An Aerosol Condensation Model for Sulfur Trioxide

This document describes a model for condensation of sulfuric acid aerosol given an initial concentration and/or source of gaseous sulfur trioxide (e.g. fuming from oleum). The model includes the thermochemical effects on aerosol condensation and air parcel buoyancy. Condensation is assumed to occur heterogeneously onto a preexisting background aerosol distribution. The model development is both a revisiting of research initially presented at the Fall 2001 American Geophysical Union Meeting [1] and a further extension to provide new capabilities for current atmospheric dispersion modeling efforts [2]. Sulfuric acid is one of the most widely used of all industrial chemicals. In 1992, world consumption of sulfuric acid was 145 million metric tons, with 42.4 Mt (mega-tons) consumed in the United States [10]. In 2001, of 37.5 Mt consumed in the U.S., 74% went into producing phosphate fertilizers [11]. Another significant use is in mining industries. Lawuyi and Fingas [7] estimate that, in 1996, 68% of use was for fertilizers and 5.8% was for mining. They note that H{sub 2}SO{sub 4} use has been and should continue to be very stable. In the United States, the elimination of MTBE (methyl tertiary-butyl ether) and the use of ethanol for gasoline production are further increasing the demand for petroleum alkylate. Alkylate producers have a choice of either a hydrofluoric acid or sulfuric acid process. Both processes are widely used today. Concerns, however, over the safety or potential regulation of hydrofluoric acid are likely to result in most of the growth being for the sulfuric acid process, further increasing demand [11]. The implication of sulfuric acid being a pervasive industrial chemical is that transport is also pervasive. Often, this is in the form of oleum tankers, having around 30% free sulfur trioxide. Although sulfuric acid itself is not a volatile substance, fuming sulfuric acid (referred to as oleum) is [7], the volatile product being sulfur trioxide. Sulfate aerosols and mist may form in the atmosphere on tank rupture. From chemical spill data from 1990-1996, Lawuyi02 and Fingas [7] prioritize sulfuric acid as sixth most serious. During this period, they note 155 spills totaling 13 Mt, out of a supply volume of 3700 Mt. Lawuyi and Fingas [7] summarize information on three major sulfuric acid spills. On 12 February 1984, 93 tons of sulfuric acid were spilled when 14 railroad cars derailed near MacTier, Parry Sound, Ontario. On 13 December 1978, 51 railroad cars derailed near Springhill, Nova Scotia. One car, containing 93% sulfuric acid, ruptured, spilling nearly its entire contents. In July 1993, 20 to 50 tons of fuming sulfuric acid spilled at the General Chemical Corp. plant in Richmond, California, a major industrial center near San Francisco. The release occurred when oleum was being loaded into a nonfuming acid railroad tank car that contained only a rupture disk as a safety device. The tank car was overheated and this rupture disk blew. The resulting cloud of sulfuric acid drifted northeast with prevailing winds over a number of populated areas. More than 3,000 people subsequently sought medical attention for burning eyes, coughing, headaches, and nausea. Almost all were treated and released on the day of the spill. By the day after the release, another 5,000 people had sought medical attention. The spill forced the closure of five freeways in the region as well as some Bay Area Rapid Transit System stations. Apart from corrosive toxicity, there is the additional hazard that the reactions of sulfur trioxide and sulfuric acid vapors with water are extremely exothermic [10, 11]. While the vapors are intrinsically denser than air, there is thus the likelihood of strong, warming-induced buoyancy from reactions with ambient water vapor, water-containing aerosol droplets, and wet environmental surface. Nordin [12] relates just such an occurrence following the Richmond, CA spill, with the plume observed to rise to 300 m. For all practical purposes, sulfur trioxide was the constituent released from the heated tank car. The behavior of the resulting plume suggested that initially sulfur trioxide behaved as a dense gas, but the chemical reacted with air humidity, producing sulfuric acid and heat. The heat caused the plume to rise. Eventually the plume cooled, resulting in sulfuric acid descending towards people on the ground. This kind of behavior is not accounted for in the popular gas dispersion models. In the presence of complex terrain, such heat induced buoyancy could enable a sulfur trioxide cloud to leap local drainage boundaries with a single bound. Unless there were insufficient water/humidity to fully react with the SO{sub 3} and H{sub 2}SO{sub 4} on the first ascent, no secondary bounds would be expected, the cloud then behaving as a heavy tracer until sufficiently diluted.

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