1、American Petroleum 11 Institute API PUBLX4619 95 0732290 0545622 879 - *!iw: - A Study to Characterize Air Concentrations of Methyl Tertiary Butyl Ether (MTBE) at Service Stations in the Northeast Health and Environmental Sciences Department Publication Number 4619 March 1995 API PUBL*:YbLS 95 07322
2、90 0545623 705 = One of the most significant long-term trends affecting the future vitality of the petroleum industry is the publics concerns about the environment. Recognizing this trend, API member companies have developed a positive, forward-looking strategy called STEP: Strategies for Todays Env
3、ironmental Partnership. This program aims to address public concerns by improving our industrys environmental, health and safety performance; documenting petformance improvements; and communicating them to the public. The foundation of STEP is the API Environmental Mission and Guiding Environmental
4、Principles. API ENVIRONMENTAL MISSION AND GUIDING ENVIRONMENTAL PRINCIPLES The members of the American Petroleum Institute are dedicated to continuous efforts to improve the compatibility of our operations with the environment while economically developing energy resources and supplying high quality
5、 products and services to consumers. The members recognize the importance of efficiently meeting societys needs and our responsibility to work with the public, the government, and others to develop and to use natural resources in an environmentally sound manner while protecting the health and safety
6、 of our employees and the public. To meet these responsibilities, API members pledge to manage our businesses according to these principles: 9 9 9 9 9 9 9 9 9 9 9 To recognize and to respond to Community concerns about our raw materials, products and operations. To operate our plants and facilities,
7、 and to handle our raw materials and products in a manner that protects the environment, and the safety and health of our employees and the public. To make safety, health and environmental considerations a priority in our planning, and our . development of new products and processes. To advise promp
8、tly, appropriate officials, employees, customers and the public of information on significant industry-related safety, health and environmental hazards, and to recommend protective measures. To counsel customers, transporters and others in the safe use, transportation and disposal of our raw materia
9、ls, products and waste materials. To economically develop and produce natural resources and to conserve those resources by using energy efficiently. To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and
10、waste materials. To commit to reduce overall emission and waste generation. To work with others to resolve problems created by handling and disposal of hazardous substances from our operations. To participate with government and others in creating responsible laws, regulations and standards to safeg
11、uard the community, workplace and environment. To promote these principles and practices by sharing experiences and offering assistance to others who produce, handle, use, transport or dispose of similar raw materials, petroleum products and wastes. API PUBLm4bL9 95 = 0732290 0545624 641 m A Study t
12、o Characterize Air Concentrations of Methyl Tertiary Butyl Ether (MTBE) at Service Stations in the Northeast Health and Environmental Sciences Department API PUBLICATION NUMBER 461 9 PREPARED UNDER CONTRACT BY: TED JOHNSON, MICHAEL MCCOY, AND TONY WISBITH IT CORPORATION 3710 UNIVERSITY DRIVE, SUITE
13、201 DURHAM, NORTH CAROLINA 27707 OCTOBER 1994 American Petroleum Institute API PUBL*4bL9 95 0732290 0545625 588 FOREWORD API PUBLICATIONS NECESSARILY ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDEML LAWS AND REGULATiONS SHOULD BE REVIEWED. API
14、IS NOT UNDERTAKING To MEET THE DUTIES OF EMPLOYERS, MANUFAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, AND OTHERS EXPOSED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTmG THEIR OBLIGATIONS UNDER LOCAL, STATE, OR FEDERAL LAWS. NOTHING CONTAINED IN ANY
15、 API PUBLICATION IS TO BE CONSTRUED AS GRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANU- FACTURE, SALE, OR USE OF ANY METHOD, APPARATUS, OR PRODUCT COV- ERED BY LETTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LETIERS PATF“. THE PUBLICATION BE CONSTRUED AS IN
16、SURING ANYONE AGAINST LIABIL- Copytight 2. Three self-service stations with Stage II vapor recovery in Westchester County, New York; and 3. Five self-service stations without Stage II vapor recovery in Fairfield County, Connecticut. The selection of full-service stations in New Jersey was unavoidabl
17、e, as self-service stations are not permitted in that state. Each station was sampled on a separate day between April 7, 1993 and April 23, 1993. The monitoring activities at each station were conducted during two four-hour periods, nominally 9 a.m. to 12 a.m. and 2 p.m. to 6 p.m. Four-hour canister
18、 and impinger samples were collected at four perimeter locations (north, east, south, and west) and one pump location at each station, in customer breathing zones at the New ES-I API PUBL*4bLS 95 0732290 0545635 427 York and Connecticut stations, and in attendant breathing zones at the New Jersey st
19、ations. In addition, four-hour charcoal tube samples were collected in the breathing zones of all stations. These samples were analyzed to determine air concentrations of MTBE, BTEX (benzene, toluene, ethyl benzene, xylene), total hydrocarbon (THC) concentration, and formaldehyde. Continuous carbon
20、monoxide measurements were made in the pump area of each station using a Metrosonics“ pm-7700 monitor. Organic vapor analyzers (OVA) were used to continuously monitor THC concentrations in the pump areas and breathing zones. These measurements were made as a means of identifying individual refueling
21、 events which could not be distinguished in the four-hour samples collected by the canister samplers. Field personnel monitored meteorological parameters, gasoline composition (oxygenate content, Reid vapor pressure, BTEX), and gasoline sales as well as deliveries during each sampling period. Person
22、nel also noted the time each vehicle was refueled and conducted regular counts of traffic on nearby roadways. Gasoline pumping activities were continuously recorded by a stationary video camera. Statistical analyses of the data obtained from the field monitoring activities support the following gene
23、ral findings. 1. Mean and maximum four-hour average MTBE concentrations generally decrease from breathing zone to pump island to perimeter, suggesting that refueling activities are the principal source of MTBE measured at service stations. 2. MTBE concentrations are generally lower at stations with
24、Stage II vapor controls. 3. Median four-hour MTBE concentrations for all stations are below 2 ppm at breathing zone and pump island locations and below 0.02 ppm at the station perimeters. ES2 API PUBL*YbL 95 0732290 0545636 363 = 4, Maximum four-hour MTBE concentrations for all stations are below 2.
25、6 ppm at breathing zone and pump island locations and below 0.2 ppm at station perimeters. . 5. For all stations, because the canisters also sampled nonrefueling periods, breathing zone measurements of MTBE concentration may underestimate actual breathing zone concentrations during fuel dispensing b
26、y station-specific factors ranging from 1 to 3. Most factors fall between 1 .O and 1.4. A series of special statistical analyses were performed to identify patterns in the individual component data and to compare sampling methodologies. An analysis of concentration ratios (the ratio of MTBE to a sec
27、ond component) found that ratios were generally larger for pump and breathing zone canister samples than for perimeter canister samples. This pattern suggests that refueling operations were the principal source of MTBE at each station, whereas other sources (e.g., local traffic) contributed signific
28、antly to the levels of BTEX and THC. The results of stepwise regression analyses performed on the four-hour canister data indicate that MTBE concentration can be predicted well (R2 = 0.886) as a linear function of simultaneously-measured concentrations of benzene, toluene, ethyl benzene, and THC. Of
29、 these four predictors, benzene provides the best single means of predicting MTBE concentration. Benzene also provides the best prediction of toluene and THC concentration. Toluene is the best predictor of ethyl benzene concentration. . Other stepwise regression analyses were performed on the four-h
30、our canister measurements to identify factors that potentially affect component concentration values. The analyses suggest that following conditions are associated with an increase in MTBE concentration: Measurements are made at pump island or breathing zone locations rather than perimeter locations
31、; ES-3 API PUBL*kLibLS 95 0732290 0545b37 2TT = Measurements are made at a Connecticut station (Le., a station with no Stage II vapor recovery) rather than a New York or New Jersey station; Low wind speed; High traffic on nearby roads. Analysts also attempted to identify possible conditions that cou
32、ld explain fourteen high MTBE values. Seven of the 14 values were found to be associated with the combination of two unusual conditions: (I) average wind speed less than 3 mph and (2) number of serviced vehicles exceeded 115. Four of the high values were associated with spills or overflows, two were
33、 associated with cumulative street traffic exceeding i 0,000 vehicles, and three were associated with average gasoline dispensing rates exceeding 325 gallons/hour. Active use of garage bays may have contributed to two of the high values. Other potential events that may be relevant include a gasoline
34、 delivery and a vehicle running during refueling. Although the field study was conducted primarily to obtain representative air concentrations of MTBE at service stations, the collected data also provide a means for comparing canisters and charcoal tubes. These sampling methodologies are routinely u
35、sed in chemical exposure studies. The data base contains 20 cases in which canister and charcoal tube samples were collected at the same location for the same time period. An analysis of the 14 cases in which MTBE concentrations exceeded the limit of detection for both sampling methodologies found t
36、hat the ratio of canister MTBE to tube MTBE ranged from 0.52 to 9.74. Fifty percent of the canister-to-tube ratios were between 0.62 and 1.17; the median ratio was 1 .OO. Ten pairs of duplicate samples were collected using canister samplers, and ten pairs were collected using impinger samples. The m
37、edian percent difference in concentration between the duplicate measurements was 21.8 percent for MTBE, 12.2 percent for benzene, 19.4 percent for toluene, 30.5 percent for ethyl benzene, 11.8 percent for xylene, and 19.0 percent for formaldehyde. Note that duplicate pairs ES4 API PUBL*4bL 95 O73229
38、0 0545b38 13b W containing values below the detection limit were not considered in calculating these values. During the ITAQS service station study, an independent research team headed by Dr. Paul Lioy of the Environmental and Occupational Health Sciences Institute (EOHSI) collected air samples in t
39、he passenger compartments of automobiles during typical home-to-work commutes (manuscript in preparation). Selected automobiles in the Lioy study were refueled at stations included in the service station study. Breathing zone MTBE concentrations measured by the EOHSI team during these refueling even
40、ts were comparable to breathing zone measurements made by the ITAQS team. ES-5 API PUBL*:4619 95 0732290 05Y5b39 072 = Section 1 INTRODUCTION The compound methyl tertiary butyl ether (MTBE) is routinely added to gasoline during the winter driving season to reduce carbon monoxide (CO) emissions from
41、motor vehicles. In 1992, the U. S. Environmental Protection Agency (EPA) began receiving anecdotal complaints about headaches, nausea, and other symptoms following alleged exposure to MTBE. In early 1993, EPA began planning a series of clinical research studies to investigate the validity of these c
42、laims. To properly design these studies, EPA solicited data which could be used to estimate the MTBE exposures of motorists during refueling at service stations that dispense gasoline containing MTBE. EPA also expressed interest in determining typical “fenceline“ concentrations of MTBE at service st
43、ations. In response to these needs, the American Petroleum Institute (API) supported two related studies in the New York Metro area: a service station study conducted by IT Air Quality Services (ITAQS) and a commuter study conducted by the Environmental and Occupational Health Sciences Institute (EO
44、HSI). In addition to MTBE, both studies measured air concentrations of the four BTEX compounds (benzene, toluene, ethyl benzene, and xylene), formaldehyde, and carbon monoxide (CO). During the service station study, ITAQS collected air samples at stations located in East Brunswick, NJ (two stations)
45、; Mamaroneck, NY (two stations); Port Chester, NY (one station); Greenwich, CT (four stations); and Stamford, CT (one station). The samples represented four general locations: the breathing zone of customers, the breathing zone of attendants, the general vicinity of the pumps, and the property bound
46、ary. Field personnel also monitored meteorological parameters, gasoline composition, gasoline sales as well as deliveries during each sampling period. Gasoline pumping activities were recorded by a stationary video camera. 1-1 In the commuter study, an EOHSI research team directed by Dr. Paul Lioy c
47、ollected air samples in the passenger compartments of automobiles during typical home-to- work commutes. These automobiles were fueled with gasoline containing MTBE and were driven through areas in which MTBE use was mandatory. Selected automobiles in the commuter study were refueled at stations inc
48、luded in the service station study. The refueling operations were timed to coincide with the collection of air samples at the stations. Further information concerning the commuter study can be obtained from the Lioy research team. This report provides a description of the service station study and s
49、ummarizes the results of statistical analyses performed on data collected during the study. Section 2 of the report briefly discusses the procedures used in selecting service stations for the study, lists the sampling dates and times associated with each station, and presents the general characteristics of each station. Section 3 provides a detailed description of the monitoring activities performed at each station. Section 4 provides summary statistics for the data collected during the field portion of the study. The results of a series of special statisti
