Jpn. Soc. Atom. Env. 50(6): (2015)

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1 266 J. Jpn. Soc. Atmos. Environ. Vol. 50 No * Volatile Organic Compounds and Air Quality Assessment Using Ozone Formation Potential in Refueling Loss Tests and Diurnal Breathing Loss Tests Using a Gasoline Fuel with Low Olefins Hiroyuki Hagino 1, Tazuko Morikawa 1, Kenichi Akiyama 1, Sousuke Sasaki 1 * Japan Automobile Research Institute, 2530 Karima, Tsukuba, Ibaraki , Japan *Corresponding author: ( ) [email protected] In this study, the volatile organic compounds (VOCs) in evaporative gas from gasoline fuel were observed and the air quality evaluated during the refueling loss tests and the diurnal breathing loss (DBL) tests according to a gasoline fuel with a lower content of olefins compared to retail market fuels. The gasoline vapor compositions observed during the refueling loss tests were compared to the estimation calculated from the measured liquid gasoline composition using Raoult s law. As a result, there was no significant difference between the observations and the estimations of the gasoline vapor compositions according to refueling flows and environmental temperatures. During the DBL tests, the aromatics were predominant in the day 1 DBL, while the paraffins were predominant after the day 2 DBL. It is indicated that the permeation (the leakage of fuel from the fuel tank and tube) contributed to the day 1 results and the breakthrough (the overflow of fuel vapor from the carbon on the recovery equipment (canister)) To evaluate the air quality using the gasoline vapor composition data, the ozone formation potential (OFP) was performed using the maximum incremental reactivity (MIR) with the VOC data on the refueling loss and the DBL. It was indicated that the OFP of the gasoline fuel vapor in this study is similar to the OFP of the vapor from the refueling and breakthrough on the DBL. Furthermore, it is indicated that the olefin in the gasoline fuels can also effectively contribute to the OFP weighted emissions (OFP EW ) according to a comparison with the gasoline compositions in these test fuels and widely available fuels in Tokyo, and the values reported in a previous study. The OFP of the fuel vapors (e.g., refueling and breakthrough) and other emissions (e.g., biogenic VOC and stationary source) were estimated by the emission data from several prefectures. It indicated that the contribution of the refueling and breakthrough varied depending on the area. Furthermore, it was estimated that the OFP EW of the fuel vapors contributed 4 21 of the total OFP EW of the VOC emissions during August of Key words : VOC, gasoline passenger car, refueling loss, evaporative emissions, breakthrough emissions ,172 1, (0.3 ) 0 (0 ) 2015 (VOC, Volatile Organic Compound) (NO X ) VOC Carter, 1994 (Atkinson, 2000) VOC (NMHC, Non- Methane HydroCarbon) VOC

2 NMHC VOC VOC 2008; 2010 VOC 2007; 2009 VOC (LPG) 2007; 2009 (OFP, Ozone Formation Potential) VOC VOC 2008; ; ; 2003 Stage ; California Environmental Protection Agency Air Resource Board, 2012 VOC t/y t/y VOC (VOC) 2015 Stage 2 (ORVR, Onboard Refueling Vapor Recovery) 2003 Stage 2 ORVR ORVR 2003; Environment Canada, 2010 (HSL, Hot Soak Loss) (DBL, Diurnal Breathing Loss) 2009; Yamada et al., 2015 DBL (SHED, Sealed Housing Evaporative Determination) 2009; Yamada et al., 2015 DBL HSL DBL 1 2 g/test 2 (Yamada et al., 2015) DBL (Yamada et al., 2015) VOC 2012 VOC (Yamada et al., 2015) VOC 2004; 2008 (Kirchstetter et al., 1999; Zhang et al., 2013) DBL DBL VOC OFP Table 1 Certified Observed 62.9 kpa L

268 J. Jpn. Soc. Atmos. Environ. Vol. 50 No. 6 2015 Table 1 Specification of gasoline for this study. Table 2 Refueling Test conditions. Contents Certified Observed Density (15 ) 0.7409 g/cm 3 0.

3 268 J. Jpn. Soc. Atmos. Environ. Vol. 50 No Table 1 Specification of gasoline for this study. Table 2 Refueling Test conditions. Contents Certified Observed Density (15 ) g/cm g/cm 3 Octane rating RON 90.0 Reid vapor pressure, 63.7 kpa 62.9 kpa RVP (37.8 ) Distribution temperature Hydrocarbons Aromatics 35.8 Olefins 2.3 Paraffins 60.0 Naphthenes 2.0 Elements Carbon 86.6 wt Hydrogen 13.4 wt Oxygen 0 wt Sulfur ppm Contents Dispensed fuel temperature Dispensed tank (environmental) temperature Fill rate Initial fill amount Total fill amount Soak time Sampling time table Conditions 20 10, 20, 30 25, 35, 45 L/min 4.5 L (10 of full (45 L)) L (85 of full (45 L)) 16 h Before refueling: 5 s Refueling: 51, 66, 92 s End refueling: 5 s L L 45 L 0.5 L L/min 45 L/min (10 30 ) EPA (California Environmental Protection Agency Air Resource Board, 2012) Table 2 (Fig. 1) 50 L 20 Fig. 1 Outline of refueling loss measurement system L L L PA GL ppm

4 Table 3 Analytical conditions for liquid fuel, refueling, and DBL test. Liquid fuel compositions Refueling test DBL test PONA* 1 (C3 C9) Hydrocarbons (C3 C9) CH 4 Light-end hydrocarbons (C2 C7) Mid-range hydrocarbons (C7 C13) Instrument 1st column 2nd column Detector Oven program Injection Shimazu C-2010 Rtx-5 (2 m 0.25 mm 1.0 μm) Petrostar (100 m 0.25 mm 0.5 μm) FID (10 min) 5 /min 46 (53.3 min) 1.3 /min 200 (5 min) μl Split ratio:100 Agilent 6890N DB-1 (60 m 0.25 mm 0.25 μm) FID (5 min) 3 /min 200 (60 min) 3 /min 210 (2 min) 3 /min Gas loop (0.1 ml) Split ratio: 50 Shimadzu C-14A (Precut column) Pora pack N (3 mm i.d. 1 m) (Main column) Shin pack Q (3 mm i.d. 1 m) Molecular sieve 13X (3 mm i.d. 0.5 m) Pora pack N (3 mm i.d. 0.2 m) FID 60 Precut column 80 Main column ml Agilent 6890N CP-AL203/KCL (50 m 0.25 mm) FID (10 min) 5 /min /min (8 min) ml or 100 ml Agilent 6890N Rtx-5 (3 m 0.25 mm 1 μm) Rtx-1 (100 m 0.25 mm 0.5 μm) FID (25 min) 5 /min 46 (53.3 min) 1 /min 200 (4.5 min) ml Carrier gas He He He He He * 1 PONA; P: Paraffins, O: Olefins, N: Naphthenes, A: Aromatics DBL 2009; Yamada et al., ; Yamada et al., 2015 (Yamada et al., 2015) 3 DBL (3 days-dbl) SHED 0.5 L 2 Run 1 Run VOC (GC-FID) VOC (THC, Total Hydro Carbon) DBL (Table 3) GS5100 GL (vol ) (g/test) Fig. 2 VOC

270 J. Jpn. Soc. Atmos. Environ. Vol. 50 No. 6 2015 Fig. 2 Contributions and carbon distribution of the VOC components for fuel and refueling vapor.

5 270 J. Jpn. Soc. Atmos. Environ. Vol. 50 No Fig. 2 Contributions and carbon distribution of the VOC components for fuel and refueling vapor. Note) E: Oxygenated (ethyl tert-butyl ether (ETBE)), A: Aromatics, D: diolefines, O: Olefines, N: Naphthenes, I-P: i-paraffins, N-P: n-parafines (Kirchstetter et al., 1999) (Zhang et al., 2013) 5(C5) 2-methyl butane (14 vol ) (Fig. 2) VOC (Fig. 3) Eq. (1) (Kirchstetter et al., 1999) 0 P i γ i x i P i (1) P i VOC i γ i 1 x i VOC i P 0 i VOC i i P i i (m i ) Eq. (2) P mi = i i pi VOC EPA EPI-Suite 25 (U.S.EPA, 2013) (2) Fig. 3 Comparison of molar fraction of the VOC pressure in the gaseous phase by observation and calculation. (Fig. 3) 25 (10 30 ) (25 45 L/min) SHED (2012) VOC FID THC CH 4 GC-FID VOC L/min g/l g/l g/l g/l

6 g/l g/l g/l SHED (2012) L/min g/l g/l (2003) 3 (0.7 2 g/l) 2 5 (2012) ( ) GC-FID L/min 6.6 L/min 2012 (35 L/min) 7.3 L (38.25 L) 19 SHED EPA (Spillage) 0.08 g/l (U.S.EPA, 2008) VOC 3. 2 DBL THC SHED 3 days-dbl (Run 1) Fig. 4 Time profiles of temperature and concentrations of total hydrocarbon and during a diurnal breathing loss (DBL) test (Run 1). Fig. 5 Hydrocarbon (HC) emissions during a hot soak loss (HSL) and diurnal breathing loss (DBL) tests. Fig. 4 Reddy (1989) (ΔT) (Fig. 4) SHED THC 2 3 DBL THC Fig. 5 2 THC 5 g/test 3 7 g/test 3 days-dbl (Yamada et al., 2015) 3 7 g/test 9 3 DBL HSL Fig. 6 GC-FID VOC THC HSL Fig. 6 A (35 ) 50 Run#2 Run#2 Day

272 J. Jpn. Soc. Atmos. Environ. Vol. 50 No. 6 2015 Fig. 6 Contributions and carbon distribution of the VOC components for HSL and DBL.

7 272 J. Jpn. Soc. Atmos. Environ. Vol. 50 No Fig. 6 Contributions and carbon distribution of the VOC components for HSL and DBL. Note) E: Oxygenated (ethyl tert-butyl ether (ETBE)), A: Aromatics, D: diolefines, O: Olefines, N: Naphthenes, I-P: i-paraffins, N-P: n-parafines C4 10 (Yamada et al., 2015) Day 2 THC (98 ) 84 C4 C4 4 Day 3 C5 C6 (Fig. 6) DBL 1 2 VOC C VOC OFP Carter, 1994; 2010; 2012; Yamada et al., 2015; Zhang et al., 2013 OH 2010; ; Yamada et al., 2015 OFP OFP (MIR: Maximum Incremental Reactivity) Eq. (3) OFP i w i MIR i (3) w i VOC i (g/g) MIR i VOC i MIR (go 3 /gvoc) (Carter, 2012) OFP MIR (averaged weighted MIR) (Carter, 1994) SR (Specific Reactivity) (Gruden, 2003) MIR NO X VOC Carter, 1994; 2005 (Refueling) VOC (Fuel vapor) (Fig. 3) OFP OFP Fig OFP OFP OFP OFP (Fuel vapor, OFP 1.86) (Fuel vapor, OFP 1.56) OFP OFP 2012 (n 16) 2013 (n

50 6 2015 273 Fig. 7 Ozone formation potential (OFP) of VOCs in gasoline vapors predicted by liquid gasoline compositions ( Fuel Vapor in the graph) and observed by refueling tests.

9 Ozone formation potential (OFP) of VOCs in gasoline vapors during 3 Days-DBL test in SHED and liquid gasoline compositions ( Liquid Fuel in the graph), and previous 3-Days-DBL test (Yamada et al.

8 Fig. 7 Ozone formation potential (OFP) of VOCs in gasoline vapors predicted by liquid gasoline compositions ( Fuel Vapor in the graph) and observed by refueling tests. Note) A: Aromatics, NO: Naphthenes/Olefines, N: Naphthenes, O: Olefines, P: Paraffines. Fig. 9 Ozone formation potential (OFP) of VOCs in gasoline vapors during 3 Days-DBL test in SHED and liquid gasoline compositions ( Liquid Fuel in the graph), and previous 3-Days-DBL test (Yamada et al., 2015). Note) A: Aromatics, NO: Naphthenes/Olefines, N: Naphthenes, O: Olefines, P: Paraffines. Fig. 8 Ozone formation potential (OFP) of VOCs in gasoline vapor estimated by different liquid gasoline compositions. The fuels in Tokyo are sold on the retail market for each year. Note) A: Aromatics, NO: Naphthenes/Olefines, N: Naphthenes, O: Olefines, P: Paraffines. 15) 2014 (n 15) (Zhang et al., 2013) OFP Fig. 8 OFP (CaRFG3) 5.9 vol OFP 2 OFP (1.56) (1.53) Fig. 7 Fig. 8 (GB ) (Zhang et al., 2013) 28 vol OFP OFP (Liquid fuel) HSL 3 Days-DBL Day 1, Day 2, Day 3 OFP (Yamada et al., 2015) OFP (Fig. 9) (Fig. 7) (Liquid fuel) OFP DBL (Yamada et al., 2015) (Liquid fuel) OFP 2.92 (Yamada et al., 2015) OFP Day 1 (Yamada et al., 2015) Day 1 OFP (2.64) (Yamada et al., 2015) (3.31) OFP Day 2 (1.38) Day 3 (1.54) (1.56) (Fig. 7) Fig. 2 Fig. 6 (Yamada et al., 2015) OFP 3.89 VOC OFP DBL VOC

9 274 J. Jpn. Soc. Atmos. Environ. Vol. 50 No Fig. 10 Emission weighted ozone formation potential (OFP EW ) of VOCs in refueling (gasoline car), refueling (underground storage tanks), car exhausts (running), car exhausts (start), DBL (permeation, other), DBL (breakthrough), anthropogenic combustion, anthropogenic evaporation, biogenic VOC at the typical prefectures. The VOC emission data used at August of (a) Comparison of OFP EW for car exhaust and gasoline evaporations (refueling and breakthrough) contribution to total emission. (b) Comparison of OFP EW for total emission and averaged O 3 concentrations at August of VOC OFP VOC VOC OFP VOC 8 OFP (Yamada et al., 2015) OFP 3.77 DBL 3.89 DBL 3.31 JEI-DB (JATOP Emission Inventory-Data Base) 2012; OFP OFP EW (Emission weighted OFP) (go 3 / month) JEI-DB 2000 (Yamada et al., 2015) VOC VOC 2012 MIR (go 3 /gvoc) (Carter, 2012) OFP JEI-DB OFP EW VOC 58 VOC 54 VOC 8 JEI-DB MEGAN (The Model of Emissions of Gases and Aerosols from Nature) ver 2.10 (Jiang et al., 2012; Chatani et al., 2015) OFP EW VOC OFP EW Fig. 10(a) OFP EW VOC OFP EW 4 21 OFP EW DBL OFP EW 2012 OFP 3.12 (1.56) 1/2 DBL OFP 1/2 VOC

10 VOC OFP EW Fig. 10(b) (O 3 ) OFP EW OFP EW OFP EW VOC VOC VOC NO X VOC DBL VOC DBL 1 2 VOC MIR OFP DBL OPF OFP OFP VOC OFP (3) VOC SS VOC 14 (2003) japanese/report/reserch/report-pdf/h15_2003/03cho4 3. pdf pp. 93 (2004). Atkinson, R.: Atmospheric chemistry of VOCs and NO X, Atmos. Environ., 34, (2000). California Environmental Protection Agency Air Resource Board: California refueling emission standards and test procedures for 2001 and subsequent model motor vehicles (2012), regact_phev/orvr_tst_procedures_clean.pdf Carter, W. P. L.: Development of ozone reactivity scales for volatile organic compounds, J. Air Waste Manage. Assoc., 44, (1994). Carter, W. P. L.: SAPRC Atmospheric chemical mechanisms and VOC reactivity scales (2012), edu/~carter/saprc/saprc07.xls Chatani, S., Matsunaga, S.N., Nakatsuka, S.: Estimate of biogenic VOC emissions in Japan and their effects on photochemical formation of ambient ozone and secondary organic aerosol, Atmos. Environ., 120, (2015). PRTR 24 PRTR (2015) est24.html (2003) report/2013report/h25data/12w111.pdf Environment Canada: Gasoline and gasoline blend dispensing flow rate regulations (2010), gc.ca/lcpe-cepa/default.asp?lang En&n 54FE &wsdoc F069AA2D-C7A8 44D8 848B-EEDEB77C D4E

11 276 J. Jpn. Soc. Atmos. Environ. Vol. 50 No Gruden, D.: Ozone formation potential (Traffic and Environment, Springer, Berlin Heidelberg), p. 118 (2003). VOC 2008, (2008). Jiang, X., Guenther, A., Duhl, T., Sakulyanontvittaya, T., Wang, X.: MEGAN version 2.10 User s Guide (2012), v2.10_beta/megan2.1_user_guide_ pdf VOC (2005) /07air/y075 04/mat03 2.pdf (O X ) (2015) rep03.pdf (2012) or.jp/news2012/document/120626/kankyo38_01.pdf (VOC) (VOC) 26 (2015) main.pdf (2009) pdf Kirchstetter, T. W., Singer, B. C., Harley, R. A., Kendall, G. R., Hesson, J. M.: Impact of California reformulated gasoline motor vehicle emissions. 2. Volatile organic compound speciation and reactivity, Environ. Sci. Technol., 33, (1999). JATOP JEI-DB (JATOP Emission Inventory-Data Base) 513 (2012). PM 2.5 VOC, PM NOx JATOP JPEC-2011AQ (2012). 3 pp (2008). Reddy R. S.: Prediction of fuel vapor generation from a vehicle fuel tank as a function of fuel RVP and temperature, SAE Technical Paper Series, (1989). VOC 42, (2007). VOC 44, (2009) (1997) go.jp/html/data/tuchi1903/pdf/190316ki61_h_2.pdf Jeeranut Suthawaree OH 45, (2010). U.S. EPA: Emissions factors & AP 42, Compilation of air pollutant emission factors, transportation and marketing of petroleum liquids (2008), ttnchie1/ap42/ch05/final/c05s02.pdf U.S. EPA: Estimation program interface (EPI) (2013), VOC 47, (2012). Yamada, H., Inomata, S., Tanimoto, H.: Evaporative emissions in three-day diurnal breathing loss tests on passenger cars for the Japanese market, Atmos. Environ., 107, (2015). Zhang, Y., Wang, X., Zhang, Z., Lü, S., Shao, M., Lee, F. S. C., Yu, J.: Species profiles and normalized reactivity of volatile organic compounds from gasoline evaporation in China, Atmos. Environ., 79, (2013)

12 * (DBL) DBL 1 2 VOC C5 1 2 (MIR) (OFP) DBL OPF OPF OFP VOC OFP EW VOC OFP EW

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