A Reactivity Based Emission Inventory for the South Pars and Its Implication for Ozone Pollution Control

Document Type: Research Article

Authors

School of Environment, College of Engineering, University of Tehran, Tehran, I.R. IRAN

Abstract

The South Pars zone in Iran encompasses the largest gas refineries and petrochemical complexes in the world. In the South Pars zone, elevated concentrations of reactive hydrocarbons co-emitted with nitrogen oxides from industrial facilities lead to substantial ozone production downwind. To understand the role of these emissions on the ozone formation and, to formulate appropriate control strategies in this zone, emissions of precursors of ozone were quantified, and compounds that deserve relatively more attention were determined. To do this, first, a fully- speciated ozone precursors emission inventory was prepared to provide necessary input data for air quality simulation models. Then, the emission inventory was weighted by emitted mass and incremental reactivity scales to determine which compounds deserve relatively more detailed representation in the modeling. Afterward, a photochemical model was applied to determine the ozone sensitivity to its precursors. Finally, source apportionment was done for the most important compounds. Additionally, the reactivity-based inventory was compared with other regions. Results show that nitrogen oxides -sensitive chemistry is dominant in the zone thus the most effective control strategy is the mitigation of the nitrogen oxides emissions. Gas refinery plants have a larger share than petrochemical plants in the nitrogen oxides emission and, the gas turbines are the main sources of nitrogen oxides emission in this region. Emitted volatile organic compounds contain more highly reactive species in comparison with the ambient air composition of typical urban areas and areas with gas production industries. Propylene and ethylene have the most contribution to the ozone formation in comparison with other volatile organic compounds. The major sources of their emissions are the olefin processes and polymer production plants.

Keywords

Main Subjects


1]  Haagen-Smit A.J., Chemistry and Physiology of Los Angeles Smog, Ind. Eng. Chem., 44(6): 1342-1346 (1952).

[2] Pourfayaz F., Ahmadi-Avval P., Haji Tarverdi M.S., Maleki A., Ahmadi M.H., A Study of Effects of Different Surface Modifications of MWCNTs on Their Adsorption Capacity of Benzene and Toluene, Iran. J. Chem. Chem. Eng. (IJCCE), 36(6): 107-114 (2017).

[3] Carter W.P., Atkinson R., An Experimental Study of Incremental Hydrocarbon Reactivity, Environ. Sci. Technol., 21(7): 670-9 (1987).

[7] Sexton, K., Westberg H., Ambient air Measurements of Petroleum Refinery Emissions, J Air Pollut Control Assoc,. 29(11): 1149-1152 (1979).

[8] Sexton K., Westberg H., Photochemical Ozone Formation from Petroleum Refinery Emissions, Atmos Environ,. 17(3): 467-475 (1983).

[9] Barkley, M.P., et al., OMI Air-Quality Monitoring over the Middle East. Atmos. Chem. Phys., 17(7):  4687-4709 (2017).

[10] Van Der A R.J., Eskes H.J., Boersma K.F., Van Noije T.P.C., Van Roozendael M., De Smedt I., Peters D.H.M.U., Meijer E.W., Trends, Seasonal Variability and Dominant NOx Source Derived from a Ten Year Record of NO2 Measured from Space, J Geophys Res Atmos, 13(D4). (2008).

[12] Lelieveld, J., et al., Severe Ozone Air Pollution in the Persian Gulf Region. Atmos. Chem. Phys., 9(4) (2009).

[13] Worden J., et al., Observed Vertical distribution of Tropospheric Ozone During the Asian Summertime Monsoon, J Geophys Res Atmos,. 114(D13)  ( 2009).

[14] Smoydzin L., Fnais M., Lelieveld J., Ozone Pollution over the Arabian Gulf--Role of Meteorological Conditions, Atmos Chem Phys Discuss, 12(2) (2012).

[15] Zanis, P., et al., Summertime Free-Ttropospheric Ozone Pool over the Eastern Mediterranean/Middle East, Atmos. Chem. Phys., 14(1): 115-132 (2014).

[18] Spohn T.K., Rappenglück B., Tracking Potential Sources of Peak Ozone Concentrations in the Upper Troposphere over the Arabian Gulf Region, Atmos Environ, 101: 257-269 (2015).

[19] Li Q., et al., A Tropospheric Ozone Maximum over the Middle East. Geophysical Research Letters, Geophys Res Lett, 28(17): p. 3235-3238 (2001).

[25] Edwards, P.M., et al., High Winter Ozone Pollution from Carbonyl Photolysis in an Oil and Gas Basin, Nature,. 514: 351-   (2014).

[27] Gilman, J.B., et al., Source Signature of Volatile Organic Compounds from Oil and Natural Gas Operations in Northeastern Colorado, Environ. Sci. Technol,. 47(3): 1297-1305(2013).

[28] McDuffie, E.E., et al., Influence of Oil and Gas Emissions on Summertime Ozone in the Colorado Northern Front Range, J Geophys Res Atmos,. 121(14): 8712-8729 (2016).

[29] Gery M., Crouse R., "User's Guide for Executing OZIPR”, US Environmental Protection Agency, Atmospheric Research and Exposure Assessment Laboratory (1991).

[30] da Silva, C.M., et al., A Minimum Set of Ozone Precursor Volatile Organic Compounds in an Urban Environment, Atmos Pollut Res,. 9(2): 369-378(2018).

[31] Alvim D.S., et al., Determining VOCs reactivity for Ozone Forming Potential in the Megacity of
São Paulo
, Aerosol Air Qual. Res., 18(9): 2460-2474 (2018).

[32] Guarieiro L., et al., Use and Application of Photochemical Modeling to Predict the Formation of Tropospheric Ozone, Revista Virtual de Quimica, 9(5): 2082-2099 (2017).

[34] RTI International, "Emissions Estimation Protocol for Petroleum Refineries", RTI International (2011).

[35] Eastern Research Group, "I. Air Emissions Inventory Improvement Program (EIIP)", Volume 2, Eastern Research Group (1997).

[36] EPA, SPECIATE Version 4.4. (2014).

[37] Carter, W.P., "Estimation of Ozone Reactivities for Volatile Organic Compound Speciation Profiles in the Speciate 4.2 Database", Center for Environmental Research and Technology, University of California, USA, (2013).

[38] Carter, W.P., Development of Ozone Reactivity Scales for Volatile Organic Compounds, J Air Waste Manag Assoc, 44(7): 881-899 (1994).

[42] Carter, W.P.L., Scales07. 2013: http://www.cert.ucr.edu/~carter/SAPRC/.

[43] Carter, W.P., Development of a Condensed SAPRC-07 Chemical Mechanism, Atmos Environ., 44(40): 5336-5345 (2010).

[44] Whitten, G.Z., Hogo H., Killus J.P., The Carbon-Bond Mechanism: A Condensed Kinetic Mechanism for Photochemical Smog, Environ Sci Technol,. 14(6): p. 690-700 (1980).

[45] Yarwood G., et al., "Updates to the Carbon Bond Mechanism for version 6 (CB6)", in 2010 CMAS Conference, Chapel Hill, NC. (2010).

[47] Carter W.P., Development of a Database for Chemical Mechanism Assignments for Volatile Organic Emissions, J Air Waste Manag Assoc., 65(10):1171-84(2015).

[48]. Jeffries H.E., Sexton K.G., Arnold J.R., Kale T.L., Validation Testing of New Mechanisms with Outdoor Chamber Data. Volume 2: Analysis of VOC Data for the CB4 and CAL Photochemical Mechanisms, Final Report, EPA-600/3-89-010b. (1989).

[49] Lurmann, F.W., Main H.H., Analysis of the Ambient VOC data Collected in the Southern California
Air Quality Study
, Final report., Sonoma Technology, Inc., Santa Rosa, CA (United States) (1992).

[50] Carter W.P., Seinfeld J.H., Winter Ozone Formation and VOC Incremental Reactivities in the Upper Green River Basin of Wyoming, Atmos Environ., 50: 255-266 (2012).