1、 API PUBLm4b25 95 m 0732290 05iIALL7 679 m American Petroleum Institute Service Station Personnel Exposures to Oxygenated Fuel Components = 1994 Health and Environmental Sciences Department Publication Number 4625 August 1995 API PUBLr4625 95 0732290 0548LLB 505 I- One of the most significant long-t
2、erm trends affecthg the future vitality of the petroleum industry is the publics concems about the environment. Recognizing this trend, API member companies have developed a positive, fotward-looking strategy called STEP: Strategies for Todays Environmental Partnership. This program aims to address
3、public concerns by improving our industrys environmental, health and safety performance; documenting performance improvements; and communicating them to the public. The foundation of STEP is the API Environmental Mission and Guiding Environmental Principles. API ENVIRONMENTAL MISSION AND GUIDING ENV
4、IRONMENTAL PRINCIPLES The members of the American Petroieum 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 products and services to consumers. The members reco
5、gnize 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 of our employees and the public. To meet these respo
6、nsibilities, API members pledge to manage our businesses according to these principles: O To recognize and to respond to community concerns about our raw materials, products and operations. 4 To operate our plants and facilities, and to handle our raw materials and products in a manner that protects
7、 the environment, and the safety and health of our employees and the public. O To make safety, health and environmental considerations a prioriiy in our planning, and our development of new products and processes. O To advise promptly, appropriate officials, employees, customers and the public of in
8、formation on significant industry-related safety, health and environmental hazards, and to recommend protective measures. O To counsel customers, transporters and others in the safe use, transportation and disposal of our raw materials, products and waste materials. O To economically develop and pro
9、duce natural resources and to consewe those msoutces by using energy efficiently. 9 To extend knowledge by conducting or supporting research on the safety, health and environmental effects of our raw materials, products, processes and waste materials. O To commit to reduce overail emission and waste
10、 generation. 9 To work with others to resolve problems created by handling and disposal of hazardous substances from our operations. O To participate with government and others in creating responsible laws, regulations and standards to safeguard the community, workplace and environment. O To promote
11、 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 PUBLU4625 95 O732290 0548LL9 YYL W Service Station Personnel Exposures to Oxygenated Fuel Components =
12、1994 Health and Environmental Sciences Department API PUBLICATION NUMBER 4625 PREPARED UNDER CONTRACT BY: NATLSCO, A DIVISION OF KRMS ONE KEMPER DRIVE LONG GROVE, ILLINOIS 60049-0075 AUGUST 1995 American Petroleum Institute API PUBL*Yb25 95 = 0732290 0548120 163 FOREWORD API PUBLICATIONS NECESSARILY
13、 ADDRESS PROBLEMS OF A GENERAL NATURE. WITH RESPECT TO PARTICULAR CIRCUMSTANCES, LOCAL, STATE, AND FEDERAL LAWS AND REGULATIONS SHOULD BE REVIEWED. API IS NOT UNDERTAKING TO MEET THE DUTIES OF EMPLOYERS, MANUFAC- TURERS, OR SUPPLIERS TO WARN AND PROPERLY TRAIN AND EQUIP THEIR EMPLOYEES, AND OTHERS E
14、XPOSED, CONCERNING HEALTH AND SAFETY RISKS AND PRECAUTIONS, NOR UNDERTAKING THEIR OBLIGATIONS UNDER LOCAL, STATE, OR FEDERAL LAWS. NOTHING CONTAINED IN ANY API PUBLICATION IS TO BE CONSTRUED AS GRANTING ANY RIGHT, BY IMPLICATION OR OTHERWISE, FOR THE MANU- FACTURE, SALE, OR USE OF ANY METHOD, APPARA
15、TUS, OR PRODUCT COV- ERED BY LETTERS PATENT. NEITHER SHOULD ANYTHING CONTAINED IN ITY FOR INFRINGEMENT OF LETIERS PATENT. THE PUBLICATION BE CONSTRUED AS INSURING ANYONE AGAINST LIABIL- Copyright 8 1995 Anexican Petroleum Institute i API PUBL*4625 95 0732290 0548121 OTT = ACKNOWLEDGMENTS THE FOLLOWI
16、NG PEOPLE ARE RECOGNIZED FOR THEIR CONTRIBUTIONS OF TIME AND EXPERTISE DURING THIS STUDY AND IN THE PREPARATION OF THIS REPORT: API STAFF CONTACTS Will Ollison, Heaith and Environmental Sciences Department James Vail, Health and Environmental Sciences Department MBERS OF THE WORKGROUP Jack Hinton, T
17、exaco John Hoban, Mobil Oil Corporation David Risi, Exxon Company USA Paul Schubert, BP Oil Company - Joseph W. Aherne, Assistant Manager, Industrial Hygiene Joseph J. Fater, Manager, Industrial Hygiene Sandra Wroblewski, Manager, Marketing sampling durations ranged between 93 and 570 minutes with m
18、ost durations longer than 6 hours. Short-term samples were taken to approximate peak exposures and ranged between 8 and 35 minutes with most sample durations within the 15-20 minute range. 1-1 API PUBL*4625 95 = 0732290 0548328 454 The long-term and short-term samples were often collected concurrent
19、ly. Therefore, if a significant exposure occurred during a specific task or special event, such as during carburetor repair or a fuel spill, the exposure is also included within the full-shift sample for those individuals also undergoing full-shift sampling. Table 1-1 presents the numbers of samples
20、 collected during the Winter Phase from mid-February to mid-April and during the Summer Phase from mid-July to mid-August. The air samples were collected according to the method described in Appendix H. Following collection the samples were shipped to the analytical laboratory for analysis according
21、 to the methods described in Appendix I. During both Winter and Summer sampling studies, there were a few cases when data from two employees were combined to represent an approximate 8-hour full-shift exposure. These cases resulted when the first employee completed a partial shift and was relieved b
22、y a second employee or, in a couple of cases, declined to participate during the second part of the day. In most cases, the sampling pump was transferred to a second station employee who completed the shift and a second sampling tube was attached to the second employee. Each set of these samples was
23、 combined in a time-weighted manner prior to use in statistical calculations to generate a full-shift equivalent exposure that was comparable with other data. In several other cases, a single sampling tube was used to measure the exposure of two employees. After completing the sampling on the first
24、employee, the same sampling train was transferred to the second employee for the remainder of the shift. During the Winter Phase, 95 long-term exposures and 105 Short-term exposures were sampled. One of the long-term exposures, represented by samples AZ4-02A 5 stations in Northern New Jersey and 2 i
25、n Connecticut. In the summer, 6 service stations; 4 stations in Northern New Jersey and 2 in Connecticut. 3 Service Stations in Oregon 3 truck drivers were monitored during bulk fuel deliveries. The results of these samples are not included in the statistical analysis. C d 1-3 API PUBLu4625 95 07322
26、90 0548330 002 = OXYGENATE AND AROMATIC CONTENT OF BULK LIQUID FUELS At each station, two samples of each octane grade of dispensed gasoline were collected. One buik sample set was submitted to determine volatility by determining the Reid Vapor Pressure (RVP). The second set was initially analyzed b
27、y mass spectrophotometry (MS) to identi9 the species of oxygenate and the aromatic content and subsequently analyzed by gas chromatography (GC) to determine the percentage of each component. Table 1-2 summarizes the Winter and Summer data on oxygenate content. The buik analysis data is presented in
28、Appendix A. The bulk sample analysis was used to determine which oxygenates were present and which should be subject to analysis in the air samples. Although the percent of the oxygenate was measured, the purpose of this analysis was only to determine which oxygenate was present. Since the oxygenate
29、s are more volatile than the remainder of the gasoline, this analysis should - not be considered a definitive quantitative indicator of the amount of oxygenate which had been added to the fuel. In two cases during the Winter Phase, OR1 (88 octane) and MN2 (92 octane), the bulk sample submitted to th
30、e laboratory had leaked into the shipment case. However, a sufficient quantity of fuel remained to conduct the GC/MS analysis. The loss of part of the sample may have affected the character of the sample. Although 16 stations were initially included in the study, an additional station was added (as
31、discussed on page 1-2) and a bulk sample was analyzed fkom this station during the Winter Phase. 1 -4 API PUBL*4625 95 0732290 0548131 T49 = Service Stations Az- 1 Az-2 Az-3 Az-4 MN-2 MN-3 MN-4 NY-1 NY-2 NY-3 NY-4 NY-6 NY-7 NY-9 OR- 1 OR-2 OR-3 Service stations Az-1s Az-2s Az-3 s Az-4s MN-2s MN-3 s
32、MN4s NY-1 s NY-2S NY4S NY-6S NY-7s NY-9S OR- 1 S OR-2s OR-3 S TABLE 1-2 3ulk Liquid Samples - Oxygenate Content (%I Winter Phase Ethanol 6.7 - 7.6 ND 7.2 - 8.0 8.4 - 8.7 10 6.6 - 7.1 6.2 - 7.3 ND ND ND ND ND ND ND 6.4 - 7.4 6.9 - 7.1 4.6 - 8.2 MTBE NDb 11 - 12 ND ND ND ND ND 11 - 14 10 - 13 14 - 16
33、14 - 17 13 - 15 12 - 13 13 - 14 ND ND ND Bulk Liquid Samples - Oxygenate Content (9 Ethanol ND ND ND ND 9.5 - 9.7 ND 10- 11 ND ND ND ND ND ND ND ND ND MTBE NDb ND ND ND ND ND ND 0.1 - 5.2 4.1 - 8.8 4.1 - 1.3 0.1 - 0.97 CO.1 - 3.3 0.34 - 1.7 ND XO.1 - 0.71 ND TAME ND ND- ND ND ND ND ND 1.4 - 3.7 4.12
34、 - 3.4 ND ND 0.11 - 1.1 0.11 - 0.52 ND ND ND ND I Snmmer Phase ND ND ND ND ND ND ND 0.1 - 0.30 XO.1 - 1.0 ND ND ND 0.1 - 2.2 ND ND ND a % denotes percent by weight ND denotes “not detected“ at a limit of 0.1% b 1-5 API PUBLX4625 95 m 0732290 0548132 985 m For the Winter Phase, the bulk fuel analysis
35、 identified fuels from nine service stations which contained ethanol and fuels from eight service stations which contained MTBE. In addition to ethanol and MTBE, the fuels of three service stations contained TAME in relatively low amounts (0.11 - 3.7%). Where TAME was detected, MTBE was the main oxy
36、genate . present. The results of the bulk fuel analysis for the Summer Phase identified fuels from two service stations which contained ethanol and fuels fkom seven service stations which contained MTBE. Again, fuels from three service stations contained TAME in relatively low amounts (0.1 - 2.2%).
37、Where TAME was detected, MTBE was the main oxygenate present. As expected with the end of the winter CO oxyfuel program, generally lower oxygenate concentrations and fewer numbers of stations with oxygenated fuels were present in the summer months, although ethanol levels in gasohol fuels increased.
38、 Oxygenates are used during the summer season to increase fuel octane. The results of the aromatic analyses are summarized by geographical area in Table 1-3. The complete buk analysis data is provided as Appendix A. Oxygenates and aromatic components detected in the bulk liquid fuels were assayed in
39、 the air samples with the exception of p-xylene, which is included in the total xylene result. 1-6 API PUBL*1i625 75 0732290 0548333 833 = Geographic Area Southwest Midwest Northeast Northwest Geographic Area Southwest Midwest Northeast Northwest TABLE 1-3 _ - Bulk Liquid Samples - Aromatic Content
40、(%) Winter Phase B 0.95 - 2.7 0.79 - 3.2 0.57 - 2.4 0.24 - 3.5 T 5.4 - 11 7.5 - 11 3.2 - 13 7.1 - 18 EB 1.5 - 2.6 1.3 - 2.4 0.93 - 2.6 1.5 - 3.2 X 6.6 - 12 6.0 - 12 5.8 - 13 7.0 - 15 P-x 1.8 - 3.0 1.7 - 3.0 1.4 - 3.9 1.9 - 3.8 Bulk Liquid Samples - Aromatic Content (%I.) Summer Phase B 1.3 - 2.7 0.2
41、9 - 1.9 0.75 - 2.2 1.8 - 3.0 T 7.0 - 14 6.7 - 8.7 5.7 - 17 5.2 - 11 EB 1.8 - 3.5 0.64 - 2.0 1.3 - 4.0 1.4 - 2.6 X 9.8 - 16 2.2 - 9.7 7.2 - 16 8.1 - 12 P-X 2.6 - 4.5 0.63- 2.7 2.1 - 4.9 2.2 - 3.5 a % denotes percent by weight METEOROLOGICAL CONDITIONS Meteorological conditions including temperature,
42、wind speed, wind direction, relative humidity and barometric pressure were recorded at each station on each day of the study. An electronic weather station was set up on the service station property. Temperature and relative humidity measurements were recorded both inside (Ti, Hi) near the mechanic
43、and outside (To, Ho) near the refueling attendants. For the outside measurements, the temperature and relative humidity probes were placed out of direct sunlight (a radiant energy source). The 1-7 windspeed and direction were recorded, as was the average barometric pressure (inches of mercury). Baro
44、metric pressures during the winter phase were obtained from the National Weather Service for the date and location of sampling. During the summer sampling phase the barometric pressure was recorded on site. The meteorological data are summarized in Table 1-4. The daily averages are presented in Appe
45、ndix B. 45-90 30-88 39-87 38-73 NATLSCO staff also noted the type and quantity of precipitation (rain and snow) during the study. Early in the study, NATLSCO was requested to discontinue air sampling if heavy 44-79 13-45 17-57 0-1 1 10-5 1 20-56 28-78 0-18 30-8 1 19-8 1 19-93 0-16 3 7-62 28-85 37-84
46、 0-10 TABLE 1-4 Temperature (OF) Date Inside Outside SUMMARY OF METEOROLOGICAL DATA WINTER PHASE II Yo RH Inside Outside Geographic Area 7/11-23 7/19-28 7120-8/18 818- 17 Southwest Midwest Northeast Northwest 84-1 10 80-1 12 21-61 16-75 66-103 61-96 26-72 28-92 67-92 63-97 38-83 28-100 68-102 61-97
47、21-58 17-71 Date Temperature (OF) Wind Speed 211 7-26 211 5-24 212 1-411 4 21 1 4-24 Geographic Area Southwest Midwest Northeast Northwest Wind Speed (Mpm 0-6 0-1 o 0-6 0-8 1-8 API PUBLr4625 95 m 0732290 0548335 b9Y m precipitation (rain or snow) occurred. The only instance where this affected the s
48、tudy was during sampling at location NY9 on February 23. A steady rain was reported in the late morning and air sampling was halted after 260 minutes. However, the results of this sample were considered to be representative of the entire day and were included in the statistical analysis. STAGE II VA
49、POR RECOVERY SYSTEMS To help control gasoline vapor emissions, many service station pump nozzles are equipped with Stage II vapor recovery systems. Stage II vapor recovery systems capture vapors displaced from the vehicle fuel tank during refueling (Stage I systems capture vapors displaced from service station storage tanks during tank truck fuel deliveries). The presence of “Stage II Vapor Recovery Systems“ was recorded (Table 1-5) during the study. The presence of Stage II systems would be expected to lower potential exposure in refueling attendants since they often work in
