Sensitivity analysis of O{sub 3} and photochemical indicators using a mixed-phase chemistry box model and automatic differentiation technology

Conference · Wed Dec 31 04:00:00 EST 1997

OSTI ID:351053

Zhang, Y; Easter, R C ^[1]; Bischof, C H; Wu, P T ^[2]

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1. Pacific Northwest National Lab., Richland, WA (United States)
2. Argonne National Lab., Argonne, IL (United States)

A comprehensive sensitivity analysis of a multi-phase atmospheric chemical mechanism is conducted under a variety of atmospheric conditions. The ADIFOR automatic differentiation technology is applied to evaluate the local sensitivities of species concentrations in gas, aqueous and aerosol phases with respect to a variety of model parameters. In this paper, sensitivities of tropospheric ozone and photochemical indicators with respect to species initial concentrations, gas-phase reaction rate constants, and aerosol surface uptake coefficients are presented and analyzed. The main gas-phase reaction pathways and aerosol surface uptake processes that affect tropospheric O{sub 3} formation, O{sub 3}-precursor relations and sensitivity of indicators are identified. The most influential gas-phase reactions include the photolytic reactions of NO{sub 2}, O{sub 3}, H{sub 2}O{sub 2}, HCHO, ALD{sub 2} and MGLY, the conversion of NO to NO{sub 2}, the generation and inter-conversion of OH, HO{sub 2} and RO{sub 2} radicals, and the formation and dissociation of oxidants and acids. Photochemical indicators such as O{sub 3}/NO{sub x} and H{sub 2}O{sub 2}/HNO{sub 3} are sensitive to changes in reaction rate constants, initial species concentrations, and uptake coefficients. These indicators are found to have higher sensitivities for hydrocarbon reactions and lower sensitivities for NO{sub x} reactions under polluted conditions as compared to less polluted conditions. Aerosol surface uptake is important when the total surface area is larger than 1,000 {micro}m{sup 2} cm{sup {minus}3}. The identified important heterogeneous processes include aerosol surface uptake of HCHO, O{sub 3}, HO{sub 2}, HNO{sub 3}, NO, NO{sub 2}, N{sub 2}O{sub 5}, PAN, H{sub 2}O{sub 2}, CH{sub 3}O{sub 2} and SO{sub 2}. These uptake processes can affect not only O{sub 3} formation and its sensitivity, but also O{sub 3}-precursor relations and sensitivities of indicators.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL
• Sponsoring Organization: USDOE, Washington, DC (United States)
• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 351053
• Report Number(s): CONF-970677--
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
AIR POLLUTION
ATMOSPHERIC CHEMISTRY
BOX MODELS
FORMALDEHYDE
HYDROGEN PEROXIDE
NITRIC ACID
NITROGEN OXIDES
OZONE
PEROXYACETYL NITRATE
PHASE STUDIES
PHOTOCHEMICAL REACTIONS
RADICALS
SENSITIVITY ANALYSIS
SULFUR DIOXIDE