are listed here, along with their abbreviations:
Naphthalene (NaP) acenaphthylene (AcN) flourene (Fl) phenanthrene (PhA anthracene (AN) flouranthene (FlA) pyrene (Py) benz(a)anthracene (BaA) chrysene (Chy) benzo(b)flouranthene (BbFlA) benzo(k)flouranthene (BkFlA) benzo(a)pyrene (BaP) indeno(1,2,3,-cd)pyrene (IP) Dibenzo(a,h)anthracene (dBahA) benzo(ghi)pyrene (BghlP)

sions were from fuel marketing, dry cleaning, surface coating and burning wood from forestry operations (the greatest natural source). This 38% also includes the total of 85% of volatile aromatic hydrocarbon (VAH, which are believed to be involved in ground-level ozone formation) emissions. The petroleum industry is responsible for the remaining 15%, which is more than 100 t per year (Hilborn and Still, 1990). Surface coating pertains to asphalt roofing, and in addition, dry cleaning solvent is one of the solvents used for preparing the surface for coating. Trichlorethylene is another substance used as a cleaning solvent, it has toxic effects upon the central nervous system, and can also oxidize in the environment to tetrachlorethylene, i.e. perchlorethylene. TCE has been found to be in the drinking water of 38% of North American cities (Amdur, Doull and Klaassen, 1991). Aromatic hydrocarbons can oxidize at sluggish rates to form alcohols, ketones, organic acids and other organic compounds. This makes them water soluble, therefore more amenable to absorption in the biota. In water treatment plants, sodium hypochlorite is added, thus exposing PAHs and other organics. to oxidative chlorination. Chlorinated hydrocarbons can be considered extremely toxic (Amdur, Doull and Klaassen, 1991; Maly, 1994). In the atmosphere, larger PAH molecules absorb UV radiation and are split into smaller entities. Singh et al. 1993} states that the main route for the transportation of anthropogenic PAHs is through the atmosphere and is in association with particulate matter of the size range 0.1-0.3 m, which is not efficiently removed by rain. Baek et al. (1991) classifies two size ranges of particles with which PAH associate, the larger of which can be removed by rain. The atmospheric residence time of a 1 m diameter particle ranges from a few days to a few weeks,

and several others (Singh et al., 1993; Machado et al., 1993; Baek et al., 1991). There are several hundred species of PAH in total, 100 of which are found in air (Baek et al., 1991; Singh et al., 1993). They are ubiquitous in animal and plant tissues, sediments, soils, air, and surface waters. They are produced when organic material is burned, and the yield is particularly high when there is an insufficient supply of oxygen. Coke ovens are a significant point source. PAHs are currently being released at a rate to about 2500 t per year (Canada). General aromatic hydrocarbon emissions from industrial processes (largely uncontrolled) increased 60% between 1970 and 1985. 38% of the total emis-

2 of 5

Roofing Asphalt and Pitch Fumes: Their Composition and Cycling in the Atmosphere, in particular

Discussion

therefore it is of little wonder that PAHs are found ubiquitously. They eventually impact or sediment onto soils, vegetation and aquatic systems, and are subsequently deposited in the sediments via runoff or in estuaries or coastal waters. Apparently, by knowing the characteristic PAH composition of a source emission, one can trace the sources responsible for PAH composition in the environment. One must take into account PAH deposited from distance sources, however, when generating a best-fit model for what the sources in a given pollution situation. Singh used sediments to predict the probable sources of PAH in the Milwaukee Harbor estuary, and there have been many analyses performed on the particulate composition of PAH in the atmosphere. Data from Peters et a1. (1981) and Ramdahl et a1. (1983) (see Bask et al. 1991) states that asphalt production is of a single order of magnitude in production of PAH when compared to coal and wood heating, open fires, coke manufacturing and aluminum smelting (three to four orders of magnitude), while gasoline engines emit in quantities of four orders of magnitude (U.S. study). Comparative studies in Sweden and Norway are of one order of magnitude less, or there are no emissions or data at all. Since a city tends to have high volumes of vehicular traffic and tar trucks are nowhere so ubiquitous, the correlation of urban atmospheric PAH can only be traced to roofing tar if it contains one specie of PAH that no other local industry emits. While the comparative burden of PAH emissions and the hazards they pose is very light on this industry, this industry must be responsible to any health hazards its workers face. Twenty-seven PAH compounds have been shown to be carcinogenic. Non-carcinogenic effects are growth retardation, tissue necrosis, and irritancy of the skin and eye (Maly, 1994; Hilborn and Still, 1990).

The isolation of pure aromatic hydrocarbons from coal tar and the demonstration of their carcinogenicity by...Kennaway in the 1930s was one of the milestones in studies on chemical carcinogenesis. There is good reason to suspect that these carcinogens are involved, for example, in lung cancer seen in cigarette smokers or tar roofing workers. Amdur, Doull and Klaassen, p. 172

There are also synergistic and antagonistic effects between compounds in mixtures pertaining to their carcinogenicity. BaP is a notable carcinogen; yet the carcinogenic activity of the asphalt fume condensates that the National Institute for Occupational Safety and Health investigated led them to conclude that BaP was not solely responsible. In a follow-up study, they hypothesized that sulfur heterocyclics may have contributed to the overall carcinogenicity (cited in Machado et al., 1993). In a classic paper on synergistic and antagonistic effects of individual PAHs on the mutagenicity of their mixtures, Monique Hermann discovered that several nonmutagenic hydrocarbons enhanced the mutagenicity of BaP, while most mutagenic PAH produced a decrease (and sometimes abolition) of the mutagenicity of BaP. To make predictions based on what we know of the PAH content of asphalt and coal tar pitch is too large a scope to address in this paper. What we can note is that coal tar pitch has been proven far more mutagenic than asphalt (Machado et a1., 1993). Incidentally, in Machado et al.s study, there was a strange correlation to higher condensate temperatures to increased mutagenicity, since PAH and in particular, BaP, are generated at low temperature, inefficient (i.e. oxygen-limited) combustions (Baek et a1, 1991). BaP acts mutagenicly by reacting directly with DNA and altering the base-pair sequences.

Roofing Asphalt and Pitch Fumes: Their Composition and Cycling in the Atmosphere, in particular Polycyclic

Conclusion

This will induce any proto-oncogene to become an oncogene, which is the first of many steps in the induction of cancer. Conclusion We can see that the two types of roofing tars are hazardous to health when working constantly within or when in close proximity to it. It seems necessary to use, and when compared with automobiles and coal-using factories it emits a negligible amount of PAH, NO x and SOx. My suggestion to city councils in every city having a damp climate like Montreal: to reduce the number of tar trucks in operation and make control of these emissions more possible, then legislate that all new and renovated buildings under 5 storeys have a fully sloping roof (taller than 5 storeys may have safety problems in winter for ground traffic). The asphalt shingles used would result in emissions from a point source, and aluminum or tile roofs can also be used. References Amdur, M., J. Doull, and C. Klaassen, eds. (1991). Casarett and Doulls Toxicology 4E. Pergamon Press Inc., New York. Bask, S.O., R.A. Field, M.E. Goldstone, P.W. Kirk, J.N. Lester and R. Perry (1991). A review of atmospheric polycyclic aromatic hydrocarbons: sources, fate and behaviour. Water, Air, and Soil Pollution 60: 279-300

Hermann, M.(1981). Synergistic effects of individual polycyclic aromatic hydrocarbons on the mutagenicity of their mixtures. Actuation Research 90: 399-409 Hilborn, J. and M. Still (1990). Canadian Perspectives on Air Pollution, a State of the Environment Report, No. 90-1. Environment Canada. Machado, M.L., P.W. Beatty, J.C. Fetter, A.H. Blackman, and E.L. McGinnis (1993). Evaluation of the relationship between PAH content and mutagenic activity of fumes from roofing and paving asphalts and coal tar pitch. Fundamental and Applied Toxicology 21: 492499 Maly, M.(1994) Class Notes for Biology of Pollutants. Singh, A.K., M.F. Gin, F. Ni and E.R. Christensen (1993). A source-receptor method for determining non-point sources of PAHs to the Milwaukee Harbor estuary. Water Science and Technology v. 28 n.89: 91-102 Standard for: Application of Hot Asphalt for Damp-proofing or Waterproofing, Canadian Standards Association 31-GP-37M, covering numbers CSA A 123.7 and 123.4 M1973. Graciously supplied by A. Chouinard at Asphalt Sales, Petro-Canada, Montreal.

4 of 5

Roofing Asphalt and Pitch Fumes: Their Composition and Cycling in the Atmosphere, in particular

Appendix

Appendix The particulate matter that combustion processes contribute to the environment decrease visibility through the scattering of light, and also carry molecules of other compounds on their surfaces. They are used as condensation nuclei in the upper troposphere and stratosphere and they are washed out by the rain or snow in a process called wet deposition or they eventually circulate low enough to fallout onto surfaces. It is in this manner they contribute to acid deposition. They are carried long distances by wind, particularly if their point source is a super stack (the faster winds in the upper troposphere pick them up). The human nasal and tracheary passages have mucus traps for particulate matter, but the smallest particles will reach the alveoli in the lungs and be engulfed by the lung cells and possibly be transported in the blood. This can have a synergistic effect when other chemical pollutants are taken up in the same manner. Sulfur dioxide and nitrogen oxides are produced through combustion and smelting processes, and are often associated with the surfaces of particles. Oxidation reactions lead to the formation of sulfate and nitrate particles, which react acidicly when they come into contact with wet surfaces. In industrial processes, sulfur dioxide can be captured to be utilized in the production of sulfuric acid. SO2 induces chronic lung disease, and acute concentrations sting eyes and result in increased airway resistance. The maximum acceptable limits are of 340 ppb/1 hr, 60 ppb/24 hr, and 10 ppb/1 yr. In studies on guinea pigs, 5.7 ppm were found to be beneficial, presumably because it kills airborne pathogens. As a warning, however, hormesis (benefits through nutritional or ecological release) will happen with most harmful

compounds when in the lowest concentrations. 200 ppm of SO2 is often lethal. The toxicity for plants is 3 times more acute than it is for animals. Nitrogen oxides are readily formed by the direct reaction of nitrogen and oxygen in the air via combustion processes (including forest fires), natural biogenic (i.e. bacterial) processes, lightning, and volcanic action. Nitric oxide is the first product from the combustion of fuel, it is easily converted to NO 2 . in the atmosphere. Their respective residence times ln the atmosphere are 4 and 3 days. N20 is also formed, and while this gas is harmless at ground level, it has been implicated ln global warming. NOx can be oxidized further in the atmosphere to form nitric acid or nitrate salts, such as ammonium nitrate, which will react with volatile organic compounds in the presence of light to form groundlevel ozone. NO x can cause lung disease, pulmonary edema or even death. Sometimes sufficient exposure of NO x will result in it entering the blood, being converted to nitrite, and then blading to the hemoglobin. This condition is known as methaemoglobinemia. 500 ppb/4 hr has been found to reduce host resistance to bacterial and viral infection. There are effects on pulmonary function at 100 ppb; children are particularly susceptible, chronic bronchitis being a possible indicator of constant exposure. NO 2 suppresses growth of vegetation, corrosion of metals, fading of dyes, and degradation of rubber, plastics and textiles. The maximum acceptable limits are 210ppb/1 hr,110ppb/24 hr, and 50 ppb/yr. The 24-hour limit has been exceeded 29 times as of 1990 at a National Air Pollution Surveillance site in Montreal.

Roofing Asphalt and Pitch Fumes: Their Composition and Cycling in the Atmosphere, in particular Polycyclic