United States Environmental Protection Agency Environmental Monitoring Systems Laboratory Las Vegas, NV 89193 Research and Development EPA/600/S4-91/009 July 1991 EPA Project Summary Background Hydrocarbon Vapor Concentration Study for Underground Fuel Storage Tanks Claude A.J. Schleyer This project was initiated to investi- gate the effectiveness of soil gas sam- pling in leak detection. Soil gas sur- veys were performed at 27 active gaso- line service stations in three diverse geographic regions. Hydrocarbon va- por concentrations in the backfill sur- rounding the underground storage tanks were sampled and analyzed. The 27 gasoline service stations were se- lected as non-leaking sites and the three regions were selected for their active underground storage tank regu- latory programs, as well as their differ- ences in geology, hydrology and cli- mate. A comparison was made with con- taminated site data obtained from Tracer Research Corporation's histori- cal records and significant differences can be seen between the two distribu- tions. It was determined that the best approximation of total hydrocarbon (less light aliphatics) concentrations, based on available calibration data, was achieved using an average response factor calculated from the daily re- sponse factors of benzene, toluene, ethylbenzene, and ortho-xylene. This Project Summary was developed by EPA's Environmental Monitoring Systems Laboratory, Las Vegas, NV, 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 A field sampling program was under- taken around underground storage tanks (USTs) to establish a baseline data set of hydrocarbon vapor concentrations. Data were collected from 27 gasoline service stations selected as non-leaking sites, in three diverse geographic regions: Central Texas (Austin, Texas); areas surrounding Long Island Sound (Suffolk County, New York; Providence, Rhode Island; Storrs, Connecticut); and Southern California (San Diego, California). The three regions were selected for their active UST regulatory programs, as well as their differences in geology, hydrology, and climate. Procedures A site was considered to be non-leak- ing if it had good inventory and mainte- nance records, or had recently passed a tank tightness test. The non-leaking data- base consists of 279 soil vapor samples from 25 service stations. At the other two stations, observed or suspected leaks pre- vented their data from being used in the non-leaking database. At each location, soil was sampled at varying distances and depths from UST appurtenances (such as submersible pumps, vents, and product flow lines) to determine if a particular pattern of hydro- carbon concentration existed. Samples were collected by driving a hollow steel probe into the ground, and evacuating 5 to 10 liters of soil vapors with a vacuum pump. Volatile hydrocarbon species were Printed on Recycled Paper ------- Identified and quantified at the site by utilizing gas chromatograph/flame ioniza- tion detection (GC/FID) equipment. Ten to fifteen samples were collected and ana- lyzed at each site. The types of compound groups that were studied were aliphatics, aromatics, and total hydrocarbons. The concentra- tions of volatile aliphatics that elute from the GC column before benzene were re- ported as a group called "light aliphatics." At 18 of the sites, the "light aliphatics" represent aliphatic compounds such as methane, ethane, propanes, butanes, and pentanes. At seven of the sites where butanes and pentanes could be quantified and reported, the concentration of "light aliphatics" represent only methane, ethane, and propanes. The aromatics reported were benzene, toluene, ethylbenzene, and the xylenes. Hydrocarbon concentrations in soil gas are reported in micrograms per liter (mg/ L). These concentrations were calculated directly from the GC/FID using calibration gas response factors and sample volumes. The concentration of total hydrocarbons (less light aliphatics) were estimated us- ing an average response factor from the gas standards; benzene, toluene, ethylbenzene and ortho-xylene (BTEX). The concentrations in mg/L were converted to parts per million by volume (ppmv), using average molecular weights of BTEX at each site, and the ambient tempera- tures and pressures. Hydrocarbon vapor concentrations from the non-leaking sites range from detection limit levels of 0.02 micrograms per liter (Hg/L) to maximum values of 1,500,000 pg/L of light aliphatics, 110,000 u.g/L of benzene, 160,000 ug/L of toluene, 25,000 ug/L of ethylbenzene, and 110,000 ug/L of xylenes. The maximum concentration of total hydrocarbons (less light aliphatics) 1,100,000 ug/L. Determination of total hy- drocarbon concentrations exclude the light aliphatic peaks in order to elevate the compounds most representative of gaso- line. Additionally, subtraction of the light aliphatics peaks precludes the inclusion of methane concentrations caused by natu- rally occurring organic decomposition. Results and Discussion The statistical distribution of total hydro- carbons (less light aliphatics) indicates that a majority of the concentration values are in the lower concentration ranges. The relative frequency distribution shows 53.2 percent of the samples below 1,500 ug/L (500 ppm by volume) and 93.1 percent below 100,000 ug/L (27,000 ppm by vol- ume). The median is 800 ug/L and the mean is 23,300 ug/L. Contamination site data were obtained from Tracer Research Corporation's his- torical records. The contaminated site data consists of 60 soil vapor samples taken from nine sites having known contamina- tion from petroleum fuel leak or spill. These sites were all active gasoline service sta- tions or fueling facilities. The contaminated site data also shows much variability. The statistical distribution of total hydrocarbons (less light aliphatics) shows a majority of sample values to be in the lower concen- tration ranges. The relative frequency dis- tribution shows 35 percent of the samples below 1,500 ug/L (500 ppm by volume) and 66.7 percent below 100,000 ug/L (27,000 ppm by volume). The median is 9,000 ug/L and the mean is 160,000 ug/L. Although much variability exists in both the non-leaking and contaminated site data, significant differences could be seen between the two distributions. A 10-fold difference exists between the numbers of samples with concentrations above 100,000 ug/L (3,000 ppmv) for the two data sets. For example, 29.6 percent of the non-leaking samples occurred in the range of 10,000 ug/L to 100,000 ug/L while 33.3 percent of the contaminated samples concentrations occurred in the range of 100,00 ug/L to 1,000,000 ug/L. Statistical data patterns associated with site location and sample depth were de- lineated using non-parametric statistical methods. Statistically significant differences were found to exist between the total hy- drocarbon (less light aliphatics) vapor con- centrations among the five locations stud- ied for steel tank systems, whereas these differences were not significant for fiber- glass tank systems. Statistically significant differences also occurred between the to- tal hydrocarbon (less light aliphatics) va- por concentrations among the sample depths of 2,6, and 10 feet for both steel and fiberglass tank systems. Higher con- centrations were found at the lower depths. A fresh spill at one station in Austin provided an opportunity to add butane to the list of analytes under study. The bu- tane concentration in 15 soil gas samples taken during the first four days after the spill occurred ranged from 530 ug/L to 300,000 ug/L. Butane was also sampled at sites in Storrs, Connecticut, and Provi- dence, Rhode Island, both of which had no evidence of recent leaks or spills. At these two sites, butane concentrations in 65 soil gas samples ranged from the mimimum detection limit of 0.02 ug/L to 930 ug/L. The large difference between the butane concentrations at the fresh spill site in Austin and the non-leaking sites in Connecticut and Rhode Island suggest that butane may be a good indicator of a fresh spill or leak. Conclusion Because there are no standard proce- dures for estimating and reporting total hydrocarbon concentration data, Geo- science Consultants, Ltd. evaluated differ- ent estimation methods. It was determined that the best approximation of total hydro- carbon (less light aliphatics) concentra- tions, based on available calibration data, was achieved using an average response factor calculated from the daily response factors of benzene, toluene, ethylbenzene, and ortho-xylene. •ifV.S. GOVERNMENT PRINTING OFFICE: 1991 - 548-028/40039 ------- ------- Claude A. J. Schleyerls with Geoscience Consultants, LTD., Albuquerque, NM 87102. Katrlna E. Varner is the EPA Project Officer (see below). ThB complete report, entitled "Background Hydrocarbon Vapor Concentration Study for Underground Fuel Storage Tanks," (Order No. PB91-191353/AS; Cost: $31.00, subject to change) will 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: Environmental Monitoring Systems Laboratory U.S. Environmental Protection Agency Las Vegas, NV 89193 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati, OH 45268 BULK RATE POSTAGE & FEES PAID EPA PERMIT No. G-35 Official Business Penalty for Private Use $300 EPA/600/S4-91/009 ------- |