Copyright. Dyron Thomas Hamlin

Transcription

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2 Copyright by Dyron Thomas Hamlin 2002

3 Modeling Ozone Formation in a Central Texas Power Plant Plume by Dyron Thomas Hamlin, B.S.ChE Thesis Presented to the Faulty of the Graduate Shool of The University of Texas at Austin in Partial Fulfillment of the Requirements for the Degree of Master of Siene in Engineering The University of Texas at Austin May 2002

4 Modeling Ozone Formation in a Central Texas Power Plant Plume APPROVED BY SUPERVISING COMMITTEE Gary T. Rohelle David T. Allen Elena C. MDonald-Buller

5 ACKNOWLEDGEMENTS This researh has been funded by the Texas Air Researh Center. I would like to thank Yosuke Kimura for his help in understanding UNIX, C, and theories of debugging. I send warmest well-wishes to Matt Russell for misellaneous assistane in CAMx proessing. I would also like to thank Amy Nowlin for allowing me to start a bit above ground zero. Most of all, thank you, Marria and Asher Hamlin, for ontinuing to allow Daddy to pursue wild ideas, like moving to Austin, Texas. iv

6 Modeling Ozone Formation in a Central Texas Power Plant Plume by Dyron Thomas Hamlin, MSE The University of Texas at Austin, 2001 ABSTRACT SUPERVISOR: Gary T. Rohelle Senate Bill 7, passed by the Texas Legislature in 1999, requires Eletri Generating Utilities to redue their NOx emissions to 50% of their 1997 levels by May, This ontrol strategy does not take into aount the diurnal variation in Ozone Prodution Effiieny (OPE) of NOx emissions. OPE is largely determined by meteorologial mixing phenomenon and distint diurnal differenes in ozone hemistry. These differenes are addressed in this researh using the Comprehensive Air Quality Model with extensions (CAMx). Inremental inreases in nighttime emissions from a rural power plant are found to form signifiantly more ozone (as measured during peak afternoon hours) than the same inreases in afternoon emissions for all four modeling days analyzed. This apability is quantified as both peak onentration (and loation) and total ozone present (spatially integrated) during sensitive afternoon hours. Nighttime OPE ranged from 4 to 10, while daytime emissions yielded from 1 to 4 (moles O 3 formed / moles NOx emitted). The range of high-impat emissions is from approximately 7 p.m. to 10 a.m. However, emissions from 7-9 p.m. and 8-10 a.m. are not onsistently high-impat. v

7 A limited validation of CAMx was performed using data olleted by the Department of Energy s G-1 airraft during the 2000 TEXas Air Quality Study (TEXAQS). On September 10, 2000, the U.S. Department of Energy s G-1 airraft sampled the plume of emissions from the Fayette Power Projet (FPP), loated in Fayette County, Texas. The results of the airraft plume sampling are ompared with a similar day of a July 1995 CAMx modeling episode, namely July 9. Model preditions for FPP OPE are lower (1-4) than those measured by airraft data (2-9). Domain-wide, threefold inreases in the biogeni hydroarbon emission inventory ause modeled OPEs to beome omparable to measured OPEs. vi

8 Table of Contents ACKNOWLEDGEMENTS... iv ABSTRACT... v Table of Contents... vii List of Figures and Tables... ix Chapter I: Introdution and Bakground Ozone as an Air Pollutant Ozone Status in Texas Control Strategies Diurnal Variations Chemistry Definitions OPE Meteorology Researh Objetives...11 Chapter II. Atmospheri Modeling The Comprehensive Air Quality Model with Extensions (CAMx) Deposition Plume-in-Grid (the PiG) PiG Growth PiG Chemistry Episode Details...27 Chapter III. Modeled / Airraft Data Comparison Bakground Airraft Data Analysis Bakground Approahes to Analysis and Comparison Fayette Power Projet (FPP) Data Conentration Ratio Approah Plume-Averaged OPE for FPP Conentration Ratio Approah Transet-Averaged OPE for FPP Mass Balane Approah Transet-Averaged OPE for FPP Calulation of Chemial and Physial Age of FPP Transets Comparison of Airraft Data and Modeled Data Relevant Parameters for Comparison Virtual Airraft Flight Comparison-Conentration Ratio Approah Virtual Airraft Flight Comparison-Mass Balane Approah...57 vii

9 3.4.4 Dimensional Analysis of the Virtual Airraft Flight Plant On Plant Off Comparison-Conentration Ratio Approah Plant On Plant Off Comparison-Mass Balane Approah Plant On Plant Off Comparison-Ozone Prodution Approah Conlusions...69 Chapter IV: Temporal Sensitivity of O 3 Formation to NOx Emissions from a Large, Rural Point Soure in Eastern Texas Modeling Approah Reeptor Site Analysis Plume Loation Analysis Conlusions...84 Chapter V: Summary and Conlusions Chapter VI: Reommendations APPENDICES APPENDIX A: Computer ode...90 APPENDIX B: Airraft Data Comparison APPENDIX C: Diurnal Sensitivity Figures and Spreadsheet Data APPENDIX D: Episode Base Case Tables and Figures Referenes VITA viii

10 List of Figures and Tables Figure NOx Contribution (tons per year) by Soure Category. (Std. Ex. = Standard Exemption, Gfr. = Grandfathered, Perm.=Title V Operating Permitted Faility) (All NOxgenerating Failities)...3 Figure 1-2. Photostationary State Between O 3 and NOx....4 Table 1-1. NOz Speies in the Fayette Power Projet Plume of Emissions and Their Relative Daytime Contributions to NOz....7 Figure 1-3. Diurnal Variation in Atmospheri Mixing...10 Figure 1-4. Noturnal Temperature Inversion Formation...11 Figure 2-1. Grid Struture employed by CAMx Table 2-1. July 1995 Modeling Episode Days...14 Table 2-2. Summary of the CAMx Modules for Key Physial Proesses...15 Table 2-3. Day and Night Deposition Veloities (m/s) for Ozone and Nitri Aid Figure 2-2. Average Instantaneous OPE (do 3 /dnoz) by Layer (CAMx Vertial Layers 1-7, Using [Plant On-Plant Off] Analysis and O 3 Threshold of 2.0 ppb, Day 3 of July 1995 Modeling Episode)...17 Figure 2-3. Simplified PiG Shemati Figure 2-4. PiG NOy (NO + NO 2 + HNO 3 ) for Puffs Loated in All Vertial Layers at 1:00 a.m, Day 2 of Modeling Episode, Base Case Table 2-4. Layer Heights Used in July 1995 CAMx Modeling Episode...28 Figure 2-5. Wind Veloity (Saled from m/s) by Day for July 1995 Episode (Instantaneous Model Value at 15:00 on eah day) Figure 3-1. Typial Plume Sampling Flight Path and Large NOx Soure Plume Dimensions (Baylor University Twin Otter, Flight 39, August 25, 1997). (Adapted from MaDonald et al., 1999)...32 Figure 3-2. Time Series Plot of Flight 39 of the Baylor University Twin Otter, August 25, (Courtesy TNRCC)...33 Figure 3-3. Time Series Plot of Flight 7 of the Baylor University Twin Otter, June 4, (Courtesy TNRCC) Figure 3-4. Time Series of FPP Data Aquired through TEXAQS (Number indiates transet) Figure 3-5. OPE for FPP, Derived from Airraft Data Taken 9/10/2000 (all NOz assumed to be due to soure) Figure 3-6. OPE by Transet for FPP Data Colleted 09/10/ ix

11 Table 3-1. Flux (Flow rate) of NOy at Conseutive Transets; Calulation Based Upon Equation 3-1 (Data Taken by NOAA G-1 Airraft from FPP Plume on 9/10/2000) Table 3-2. FPP NOx Emission Rate (tons/hr) for Eah of Three Large Boilers (FPP-1,2, and 3) Reported by LCRA for 9/10/ Table 3-3. Ozone Flux (Flow Rate) Calulation Based Upon Equation Table 3-4. OPE by Transet Using Mass Balane Approah, NOx Flux Assumed from Data Obtained from LCRA for FPP, 9/10/ Table 3-5. OPE by Transet Using Mass Balane Approah, NOx Flux Calulated Figure 3-7. Regression of NOx and NOy for FPP G-1 Data 09/10/ Figure 3-8. Cumulative Loss of NOx in FPP Plume (G-1 Data 09/10/2000)...46 Figure 3-9. NOz/NOy (NOy Correted Based Upon Initial NOx/NOy Ratio of 1.3)...47 Table 3-6. Chemial Age (NOz orreted /NOy orreted ) by Transet for FPP Plume (NOAA G-1 Data 09/10/2000)...47 Table 3-7. Physial Age of Transets for FPP Plume (NOAA G-1 Data 09/10/2000)...48 Figure Regressed value of NOz orreted /NOy orreted Plots for Eah Transet versus Physial Age of Eah Transet (NOy Correted by Assuming Initial NOx/NOy Ratio=1.0; Physial Age alulated by distane between transet and soure, assuming a onstant wind speed of 4 m/s) Figure OPE (using Conentration Ratio Approah, by Transet) for Individual Transets versus Corresponding Chemial Ages...50 Figure OPE (using Mass Balane Approah, by Transet) for Individual Transets versus Corresponding Chemial Ages...51 Figure O 3 Conentrations in Modeled FPP Plume at Comparable Physial Age and Altitude (CAMx Layer 5) to FPP G-1 Data olleted 9/10/2000 (Model Day 3, 15:00 data, wind speed = 2.0 m/s) Figure OPE for Modeled Data with Similar Physial Age and Altitude to FPP G-1 Data Colleted 9/10/ Figure Ozone Conentrations (ppb) from Airraft and Modeled data (Airraft on left, FPP data olleted by NOAA G-1, 9/10/2000; Modeled on right, CAMx, July 9, 1995, 15:00; both interpolated using Krieging method and plotted using Golden Surfer Software)...58 x

12 Figure NOx Soures within 40 km of FPP (Total NOx ontribution ~10% of FPP soure strength)...59 Figure O 3 Puff (Plant On Plant Off Differene Plot) Due to Emissions from FPP at 2:00 p.m. on July 8, Figure OPE Puff (Plant On Plant Off Differene Plot) Due to Emissions from FPP at 2:00 p.m. on July 8, Figure OPE of FPP at 3:00 p.m. on July 9, 1995; Plant On Plant Off Analysis...62 Figure OPE of FPP at 3:00 p.m. on July 9, 1995; Plant On Plant Off Analysis; Three Times Original Biogeni Hydroarbons...63 Figure OPE of FPP at 3:00 p.m. on July 9, 1995; Plant On Plant Off Analysis; Six Times Original Biogeni Hydroarbons...64 Table 3-8. Data used for Calulation of Integrated Ozone over FPP Plume (based on airraft data olleted by NOAA G-1 9/10/2000, height assumed 1105 m, wind speed 2 m/s, atmospheri density 37 mol/m 3 ) Table 3-9. Data used for Calulation of Integrated Ozone over FPP Plume (based on airraft data olleted by NOAA G-1 9/10/2000, height assumed 1105 m)...67 Table Summary of Comparisons of Modeled Data (July 9, 1995 CAMx Episode, 15:00) to Airraft Data (NOAA G-1 9/10/2000)...68 Figure 4-1. Diurnal Impat of NOx Emissions (Nowlin, 2001) Figure 4-2. FPP Impat (do 3 /Two Hours of Inreased Emissions) in 6- grid ell (4x4 km) Region Surrounding Austin, TX for Emissions Inreases (Day 6 of Modeling Episode)...76 Figure 4-3. Ozone Puff (Differene plot of [2-hr Inrease Base Case]) for a Midnight-2am NOx Inrease on July 9, 1995, snapshot taken at 14:00, ground layer Figure 4-4. Relative Impats of Two-Hour Emissions Inreases; 14:00 Analysis Figure 4-5. Relative Impats of Two-Hour Emissions Inreases; 17:00 Analysis Figure 4-6. Relative Impats of Two-Hour Emissions Inreases; 15:00 Analysis Figure 4-7. Positions of Maximum?O 3 for Two-Hour Emissions Inreases, all Layers; 14:00 Analysis (darker symbol olor indiates higher impat; blue indiates negative impat, open star loates maximum impat of all-day, 50% redution)...82 xi

13 Chapter I: Introdution and Bakground 1.1 Ozone as an Air Pollutant Ozone (O 3 ) is a gaseous pollutant whih auses many adverse health effets, inluding inflammation and irritation of the respiratory trat (EPA, 1999). It is lassified as a riteria pollutant by the United States Environmental Protetion Ageny (EPA). Control of ozone is diffiult, however, beause it is a seondary pollutant; it is formed in the atmosphere, by the reation of nitrogen oxides (NOx) and volatile organi ompounds (VOC) in the presene of sunlight. As a riteria pollutant, Ozone is subjet to a National Ambient Air Quality Standard (NAAQS). The urrent NAAQS for ozone is 0.12 parts per million (ppm), whih is equivalent to 125 parts per billion (ppb) (one-hour average). Currently, a proposed NAAQS of 85 ppb (eight-hour average) has been suessfully hallenged in the ourt system, was upheld by the Supreme Court, and has been remanded to the EPA (D.C. Ciruit Court, 1999). Until the proposed NAAQS is aepted, the one-hour, 125 ppb standard will remain in effet. 1.2 Ozone Status in Texas Four urban areas in Texas exeed the urrent NAAQS for ozone under the one-hour standard: Houston-Galveston, El Paso, Dallas-Fort Worth, and Beaumont-Port Arthur. Four more areas are in danger of beoming non-attainment under the proposed 8-hour standard: Austin, San Antonio, Tyler-Longview- Marshall, and Vitoria. To deal with non-attainment status, the State of Texas has developed a State Implementation Plan (SIP), in aordane with the requirements of the EPA. 1.3 Control Strategies Reent land use studies indiate that biogeni VOC emissions omprise a large fration of total VOCs in eastern Texas (Wiedinmyer et al., 2000). Therefore, 1

14 regulatory attention has foused on anthropogeni NOx emissions rather than anthropogeni VOC emissions (Sillman et al., 1990). Reently, studies have also shown that a regional approah to ozone ontrol may be neessary in Texas (Kasibhatla et al., 1998; Saylor et al., 1998; TNRCC, 2000). A regional approah to reduing ozone formation in eastern Texas will target large-sale regional NOx redution. This neessarily inludes redution from some of the largest NOx produers in the state: eletri generating utilities. Certain of these utilites have been allowed to operate without the new onstrution permits required from all soures beginning operation after This allowane is known as grandfathering. Small soures (less than 250 Tons NOx/year) qualify for a Standard Exemption Permit; while all large, non-grandfathered soures must apply for a Title V Operating Permit. Thus, NOx ontrol by failities in operation before 1971 has been optional. Reently, however, the Texas Legislature passed Senate Bill 7 (SB7), whih requires all eletri generating utilities to redue NOx emissions to 50% of their 1997 levels by May 2003 (Texas Legislature, 1999). As part of the ontrol strategy, emissions will be alloated to eah faility based on the power generation, and a NOx trading program is undergoing further development. Figure 1 shows the 1997 ontribution of grandfathered failities (Gfr), Standard Exemption status failities (Std. Ex.), and Title V Operating Permitted failities (Perm.) to the total NOx emission inventory for the state. The total NOx inventory is the sum of the three ontributions. 2

15 Figure NOx Contribution (tons per year) by Soure Category. (Std. Ex. = Standard Exemption, Gfr. = Grandfathered, Perm.=Title V Operating Permitted Faility) (All NOx-generating Failities) Reent development of a SIP for Houston involved some atmospheri modeling, whih was performed using the Comprehensive Air quality Model with extensions (CAMx) (40 CFR, 2001). The State of Texas, in their evaluation of high O 3 in East Texas, noted from CAMx modeling that high bakground O 3 onentrations, ombined with urban O 3 onentrations led to violations of the O 3 NAAQS. Sensitivity tests performed using a July, 1993 episode of CAMx indiated that a 50% redution in NOx emissions from point soures in East Texas gave a onsistent ozone redution for some areas, suh as Longview-Tyler-Marshall for most modeling days. However, ozone was not as onsistently redued in other areas, suh as Austin (MDonald-Buller et al., 1999). Further researh using CAMx has illustrated that the ozone prodution of NOx point soures varies aording to their loation, and the time of their emissions (Nobel et al., 2000; Nowlin, 2001). Comparison of modeled data to airraft data is needed to assess the ability of CAMx to predit NOx plume phenomena. 3

16 1.4 Diurnal Variations Diurnal variations in ozone hemistry and meteorology give rise to the possibility that NOx emitted at night may have different ozone generating apaity than NOx emitted during the day Chemistry Ozone hemistry is quite omplex, and tends to be non-linear with respet to NOx. In general, ozone is generated during the day, and onsumed at night, aording to the following reations. Day A photostationary yle exists between NO x (NO and NO 2 ) and O 3, with no net hange in ozone, as shown in Figure 1-2. O 3 O 2 NO NO 2 hν O 3 O 2 Figure 1-2. Photostationary State Between O 3 and NOx. 4

17 In the presene of reative hydroarbons, the onversion of NO-NO 2 by ozone is interrupted by a peroxy radial, as summarized in the following reations. RH + OH R + H2O (R1) R (R2) + O 2 RO 2 RO + NO RO + 2 NO 2 (R3) The initiation of this step involves the hydroxyl radial, OH.. The soure of OH. in these reations is, in an initial phase, photolysis of ozone. O + hν O + O( 1 ) (R4) 3 2 D O 2 1 ( D) + H2O OH (R5) While the initiation of OH. takes plae by Reations R4 and R5, propagation of OH. is dominated by the onversion of NO to NO 2 by the alkylperoxyl radial, RO. 2 (or its orollary, the hydroperoxy radial, HO. 2 ), as in Reation R3. The daytime termination pathway is desribed by Reation R6. NO2 + OH HNO 3 (R6) Reation R6 is signifiant in that nitri aid represents the only true termination produt of NOx-VOC-O 3 hemistry. NOx whih has formed nitri aid is no longer available for prodution of ozone. Using an average urban mix of VOC, the rates of Reations R1 and R6 are equal when NOx/VOC is 1:5.5 (Seinfeld, 1998). If isoprene dominates the VOC mix, the rates are equal at NOx/VOC 1:0.25 (using k R6 =2.39x10-11 m 3 /moleule- 5

18 s, and k R1 =1.01x10-10 m 3 /moleule-s, from Seinfeld, 1998). Sine Reation R6 represents removal of both NOx and OH., it ontributes to retardation of O 3 formation. Thus, under high-nox onditions (suh as in a power plant plume, where NOx/VOC is muh higher than 1:5.5), Reation R6 will predominate, and retard O 3 formation. As NOx is depleted through Reation R6, NOx/VOC beomes smaller, and aelerates O 3 formation. Emissions into an isoprene-rih region from a rural plant will begin to yield O 3 muh more quikly than emissions from an urban plant. This leads to the formation of ozone wings, or high-ope zones at the edges of plumes. These are ommonly reorded at the edges of large industrial NOx plumes (Gillani and Pleim, 1996; Sillman, 2000), and will be disussed further in Chapter III. Night Nighttime hemistry differs from daytime hemistry due to the absene of photolysis reations that annot take plae during sunlight hours. Speifially, Reations R7 through R9 are signifiant only in the absene of sunlight (Seinfeld, 1998). NO + + k=2.8e-3 ppb -1 hr -1 (R7) 2 O3 NO3 O2 NO 3 + NO2 + M N2O5 + M (R8) N 2O5 H 2O 2HNO3 + (R9) During the day, NO 3 is rapidly photolyzed bak to NO 2 and O 3. However, during the night, this pathway provides the net sink for NOx (Platt et al., 1994). With negligible loss of NO 3 to other proesses, the net loss is limited by the initial reation with ozone and the first order rate onstant with 50 ppb ozone is 0.28 hr -1 : 6

19 O NO 2 + H 2 O? 2HNO 3 ; dno 2 /dt = 5.6e-3 hr -1 ppb-1 [O 3 ] [NO 2 ] Definitions It is useful to define speifi lasses of the above speies involved in nitrogen oxide hemistry. NOy = NOx + NOz Total Nitrogen Speies = NO + NO 2 + Oxidized produts of NOx (1-1) Table 1 lists various speies inluded in NOz for a power plant plume of emissions, and reports a typial daytime range of their frational ontributions to total oxidized speies of NOx. Table 1-1. NOz Speies in the Fayette Power Projet Plume of Emissions and Their Relative Daytime Contributions to NOz. Speie Name Frational Contribution to NOz (Average model values from CAMx July 1995 modeling episode output) Nitri Aid 65-70% Peroxyaetyl Nitrate (PAN) 6-10% Nitrous Aid 0 N x O y (e.g., N 2 O 5 ) 0 Organi Nitrates 15-25% 7

20 Nitrous Aid and N x O y do not exist during the day due to photooxidation. Organi nitrates inlude peroxyalkyl nitrates (ROONO 2 ), peroxyayl nitrates (RC(O)OONO 2 ), and alkyl nitrates (RONO 2 ). All of the organi peroxynitrate speies (inluding PAN) may thermally deompose bak to a peroxy (or peroxyaetyl) radial and NO 2. A metri for determining ozone formation apability is known as Ozone Prodution Effiieny (OPE). OPE is defined, qualitatively, in Equation 1-2. d[ O OPE = 3] (1-2) d[ NOx] original OPE Beause it is impossible to trak the exat origin of a NOx moleule present in the atmosphere, other definitions have been proposed for OPE. Eah of these definitions has been employed in this researh. There is no universally aepted definition of OPE (Gillani et al., 1998b). A ommon alternative definition used is the ratio O 3 /(NOy-NOx), or O 3 /NOz (Olszyna et al., 1994). d[ O ] 3 OPE = (1-3) d[ NOz] This definition aounts for ozone that has been produed by NOx that has been oxidized to form NOz. It will not, beause of dry deposition of NOz, aount for all of the original NOx emitted. The primary NOz speie involved in dry and wet deposition is nitri aid, HNO 3, whih deposits from 2 to 10 times as fast as ozone (Seinfeld, 1998). One way to estimate this loss is to relate the ozone and NOz present at a given point in spae to a onserved speies, one whih is not affeted to suh a great degree by dry deposition. Corretions an then be made to estimate onentrations based upon pre-loss irumstanes. Corretions of this 8

21 nature have been employed for the OPE metri desribed in Equation 1-3 (Gillani et al., 1998a; Ryerson et al., 1998). The use of total nitrogen speies present, NOy, has also been employed as a onvenient metri whih relates to original NOx (Trainer et al., 1993). d[ O3 ] OPE = (1-4) d[ NOy] However, it has been estimated that NOy is lost anywhere from 3-17% per hour, based upon an atmospheri mixing layer depth of 1 km. Few experiments have yielded reliable results (Gillani et al., 1998; Imhoff et al., 2001). Still another way to represent OPE is to onsider the ratio of the rise in ozone to the rise in nitri aid at a given point in spae. d[ O3] OPE = (1-5) d[ HNO ] 3 Nitri aid is the only true termination produt of NOx oxidation, onsidering the thermal deomposition of other NOz speies as desribed above. These oxidized nitrogen speies an partiipate in regeneration of NOx, and therefore ontinue to play a role in the prodution of ozone. Beause only a fration (although up to 80%) of NOz is aounted for by using HNO 3 in Equation 1-5, values will be systematially higher than OPE as defined by Equation 1-3. The differene between do 3 /dnoz and do 3 /dhno 3 will vary as the fration of NOz as nitri aid varies. OPE is affeted greatly by NOx/VOC. In general, smaller NOx/VOC will yield higher OPE. This fat implies that smaller NOx soures, given equivalent bakground hydroarbon onentrations, will have higher OPE 9

22 than larger NOx soures. This has indeed been onfirmed in multiple studies (Gillani et al., 1998; Ryerson et al., 1998, 2001; Nunnermaker et al., 2000). OPE sensitivity to the NOx/VOC also impliates diurnal sensitivity to NOx emissions due to diurnal variation in atmospheri mixing Meteorology 10 km Free Atmosphere 1 km Convetive Mixed Layer Residual Layer stable boundary layer surfae layer Mixed Layer Noon Sunset Midnight Sunrise Noon Figure 1-3. Diurnal Variation in Atmospheri Mixing. Atmospheri mixing varies greatly due to the diurnal differene in heat supplied to the Earth s atmosphere. During the day, heat flows from the hot surfae of the Earth into the atmosphere just above the surfae through diffusive mehanisms. The warmed air parel may be onsidered a buoyant thermal, due to its higher temperature relative to surrounding air. As the heated air rises, the pressure surrounding the air parel will drop, ausing adiabati expansion and ooling of the air parel. The ontinual formation and vertial transport of these air parels gives rise to the onvetive mixed layer, as depited in Figure 1-3. The Earth s surfae ools upon sunset, and a temperature inversion forms during the night, as depited in Figure

23 Day Night Altitude Heat flux Altitude Inversion level Heat flux Temperature Temperature Figure 1-4. Noturnal Temperature Inversion Formation. The inrease in temperature with elevation auses the formation of a stable noturnal boundary layer, in whih there is no opportunity for turbulent, buoyant transport of air. Very little mixing takes plae in this irumstane, whih, from an air pollution standpoint, is very signifiant (Seinfeld, 1998). The resulting nighttime plume tends to be quite slender and onentrated, and provides a high- NOx region where there is opportunity for hemial neutrilization of NOx by reation with O 3, as in Figure 1, R6, and R7-R Researh Objetives This researh fouses on two major aspets of modeling the ozone problem in Texas, and proposes methods for further analysis. The ability of CAMx to aurately predit ozone prodution by a large NOx point soure is validated by omparison to airraft data taken in a plume of emissions from a grandfathered eletri generating utility. Two different analysis tehniques for performing suh validation are proposed. The diurnal variability of ozone prodution by this large utility is examined, and new methods are proposed. Methods for further omparison of modeled data and airraft data are proposed. 11

24 Chapter II. Atmospheri Modeling 2.1 The Comprehensive Air Quality Model with Extensions (CAMx) CAMx was developed by Environ, and is available on-line at The EPA requires that any model used for State Implementation Plan (SIP) development meet ertain preision riteria (EPA, 1991). The Comprehensive Air Quality Model with extensions (CAMx) is one of only three or so models urrently used by states to legislate State Implementation Plans. Others inlude UAM-IV and SARMAP (California). CAMx is used for SIP development in Texas, and is therefore the model employed in this researh to investigate diurnal NOx ontrol options (40 CFR, 2001). CAMx utilizes a fixed-grid ell struture to report onentrations spatially in a speified domain. For the episode employed in this researh, these grid ells have onstant dimensions (although in some formulations, grid ell height an vary) throughout eah modeling episode. CAMx allows the user to speify vertial and horizontal grid dimensions, the number of vertial layers, and the number of nested grids. Figure 2-1 depits the gridded domain used in this researh. The domain was developed for use in regional modeling for the Austin and San Antonio urban areas. It ontains 2 nested grids. 12

25 Figure 2-1. Grid Struture employed by CAMx. The oarse grid pitured in Figure 2-1 utilizes 32x32 km grid ells; the nested grids ontain 16x16 km and 4x4 km grid ells. For ontinuity, eah grid ell struture must have the same number of layers, and the same layer heights. Modeling episodes are typially hosen based upon ourrenes of high ozone. The episode used in this researh is from July 7-12, 1995, and will be desribed in detail later in this hapter. It is onvenient at this point to define the days of the episode. Table 2-1 summarizes the episode days. 13

26 Table 2-1. July 1995 Modeling Episode Days. Day Referred to as: Comments July 7 Day 1 Model Initialization July 8 Day 2 Model Initialization July 9 Day 3 July 10 Day 4 July 11 Day 5 July 12 Day 6 Model initialization days are ones for whih results are questionable. Results from Days 1 and 2 of the modeling episode are suspet due to the establishment of boundary onditions in the internal grids. For these days, there is too muh dependene of model preditions on initial onditions. Day 3 utilizes boundary onditions alulated on Days 1 and 2 to model hemistry and transport. Days 1 and 2 do not have well-established boundary onditions; thus, they are not inluded in analysis. In eah of the grid ells, various routines are employed whih eventually yield preditions for speies of interest, inluding ozone. Table 2-2 has been adapted from the User s Guide for CAMx version 2.00 (Environ, Deember 1998). It summarizes the CAMx modules employed for desription of key physial proesses. 14

27 Table 2-2. Summary of the CAMx Modules for Key Physial Proesses. Module Physial Model Numerial Method Horizontal Continuity equation Smolarkiewiz (1983) or advetion/diffusion losed by K-theory Bott (1989) for advetion, Vertial transport/diffusion Chemistry Dry deposition Wet deposition Plume-in-Grid Two-way grid nesting Continuity equation losed by K-theory Carbon Bond IV (CB- IV) Resistane model of Wesely (1989) Savenging model as in CALPUFF (EPA, 1995) expliit diffusion Crank-Niholson for transport, impliit diffusion ENVIRON CMC Solver (hybrid expliit/impliit/ steady-state) Speified as surfae boundary ondition for vertial diffusion Exponential deay in eah ell, eah time step Continuous-leaking ylindrial plume segment model with expliit inorgani hemistry Grids solved separately with one ell overlap at boundaries to handle inter-grid pollutant flux via boundary onditions. Fine grids sub-divide the oarse grid time-step Of the proesses listed above, the ones of greatest interest to this researh are the proesses for dry deposition and Plume-in-Grid. Both of these will diretly affet predited OPE of large point soures and, therefore, omparison with airraft data. 2.2 Deposition Beause dry deposition has a diret effet on OPE (see Equation 1-3), it is important that CAMx reflet physial phenomenon effetively in its formulation. Typial CAMx values for O 3 and HNO 3 deposition veloity are tabulated in Table

28 Table 2-3. Day and Night Deposition Veloities (m/s) for Ozone and Nitri Aid. Modeled Values Seinfeld, 1998 Day Night Day O HNO It is onvenient to show how model values were alulated. The physial model employed by CAMx is one developed by Wesely (Wesely, 1989; Environ, 1998). This model inorporates a 3-phase resistane mehanism whih varies aording to land use data. The three-phase resistane model is summarized in Equation 2-1. v d = R a 1 + R d + R s (2-1) Where R a is the atmospheri resistane, R d is the deposition layer resistane, and R s is the surfae layer resistane. Atmospheri resistane desribes the extent to whih turbulent transport brings material from the onvetive mixed layer to the surfae. It is based on mass transfer/momentum transfer similarity theory. Deposition layer resistane is a funtion of the diffusivity of a partiular speie through an effetive laminar boundary layer very near the surfae. The surfae layer resistane is a funtion of the surfae type (water, land with or without dead or living vegetation, et.), and inorporates an additional series resistane formula to inlude various levels of vegetative anopy. The methods employed in the Wesely model for dry deposition are not neessarily the best methods available for estimation; however, it is the model used most widely by regional photohemial models (Wesely, 1989; Seinfeld, 1998). Modifiations proposed to Wesely s sheme have shown 16

29 signifiant (up to 23% for O 3 or NOz speies) differenes in surfae resistanes (Welmsley et al., 1996). Data onfirming these alulated resistane values are not widely available; validation of the deposition model is outside the sope of this researh. However, as Figure 2-2 indiates, deposition will likely have little effet on OPE between layers during the middle of the day. 4 Layer 1 Layer 2 Layer 3 Layer 4 Layer 5 Layer 6 Layer 7 Layer-Average Instantaneous OPE Hour Figure 2-2. Average Instantaneous OPE (do 3 /dnoz) by Layer (CAMx Vertial Layers 1-7, Using [Plant On-Plant Off] Analysis and O 3 Threshold of 2.0 ppb, Day 3 of July 1995 Modeling Episode). As seen in Figure 2-2, nighttime differene in model-predited OPE is expeted between layers. During the afternoon, however, when the atmosphere is well-mixed, deposition rates have a near equal effet (instantaneous OPE within 5%) at all layers. Data for Figure 2-2 is loated in Appendix B. 17

30 2.3 Plume-in-Grid (the PiG) The PiG is a puff model, whih assumes a Gaussian distribution of mass in a puff with defined length and variable ross-setional area. Eah PiG puff is emitted to a final plume rise, and is added, at eah time step of the model, to a partiular vertial layer of emission. The only speies arried by PiG puffs are NO, NO 2, HNO 3, and O 3, and only O 3 is entrained during the life of the puff. The interation between the bakground atmosphere and the NOx in the plume, is ontrolled by leakage, whih will be disussed in detail below. The puff length is determined by the wind speed at the urrent time step, and the duration of the time step. L = u dt (2-2) ij ij Where L ij is the 2-dimensional length of the puff segment, u ij is the 2-dimensional wind vetor, and dt is the disrete time step employed in the Eulerian sheme. The maximum length of a puff is defined by the user in the CAMx run ontrol file (Appendix A). Should the potential length of a puff exeed the userdefined maximum length, multiple puffs are generated during the time step. N ( uij dt) = int + 1 Lmax puffs (2-3) Where N puffs is the number of puffs formed per disrete time step, int is the trunation integer funtion, and L max is the user-defined maximum puff length. 18

31 The PiG allows for simplified, inorgani hemistry (involving only the four speies in eah puff, noted above), and transport under a Lagrangian box model sheme. Figure 2-2 shows a simplified piture of PiG transport. Figure 2-3. Simplified PiG Shemati. The Lagrangian puffs are adveted horizontally through CAMx grid ells, and experiene growth and internal hemistry. As mentioned, the puffs will remain in their layer of emission, loated at the final plume rise. Eah of the individual puff setions above, it must be noted, ould very well be disontinuous with one another; in other words, there is a distint possibility that an individual puff ould find itself disjoined from any other puffs. During a single Eulerian time step within the CAMx framework, puffs may be emitted to different layers. Wind shears between different model layers may produe puffs from different hours of the same day whih are transported to positions far from one another. An example is shown in Figure

32 Fayette Power Projet Figure 2-4. PiG NOy (NO + NO 2 + HNO 3 ) for Puffs Loated in All Vertial Layers at 1:00 a.m, Day 2 of Modeling Episode, Base Case. Figure 2-4 represents PiG NOy from a partiular point soure, namely the Fayette Power Projet, loated in Fayette County, Texas. PiG NOy is simply the onentration of the only three NOy speies arried by the PiG: NO, NO 2, and HNO 3. We might use PiG NOy as a traer to loate modeled puffs. Figure 2-3 learly shows the potential for disontinuity between individual PiG puffs. Suh disontinuity may well represent the possibility for emissions from one soure to have simultaneous impat at multiple reeptor loations. This possibility was realized during the sixth day of the modeling episode utilized in this researh, and will be disussed in Chapters 3 and 4. 20

33 2.3.1 PiG Growth PiG growth is assumed to be the age-limiting fator in PiG puffs, as opposed to PiG hemistry. The impliations of this hoie are potentially huge. As the PiG puffs are adveted downwind, they grow in ross-setion, thereby diluting the onentration of the speies inside the puff. One the physial boundaries of the host grid ell have been reahed (either layer height or horizontal grid ell dimension), the puff begins to leak its mass. The CAMx mehanism for PiG growth (piggrow.f) is inluded in Appendix A for referene. To understand when puff mass is leaked, one must understand how PiG dimensions are defined. Upon initial release from the stak, the puffs have a volume equal to a ylinder with ross-setional area equal to that of the stak from whene the emissions ame. At the final plume rise, the puffs are assumed to have grown through adiabati expansion, aording to loal pressure and temperature. This final plume volume is divided by the puff length, and the ross-setional area is onsidered to be irular. One initial dimensions are established, the new puff is sent, along with all other puffs, to a growth routine at eah time step. Cross-setional growth ours as a result of vertial and horizontal diffusivity, aording to the following equation. σ t) = 2* K * t + U y h xy dσ t dx y ( (2-4) Where s y is the horizontal dimension of the puff (m), K h is the horizontal eddy diffusivity (m 2 /s), t is the time step (s), U xy is the horizontal wind vetor (m/s), and ds y /dx is the hange in dispersion parameter as a funtion of downwind distane (dimensionless). 21

34 The dispersion parameter is essentially an empirially derived estimation of the inreased growth due to horizontal advetion. In other words, plumes will tend to spread longitudinally in addition to ross-setional growth. The fat that PiG puffs are assigned a onstant length auses underestimation of atual dispersion; a fat whih is aounted for by the seond term of Equation 2-4. Correlations for this quantity are readily available (see, e.g., Seinfeld, 1998). The example given in Equation 2-4 is for the horizontal growth. Vertial growth differs only in its use of a vertial eddy diffusivity and hange in dispersion parameter. After a ertain amount of time, the puff dimensions will exeed those of their host grid ell. Beause vertial diffusivities are typially on the order of 1% of horizontal diffusivities, horizontal growth will far exeed vertial growth. This leads to short, squat puffs. Also, growth in both diretions ours muh more rapidly during the day than at night, for meteorologial reasons summarized in Chapter 1. Thus, puffs may only exist for one hour during the day before reahing the physial limits of their host grid ell; while nighttime puffs tend to last muh longer (on the order of 12 hours) before being dispersed by the morning time formation of the onvetive boundary layer. The eventual slaughter of these puffs (rapid during day, slow at night) ours as a result of leakage. Basially, small amounts of a puff s NOx are removed from the puff and introdued to the grid ell in whih the puff is loated. This proess begins after the puff outgrows the grid ell boundaries. When dumping the mass remaining in the puff will ause a grid ell onentration inrease of less than 0.1 ppb, the puff is slaughtered. Slaughtering a PiG is simply removing all of the remaining puff mass from the PiG puff and adding the 22

35 mass to the grid ell. A ase study of a puff emitted at midnight is presented to assist with understanding of puff growth and leakage. A typial mass of NOx is derived from emission rates from the Fayette Power Projet, known to be approximately 0.5 tons / hour-stak. Using a wind veloity of 5 m/s (11 mph), and a 6 minute time step, the length of the puff will be 1800 m, aording to Equation 2-2. Only one puff will be formed during this time step, onsidering a maximum puff length of 2000 m. The mass in this puff is simply the emission rate multiplied by the time step. Should there have been more puffs formed, the emissions would have been divided proportionally amongst the puffs. Using the frations 85.5% NO and 14.5% NO 2, as provided by the emissions inventory, a total mass in the puff of 43 kg is alulated. Vertial and horizontal diffusivities and the hange in dispersion parameter with downwind distane were derived from atual model input. Allowing for one hour of growth aording to Equation 2-4, and assuming a Gaussian distribution of mass within the onfines of the puff dimensions, the onentration profile an be developed. Allowing for another 1.5 hours of growth auses the puff to exeed the grid ell boundaries; the NOx within 1.5 s of the distribution and outside the grid ell boundaries is leaked to the host grid ell (NOT the ells on either side of the host grid ell). Figure 2-4 depits growth and leakage for this ase study. 23

36 Conentration NOx (ppb) =leakage hr 1.5s y 2.5 hr Crosswind Distane (m) Figure 2-4. Growth and Leakage of a Midnight Puff of Emissions into the 4-km Grid Cell Struture (Conentration and 1.5s Inferred by Gaussian Distribution of Known Mass and Volume; Snapshots Taken at 1 and 2.5 hr after Puff Emission). As an be seen from Figure 2-4, the mass leaked is within 1.5 s y of the mass distribution and outside the limits of the host grid ell. The signifiane of suh a leaking proess is that emissions are not allowed to interat with bakground air (inluding VOCs); in a word, they are anned. Upon release by leakage, the NOx is free to interat with bakground VOCs and go about produing O 3 by the mehanisms ontained in the CB-IV hemial mehanism whih is used for grid ell hemistry. Until that point, however, the emissions undergo a simplified inorgani hemistry, whih is desribed below. A way to desribe the persistene of the anned nature of a PiG puff is by quantifying a time delay. Nighttime releases will grow slowly, under stable nighttime atmospheri onditions; while daytime puffs will be quikly dispersed and slaughtered, due to the turbulene of the onvetive mixed layer. In general, 24

37 PiG puffs formed at night last from their time of emission until 9:00 a.m. PiG puffs formed during the day tend to last only on the order of an hour, or at most, two hours. The NOx that has been released will yield O 3, and its onentration upon introdution to the host grid ell will impat the effiieny with whih O 3 will be formed. This diurnal differene in puff life has diret relevane towards temporal sensitivity of O 3 formation to NOx emissions. Speifially, we might onsider two puffs with the same initial mass; one originates at night, the other during the day. The nighttime puff will have a hane to leak a signifiant amount of its NOx before interating with bakground VOCs. Its onentration in the host grid ell, when the puff is eventually slaughtered, will be smaller than that of the daytime puff. This will redue the loal NOx/VOC ratio, whih will inrease OPE in a NOx-limited region. However, this will hold true only if nighttime hemistry in the PiG does not ompletely remove NOx through onversion to HNO PiG Chemistry PiG hemistry is simplified, inorgani hemistry. The FORTRAN ode employed by CAMx is inluded in Appendix A, for referene. No reations between NOx and hydroarbons an take plae in the PiG, beause hydroarbons are not arried by PiG puffs. Kumar and Russell have asserted that suh simplifiations do not impair model auray (Kumar et al., 1996); efforts are now being taken at the University of Texas at Austin to test this hypothesis. Upon entry to the hemistry module, any NO present in the PiG puff is onverted to NO 2, aording to Reation R10. NO+ NO+ O 2 2NO 2 (R10) 25

38 Any remaining NO is onsumed via O 3 titration, as depited in the photostationary yle of Figure 1-2. If any O 3 is left after this titration, it is used in one of two ways, depending on whether the model onsiders it to be daytime, or nighttime. There is no in-between period for CAMx it is either day, or night. A steady-state assumption is made for prodution and deay of N 2 O 5, whih is assumed to be limited by O 3 availability. Any N 2 O 5 formed will reat with available water, as stated in Setion , to form HNO 3. During the day, O 3 photolysis generates OH radials, whih oxidize NO 2 to HNO 3, aording to Reations R4-R6. Of speifi interest to this researh is the fat that only O 3 onsumption is allowed by the hemistry, whether day or night. Consumption of O 3 happens by initial titration of O 3 with NO. Consumption of O 3 happens via formation of HNO 3 in the two ways mentioned above. Ozone entrainment is extremely ritial in determining the daytime reativity of the nighttime emissions. If the NOx is onsumed by O 3 through the two pathways listed above, none will be left to reat with bakground VOCs. If not enough O 3 is allowed to interat with PiG emissions, the amount of NOx present the next morning will be overpredited. Ozone entrainment ours, in the model, as a result of PiG growth. Nighttime plumes last a signifiant amount of time and grow slowly. At eah time step, O 3 is entrained aording to the growth experiened during that time step. Equation 2-5 summarizes this entrainment. O = C O, Volume 3, entrained 3 hostgride ll (2-5) Where O 3,entrained is the quantity of O 3 entrained at eah time step (mol), C O3,hostgridell is the onentration of O 3 in the urrent grid ell (mol/m 3 ), and?volume is the hange in volume during the time step (m 3 ). 26

39 The moles of O 3 entrained are added to the total moles of the puff, and future onentration distribution alulations aount for both the inreased size of the puff and the inreased amount of O 3. The extent of O 3 entrainment for the puff in the growth example above, over the life of the puff, onsidering a onstant bakground onentration of 40 ppb, is approximately 8000 moles. Aording to the emission rate, 1300 moles NO would originally be in the puff. Thus, through entrainment, all of the NO would be onverted to NO 2 through O 3 -NO titration. The NO 2 still present upon sunrise, aording to PiG hemistry, is limited by the O 3 entrained at eah time step. If suffiient O 3 is present, the rate of HNO 3 formation by the NO 3 /N 2 O 5 pathway may beome the limiting fator. For the growth example, there seems to be suffiient O 3 ; thus, Reation R9 will limit the removal of NOx. The rate of Reation R9 is highly dependent upon the loal relative humidity (Platt et al., 1994). At RH > 50%, NO 3 lifetimes are on the order of a few minutes, whereas at lower RH, they are on the order of 40 minutes, implying slow removal of N 2 O 5, and deomposition of N 2 O 5 bak to NO 2 and NO 3 (Seinfeld, 1998). CAMx inludes this RH-dependene within the PiG hemistry module. 2.4 Episode Details The partiular episode used in this researh was developed using data from July 7-12, The episode was developed for Dallas Attainment Plan Evaluation modeling, and is urrently being used for air quality planning in Austin and San Antonio near non-attainment areas. Grid setup for this episode is pitured in Figure 2-1. Layer heights were onstant throughout the episode, and are summarized in Table

40 Table 2-4. Layer Heights Used in July 1995 CAMx Modeling Episode. Height (m) Layer Layer 2 > Layer 3 > Layer 4 > Layer 5 > Layer 6 > Layer 7 > Layer 8 > Layer 9 > The episode was unique due to its relatively alm wind speeds and varied wind diretion by day. To expound upon this variation, ground-level wind diretions near the Fayette Power Projet are reorded in Figure 2-5 for eah day. Ground-level wind veloities are reported for 15:00 on eah day. This time is hosen beause the plume data available from airraft measurements was taken at approximately 15:00. 28

41 Day 6 Day 1 Day 2 Day 3 Day 4 Fayette Power Projet Day 5 Figure 2-5. Wind Veloity (Saled from m/s) by Day for July 1995 CAMx Episode (Instantaneous Model Value at 15:00 on eah day). As Figure 2-5 bears out, winds varied greatly in their trajetory from day to day. The differene between Days 5 and 6 is nearly 150 degrees. The emissions estimates given for the eletri generating utilities in the episode were obtained from the Continuous Emissions Monitoring database, whih provides hourly emissions data for various pollutants. The biogeni VOC emissions database for Texas was developed by C. Wiedinmyer, and is based on the best available land use data for Texas (Wiedinmyer et al., 2000). Meteorologial data was proessed by and aquired from Environ and TNRCC (Environ, November 1998). The emission rate from the Fayette Power Projet during the modeling episode is illustrated by Figures D1-6. The maximum O 3 onentrations modeled for eah day are summarized in Figures 29

42 D7-D12. All modeling data has been arhived to tape, and is available through Dr. Gary T. Rohelle in the Department of Chemial Engineering. 30

43 Chapter III. Modeled / Airraft Data Comparison CAMx model outputs are ompared to airraft data olleted during the Texas Air Quality Study undertaken August 15 to September 15, 2000 (TEXAQS 2000). The Department of Energy s G-1 airraft was used to sample the plume of emissions from the Fayette Power Projet (FPP), loated in Fayette County, Texas on September 10, Data from this flight are arhived in Appendix B, and are also available online, at ftp://aerosol.das.bnl.gov/pub/houston00/. 3.1 Bakground Although airraft data are useful for estimation of plume OPE during ertain periods, the data available for photohemial grid model validation is laking. Intense efforts are required to aquire neessary data for an EPA-approved modeling episode, and it is diffiult to arrange for olletion of flight data that will oinide with these episodes. The reent study undertaken in Texas, the TEXas Air Quality Study (TEXAQS) will hopefully provide suffiient data to set up modeling episodes; the airraft data available from the study should be suffiient for omparison to CAMx modeling results. In this way, the performane of the Plumein-Grid submodel may be validated. Until that time, it is useful to look at arhived data to extrat whatever meaningful lessons may be derived. In general, information on the proesses of plume sampling and analysis may be gathered from existing plume data sets. One good soure of data in Texas is the Baylor University Airborne Sampling Projet (available online at In onert with the Texas Natural Resoure Conservation Commission and Sonoma Tehnology, In., some analysis of this data has been performed, and is available online (MaDonald et al., 1999). 31

44 In general, plume sampling is performed by flying in a transverse manner aross a plume, perpendiular to the loal wind diretion. An example of this is seen in Figure 3-1, whih represents a flight taken on August 25, 1997, by the Baylor Airraft. This image is hosen beause it is a good example of the extent of an industrial plume in East Texas. 9 mi 45 mi Figure 3-1. Typial Plume Sampling Flight Path and Large NOx Soure Plume Dimensions (Baylor University Twin Otter, Flight 39, August 25, 1997). (Adapted from MaDonald et al., 1999) The extent of the Big Brown Power Plant plume, pitured above, is typial for a large industrial soure. The dimensions of plumes are often indiated by a sulfur dioxide, (SO 2 ) peak, whih is a harateristi onstituent of oal-fired power 32

45 plant emissions. Data taken by the airraft at eah transet of the plume an be plotted as a time series, to demonstrate dispersion and photooxidation of hemial speies. Figure 3-2 shows a time series plot for a portion of the flight pitured in Figure 3-1. Conentration (ppb) or Altitude (hundreds of feet) Altitude O3 NO NOy SO2 Peak Bakground Time (CDT) Figure 3-2. Time Series Plot of Flight 39 of the Baylor University Twin Otter, August 25, (Courtesy TNRCC). As an be seen from Figure 3-2, O 3 peaks (red line) beome quite lear within the plume (as defined by the SO 2 peak, blue dotted line). This is typial of a mature plume. Ozone titration is not aptured by this portion of the time-series, whih represents transets approximately miles from the soure. Yields for the above data were alulated by MaDonald et al. by omparing the instantaneous peak O 3 to the instantaneous peak NOy for a given 33

46 transet. The boxed regions are onsidered to be the Peak (left box), and Bakground (right box) values for O 3 and NOy. Considering O 3,peak -O 3,bg = = 27.7 ppb, and NOy,peak -NOy bg = = 3.35 ppb, The yield at this transet, aording to MaDonald et al., is 5.3 moles O 3 per mole NOx emitted by Big Brown (NOy basis). Where NO and NO 2 data are available, the same analysis an be done for OPE as defined by do 3 /dnoz (NOz=NOy-NOx). The next setion disusses other useful ways to derive OPE values for omparison. 3.2 Airraft Data Analysis Bakground A number of unertainties are impliit in omparisons of airraft data to modeled data. First, airraft data are instantaneous, while modeled data are hourly averages. Seond, modeled data from all layers of the atmosphere are available; one must assume the presene of a well-mixed atmosphere when interpreting airraft data. Third, it is rare to have a modeling episode for whih airraft data is available. It is this lak of data whih will first be disussed. Currently, there are a few models whih adequately reflet the proesses observed by airraft in large industrial plumes (Karamhandani et al., 2000; Sillman, 2000). Most models still find diffiulty in prediting O 3 wings, the produtive zones at the edges of plumes, where the NOx/VOC ratio has beome suffiiently low to generate O 3 quikly. However, of the Baylor airraft data olleted in East Texas, there is only one flight whih deteted O 3 wings, Flight 7. A time series of Flight 7 from the Baylor airraft data is shown in Figure 3-3. The 34

47 time series represents a transet taken approximately 2 km downwind from the City Publi Servie Power Plant in San Antonio. O3 NO NOy Conentration (ppb) Possible Wings Time (CDT) Figure 3-3. Time Series Plot of Flight 7 of the Baylor University Twin Otter, June 4, (Courtesy TNRCC). Even these wings are not as prominent as some that have been witnessed in other areas, suh as Tennessee (Gillani and Pleim, 1996; Sillman, 2000). Peaks on either side of the O 3 trough, where NO-O 3 titration is ourring in the plume, only reah approximately 15 and 10 ppb above bakground onentrations. The onditions on the day of Flight 7 inluded ground level temperatures of 35 o C, wind from the SW at approximately 4 mph, and mostly sunny skies. These onditions do not appear to be partiularly unique amongst other flights taken either near the San Antonio City Publi Servie Power Plant, or at other loations in East Texas. The FPP data olleted during TEXAQS did not indiate any wings, either. This phenomenon seems to be unique to Texas data, and ould possibly be explained by onditions that are unique to Texas, suh as unique biogeni hydroarbon mixtures 35

48 and levels, whih would affet the extent and kinetis of reations at the dilute edges of NOx plumes Approahes to Analysis and Comparison There is fair agreement amongst the modelers mentioned so far (Karamhandani, Sillman, Ryerson, et.) as to the methods to be employed for modeling validation. Both of these omparison methods are utilized in this researh Conentration Ratio Approah Entire Plume One method of omparing values of OPE between model output and airraft data, is to look at a umulative value for OPE over the entire plume, rather than an instantaneous value (Ryerson et al., 2001). Sillman (2000) asserts that the umulative value for OPE is to be favored beause it an be used more readily to estimate the amount of downwind transport of O 3 and ontribution to global-sale photohemistry for a given NOx emission rate, and beause the average lifetime an be related to measured quantities, suh as O 3 /(NOy-NOx). The onentration ratio approah effetively ombines all of the data from every transet into a plume averaged OPE. Ozone onentration at eah point in the plume is plotted versus NOz onentrations at eah point in the plume. The resulting slope is the OPE (Nunnermaker et al., 2000); it should be onsidered an upper limit, for reasons noted above. One an also use this approah to ompare OPE at eah transet to the plumes state of oxidation, or hemial age, as disussed below Mass-Balane Approah A seond approah, employed by Ryerson et al. (1998) utilizes a massbalane approah to deal with the fat that O 3 /NOz may be onsidered an upper limit due to the longer atmospheri lifetime of O 3 relative to NOz (Trainer et al., 1993; Chin et al., 1994). Ryerson s mass balane approah ompares the flux 36

49 (better termed flow rate ) of O 3 at a given transet to the reported plant NOx emission rate. Flux, or flow rate, is alulated aording to Equation 3-1. z y y net _ flux = v osα n( z) dz X ( y) dy (3-1) 0 m Where net_flux is the flow rate of the omponent of interest (mol/s), v is the wind veloity vetor at the stak of interest (m/s), a is the angle between the transet path and the diretion normal to the wind vetor, n(z) is the number density of the atmosphere (mol/m 3 ), z is the height of the atmospheri mixed layer, X m (y) is the inrease in mixing ratio of the omponent of interest above the bakground (mol/mol), and y, -y are the rosswind plume positions, whih define the plume dimension as observed by the transet (m). This approah will yield a lower limit for OPE, as it does not aount for loss of NOx through pathways other than partiipation in photohemial proesses. OPE alulated by transet also varies temporally; eah transet only provides a part of the piture whih paints the overall impat of a NOx point soure (and, therefore, its regional impat) Chemial and Physial Age Calulation Two methods of hoosing when to ompare modeled and measured OPEs have been reported. One draws omparison between transets of similar physial age, as alulated by wind speed and sampling loation (Ryerson et al., 1998; Sillman, 2000). This method is summarized by Equation 3-2. Transet_Distane Physial _ Age = (3-2) Wind_Speed 37

50 The other method ompares transets of similar hemial age (Gillani et al., 1998b). Chemial age is defined in Equation 3-3, below. NOz Age hemial = (3-3) NOy Qualitatively, this ratio desribes the extent to whih the original NOx emissions (NOy) have been oxidized to NOz. 3.3 Fayette Power Projet (FPP) Data SO2, O3, NOy (ppb) NOz O 3 NOy SO NOz (ppb) :00 PM 3:07 PM 3:14 PM 3:21 PM 3:28 PM Hour -2 Figure 3-4. Time Series of FPP Data Aquired through TEXAQS (Number indiates transet). FPP represented 2.3% of all NOx emissions in Texas in 1999, or nearly 20,000 tons. Only four other failities emitted more NOx. Six transets were made through the FPP plume on September 10, Figure 3-4 is a time series representing those transets. As an be seen from Figure 3-4, no O 3 wings were 38

51 realized. The dip in O 3 onentration in transet 6 appears to depit wings. However, the dip is due to the airraft turning parallel to the plume at that point. It essentially represents a half-transet, where the plane flew to the middle of the plume, and then turned downwind. Ozone generation was realized by the third transet. Sulfur dioxide is a harateristi pollutant emitted by oal-fired eletri generating utilities, and an be used to trak the emissions plume. Therefore, transets throughout this setion (the transition point from outside the plume to inside the plume ) will be defined as the point at whih the SO 2 onentration hanged threefold or better between suessive data points Conentration Ratio Approah Plume-Averaged OPE for FPP Following Gillani et al. (1998b), OPE was alulated for the entire plume using the onentration ratio approah. OPEs were alulated by regression of O 3,bakground orreted versus NOz for eah timestep for all transets, using O 3,original data -O 3,bakground = O 3,bakground orreted. Beause the first transet (alled the fresh plume ore ) ontained data points whih were widely sattered, its data is not inluded in the analysis of the plume-averaged OPE. Figure 3-5 shows this analysis. 39

52 O3 (ppb; bakground orreted by transet) FPP Data olleted 9/10/00 OPE Chart, Exluding Fresh Plume Core y = 9.03x R 2 = NOz (ppb) Figure 3-5. OPE for FPP, Derived from Airraft Data Taken 9/10/2000 (all NOz assumed to be due to soure). Thus, a plume-averaged OPE of 9 was observed for FPP. This is within a reasonable range of OPEs reported for power plants the size of FPP loated in rural areas in Tennessee (Ryerson et al., 1998). Comparison with model output is still desirable to further validate the result Conentration Ratio Approah Transet-Averaged OPE for FPP Again, following Gillani et al. (1998b), OPEs were alulated for eah transet. OPEs were alulated by regression of O 3,bakground orreted versus NOz for eah timestep for individual transets, using methods similar to those used in the OPE regression desribed above for the entire plume. Beause the first transet only yielded two data points, its regression is not inluded. Regressions were basially a sub-set of Figure 3-5, and an be seen in Figure 3-6. The data is loated in Appendix B. 40

53 Delta O3 (Bakground orreted by Transet), ppb Transet 2 Transet 3 Transet 4 Transet 5 Transet 6 y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = y = 7.022x R 2 = NOz, ppb Figure 3-6. OPE by Transet for FPP Data Colleted 09/10/ Mass Balane Approah Transet-Averaged OPE for FPP OPE an be inferred from flux alulations. Flux is alulated following the approah of Ryerson et al. (1998), as summarized in Equation 3-1. A mixing height had to be assumed; thus the mixing height modeled in CAMx of 1105 m was used. Table 3-1 shows data used in these alulations. Table 3-1. Flux (Flow rate) of NOy at Conseutive Transets; Calulation Based Upon Equation 3-1 (Data Taken by NOAA G-1 Airraft from FPP Plume on 9/10/2000). V (m/s) n(z) (mol/m 3 ) dz (m) X m,noy (ppb above bakground) dy (m) ER NOx (tons/hr) Transet , Transet , Transet ,

54 V (m/s) n(z) (mol/m 3 ) dz (m) X m,noy (ppb above bakground) dy (m) ER NOx (tons/hr) Transet , Transet , Transet , In this ase, NOy was averaged for eah transet, and assumed to reflet the original NOx emissions. These alulated emission rates math fairly well with the emission rate data used in the model, whih averaged 1.5 tons/hr when all three boilers were in operation (see Appendix D). The assumptions of mixing layer height (1105 m) and molar density (40 mol/m 3 ) of the atmosphere are onservative; this is likely a low estimate of the emission rate. These alulated emissions orrespond well with measured emission rates on the day of the airraft sampling. Table 3-2 shows the NOx emission values for September 10, Data is ourtesy LCRA. Table 3-2. FPP NOx Emission Rate (tons/hr) for Eah of Three Large Boilers (FPP-1,2, and 3) Reported by LCRA for 9/10/2000. Time FPP-1 FPP-2 FPP-3 Total 13: : : : In order to ensure a lower bound for OPE, whih is the purpose of the Mass Balane approah, the atual emission rate was hosen as the basis for OPE estimation. Thus, OPE for this approah will be defined aording to Equation 1-3, 42

55 or the ratio of the flux of exess O 3 at a given transet to the flux of original NOx emissions. Although no O 3 was generated until the third transet, all transets are inluded in this analysis. Negative O 3 fluxes should orrelate to fresh (low hemial age) transets. Molar density of the atmosphere is based upon pressure data alulated during the flight (37 mol/m 3 ). Mixing height was hosen as 1105 m, in the absene of mixing height data, to orrespond to the mixing height modeled by CAMx. Calulated O 3 fluxes are summarized in Table 3-3. Table 3-3. Ozone Flux (Flow Rate) Calulation Based Upon Equation 3-1. V (m/s) n(z) (mol/m 3 ) dz (m) X m,o3 (ppb) dy (m) Flux O3 (tons/hr) Transet , Transet , Transet , Transet Transet , Transet , Now, dividing the O 3 flux at eah transet by the original NOx emission rate gives an OPE for eah transet. Table 3-4 summarizes these results. 43

56 Table 3-4. OPE by Transet Using Mass Balane Approah, NOx Flux Assumed from Data Obtained from LCRA for FPP, 9/10/2000. Flux O3 (tons/hr) Flux NOx (tons/hr) OPE (mol O 3 /mol NOx) Transet Transet Transet Transet Transet Transet * 1.40 *Data from 13:00, as transet represented emissions from that time. All other data from 14:00. Table 3-5 shows the same analysis, with one exeption. In this alulation of OPE, the true Mass Balane Approah is employed, by alulating values for NOx flow rate at eah transet in the same way as the O 3 fluxes were alulated. Table 3-5. OPE by Transet Using Mass Balane Approah, NOx Flux Calulated. Flux O3 (tons/hr) Flux NOx (tons/hr) OPE (mol O 3 /mol NOx) Transet Transet Transet Transet Transet Transet These instantaneous OPE values for eah transet are most meaningful when orrelated with the hemial and physial ages of the transet. For that reason, these ages were alulated for eah transet Calulation of Chemial and Physial Age of FPP Transets Chemial and physial ages of transets are useful for model omparison, for reasons mentioned in Setion To determine hemial age of eah 44

57 transet, NOz onentrations were first inferred from (NOy-NOx) at eah time step. NOz/NOy regressions were alulated for eah transet by plotting NOz and NOy at eah time step. The resulting regressions showed poor orrelation between NOz and NOy. Figure B-1 illustrates this poor orrelation. From the original data, NOx and NOy data were regressed for eah transet. These NOx/NOy regressions showed a good orrelation. They are pitured in Figure Transet 1 Transet 2 Transet 3 Transet 4 Transet 5 y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = NOx NOy Figure 3-7. Regression of NOx and NOy for FPP G-1 Data 09/10/2000. Due to the good orrelation of NOx/NOy, NOy values were orreted by assuming the initial ratio of NOx/NOy refleted a pure-nox plume. As seen from Figure 3-7, the initial ratio NOx/NOy (first transet) was approximately 1.3. A linear derease in NOx/NOy an be see in Figure

58 y = x R 2 = Slope of NOx/NOy Regression Plume Age (hr) Figure 3-8. Cumulative Loss of NOx in FPP Plume (G-1 Data 09/10/2000). From this onstant loss of NOx, and the initial ratio NOx/NOy of 1.3, one might infer that NOy values are all artifiially 30% low. To further investigate hemial age, all NOy values were inreased by 30%, and alled NOy orreted. NOy orreted = NOy 1.3 (3-4) New NOz values (alled NOz orreted ) were alulated based upon the NOy orreted and original NOx values, as in Equation 3-5. NOz orreted = NOy NOx (3-5) orreted original _ data Next, to ompute a orreted hemial age at eah plume transet, NOz orreted and NOy orreted were plotted for eah time step. The regressions alulated for NOz orreted /NOy orreted an be seen in Figure

59 Transet 2 Transet 3 Transet 4 Transet 5 Transet y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = NOz [(NOy orreted )-NOx] NOy (Correted by NOx/NOy) Figure 3-9. NOz/NOy (NOy Correted Based Upon Initial NOx/NOy Ratio of 1.3) With the exeption of Transet 5, the regressions show good orrelations. The hemial age for eah transet is simply the orresponding slope of the line in Figure 3-9. Chemial ages for eah transet are summarized in Table 3-6. Table 3-6. Chemial Age (NOz orreted /NOy orreted ) by Transet for FPP Plume (NOAA G-1 Data 09/10/2000). Chemial Age Transet 1 0* Transet Transet Transet Transet Transet *Chemial Age assumed 0 beause of assumption that Transet 1 NOx/NOy =

60 To relate aging of the plume to physial age, physial ages were alulated using the plume-average wind speed of 4 m/s (See Figure B-5), and the distane from the plant of eah transet (See Table B-1), aording to Equation 3-2. Table 3-7 summarizes the physial age of eah transet. Table 3-7. Physial Age of Transets for FPP Plume (NOAA G-1 Data 09/10/2000). Distane from Wind Speed (m/s) Physial Age (hr) Soure (m) Transet 1 1, Transet 2 7, Transet 3 9, Transet 4 14, Transet 5 19, Transet 6 36, Taking the regressed values for NOz orreted /NOy orreted from Table 3-6 and plotting them versus the physial age of eah transet implies stage-wise aging of the plume. Figure 3-10 illustrates this sequential oxidation. 48

61 Chemial Age (NOz/NOy orreted ) Transet 2 Transet 3 Transet 5 Transet 4 Transet Physial Age (hr) Figure Regressed value of NOz orreted /NOy orreted Plots for Eah Transet versus Physial Age of Eah Transet (NOy Correted by Assuming Initial NOx/NOy Ratio=1.0; Physial Age alulated by distane between transet and soure, assuming a onstant wind speed of 4 m/s). If the plume had oxidized ontinuously after its emission from FPP, these points would lie in a straight line. Although there is lear stage-wise aging of the plume between transets 4 and 5, aging is not lear between the other transets. Next, it is useful to relate the regressed OPE values derived in Figure 3-6 for eah transet to the transet s hemial age, from Table 3-6. This relationship is 49

62 shown in Figure OPE (do3/noz) Transet 3 Transet 2 Transet 4 Transet 6 Transet Chemial Age (NOz/NOy) Figure OPE (using Conentration Ratio Approah, by Transet) for Individual Transets versus Corresponding Chemial Ages. Further omparison was done between transet hemial age and OPEs derived using the mass balane approah for eah transet. Figure 3-12 shows the results of this analysis. 50

63 Transet OPE (do3/noz) Transet 4 Transet 3 Transet Transet Chemial Age (NOz/NOy) Figure OPE (using Mass Balane Approah, by Transet) for Individual Transets versus Corresponding Chemial Ages. With the exeption of Transet 5, Figure 3-12 may show an inreasing trend in OPE with inreasing hemial age. However, there is no justifiation for disarding that point. Thus, Figures 3-11 and 3-12 show no lear orrelation between OPE and hemial age. This is ontrary to other findings (e.g., Gillani et al., 1998b); however, the data had to be severely manipulated to arrive at this onlusion. To summarize the data manipulation required to arrive at Figure 3-8, orretions of NOy were based upon the assumption that initial NOx/NOy was 1.0, rather than 1.3. New values for NOy were alulated simply by multiplying original data values by 1.3, whih would orret the ratio NOx/NOy to 1.0. This manipulation was followed by re-alulation of NOz based upon this new value for NOy, simply by subtrating the orresponding original NOx datum. 51

64 NOx/NOy ratios higher than 1.0 (not possible, aording to Equation 1-1) have been observed in other studies, yet they have not been addressed as being in serious error (Nunnermaker et al., 2000; Springston et al., 2000). These ratios are ertainly not possible; they indiate either under estimation of NOy or over estimation of NOx. Under estimation of NOy ould result from loss of speies in the sampling inlet, suh as HNO 3, whih is notorious for doing so (Imhoff et al., 2000). Finally, the NOz orreted /NOy orreted regressions (hemial ages) of the individual transets ertainly arry a great deal of error. Any error present in the data measurements was propagated during eah manipulation step, and should be viewed with aution. Data from the airraft flight on September 10, 2000, did not yield reliable estimates of hemial plume age. 3.4 Comparison of Airraft Data and Modeled Data The data available from TEXAQS for FPP provides a soure for model omparison. No modeling episodes are urrently available for the days on whih the airraft data was taken. Thus, modeling days have been used from the existing modeling episode desribed in Chapter II to ompare with the airraft data. The subsetions following will 1) desribe how modeling days were hosen, based upon finding similar meteorologial and hemial onditions; and 2) show a omparison between modeled output and airraft measurements using two different omparison methods. The first method of omparison utilizes modeled output for whih a virtual airraft flight is taken through the plume and diretly ompared to airraft measurements. The seond method of omparison utilizes a differene method between two runs. The differene between a modeling run with FPP 52

65 emissions turned on and another run with the emissions turned off reveals an effetive O 3 impat for the soure Relevant Parameters for Comparison Wind diretion is possibly the most important meteorologial onsideration when omparing modeled and airraft data. Land use, and, therefore, biogeni and anthropogeni emissions of pollutants of hemial onern, shows wide spatial variation. On Day 3 of the modeling episode, at 15:00, as depited in Figure 2-5, winds were from the south. Wind speeds and trajetories for the airraft data olleted September 10, 2000, an be seen in Figure B-5 (note that 180 o means winds are from due south). Wind diretion ompares well between modeled and airraft data. Thus, to minimize unertainty between the modeled and airraft omparison, Day 3 of the modeling episode was hosen. Although wind diretion was similar, wind speed measured by the G-1 airraft was approximately double the speed input to the model for the available 1995 episode. The emission rate modeled by CAMx for Day 3 was 0.8 tons/hr. Only one boiler was in operation during the afternoon. The emission rate on the day of the TEXAQS airraft flight was approximately 2.3, as summarized in Table 3-2. This disparity would likely ause higher modeled OPE, beause larger soures (higher NOx emission rates) tend to have lower OPE, as disussed in Chapter 1. Unfortunately, atual emission rates were not available when modeling ommened. Temperature has signifiant effets on isoprene emissions (Weidenmeyer et al., 2001). The ground-level temperature on July 9, 1995 during the afternoon was approximately 33.5 o C, whih orrelates well with the temperature during the airraft data olletion, whih ranged from 31.7 to 32.5 o C. Temperature data 53

66 (hourly for model, during FPP flight for airraft; all ground-level) are plotted in Figure B-6. A linear interpolation was performed on model temperature data to show variation over the hours of interest; however, analysis for model validation will be onfined to a single hour. Bakground O 3 onentrations for the modeling episode on July 9, 1995 were approximately 60 ppb (see Figure B-7), whih ompares with bakground O 3 values (on average, 50 ppb) observed on September 10, 2000, as seen in the time series below Virtual Airraft Flight Comparison-Conentration Ratio Approah Beause hemial age inferenes from the airraft data did not orrelate with OPE, a physial age omparison was made between the airraft data and the model. This is a fair omparison, onsidering that physial growth riterion is the most signifiant in the formulation of the Plume-in-Grid submodel used by CAMx. To hoose a spatial extent of model results similar to that overed by the airraft in obtaining the flight data, physial plume age was alulated for eah transet flown by the airraft, using the wind speed data available (loated in Appendix B), and the position of the airraft at eah transet. Physial age ranged (as seen in Table 3-7) up to 2.5 hours, or about 36 km from the soure. These physial ages were transposed to ages for the plume in the modeling episode, where the wind speed was roughly half that of the airraft data episode. This translated to a furthest approximate distane of 18 km from the soure. All wind data was taken at orresponding heights of the atmosphere. The wind data for the airraft sampling was taken at approximately 610 m above ground level. Thus, Layer 5 was hosen as the soure for wind data from the model (see Table 2-4). Modeled O 3 and NOz onentrations were sampled at distanes orresponding to the NOAA G-1 transets physial ages. These points were used 54

67 to generate a plume-averaged OPE, as in the airraft data analysis in Setion 3.3. The finest grid resolution in this modeling episode was only 4 km; thus, an extremely limited number of ells (21 total) were available to math the airraft data. Figure 3-13 illustrates the extent of this analysis. Figure O 3 Conentrations in Modeled FPP Plume at Comparable Physial Age and Altitude (CAMx Layer 5) to FPP G-1 Data olleted 9/10/2000 (Model Day 3, 15:00 data, wind speed = 2.0 m/s). It should be noted that the extent to whih the physial age of the modeled plume mathes the physial age the above plot is only within the boxed area. The plot is also from level 5 of the model output, whih orresponds to atmospheri heights between 400 and 670 m. The airraft data were taken at approximately 600 m altitude. An area of high O 3 onentrations north of FPP is apparent beyond the extent of analysis. It may be that the airraft data were not gathered far enough 55

68 downwind to pik up the peak O 3 in the plume, as well. The time series plot of the airraft data in Figure 3-4 shows the O 3 onentration still rising from transet 5 to transet 6, whih was the final transet. However, as the plane turned parallel to the wind diretion during the middle of transet 6, no higher O 3 values were noted; thus, it is assumed that the peak in transet 6 represents the maximum O 3 onentration realized in the sampled plume. NOz was measured in the same manner as listed above for O 3. OPE was then alulated as was done for the airraft data (using the onentration ratio approah); the result is shown in Figure y = x R 2 = O3 (ppb) NOz (ppb) Figure OPE for Modeled Data with Similar Physial Age and Altitude to FPP G-1 Data Colleted 9/10/2001. Again, the data is quite limited due to a oarse grid ell resolution. A bakground O 3 value of 50 ppb was assumed, as there is no apparent break in the plume (ref. Figure 3-13). The slope of the line is not affeted by the hoie of 56

69 bakground values for O 3, however, so the predited OPE within this short plume age is 1.6. This is notably lower than that observed by the airraft Virtual Airraft Flight Comparison-Mass Balane Approah The above analysis utilizes the onentration ratio approah, as desribed in Setion In order to analyze the model output using the mass balane approah, data is needed at eah transet, for alulation of flux aording to Equation 3-1. Speifially, average O 3 and NOy onentrations above bakground are needed for eah transet. This is not possible under the analysis using the Virtual Airraft Flight, beause plume boundaries are not apparent. As mentioned, the onentration ratio approah is not affeted by hoie of bakground O 3 onentration Dimensional Analysis of the Virtual Airraft Flight As noted in Chapter II, the PiG is slaughtered to the host grid within one grid ell (4km) of the soure during the day. The first airraft transet was approximately 3 km aross, at a distane of 2 km downwind from the soure. The widest the plume was observed was 17 km, or about 10 miles, whih ompares well with the Big Brown Power Plant Plume, depited in Figure 3-1. Modeled data, as in Figure 3-13, shows a distint plume as muh as 40 km (10 grid ells) aross (green area on either side of the O 3 peak). A omparison between the ozone plume dimensions of the two data sets, interpolated using the Krieging method within the Golden Surfer Software, is depited in Figure

70 UTM oordinates (km) FPP UTM oordinates (km) FPP Figure Ozone Conentrations (ppb) from Airraft and Modeled data (Airraft on left, FPP data olleted by NOAA G-1, 9/10/2000; Modeled on right, CAMx, July 9, 1995, 15:00; both interpolated using Krieging method and plotted using Golden Surfer Software). The ozone plume predited by the model is muh greater in both magnitude and width than that measured by the airraft data, as desribed above. Note that the isopleth lines are at intervals of 2 ppb for the airraft data, and 5 ppb for the modeled data. The reason for this is simple: bakground onentrations are different for eah ase. Soures totaling approximately 10% of FPP s full-load emission rate dot the ountryside within 40 km to the north of FPP. Figure 3-16 illustrates this fat. 58

71 FPP Figure NOx Soures within 40 km of FPP (Total NOx ontribution ~10% of FPP soure strength). As mentioned in Chapter 2, CAMx utilizes a 4km x 4km grid ell struture around FPP. All NOx emission introdued to grid ells within this struture are immediately distributed amongst the host grid ell, whih is 4km x 4km, and has a height orresponding to the level of release, as tabulated in Table 2-4. Thus, it is diffiult to extrat from plumes, suh as the ones in Figures 3-13 and 3-15, what emissions (and therefore, ozone prodution) are due to FPP, and what emissions are due to other soures. This proess may have been easier for the airraft, as there was an available traer, SO 2, whih defined lear boundaries for the plume. To deal with the lak of modeled plume boundaries, methods were developed to isolate the emissions from a partiular soure. 59

72 Plant On Plant Off Comparison-Conentration Ratio Approah Another method of omparison for these plumes was developed in onert with the temporal sensitivity studies performed and disussed in Chapter IV as part of this researh. By turning FPP s emission on and off, O 3 formed from FPP an be isolated, and ompared with the atual emission rate (or inrease, from ase to ase). In addition, the removal of all other emissions and O 3 from the bakground allows for alulation of do 3 instead of having to assume a bakground onentration where there are no lear plume boundaries, as in Figures 3-13 and Delta O 3 (or NOz) is alulated aording to the following equation. [ O do (3-6) 3 ] plant _ on [ O3 ] plant _ off = 3 Equation 3-6 an be viewed as an O 3 puff. Figure 3-17 demonstrates an O 3 puff, while Figure 3-18 portrays an OPE puff. Figure O 3 Puff (Plant On Plant Off Differene Plot) Due to Emissions from FPP at 2:00 p.m. on July 8,

73 Figure OPE Puff (Plant On Plant Off Differene Plot) Due to Emissions from FPP at 2:00 p.m. on July 8, Figure 3-18 shows an interesting result: the appearane of produtive wings at the outside of the OPE puff. As mentioned, wings were observed in only one flight of the Baylor airraft, and in none of the airraft data available so far from the TEXAQS study. It is unlear why the model predits wings. We may assume that it is due to the lower onentrations loated near the outside of the plume, as noted in the bakground of Chapter I. Why the airraft data do not show wings is outside the sope of this researh, but deserves investigation. It is neessary to onfine the analysis of these modeled plumes to only those ells whih show a differene between model runs with full emissions and model runs with no emissions. We may define this dimension by points exeeding a threshold in the differene between NOy Emissions_On and NOy Emissions_Off : 61

74 all_ grid_ ells all_ grid_ ells [ NOy emissions NOy > 0.1 ppb? in the plume _ on emissions_ off ] [ NOy emissions NOy = 0.1 ppb? outside the plume _ on emissions_ off ] Using Equation 3-6 to derive the same type of OPE plot as was used previously, there appear to be produtive areas within the plume. Figure 3-19 shows OPE results for FPP over the region overed by the airraft data. All of the following plots limit the plumes to the same physial age as that observed in the data olleted by the G-1 airraft y = x R 2 = O NOz Figure OPE of FPP at 3:00 p.m. on July 9, 1995; Plant On Plant Off Analysis. Again, the predited OPE is signifiantly less (2) than the measured OPE olleted by the G-1 airraft (9). Areas of OPE as high as 4 an be seen within the larger data set, just as in Figure A lear differene should be noted between 62

75 Figure 3-19 and Figure Whereas only an additional 9 ppb O 3 is formed due to FPP emissions aording to the Plant On-Plant Off analysis, Figure 3-15 shows, from the base ase, a peak of >95 ppb easily 30 ppb over the bakground O 3 onentration outside the plume. Sensitivity tests with biogeni emissions an be tested, to determine if artifiially low inventories are the reason for the overall low OPE. To test this hypothesis, the biogeni inventory over the entire 32x32 km domain (pitured in Figure 2-1) was inreased by a fator of three. The antiipated result was an inrease in OPE for the plume; Figure 3-20 shows the results of this analysis y = 3.471x R 2 = O3 (ppb) NOz (ppb) Figure OPE of FPP at 3:00 p.m. on July 9, 1995; Plant On Plant Off Analysis; Three Times Original Biogeni Hydroarbons. 63

76 As an be seen from Figure 3-20, a threefold inrease in OPE is predited when biogeni hydroarbons are inreased threefold. Additionally, a few zones an be seen in Figure 3-20 whih show OPEs of up to 7 (upper bound). Further inrease of the biogeni inventory to six times its original value was performed and modeled to see if an upper limit ould be reahed on hydroarbon produtivity. The VOClimiting plateau was not reahed by that estimate, and OPE for FPP was loser to airraft data preditions than either of the other two runs. Figure 3-21 shows the result of the 6-times biogeni runs. 25 y = x R 2 = O3 (ppb) NOz (ppb) Figure OPE of FPP at 3:00 p.m. on July 9, 1995; Plant On Plant Off Analysis; Six Times Original Biogeni Hydroarbons. The slope value shown above (6.8) is obviously a lower bound; zones in this plume an reah OPEs as high as 25. This is an indiation that the region is extremely NOx-limited, implying the presene of many reative hydroarbons. The region whih demonstrates extremely low OPE (points to the far right in Figure 3-64

77 17) is loated within approximately 20 km of the soure, and ontributes to formation of up to 5 ppb O Plant On Plant Off Comparison-Mass Balane Approah Transet data was obtained in the following manner: do 3 and dnoz in ells in the horizontal (East-West) diretion were averaged; eah transet was assumed to be 1 ell in length in the downwind diretion. The widths of transets, do 3, dnoz, fluxes, and Mass Balane Approah OPE are summarized in Table 3-8. Table 3-8. Data used for Calulation of Integrated Ozone over FPP Plume (based on airraft data olleted by NOAA G-1 9/10/2000, height assumed 1105 m, wind speed 2 m/s, atmospheri density 37 mol/m 3 ). do 3 dnoy Crosswind O 3 Flux NOx Flux OPE (ppb) (ppb) Width (m) (tons/hr) (tons/hr) Transet , Transet , Transet , Transet , Transet , Transet , Transet , Transet , Transet , Other transets (further distanes downwind) were analyzed; however, the ones listed above represent the peak within the plume. Other OPEs ranged up to 5.0, but did not represent a do 3 over that listed above. This approah is intended to provide a lower bound for OPE; however, it is apparent from omparison with the onentration ratio approah that it does not. Reasons for this likely inlude the assumptions that must be made to ome up with transets in the model output. This method is not to be trusted above the onentration ratio approah. 65

78 Plant On Plant Off Comparison-Ozone Prodution Approah In addition to the above OPE analysis, it is also possible, through the Plant On-Plant Off method, to define plume boundaries, and perform a gross marosopi omparison of total ozone prodution between model output and airraft measurement. Downwind distanes analyzed for the model are one-half the distanes measured by the airraft, due to the fat that the modeled wind speed was one-half the wind speed measured by the airraft. Crosswind plume boundaries were defined by a nitri aid differene: if at least 0.07 ppb more HNO 3 was reported in a ell for the modeling run with the emissions turned on than for the modeling run with no emissions, the O 3 value of that ell was inluded in the analysis. This metri allows for inlusion of ells with negative O 3 prodution (whih would our through titration with NO). All layers were inluded in the analysis. One hundred twenty ells (over 9 layers) returned a value, and most were negative, implying an extremely fresh plume. Thus, the total ozone prodution by FPP, for a omparable distane downwind, was -53,000 moles. It is likely that the above result is due to the fat that the additional NOx from FPP, when introdued to the bakground NOx from the other soures in the area, aused initial titration of ozone ( Plant On relative to Plant Off modeling runs). This aused a loalized ozone disbenefit upon addition of more NOx. Analysis further downwind would be neessary to quantify the overall impat of the plume. If the plume is left unbounded, that is, all ells are onsidered if they meet the HNO 3 threshold requirement, no matter how far downwind they are, an ozone prodution of 58,150,000 moles is predited. This may be a fair omparison to data from the airraft flight, the final transet of whih appears to have piked up the peak plume O 3 onentration. It is unertain why the peak ours so muh 66

79 further downwind (in terms of physial plume age, or time sine emission) for the model than the airraft. Again, this may be a funtion of the inorporation of many soures into large grid ells, suh as the other small NOx soures in the bakground of the FPP plume. It seems the dispersion of the plume is also aelerated by the model, due to the introdution of emissions into large grid ells upon leakage and slaughter from the PiG puffs, as desribed in Chapter 2. Sensitivity tests are reommended to determine whether retaining the integrity of the PiG puffs for longer periods of time will improve the predition of downwind distane to peak ozone onentrations. To spatially integrate ozone prodution for the airraft data, plume boundaries must be interpolated between transet widths. Mixing height data must be assumed, as there is no upper air sounding data available near Fayette County, Texas, for September 10, Thus, a mixing height equal to that modeled by CAMx, 1105 m, will be assumed. Bakground values for O 3 onentration for the airraft data are inferred from the time series plot of the airraft data (Figure 3-4). Again, the airraft did not appear to reah the end of the plume, as defined by a peak O 3 onentration. Thus, the plume extent was defined only by what data was available. Table 3-9 summarizes the alulations performed for the airraft data. Table 3-9. Data used for Calulation of Integrated Ozone over FPP Plume (based on airraft data olleted by NOAA G-1 9/10/2000, height assumed 1105 m). Avg. Con. (ppb) Distane from Soure (m) Crosswind Width (m) O 3 present (moles) Transet ,680 3, x 10 6 Transet ,700 11, x 10 7 Transet ,540 12, x 10 6 Transet ,590 17, x 10 7 Transet ,980 11, x 10 7 Transet ,040 17, x

80 The total ozone present aording to airraft measurements and assumed dimensions, is 137,180,000 moles (STP). The major differenes in airraft versus modeled data preditions for ozone prodution are summarized in Table Table Summary of Comparisons of Modeled Data (July 9, 1995 CAMx Episode, 15:00) to Airraft Data (NOAA G-1 9/10/2000). Ozone Prodution Effiieny (moles O 3 /moles NOx) Magnitude of Ozone Prodution (moles) Maximum Width of Ozone Plume (km) Downwind Distane to Peak (km) Modeled Data (Virtual Airraft Flight) Modeled Data (Plant On- Plant Off) Airraft Data n/a (no boundaries apparent) 58,150, ,180,000 > 40 > (may be due to multiple soures) ~ 50 ~ It is apparent that the model over predits dispersion in both the downwind and rosswind diretions. Even with wind speeds ½ the magnitude of those sampled by the G-1 airraft, the ozone peak within the FPP plume is predited to our between 50 and 57 km downwind. In the rosswind diretion, a maximum plume width of 18 km, noted by the airraft, ompares with a modeled maximum plume width o more than 40 km. Three horizontal advetion shemes are available in CAMx: one developed by Smolarkiewiz in 1983, and two more reent improvements to the sheme by Bott, 1989, and Colella and Woodward (known as Pieewise Paraboli Method, or PPM), 1984 (Environ, 1998). The horizontal advetion sheme utilized in this researh was PPM. Beause of the disparity in modeled and airraft-measured 68

81 plume dimensions, sensitivity analyses are reommended for this point soure, to determine if other advetion shemes improve the predition. 3.5 Conlusions Tools have been developed to ompare airraft plume measurement data to modeled data. First, a tool known as PSET, the Point Soure Evaluation Tool, is inluded in Appendix A. PSET is to be used in Plant On-Plant Off analyses to isolate O 3 formed due to a partiular soure. PSET analyzes modeled output to give plume-averaged OPE, transet-averaged OPE, hemial age, loss of NOx, and other relevant plume parameters. The desired spatial extent of analysis an be limited to plume dimensions as measured in airraft plume sampling. For diret omparison, without Plant On-Plant Off analysis, AIRCOMP (also inluded in Appendix A) is a program whih will generate spatially-assigned O 3 values for modeled output, whih an then be interpolated (using Golden Surfer software, for example) to airraft plume measurement data. This allows the user to perform a virtual airraft flight through the plume, taking samples at loations orresponding to airraft measurements. CAMx under predits Ozone Prodution Effiienies, aording to these two different types of analysis. In the Plant On-Plant Off analysis, an OPE of 1.9 was observed. Using the virtual airraft flight method, an OPE of 1.6 was predited. Data taken by the NOAA G-1 airraft on September 10, 2000, a similar day in terms of wind diretion and temperature, indiated a plume-averaged OPE of 9 (upper bound). A mass-balane approah (lower bound) to OPE alulation yields OPEs ranging from (fresh plume) to 1.4 (sixth and final transet, plume supposed to be at highest maturity). 69

82 Of these values, the best approah to be taken for omparing airraft data to model output is using the Plant On-Plant Off omparison, ombined with the onentration ratio approah. This approah requires muh less manipulation of data than the onentration ratio approah for the virtual airraft flight omparison and the mass balane approah for either omparison. The onentration ratio approah for the Plant On-Plant Off omparison requires boundaries to be set by orresponding physial age of the airraft plume. As seen in this researh, suh limitations ause muh of the plume attributable to the soure to be exluded from the analysis. Transet data is needed for the mass balane approah, and is not available in either omparison, exept through data manipulation and assumption. The ause of OPE under predition by CAMx may lie in over dispersion of emissions in both the downwind and rosswind diretions. This is proposed beause of the great disparity in plume dimensions between modeled data and airraft measurement data. Airraft data indiate a peak at 36 km downwind, and a maximum plume width (as defined by both O 3 and SO 2 onentrations above bakground) of only 18 km. For a similar set of meteorologial onditions (although not idential), CAMx predits a peak ozone onentration km downwind (at ½ the wind speed measured by the airraft), and a maximum plume width of more than 40 km. For this reason, sensitivity tests employing different horizontal advetion shemes are reommended. Biogeni inventory shortomings may be the ulprit in the appearane of lower-than-measured OPEs. Inreasing the biogeni inventory aused a rise in potential OPEs to levels near and beyond those observed in the airraft data. A more diretly orrelated modeling episode will be useful for drawing more substantial results, however. Data do not support similar emission rates nor wind 70

83 speeds. These disparities may explain the lak of omparability between the modeled and airraft data. Finally, the different emission rates between modeled and airraft data will have an effet on the resulting omparison. On the day of the airraft flight, 9/10/2000, FPP was emitting 2.3 tons/hr NOx. The modeling performed in this researh used an emission value of 0.8 tons/hr NOx on Day 3, beause atual emission rate values were not yet available. However, this fat should have aused an over predition of OPE by the model, sine smaller soures tend to have higher OPE. It is unertain, however, how great the sensitivity to this parameter may be. Additional modeling is required to further investigate this matter. When possible, the modeled emission rate of the soure being examined should math the emission rate on the day airraft data is olleted. 71

84 Chapter IV: Temporal Sensitivity of O 3 Formation to NOx Emissions from a Large, Rural Point Soure in Eastern Texas. This hapter summarizes researh started with modeling approahes previously developed at The University of Texas at Austin. The goal is to answer the following two questions: 1) What time of the day is most likely to ontribute emissions that will ause spikes in O 3 onentration by sensitive afternoon hours? 2) What time of the day is most likely to ontribute emissions that will ause high overall O 3 prodution (e.g., total moles O 3 ) by sensitive afternoon hours? 4.1 Modeling Approah The methods of Nowlin et al., originally developed by MDonald-Buller and Nobel, were utilized to reate temporal variations in NOx emissions from a single point soure in Central Texas, the Fayette Power Projet (FPP). In eah ase, modifiations were made to CAMx-ready emissions files using the ptmodpig.f program (loated in Appendix A) and a fator file, whih was generated using Mirosoft Exel (also in Appendix A). First, a base ase modeling run was performed whih normalized emissions for FPP for eah day of the modeling episode. Original and normalized emission rates are plotted in Appendix D. The normalizing emission fator was alulated aording to the following equation. ER profile ER new = old fator (4-1) Where ER new is the hourly average emission rate (tons/hr), profile is the fration of original emissions desired for the run, ER old is the original hourly emission rate (tons/hr), and fator is the fator alulated by Exel to modify emissions files. 72

85 The next step was to redue the NOx emission rate for FPP to half its normalized emission rate. For the base ase, profile, in Equation 3-1, was onsidered to be 100%; in the ase of half emissions, the profile for eah hour was hanged to 50%. Finally, emissions files with two-hour inreases of NOx emissions were reated by hanging the profile to 100% for a given two-hour time period, while leaving the other 22 hours at 50%. This was meant to simulate the NOx redution to be realized by Senate Bill 7, as mentioned in Chapter 1. By examining the impats of eah two-hour inrease in NOx, we see the impat of having no NOx ontrol for that two-hour time period. A period of the day whih is shown to form little O 3 may be suitable for environmental dispathing. This method of NOx ontrol shifts the power load from oal-fired power plants to gas-fired power plants, whih exhibit lower NOx emissions per Btu of energy produed. FPP is a base-loaded plant, whih means that it arries a full power load all day, every day. If some of the load on FPP ould be shifted to a gasfired plant during times of the day when NOx emissions have the highest OPE, regional O 3 formation ould be effetively redued. Nowlin s results indiated nighttime emissions were most effiient at produing ozone. Nighttime would be the most suitable time to employ environmental dispathing, as the power load reahes a minimum. 4.2 Reeptor Site Analysis Nowlin s analysis examined four large NOx soures and performed simultaneous redutions and temporal sensitivity analyses. To quantify impat, Nowlin hose reeptor sites, urban areas whih exeeded a daily O 3 threshold of 110 ppb, based on reasoning desribed in that work. The hange in O 3 73

86 onentrations at those sites due to NOx inreases at the four NOx soures was quantified by an impat index, whih was developed by Nobel, and is defined by Equation 4-2. OzoneIndex 3 run ells > threshold = ([ O ] [ O ] base _ ase ) Daily _ NOx _ Inrease *# Cells _ in _ Re gion 3 (4-1) units ppb : ton_ NOx day The indies were designed to offer a qualitative omparison between impat at different sites and on different days by normalizing the indies to the NOx inrease and the number of ells in eah site. Integration over the time of day during whih high O 3 onentrations are witnessed is aomplished by Equation 4-2. IntegratedIndex ([ ]* AverageOzoneIndexVal ue n+ n tn > tn + = 24hours t t 1 ) 1 (4-2) units ppb hour : ton _ NOx day The integrated index was used to derive a single impat value for emissions from a partiular time of day. Plotting these single values together illustrates the relative impat of emissions from different times of the day. Some of Nowlin s results are shown in Figure

87 INTEGRATED INDEX Houston, Day 4 110ppb Threshold 0.04 Integrated Index [ppb-hr/( ton of NOx/day)] :00 02:00 04:00 06:00 08:00 10:00 12:00 14:00 16:00 18:00 20:00 22:00 24:00 Time of Emission Inrease Figure 4-1. Diurnal Impat of NOx Emissions (Nowlin, 2001). As an be seen from Figure 4-1, nighttime NOx emissions produe more O 3 at the reeptor site in Houston than daytime NOx emissions. Clarifiation is needed from Nowlin s results, to be sure that seletion of reeptor sites to quantify impat did not slant the results. It was disovered during researh with FPP that seletion of a reeptor site an ause a partiular time of emissions to seem signifiant, when in fat, only the emissions during that time made it to the reeptor site. It is important to onsider the spatial loation of emissions as well as their hemial apaity to produe O 3. We will refer to these issues as meteorology vs. hemistry. In hoosing Austin as a reeptor site for FPP studies, for example, on July 12, the emissions whih were in Austin were from the previous afternoon. Although these emissions showed the highest impat by far, the impat itself was insignifiant. Figure 4-2 illustrates these results. 75

88 Ozone Index (do3/2-hr inrease) hr inrease 4-6 p.m. Other 2-hr inreases 10p-12a.m a.m. 2-4 a.m :00 12:00 15:00 18:00 21:00 Time of Impat Figure 4-2. FPP Impat (do 3 /Two Hours of Inreased Emissions) in 6- grid ell (4x4 km) Region Surrounding Austin, TX for Emissions Inreases (Day 6 of Modeling Episode). Aording to Figure 4-2, afternoon emissions will have the greatest impat in Austin. The index used, however, points to the fat that the hange in O 3 onentration due to the 4-6 pm doubling of NOx emissions was less than 0.5 ppb. Further analysis shows that nighttime emissions dominate O 3 prodution, no matter where the emissions have gone. This points to hemial reasons as to why nighttime emissions are signifiant, as opposed to misleading transport issues like the one shown in Figure Plume Loation Analysis To address the issue of transport, one must follow the plume. First, the differene between two modeling runs isolates the O 3 whih is solely due to a twohour NOx inrease, aording to Equation 4-3. [ O do 3 ] 2 hr _ inrease_ ase [ O3] base_ ase = 3 (4-3) 76

89 Puffs an be followed by both their absolute O 3 onentrations or their instantanteous OPEs (O 3 /NOz). Puffs loations are assigned aording to their maximum O 3 onentration, as pitured in Figure 4-3. By traking the peak onentration, one an answer the first of the two questions stated as objetives to this researh. Figure 4-3 represents a typial puff. Puffs for other time periods are depited in Appendix C. Loation of Max do 3 = Puff Loation Fayette Power Projet Figure 4-3. Ozone Puff (Differene plot of [2-hr Inrease Base Case]) for a Midnight-2am NOx Inrease on July 9, 1995, snapshot taken at 14:00, ground layer. 77

90 To further the analysis, a relative impat of moles of ozone present at a ertain time of the day was alulated for eah puff at a given time of day. The time of most interest is the afternoon, when high ozone events will typially our. Two o lok p.m. was hosen as an analysis time. Three and five o lok p.m. analyses are also inluded, to provide a more omplete piture. Results of this analysis will answer the seond question proposed at the beginning of this hapter. The total number of moles of O 3 arried by eah puff at STP (for a given instant in time) was alulated by simply integrating the onentrations of O 3 in eah grid ell over the volume of the ells. Layer heights were obtained from CAMx input files, and are summarized in Table 2-4. Beause umulative effets of O 3 prodution (for a given instant in time) were assessed by integrating spatially, no anomalous spikes in O 3 onentrations were assigned undue weight. Figure 4-4 shows the relative impats of emissions from different times of the day and night on O 3 prodution. The time seleted for analysis is 2:00 p.m. on the afternoon following the emissions. Thus, the emissions from 4:00-6:00 p.m. are emissions that originated the previous day. 78

91 Moles O3/Moles NOx emitted Day 3 Day 4 Day 5 Day 6 Figure 4-4. Relative Impats of Two-Hour Emissions Inreases; 14:00 Analysis. As Figure 4-4 bears out, nighttime NOx emissions produed more O 3 than morning or afternoon emissions by 2:00 p.m. on a given day. Although emissions from noon-2 p.m. are not expeted to have an impat at 2 p.m., this result is useful in its quantifiation of that fat. Analysis later in the day, at 5 p.m., yields similar results. 79

92 Moles O3/Moles NOx emitted Day 3 Day 4 Day 5 Day 6 Figure 4-5. Relative Impats of Two-Hour Emissions Inreases; 17:00 Analysis. The relative impat of emissions from 8-10 a.m. inreases signifiantly depending on whih window is examined. The 10 p.m.-midnight emissions from Day 2 of the modeling episode are still quite hemially ative at 5:00 p.m. the next day; most of the other nighttime emissions have been neutralized, presumably through photooxidation. Indeed, most of the impats are muh lower than those measured for the 2:00 p.m. analysis. This is likely beause photohemially ative NOx is onsumed through O 3 hemistry. Analysis performed at 3:00 p.m. indiates a signifiant redution in photohemially ative NOx between the hours of 2:00 and 3:00 p.m. Again, the peak O 3 prodution is approximately one-fifth of the prodution at 2:00. Figure 4-6 demonstrates these results. 80

93 Moles O3/Moles NOx emitted Day 3 Day 4 Day 5 Day 6 Figure 4-6. Relative Impats of Two-Hour Emissions Inreases; 15:00 Analysis. Again, the nighttime emissions ontribute more O 3 by 3:00 p.m. than emissions from other times of the day. These results must be orrelated with the loation of impat. Conlusions an be drawn about ontrol strategies for emissions with potential impat in urban areas only when the potential spatial extent of those emissions an be quantified. Figure 4-7 quantifies the impats as well as their loation (defined by maximum?o 3 in the puff). 81

94 4-6 puff hr Puff Positions at 2pm Day 5 **CAMx Layer 7 Day 3 Day 4 Day 5 Austin Day6 Fayette Power Projet Houston Figure 4-7. Positions of Maximum?O 3 for Two-Hour Emissions Inreases, all Layers; 14:00 Analysis (darker symbol olor indiates higher impat; blue indiates negative impat, open star loates maximum impat of all-day, 50% redution). Analysis of Figure 4-7 is quite signifiant to this researh. Although the symbols have been olor-oded aording to their relative impats (as quantified in Figures 4-4 through 4-6; darker olor indiates higher impat), it is not neessary to know their exat values. Qualitatively, it is equally useful to examine where the two-hour impats our relative to where the maximum 24-hour impat ours. The 24-hour impat was alulated in the same manner as the other impats, only the emissions inrease was onsidered to be the differene in emissions between the full, normalized emissions ase, and the half-emissions ase, as mentioned in 82

95 setion 4.1. The loation of an O 3 maximum for the 24-hour emission inrease reflets the position of the overall maximum impat for that partiular day. On Day 4, for instane, the maximum 24-hour impat lies at the same position as the maximum impat for the 2-4 a.m. emissions inrease ase. This implies that the 2-4 a.m. emissions were the main ontributor to maximum O 3 onentrations on that day. In fat, from looking at Figures 4-4 and 4-6, that partiular time period of emissions did dominate for Day 4. By loating the puffs at their point of maximum onentration, one an onsider the potential impat of emissions as both ozone onentration and total ozone prodution. The first metri is signifiant to work urrently being done in Houston, to address high ozone events whih arise from rapid formation of ozone. The seond metri addresses regional ontrol strategies, and the potential of the plant to ontribute to high bakground onentrations of ozone. Another important observation from Figure 4-7 is the separation of puffs from one another on Days 5 and 6. On these days, some emissions from higher levels in the CAMx grid struture were arried in those upper layers (presumably out of the modeled onvetive mixed layer) in a different diretion than the prevailing ground-level winds. This reflets the meteorologial phenomenon of wind shearing, whih, as mentioned in Chapter I, an lead to transport of emissions in different diretions, and disontinuity of plumes. Finally, a potential ontrol strategy development ould arise from this type of analysis. It is obvious from the above plot, that nighttime emissions ould have a large impat on urban areas suh as Austin or Houston, depending on prevailing wind diretion during the night. Minimizing these emissions is ruial to effiient regional ontrol of O 3 formation. This ould be aomplished through 83

96 environmental dispathing, or in a more sophistiated way, through preditive ontrol. 4.4 Conlusions Methods have been developed in this researh to ompare ozone prodution apability of emissions from different times of the day. Speifially, the Point Soure Evaluation Tool for Temporal sensitivity (PSETTEMP, available in Appendix A), is useful for integrating ozone prodution over a given period of time and spae. This tool applies to the Plant On-Plant Off tehnique, and emissions an be saled between 0 and 100% for user-defined time periods using the point soure summarization and modifiation programs also loated in Appendix A. Aording to this researh, inremental inreases in afternoon emissions from a rural point soure will not have an impat on urban areas during sensitive times of the day. Different results will likely arise for urban point soures, for theories summarized in Chapter 1. This researh has provided effetive analysis methods for suh investigations. The rural point soure studied showed high impat of emissions during the night, viewed as both ozone onentration ontribution, and spatially integrated ozone formation (total moles ozone formed by a single set of emissions). For the partiular rural point soure studied, the loation of the O 3 attributable to the soure during peak hours of the day is suh that it ould potentially impat an urban area during peak O 3 hours, and thereby ause an exeedane of the O 3 NAAQS. The emissions most likely to ause suh an exeedane originate during the night, and are transported for release in Austin or Houston during sensitive hours. Further onsideration should be given to determine 84

97 statistially when suh events are likely to our (by historial wind rose), and to determine the feasibility of preditive ontrol. The impat potential of a soure on an urban area is a funtion of wind speed, wind diretion, and soure strength. Based on a given wind speed and diretion, the soure strength ould potentially be tuned (or environmental dispathing ould be employed) during different periods of the day to minimize ozone prodution. 85

98 Chapter V: Summary and Conlusions Modeling of power plant plumes (PPPs) is a subjet whih has been approahed on a submodel level; rarely has it been investigated within a larger framework, suh as a regional photohemial grid model. The photohemial grid model investigated, CAMx, overestimates rosswind plume dispersion, and under predits OPE in a power plant plume relative to airraft plume sampling on a similar day. The large NOx soure under examination, Fayette Power Projet, loated in Fayette County, Texas, was sampled on September 10, 2000 by the National Oeani Aviation Administration s G-1 airraft. Analysis of the data aquired indiates an Ozone Prodution Effiieny (OPE) of approximately 9 (moles O 3 produed per mole NOx emitted). Analysis of a similar CAMx modeling day, July 9, 1995, indiates an OPE of only Tools have been developed to ompare airraft plume measurement data to modeled data. First, a tool known as PSET, the Point Soure Evaluation Tool, is inluded in Appendix A. PSET is to be used in Plant On-Plant Off analyses to isolate O 3 formed due to a partiular soure. PSET analyzes modeled output to give plume-averaged OPE, transet-averaged OPE, hemial age, loss of NOx, and other relevant plume parameters. The desired spatial extent of analysis an be limited to plume dimensions as measured in airraft plume sampling. For diret omparison, without Plant On-Plant Off analysis, AIRCOMP (also inluded in Appendix A) is a program whih will generate spatially-assigned O 3 values for modeled output, whih an then be interpolated (using Golden Surfer software, for example) to airraft plume measurement data. This allows the user to perform a virtual airraft flight through the plume, taking samples at loations orresponding to airraft measurements. 86

99 CAMx under predits Ozone Prodution Effiienies, aording to these two different types of analysis. In the Plant On-Plant Off analysis, an OPE of 1.9 was observed. Using the virtual airraft flight method, an OPE of 1.6 was predited. Data taken by the NOAA G-1 airraft on September 10, 2000, a similar day in terms of wind diretion and temperature, indiated a plume-averaged OPE of 9 (upper bound). A mass-balane approah (lower bound) to OPE alulation yields OPEs ranging from (fresh plume) to 1.4 (sixth and final transet, plume supposed to be at highest maturity). Of these values, the best approah to be taken for omparing airraft data to model output is using the Plant On-Plant Off omparison, ombined with the onentration ratio approah. This approah requires muh less manipulation of data than the onentration ratio approah for the virtual airraft flight omparison and the mass balane approah for either omparison. The onentration ratio approah for the Plant On-Plant Off omparison requires boundaries to be set by orresponding physial age of the airraft plume. As seen in this researh, suh limitations ause muh of the plume attributable to the soure to be exluded from the analysis. Transet data is needed for the mass balane approah, and is not available in either omparison, exept through data manipulation and assumption. The ause of OPE under predition by CAMx may lie in over dispersion of emissions in both the downwind and rosswind diretions. This is proposed beause of the great disparity in plume dimensions between modeled data and airraft measurement data. Airraft data indiate a peak at 36 km downwind, and a maximum plume width (as defined by both O 3 and SO 2 onentrations above bakground) of only 18 km. For a similar set of meteorologial onditions (although not idential), CAMx predits a peak ozone onentration km 87

100 downwind (at ½ the wind speed measured by the airraft), and a maximum plume width of more than 40 km. For this reason, sensitivity tests employing different horizontal advetion shemes are reommended. Biogeni inventory shortomings may be the ulprit in the appearane of lower-than-measured OPEs. Inreasing the biogeni inventory aused a rise in potential OPEs to levels near and beyond those observed in the airraft data. A more diretly orrelated modeling episode will be useful for drawing more substantial results, however. Data do not support similar emission rates nor wind speeds. These disparities may explain the lak of omparability between the modeled and airraft data. Afternoon emissions from a rural point soure will not have an impat on urban areas, aording to this researh. Different results will likely arise for urban point soures. This researh has provided effetive analysis methods for suh investigations. Comparison of Chapters III and IV should be approahed with aution. Note that the maximum ontribution of the 24-hour puffs from Chapter IV, Figure 4-7, ours far downwind of the maximum ozone onentration reported from the base ase, in Figure 3-18 from Chapter III. This is likely due to nonlinearity in ozone hemistry. The 24-hour puff of Chapter IV originates in a region whih already ontains the same quantity of NOx emissions (as it results from an inrease in emissions from half- to full-strength). The ozone generation in Figure 3-18 is from a soure being emitted into a region with essentially no bakground NOx. Those emissions have higher OPE and realize their hemial maturity at a more rapid rate. In other words, the ozone prodution in Chapter IV is, in every ase, due to inremental inreases in NOx emissions. In Chapter III, the ozone prodution measured is based on the absolute emission rate of the power plant. 88

101 Chapter VI: Reommendations In order to address the over dispersion of emissions, the PiG may be modified to an emissions longer. This would ause a further delay in the introdution of emissions to the oarse grid. It is quite possibly this introdution whih auses the overestimation. This is also a good first step to see whether the under predited OPE is aused by the overestimation of dispersion. Furthermore, the horizontal advetion sheme used in the model was the PPM sheme, as defined by CAMx. Two other shemes are available within CAMx, based on researh by Bott and Smolarkiewiz (Environ, 1998), and should be examined alongside the PPM sheme to test the sensitivity of the model. Other fators potentially ausing under predition of plume OPE, as mentioned, are under predition of biogeni emissions loal to FPP. Steps ontinue to be taken to address the unertainty surrounding the biogeni emissions inventory in Central and Eastern Texas. The absene of wings in Central Texas plumes sampled by airraft is an interesting phenomenon. This is ontrary to findings in other parts of the ountry, for example, Tennessee. This phenomenon should be noted and further explored. The diurnal sensitivity of Ozone formation to NOx emissions observed for a rural soure should be ompared with modeling for an urban soure, using the experimental proedure developed during this researh. By following the plumes, an impat analysis should be performed to estimate the potential for a given soure to impat an urban area whih is either non-attainment or near non-attainment. Using these results to develop ontrol strategies will inrease the effetiveness of NOx ontrol implementation in Central and Eastern Texas. 89

102 APPENDICES APPENDIX A: Computer ode 1. CAMx run ontrol file 2. PiG growth subroutine 3. PiG hemistry subroutine 4. Point Soure Modifiation Program (ptsumpig, ptmodpig.f and pigoff.f) 5. Point Soure Evaluation Tool, PSET 6. Temporal Sensitivity Evaluation Tool, PSETTEMP 7. Airraft Data Comparison Code, AIRCOMP 90

103 1. CAMx run ontrol file (3 pages) #!/bin/sh # # CAMx 2.0 run for Central TX /07-07/12 # # NOTES # # July 1995 Base Case with one exeption # # Emissions have been normalized for the Fayette Power Plant # to a steady daily emission rate. # set verbose date # set RUN = "Fayettebase" rm -rf $RUN mkdir $RUN set EXEC = "/usr/loal/models/camx2.03/camx" # set INPUT = "/yo/modeling/july95/amx" set EMIS = "/yo/emissions/july95/eps2/16km/emiss" set EMIS2 = "/yo/emissions/july95/eps2/4km/emiss" set POINT = "/yo/hamlin/ptsre" set OUTPUT = "/yo/hamlin/outputs/$run" rm -rf $OUTPUT mkdir $OUTPUT # # run the first day # at << ieof > CAMx.in CAMx2.03 CTX, , km Run: $RUN Root output name $OUTPUT/CAMx2.tx $RUN Start yr/mo/dy/hr End yr/mo/dy/hr dtmx,dtin,dtem,dtou nx,ny,nz Coordinate ID UTM xorg,yorg,dx,dy,zon time zone 6 PiG parameters Avg output speies 6 O3 NO NO2 PAN NXOY HNO3 Num fine nest 2 i1,i2,j1,j2,nz,mesh i1,i2,j1,j2,nz,mesh SMOLAR, BOTT, PPM? PPM 91

104 Restart false Chemistry true Dry dep true Wet dep false PiG submodel true Staggered winds false Treat area emiss true Treat point emiss true 1-day emiss inputs true 3-D average file true Soure Apportion false Chemparam $INPUT/ommon/CAMx2.hemparm.3 Photolysis rates $INPUT/ommon/amx.rates.tx.jul95 Landuse $INPUT/ommon/landuse.32km Height/pressure $INPUT/met/32km/amx.zp km Wind $INPUT/met/32km/amx.uv km Temperature $INPUT/met/32km/amx.tp km Water vapor $INPUT/met/32km/amx.qa km Cloud over Rainfall Vertial diffsvty $INPUT/met/32km/amx.kv km.kvpath Initial onditions $INPUT/ib/i.tx Boundary onditions $INPUT/ib/b.tx Top onentration $INPUT/ib/t.tx Albedo/haze/ozone $INPUT/ommon/alhzoz.tx a0 Point emiss $POINT/ptsre.aaog.$RUN Area emiss $EMIS/emiss.aaog.32km Landuse #1 $INPUT/ommon/landuse.tx_16km Landuse #2 $INPUT/ommon/landuse.tx_04km Height/pressure #1 $INPUT/met/16km/amx.zp km.tx Height/pressure #2 $INPUT/met/4km/amx.zp km.tx Wind #1 $INPUT/met/16km/amx.uv km.tx Wind #2 $INPUT/met/4km/amx.uv km.tx Temperature #1 $INPUT/met/16km/amx.tp km.tx Temperature #2 $INPUT/met/4km/amx.tp km.tx Vertial diff #1 $INPUT/met/16km/amx.kv km.tx.kvpath Vertial diff #2 $INPUT/met/4km/amx.kv km.tx.kvpath Area emiss #1 $EMIS/emiss.aaog.16km Area emiss #2 $EMIS2/emiss.4km.run2.wbuf ieof # $EXEC & tee $RUN/CAMx2.tx $RUN.out date # # run remaining days # foreah today ( ) set yesterday = `eho $today awk '{printf("%2.2d",$1-1)}'` # at << ieof > CAMx.in 92

105 CAMx2.03 CTX, , km Run: $RUN Root output name $OUTPUT/CAMx2.tx.9507$today.$RUN Start yr/mo/dy/hr $today 0. End yr/mo/dy/hr $today dtmx,dtin,dtem,dtou nx,ny,nz Coordinate ID UTM xorg,yorg,dx,dy,zon time zone 6 PiG parameters Avg output speies 6 O3 NO NO2 PAN NXOY HNO3 Num fine nest 2 i1,i2,j1,j2,nz,mesh i1,i2,j1,j2,nz,mesh SMOLAR, BOTT, PPM? PPM Restart true Chemistry true Dry dep true Wet dep false PiG submodel true Staggered winds false Treat area emiss true Treat point emiss true 1-day emiss inputs true 3-D average file true Soure Apportion false Chemparam $INPUT/ommon/CAMx2.hemparm.3 Photolysis rates $INPUT/ommon/amx.rates.tx.jul95 Landuse $INPUT/ommon/landuse.32km Height/pressure $INPUT/met/32km/amx.zp.9507$today.32km Wind $INPUT/met/32km/amx.uv.9507$today.32km Temperature $INPUT/met/32km/amx.tp.9507$today.32km Water vapor $INPUT/met/32km/amx.qa.9507$today.32km Cloud over Rainfall Vertial diffsvty $INPUT/met/32km/amx.kv.9507$today.32km.kvpath Initial onditions Boundary onditions $INPUT/ib/b.tx.9507$today Top onentration $INPUT/ib/t.tx Albedo/haze/ozone $INPUT/ommon/alhzoz.tx a0 Point emiss $POINT/ptsre.aaog.$RUN.9507$today Area emiss $EMIS/emiss.aaog.32km.9507$today Landuse #1 $INPUT/ommon/landuse.tx_16km Landuse #2 $INPUT/ommon/landuse.tx_04km Height/pressure #1 $INPUT/met/16km/amx.zp.9507$today.16km.tx Height/pressure #2 $INPUT/met/4km/amx.zp.9507$today.4km.tx Wind #1 $INPUT/met/16km/amx.uv.9507$today.16km.tx Wind #2 $INPUT/met/4km/amx.uv.9507$today.4km.tx 93

106 Temperature #1 $INPUT/met/16km/amx.tp.9507$today.16km.tx Temperature #2 $INPUT/met/4km/amx.tp.9507$today.4km.tx Vertial diff #1 $INPUT/met/16km/amx.kv.9507$today.16km.tx.kvpath Vertial diff #2 $INPUT/met/4km/amx.kv.9507$today.4km.tx.kvpath Area emiss #1 $EMIS/emiss.aaog.16km.9507$today Area emiss #2 $EMIS2/emiss.4km.run2.wbuf.9507$today Coarse grid restart $OUTPUT/CAMx2.tx.9507$yesterday.$RUN.inst.2 Fine grid restart $OUTPUT/CAMx2.tx.9507$yesterday.$RUN.finst.2 PiG restart $OUTPUT/CAMx2.tx.9507$yesterday.$RUN.pig ieof # $EXEC & tee $RUN/CAMx2.tx.9507$today.$RUN.out date # end exit 94

107 2. PiG growth subroutine subroutine piggrow(n,dt,rkv,axiszmx,axisymx,o3amb,wind,dumpmass) -----CAMx v PIGGROW performs the following funtions: (1) grows puffs (2) alulates the mass to dump if growth restrited (3) entrains grid mass if growth allowed Copyright 1996, 1997, 1998, 1999, 2000 ENVIRON International Corporation Modifiations: none Input arguments: n puff index dt time step (s) rkv vertial diffusivity (m2/s) axiszmx maximum allowable vertial depth (m) axisymx maximum allowable lateral size (m) o3amb ambient ozone onentrations (umol/m3) wind ambient wind (m/s) Output arguments: dumpmass NO, NO2, HNO3 mass to dump (umol) Subroutines alled: none Called by: PIGDRIVE inlude "amx.prm" inlude "pigsty.om" inlude "filunit.om" dimension dumpmass(3) data pi/ / data dsydx /2.66e-2/ data dszdx /4.95e-4/ -----Entry point -----Calulate horizontal diffusivity from Kv, and grow puff in ross-setion 95

108 only zsore = 1.5 rkh = 46.4*rkv**(2./3.) rkh = amax1(rkh,10.) volold = xlength(n)*axisy(n)*axisz(n)*pi sigzo = sigz(n) sigyo = sigy(n) sigz(n) = sqrt(sigz(n)*sigz(n) + 2.*rkv*dt) + wind*dt*dszdx sigy(n) = sqrt(sigy(n)*sigy(n) + 2.*rkh*dt) + wind*dt*dsydx if (lnewg(n)) then axisy(n) = zsore*sigy(n) axisz(n) = zsore*sigz(n) fmspig(n) = 1. - exp(-zsore*zsore/2.) goto 900 endif -----Limit puff dimensions by axiszmx and axisymx fmsold = fmspig(n) axisz(n) = zsore*sigz(n) if (2.*axisz(n).gt.axiszmx) then axisz(n) = axiszmx/2. zsore = axisz(n)/sigz(n) fmspig(n) = 1. - exp(-zsore*zsore/2.) endif axisy(n) = zsore*sigy(n) if (2.*axisy(n).gt.axisymx) then axisy(n) = axisymx/2. zsore = axisy(n)/sigy(n) axisz(n) = zsore*sigz(n) fmspig(n) = 1. - exp(-zsore*zsore/2.) endif -----Artifiially shrink puffs older than agemax so that 10% of puff mass is released eah timestep if (agepig(n).ge.agemax) then fmspig(n) = amax1(0.,fmsold - 0.1) zsore = sqrt(-2.*alog(1. - fmspig(n))) axisy(n) = zsore*sigy(n) axisz(n) = zsore*sigz(n) endif -----Pump out puff mass due to expansion delms = (fmsold - fmspig(n))/fmsold 96

109 if (delms.gt.1.e-5) then do l=1,3 dumpmass(l) = puffmass(l,n)*delms puffmass(l,n) = puffmass(l,n) - dumpmass(l) enddo else do l=1,3 dumpmass(l) = 0. enddo endif 900 volnew = xlength(n)*axisy(n)*axisz(n)*pi if (volnew.lt.0.0) then write(iout,'(//,a)') 'ERROR in PIGGROW:' write(iout,*) 'Negative puff volume' write(iout,*) 'Puff#,length,axis_x/y/z:' write(iout,*) n,xlength(n),axisy(n),axisz(n),axiszmx write(iout,*) 'Size/mass parameters:' write(iout,*) zsore,fmspig(n),fmsold write(iout,*) 'CAMx Stopping' stop endif -----Update ozone puff mass due to entrainment if (lnewg(n)) then puffmass(4,n) = o3amb*volnew elseif (volnew.gt.0.) then dvol = volold*(sigy(n)*sigz(n)/(sigyo*sigzo) - 1.) if (volnew.le.volold) dvol = amin1(dvol,volnew) onpig = puffmass(4,n)/volnew if (o3amb.gt.onpig) puffmass(4,n) = puffmass(4,n) + o3amb*dvol endif return end 97

110 3. PiG hemistry subroutine (3 pages) subroutine pighem(dt,ldark,bdnlo3,bdnlno,h2o,pk, & onvfa,onpig,o3dif) -----CAMx v PIGCHEM updates NOx and O3 onentrations in the puff Copyright 1996, 1997, 1998, 1999, 2000 ENVIRON International Corporation Modifiations: none Input arguments: dt time step (s) ldark darkness flag (logial) bdnlo3 lower bound ozone onentration (ppm) bdnlno lower bound NO onentration (ppm) h2o water vapor onentration (ppm) pk(1) rate onstant for NO2 + O3 -> NO3 pk(2) rate onstant for O3 -> O(1D) pk(3) rate onstant for O(1D) -> O(3P) pk(4) rate onstant for O(1D) -> 2 OH pk(5) rate onstant for NO3 + NO2 -> NO + NO2 pk(6) rate onstant for NO3 + NO2 -> N2O5 pk(7) rate onstant for N2O5 + H2O -> 2 HNO3 pk(8) rate onstant for N2O5 -> NO3 + NO2 pk(9) rate onstant for NO + NO -> 2 NO2 onvfa onversion fator from ug/m3 to ppm onpig onentrations of NO, NO2, HNO3, O3 (umol/m3) Output arguments: onpig onentrations of NO, NO2, HNO3, O3 (umol/m3) o3dif ozone redution due to hemistry (umol/m3) Routines Called: none Called by: PIGDRIVE dimension onpig(4), pk(9) 98

111 real no, no2, no3, n2o5 logial ldark -----Entry point -----Convert umol/m3 to ppm no = onpig(1)/onvfa no2 = onpig(2)/onvfa hno3 = onpig(3)/onvfa o3 = onpig(4)/onvfa o3old = o3 o3dif = NO-NO self reation tmpno = no/(1. + pk(9)*dt*no/3600.) no2 = no2 + (no - tmpno) no = tmpno -----NO-O3 titration if (no.le.bdnlno.or. o3.le.bdnlo3) goto 10 if (o3.le.no) then tmp = o3 - bdnlo3 o3 = bdnlo3 no2 = no2 + tmp no = amax1((no-tmp),bdnlno) else tmp = no - bdnlno no = bdnlno no2 = no2 + tmp o3 = amax1((o3-tmp),bdnlo3) endif 10 o3dif = o3 - o3old -----HNO3 prodution if (o3.gt.bdnlo3) then if (ldark) then Nighttime: Generate nitri aid via the N2O5+H2O hannel; after alulating a steady-state N2O5 onentration, assume the proess is limited by ozone availability and use this rate to alulate the deay of ozone; note that loss of one N2O5 removes two ozone moleules 99

112 flux1 = pk(1)*no2*o3 flux5 = pk(5)*no2 flux6 = pk(6)*no2 flux7 = pk(7)*h2o flux8 = pk(8) ssratio = flux6/(flux7 + flux8) no3 = flux1/(flux5 + flux6 - ssratio*flux8 + 1.e-20) n2o5 = no3*ssratio flux7 = n2o5*flux7 do3 = o3 * (1.0 - exp(-flux7*dt*2.0/(o3*3600.))) do3 = amin1(o3,do3,no2) o3 = o3 - do3 no2 = no2 - do3 hno3 = hno3 + do3 o3dif = o3 - o3old else Daytime: ozone photolysis generates OH radials, whih oxidize NO2 to nitri aid alpha = (dt/3600.)*pk(2)*pk(4)*h2o/(pk(3) + pk(4)*h2o) do3 = amin1(o3,alpha*o3,no2/2.) o3 = o3 - do3 no2 = no2-2.*do3 hno3 = hno3 + 2.*do3 o3dif = o3 - o3old endif endif -----Convert from ppm to umol/m3 onpig(1) = no*onvfa onpig(2) = no2*onvfa onpig(3) = hno3*onvfa onpig(4) = o3*onvfa o3dif = o3dif*onvfa return end 100

113 4. Point Soure Summarization Program C C Program: PTSUM.F C Program goal: This program reads binary point soure emissions files and reates an C output file with the NOx emissions (total in tons/hr) summarized for all point C soures within 2km of user speified set of oordinates. The user an speify up to C 50 oordinate pairs. They must be in the same system and units of the ooridinates in the file C file. THIS PROGRAM ASSUMES THAT THE NUMBER AND ORDER OF SOURCES IS IDENTICAL IN C THE MASTER AND HOURLY STACK LISTS. THIS MUST BE TRUE FOR CAMX PIG SIMULATIONS OVER C MULTIPLE DAYS. FUTHURMORE IT IS ASSUMED THAT NO IS THE FIRST SPECIES AND NO2 IS THE C SECOND SPECIES IN THE SPECIES LIST. C The format of the userin file for the oordinate pairs x and y is: I7,1x,I7 C Eah pair sits on a separate line. The last line must have 0 0 as the entry. C Language: Fortran C Programmers: Matt Russell and Amy Baron C Last modifiation date: 6/19/00 C C MAIN PROGRAM: parameter (NUMSPECIES=15,NUMSOURCES=20000,MAXIN=50) harater*125 INFILE,OUTFILE real NOX(2,NUMSOURCES), DUM(NUMSOURCES), HT(NUMSOURCES) real XC(NUMSOURCES),YC(NUMSOURCES), DIA(NUMSOURCES) real BEGT,ENDT,REFORX,REFORY,XLOC,YLOC,TEMP(NUMSOURCES) real XSIZE,YSIZE,SHGT,MINSD,MINDT,VEL(NUMSOURCES) integer FILETYPE(10),FILENAME(60),NAMESPE(10,15) integer SPECIE(10),numsr integer SEG,NUMSPE,BEGD,ENDD,HRNUMPT integer ZONE,NUMXCELL,NUMYCELL,NUMZCELL integer SD,DT,SEGX,SEGY,SCELLX, SCELLY integer NUMPT,index(maxin,maxin),X(MAXIN),Y(MAXIN) integer numoord(maxin),molw 101

114 integer DUM2(NUMSOURCES) C Open input and output files WRITE(*,'(A)')' Enter the EMISSIONS file to be examined: ' READ (*,'(A)') INFILE open (unit=25, file=infile, status='old',form='unformatted') WRITE(*,'(A)')' Enter the USERIN file: ' READ (*,'(A)') INFILE open (unit=10, file=infile, status='old',form='formatted') WRITE(*,'(A)')' Enter the output file: ' READ (*,'(A)') INFILE open (unit=30, file=infile, status='new',form='formatted') C Read in oordinate pairs from userin file j=1 10 read(10,*,end=30) x(j),y(j) j=j+1 goto 10 C25 format(i7,1x,i7) 30 ontinue numsr=j-1 write(30,*) "number of soures in userin file: ",numsr write(*,*) "x-oordinate=",x(1) C Read header info read(25) FILETYPE,FILENAME,SEG,NUMSPE,BEGD,BEGT,ENDD,ENDT write(30,*) "julian date of emissions: ",BEGD read(25) REFORX,REFORY,ZONE,XLOC,YLOC,XSIZE,YSIZE, $ NUMXCELL,NUMYCELL,NUMZCELL,SD,DT,SHGT,MINSD,MINDT read(25) SEGX,SEGY,SCELLX,SCELLY read(25) ((NAMESPE(K,J), K=1,10), J=1,NUMSPE) read(25) SEG,NUMPT read(25) (XC(K),YC(K),HT(K),DIA(K),TEMP(K),VEL(K),K=1,NUMPT) C San master stak list and reord number of staks per soure (max is 50) C and the reord number of eah stak do j=1,numsr numoord(j)=0 do k=1,numpt C Criteria for inluding stak is to be within 2000 meters of input oordinate 102

115 then ",HT(K) if (ABS(XC(K)-X(J)).LE.2000.AND. ABS(YC(K)-Y(J)).LE.2000) numoord(j)=numoord(j)+1 index(j,numoord(j))=k write(30,*) "Soure ",j,", stak ",numoord(j)," is write(30,*) "meters tall, has a stak diameter of ",DIA(K) write(30,*) "with its gas at ",TEMP(K)," degrees K," write(30,*) "and is moving at ",VEL(K)," meters per hour." write(30,*) "its index, for CAMx, is ",k endif enddo write(30,*) "Soure ",j," has ",numoord(j)," staks." enddo C Read hourly data and summarize NOx emissions write(30,*) "hour, soure, stak, emissions (tons/hr)" do i=1,24 read(25) BEGD,BEGT,ENDD,ENDT read(25) SEG,HRNUMPT read(25) (DUM2(M),DUM2(M),DUM2(M),DUM(M),DUM(M), M=1,HRNUMPT) C Read the first 2 speies, ASSUMED TO BE NO AND NO2!!! do k=1,2 read(25) SEG,SPECIE,(NOX(K,M),M=1,HRNUMPT) enddo C Convert to tons and write out NOx emissions for eah stak. do j=1,numsr do m=1,numoord(j) write(30,"(3(i2,','),2(e12.6,','))") i,j,m, & & (NOX(1,index(j,m))*30/454/2000), (NOX(2,index(j,m))*46/454/2000) enddo enddo C Read the rest of the speies do k=3,numspe read(25) SEG,SPECIE,(NOX(1,M),M=1,HRNUMPT) enddo enddo end 103

116 Point Soure Modifiation Program (5 pages) **ptmodpig.f and pigoff.f differ only in the emboldened part of the ode below. ptmodpig.f does not turn off the PiG for soures (does not inlude the part in bold, whih hanges the diameter of the stak to a negative value). C C Program: PIGOFF.F C C Program goal: This program reads binary point soure emissions files and reates a new C file with modified NOx emissions for PiGed point soures within 2km of user speified set C of oordinates. The modifiation is aomplished by fatoring original hourly emissions. C C *****This program also turns the PiG off for those speified soures.***** C C The user an speify up to C 50 oordinate pairs. They must be in the same system and units of the oordinates in the file C file. THIS PROGRAM ASSUMES THAT THE NUMBER AND ORDER OF SOURCES IS IDENTICAL IN C THE MASTER AND HOURLY STACK LISTS. THIS MUST BE TRUE FOR CAMX PIG SIMULATIONS OVER C MULTIPLE DAYS. FUTHURMORE IT IS ASSUMED THAT NO IS THE FIRST SPECIES AND NO2 IS THE C SECOND SPECIES IN THE SPECIES LIST. C C The format of the userin file for the oordinate pairs x and y is: I7,1x,I7 C Eah pair sits on a separate line. C C The format of the fator file for the NOx emissions is text tab delimited real C numbers, one entry for eah hour, separate lines for eah soure. Program assumes C same number of soures in fator file as in userin file. The fator is applied C to the hourly NOx emission. C C Language: Fortran 104

117 C Original Programmers: Matt Russell and Amy Baron C Signifiant Modifiations made by Dyron Hamlin for PiG on/off sensitivity analyses C Last modifiation date: 5/07/01 C C MAIN PROGRAM: parameter (NUMSPECIES=15,NUMSOURCES=20000,MAXIN=50) harater*125 INFILE,OUTFILE real EMISS(NUMSOURCES),HT(NUMSOURCES) real XC(NUMSOURCES),YC(NUMSOURCES) real BEGT,ENDT,REFORX,REFORY,XLOC,YLOC real FLRT(NUMSOURCES),EHT(NUMSOURCES) real XSIZE,YSIZE,SHGT,MINSD,MINDT,fa(maxin,24) real DIA(NUMSOURCES),TEMP(NUMSOURCES),VEL(NUMSOURCES) integer FILETYPE(10),FILENAME(60),NAMESPE(10,15) integer SPECIE(10),numsr integer SEG,NUMSPE,BEGD,ENDD,HRNUMPT integer ZONE,NUMXCELL,NUMYCELL,NUMZCELL integer SD,DT,SEGX,SEGY,SCELLX, SCELLY integer NUMPT,index(maxin,maxin),X(MAXIN),Y(MAXIN) integer numoord(maxin),ount(maxin) integer RECX(NUMSOURCES),RECY(NUMSOURCES),RECZ(NUMSOURCES) harater*30 str C Open input and output files WRITE(*,'(A)')' Enter the EMISSIONS file to be onverted: ' READ (*,'(A)') INFILE open (unit=25, file=infile, status='old',form='unformatted') WRITE(*,'(A)')' Enter the USERIN file: ' READ (*,'(A)') INFILE open (unit=10, file=infile, status='old',form='formatted') WRITE(*,'(A)')' Enter the fator file: ' READ (*,'(A)') INFILE open (unit=11, file=infile, status='old',form='formatted') WRITE(*,'(A)')' Enter the output file: ' READ (*,'(A)') INFILE open (unit=30, file=infile, status='new',form='unformatted') C Read in oordinate pairs from userin file j=1 15 read(10,*,end=30) x(j),y(j) j=j+1 goto

118 C25 format(i7,1x,i7) 30 ontinue numsr=j-1 write(*,*) "number of soures in userin file: ",numsr C Read in the fator file. PROGRAM ASSUMES SAME NUMBER OF SOURCES C IN FACTOR FILE AS IN USERIN FILE do j=1,numsr read(11,*) (fa(j,k),k=1,24) enddo C Read and write header info read(25) FILETYPE,FILENAME,SEG,NUMSPE,BEGD,BEGT,ENDD,ENDT write(*,*) "julian date of emissions: ",BEGD write(30) FILETYPE,FILENAME,SEG,NUMSPE,BEGD,BEGT,ENDD,ENDT read(25) REFORX,REFORY,ZONE,XLOC,YLOC,XSIZE,YSIZE, $ NUMXCELL,NUMYCELL,NUMZCELL,SD,DT,SHGT,MINSD,MINDT write(30) REFORX,REFORY,ZONE,XLOC,YLOC,XSIZE,YSIZE, $ NUMXCELL,NUMYCELL,NUMZCELL,SD,DT,SHGT,MINSD,MINDT read(25) SEGX,SEGY,SCELLX,SCELLY write(30) SEGX,SEGY,SCELLX,SCELLY read(25) ((NAMESPE(K,J), K=1,10), J=1,NUMSPE) write(30) ((NAMESPE(K,J), K=1,10), J=1,NUMSPE) read(25) SEG,NUMPT write(30) SEG,NUMPT read(25) (XC(K),YC(K),HT(K),DIA(K),TEMP(K),VEL(K),K=1,NUMPT) C Need to determine where the stak of interest is. The diameter of this C stak must be hanged from negative to positive. This hange turns off C the PiG for that stak. This must be done before writing the DIA(K) C array to the new emissions file. 106

119 C San master stak list and reord number of staks per soure (max C is 50) and the reord number of eah stak do j=1,numsr ount(j)=0 numoord(j)=0 do k=1,numpt C Criteria for inluding stak is to be within 2000 meters of input oordinate if (ABS(XC(K)-X(J)).LE.2000.AND. ABS(YC(K)- Y(J)).LE.2000)then numoord(j)=numoord(j)+1 C Change the diameter of any staks given negative diameter to a positive dia. if (DIA(K).LE.0) then DIA(K)= -DIA(K) ount(j) = ount(j) + 1 index(j,ount(j))=k endif C Keep trak of the stak number for hanging emissions endif enddo write(*,*) "Soure ",j," has ",numoord(j)," staks." write(*,*) ount(j)," have negative diameter." enddo do j=1,numsr do k=1,ount(j) write(*,*) "oord's of staks w/ neg dia",xc(index(j,k)) write(*,*) YC(index(j,k)) enddo enddo C Write modified emissions file 107

120 write(30) (XC(K),YC(K),HT(K),DIA(K),TEMP(K),VEL(K),K=1,NUMPT) C Read hourly data, for NOx apply fator and write new file do i=1,24 read(25) BEGD,BEGT,ENDD,ENDT write(30) BEGD,BEGT,ENDD,ENDT read(25) SEG,HRNUMPT write(30) SEG,HRNUMPT read(25) (RECX(M),RECY(M),RECZ(M),FLRT(M),EHT(M), M=1,HRNUMPT) write(30)(recx(m),recy(m),recz(m),flrt(m),eht(m),m=1,hrnumpt) C Read the first 2 speies, ASSUMED TO BE NO AND NO2!!! do k=1,2 read(25) SEG,SPECIE,(EMISS(M),M=1,HRNUMPT) C Apply NOx fator for eah stak. This is not being done for C PiG off analysis. C The ode will be left here for future use with the PiG. do j=1,numsr C This hanges emissions on PiGed staks do m=1,ount(j) EMISS(index(j,m))=fa(j,i)*EMISS(index(j,m)) enddo enddo C Write new NOx emissions. Write un-modified emissions if just turning off PiG. write(30) SEG,SPECIE,(EMISS(M),M=1,HRNUMPT) enddo C Read and write the rest of the speies do k=3,numspe read(25) SEG,SPECIE,(EMISS(M),M=1,HRNUMPT) write(30) SEG,SPECIE,(EMISS(M),M=1,HRNUMPT) enddo enddo end 108

121 5. Point Soure Evaluation Tool PROGRAM pset This program reads 2 UAM format.avrg files and subtrats speies, and writes an ASCII format file whih is useful for analyzing point soure data. Dyron Hamlin, August Define Variables integer SEG, NUMSPE, BEGD,ENDD,ZONE,NUMXCELL,NUMYCELL,M integer NUMZCELL, SD, DT, SEGX, SEGY, SCELLX, SCELLY,I,J,L,Z,H integer NUMCELLS, kount(24), SPECMOD, GRIDCELL,k,ount(9),hr,X,Y real BEGT, ENDT, REFORX, REFORY, XLOC, YLOC, XSIZE, YSIZE real SHGT, MINSD, MINDT, THRESH real hropenoz(24),hravope real DELO3(82,106,9,24),DELNOZ(82,106,9,24) real OPENOZ(82,106,9,24),PERCOX(82,106,9,24) real PERCORG(82,106,9,24) real DELPAN(82,106,9,24),DELNTR(82,106,9,24) real DUMM(82,106,9,24),DELNOX(82,106,9,24),DUMMY(82,106) real DELNA(82,106,9,24),avgopenoz real layopenoz(9) dimension MFILETYPE(10), MFILENAME(60) dimension MDUMMY(10), MSPECIES(10,30), MSPECIE2(10,30) integer SPECIE(10) harater*100 IPATH Open files and make new output file WRITE(*,'(A)')' Enter the first.avrg file to be onverted:' READ (*,'(20x,A)') IPATH open (unit=11, file=ipath, status='old',form='unformatted') WRITE(*,'(A)')' Enter the.avrg file to be subtrated: ' READ (*,'(20x,A)') IPATH open (unit=12, file=ipath, status='old',form='unformatted') 109

122 WRITE(*,'(A)')' Enter the OUTPUT file to be reated: ' READ (*,'(20x,A)') IPATH open (unit=13, file=ipath, status='unknown',form='formatted') WRITE(*,'(A)')' Enter the O3 threshold whih defines the plume: ' READ (*,'(20x,F5.2)') THRESH WRITE(*,'(a,F5.2)') 'Threshold= ',THRESH ' WRITE(*,'(A)')' Enter the gridell of the soure of interest: READ (*,'(20x,i2,1x,i2)') X,Y WRITE(*,'(a,i2,'','',i2)') 'Gridell= ',X,Y DO H=1,24 DO Z=1,NUMZCELL DO I=1,NUMXCELL DO J=1,NUMYCELL DELNOZ(I,J,Z,H)=0. DELNOX(I,J,Z,H)=0. ENDDO ENDDO ENDDO kount(h)=0 hropenoz(h)=0. ENDDO & READ(11) MFILETYPE, MFILENAME, SEG, NUMSPE, BEGD, BEGT, ENDD, ENDT READ(11) REFORX, REFORY, ZONE, XLOC, YLOC, XSIZE &, YSIZE, NUMXCELL, NUMYCELL, NUMZCELL, SD, DT, SHGT, MINSD &, MINDT READ(11) SEGX, SEGY, SCELLX, SCELLY READ(11) ((MSPECIES(M,L),M=1,10),L=1,NUMSPE) Put the speies list into a dummy array that an be hanged for reading. do L=1,NUMSPE do M=1,10 MSPECIE2(M,L)=MSPECIES(M,L) 110

123 enddo enddo C Bswap the name and number of speies to allow the flag index to read C the "integer" MSPECIE2 as haraters when onverted to big endian all bswap(mspecie2,10,30) do l=1,numspe WRITE(*,'(I5,A,10A1)') L,' ',(MSPECIE2(M,L),M=1,10) enddo C Flag indies of O3, HNO3, PAN, and NXOY. C - These will be used later to ensure that orret data is read. iflag=0 do i=1,numspe IF(MSPECIE2(1,i).EQ.'O'.AND.MSPECIE2(2,i).EQ.'3') then IFLAG=i write(*,'(a,i1)') 'found some O3. Speies = ',iflag ENDIF end do then jflag=0 do j=1,numspe IF(MSPECIE2(1,j).EQ.'H'.AND.MSPECIE2(2,j).EQ.'N' $.AND.MSPECIE2(3,j).EQ.'O'.AND.MSPECIE2(4,j).EQ.'3') JFLAG=j write(*,'(a,i2)') 'found some HNO3. Speies = ',jflag ENDIF end do Currently, for some reason, I an't reognize PAN using this same bswap tehnique. Thus, one should make sure that PAN is indeed speies #4. iiflag=4 do ii=1,numspe IF((MSPECIE2(1,ii).EQ.'P')) then IIFLAG=ii write(*,'(a,i2)') 'found some PAN. Speies = ',iiflag ENDIF end do jjflag=0 do jj=1,numspe IF((MSPECIE2(1,jj).EQ.'N'.AND.MSPECIE2(2,jj).EQ.'X'.AND. $ MSPECIE2(3,jj).EQ.'O')) then JJFLAG=jj write(*,'(a,i2)') 'found some NXOY. Speies = ',jjflag 111

124 ENDIF end do kkflag=0 do kk=1,numspe IF((MSPECIE2(1,kk).EQ.'H'.AND.MSPECIE2(2,kk).EQ.'O'.AND. $ MSPECIE2(3,kk).EQ.'N')) then KKFLAG=kk write(*,'(a,i2)') 'found some HONO. Speies = ',kkflag ENDIF end do llflag=0 do ll=1,numspe IF((MSPECIE2(1,ll).EQ.'N'.AND.MSPECIE2(2,ll).EQ.'T'.AND. $ MSPECIE2(3,ll).EQ.'R')) then LLFLAG=ll write(*,'(a,i2)') 'found some NTR. Speies = ',llflag ENDIF end do iiiflag=0 do iii=1,numspe IF((MSPECIE2(1,iii).EQ.'N'.AND.MSPECIE2(2,iii).EQ.'O'.AND. $ MSPECIE2(3,iii).NE.'2')) then IIIFLAG=iii write(*,'(a,i2)') 'found some NO. Speies = ',iiiflag ENDIF end do jjjflag=0 do jjj=1,numspe IF((MSPECIE2(1,jjj).EQ.'N'.AND.MSPECIE2(2,jjj).EQ.'O'.AND. $ MSPECIE2(3,jjj).EQ.'2')) then JJJFLAG=jjj write(*,'(a,i2)') 'found some NO2. Speies = ',jjjflag ENDIF end do READ in headers from seond reord. & READ(12) MFILETYPE, MFILENAME, SEG, NUMSPE, BEGD, BEGT, ENDD, ENDT READ(12) REFORX, REFORY, ZONE, XLOC, YLOC, XSIZE &, YSIZE, NUMXCELL, NUMYCELL, NUMZCELL, SD, DT, SHGT, MINSD &, MINDT 112

125 READ(12) SEGX, SEGY, SCELLX, SCELLY READ(12) ((MSPECIES(M,L),M=1,10),L=1,NUMSPE) Read hourly stuff. DO 9 H = 1,24 READ(11) BEGD, BEGT, ENDD, ENDT READ(12) BEGD, BEGT, ENDD, ENDT Read the two files, heking to see if the speie is either O3 or HNO3. If the speie is Ozone, read it into CONC arrays. & & DO 12 S=1,NUMSPE if (S.EQ.IFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELO3(I,J,Z,H)=DUMM(I,J,Z,H) ENDDO ENDDO READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELO3(I,J,Z,H)=DELO3(I,J,Z,H)-DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is Nitri Aid, read it into DELNA arrays. & & elseif (S.EQ.JFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELNA(I,J,Z,H)=DUMM(I,J,Z,H) ENDDO ENDDO READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELNA(I,J,Z,H)=DELNA(I,J,Z,H)-DUMM(I,J,Z,H) ENDDO 113

126 ENDDO ENDDO If the speie is PAN, read it into DELPAN arrays. & & elseif (S.EQ.IIFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELPAN(I,J,Z,H)=DUMM(I,J,Z,H) ENDDO ENDDO READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELPAN(I,J,Z,H)=DELPAN(I,J,Z,H)-DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is NTR, read it into DELNTR arrays. & & elseif (S.EQ.LLFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELNTR(I,J,Z,H)=DUMM(I,J,Z,H) ENDDO ENDDO READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELNTR(I,J,Z,H)=DELNTR(I,J,Z,H)-DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is part of NOz, read it into DELNOZ arrays elseif ((S.EQ.JJFLAG).OR.(S.EQ.KKFLAG)) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) 114

127 DO I=1,NUMXCELL DO J=1,NUMYCELL DELNOZ(I,J,Z,H)=DUMM(I,J,Z,H)+DELNOZ(I,J,Z,H) ENDDO ENDDO READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELNOZ(I,J,Z,H)=DELNOZ(I,J,Z,H)-DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is NOx (NO or NO2), save the differene as DELNOX. TO AVOID NEGATIVE VALUES, JUST REPORT THE NOX FROM THE FIRST FILE??? elseif ((S.EQ.IIIFLAG).OR.(S.EQ.JJJFLAG)) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELNOX(I,J,Z,H)=DUMM(I,J,Z,H)+DELNOX(I,J,Z,H) ENDDO ENDDO READ(12) SEG,SPECIE,((DUMMY(I,J),I=1,NUMXCELL), & J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELNOX(I,J,Z,H)=DELNOX(I,J,Z,H)-DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is none of these things, read it into a dummy array. & & else DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMMY(I,J),I=1,NUMXCELL), J=1,NUMYCELL) READ(12) SEG,SPECIE,((DUMMY(I,J),I=1,NUMXCELL), J=1,NUMYCELL) ENDDO endif 115

128 Loop through all of the Layers 12 CONTINUE Loop through all of the Hours write(*,'(a,2i)') 'Done reading Hour # ',H 9 CONTINUE write(*,'(a)') 'done with all the reading stuff' Now, we wish to find the differene in ozone and the differenes in nitri aid or NOz for the two runs. These values, when ombined, an give us an estimate for OPE. write(13,"(12(',',a))")'cell','o3','nox','pan','ntr', & 'HNO3','NOz','OPENOz','Lay Av', & 'Hrly Av','% Ox', '% Org' DO H=13,21 DO Z=1,NUMZCELL layopenoz(z)=0. ount(z)=0 DO J=1,NUMYCELL DO I=1,NUMXCELL lprint=.false. GRIDCELL=I*100+J If we're not in the "plume," set all values = 0. Note, also, that the flag for printing the values to the output files defaults to.false. if ((1000.*(delo3(i,j,z,h))).le.THRESH) then delo3(i,j,z,h)=0. delna(i,j,z,h)=0. delnoz(i,j,z,h)=0. delnox(i,j,z,h)=0. delpan(i,j,z,h)=0. delntr(i,j,z,h)=0. openoz(i,j,z,h)=0. perox(i,j,z,h)=0. perorg(i,j,z,h)=0. If we are in the "plume," meaning there is at least THRESH delta O3 between the two runs being proessed, then store the following 116

129 values only for ells within 28 km of the stak This allows for omparison with data taken in the NOAA airraft during TEXAQS, 2000, when the airraft flew only to an extent of 25 km.: else if (I.lt.(X-13).OR.I.gt.(X+13).OR. & J.lt.(Y-13).OR.J.gt.(Y+13)) then lprint=.false. else lprint=.true. The number of grid ells in the urrent layer ount(z)=ount(z)+1 The total delta NOz (update it to inlude nitri aid, PAN, and NTR) delnoz(i,j,z,h)=delnoz(i,j,z,h)+delna(i,j,z,h) & +delpan(i,j,z,h)+delntr(i,j,z,h) The perent oxidation of the plume (NOz/NOy) and the perent of oxidation produts whih are organi nitrates. perox(i,j,z,h)=delnoz(i,j,z,h)/(delnoz(i,j,z,h)+ & delnox(i,j,z,h) ) perorg(i,j,z,h)=(delntr(i,j,z,h)+delpan(i,j,z,h))/ & (delnoz(i,j,z,h) ) The OPE on NOz basis for this ell OPENOZ(i,j,z,h)=delo3(i,j,z,h)/(delnoz(i,j,z,h) & ) The umulative OPE for this layer. These values will be used to ompute a layer average. layopenoz(z)=layopenoz(z)+openoz(i,j,z,h) endif endif Then print the data for this ell, this layer. 117

130 if (lprint) then write(13,"(',',i5,7(',',f6.3),',',',',2(',',f6.3))") & gridell, & (1000.*delo3(i,j,z,h)), & (1000.*delnox(i,j,z,h)), & (1000.*delpan(i,j,z,h)), & (1000.*delntr(i,j,z,h)), & (1000.*delna(i,j,z,h)), & (1000.*delnoz(i,j,z,h)), & openoz(i,j,z,h),perox(i,j,z,h), & perorg(i,j,z,h) endif Now go bak and hek the next ell. ENDDO ENDDO Let the fun begin. Find the LAYER AVERAGE OPE on both bases if(ount(z).gt.0) then avgopenoz=layopenoz(z)/ount(z) kount(h)=kount(h)+ount(z) hropenoz(h)=hropenoz(h)+layopenoz(z) else avgopenoz=0. endif This is the end of the layer loop...go bak and start a new layer. write(13,"(a,i2,9(','),f6.3)")'layer ',Z,avgopenoz print*,'finished writing layer',z ENDDO Let the fun begin. Find the HOUR AVERAGE OPE on both bases if(kount(h).gt.0) then hravope=hropenoz(h)/kount(h) else hravope=0. endif This is the end of the hourly loop...go bak and start a new hour. hr=h-1 write(13,"(a,i2,10(','),f6.3)")'hour ',hr,hravope 118

131 print*,'finished writing hour',h ENDDO WRITE(*,'(A)')' COMPLETE ' END funtion to onvert big-endian harater strings stored as integers to little endian harater strings stored as integers arguments: integer string array to be onverted number of elements in array along 1st dimension number of elements along seond dimension Subroutine bswap (instring,num1,num2) logial*1 instring(*), tmp1, tmp2 integer*4 num1,num2 integer*4 i,j,k proess in row major order if (num2.ne. 0) goto 200 Single dimension array 100 do 150 i=1,num1 j=(i-1)*4+1 tmp1 = instring(j) instring(j) = instring(j+3) instring(j+3) = tmp1 tmp2 = instring(j+1) instring(j+1) = instring(j+2) instring(j+2) = tmp2 150 ontinue goto 300 Double dimension array 200 ontinue do 250 i=1,num2 do 240 j=1,num1 k = (i-1)*(num1*4)+(j-1)*4+1 tmp1 = instring(k) instring(k) = instring(k+3) 119

132 instring(k+3) = tmp1 tmp2 = instring(k+1) instring(k+1) = instring(k+2) instring(k+2) = tmp2 240 ontinue 250 ontinue 300 return end 120

133 6. Temporal Sensitivity Evaluation Tool PROGRAM psettemp This program reads 2 UAM format.avrg files and subtrats speies, and writes an ASCII format file whih is useful for analyzing point soure data. Dyron Hamlin, August Define Variables integer SEG, NUMSPE, BEGD,ENDD,ZONE,NUMXCELL,NUMYCELL,M,NUMSPE2 integer NUMZCELL, SD, DT, SEGX, SEGY, SCELLX, SCELLY,I,J,L,Z,H integer NUMCELLS, kount(24), GRIDCELL,k,ount(9),hr,X,Y integer gridmax,diff real BEGT, ENDT, REFORX, REFORY, XLOC, YLOC, XSIZE, YSIZE real SHGT, MINSD, MINDT, THRESH real layo3(9),masso3,hrmass,maxo3 real DELO3(82,106,9,24) real DUMM(82,106,9,24) real DELNA(82,106,9,24),height(9) dimension MFILETYPE(10), MFILENAME(60) dimension MSPECIES(10,30), MSPECIE2(10,30) integer SPECIE(10) harater*100 IPATH data height(1)/33./ data height(2)/100./ data height(3)/211./ data height(4)/390./ data height(5)/675./ data height(6)/1105./ data height(7)/1815./ data height(8)/2892./ data height(9)/3600./ Open files and make new output file WRITE(*,'(A)')' Enter the first.avrg file to be onverted:' READ (*,'(20x,A)') IPATH open (unit=11, file=ipath, status='old',form='unformatted') 121

134 WRITE(*,'(A)')' Enter the.avrg file to be subtrated: ' READ (*,'(20x,A)') IPATH open (unit=12, file=ipath, status='old',form='unformatted') WRITE(*,'(A)')' Enter the OUTPUT file to be reated: ' READ (*,'(20x,A)') IPATH open (unit=13, file=ipath, status='unknown',form='formatted') WRITE(*,'(A)')' Enter the HNO3 threshold whih defines the plume:' READ (*,'(20x,F5.2)') THRESH WRITE(*,'(a,F5.2)') 'Threshold= ',THRESH ' WRITE(*,'(A)')' Enter the gridell of the soure of interest: READ (*,'(20x,i2,1x,i2)') X,Y WRITE(*,'(a,i2,'','',i2)') 'Gridell= ',X,Y & READ(11) MFILETYPE, MFILENAME, SEG, NUMSPE, BEGD, BEGT, ENDD, ENDT READ(11) REFORX, REFORY, ZONE, XLOC, YLOC, XSIZE &, YSIZE, NUMXCELL, NUMYCELL, NUMZCELL, SD, DT, SHGT, MINSD &, MINDT READ(11) SEGX, SEGY, SCELLX, SCELLY READ(11) ((MSPECIES(M,L),M=1,10),L=1,NUMSPE) Put the speies list into a dummy array that an be hanged for reading. do L=1,NUMSPE do M=1,10 MSPECIE2(M,L)=MSPECIES(M,L) enddo enddo C Bswap the name and number of speies to allow the flag index to read the C "integer" MSPECIE2 as haraters when onverted to big endian all bswap(mspecie2,10,30) (see pset.f) 122

135 do l=1,numspe WRITE(*,'(I5,A,10A1)') L,' ',(MSPECIE2(M,L),M=1,10) enddo C Flag indies of O3, HNO3, PAN, and NXOY. C - These will be used later to ensure that orret data is read. iflag=0 do i=1,numspe IF(MSPECIE2(1,i).EQ.'O'.AND.MSPECIE2(2,i).EQ.'3') then IFLAG=i write(*,'(a,i1)') 'found some O3. Speies = ',iflag ENDIF end do then jflag=0 do j=1,numspe IF(MSPECIE2(1,j).EQ.'H'.AND.MSPECIE2(2,j).EQ.'N' $.AND.MSPECIE2(3,j).EQ.'O'.AND.MSPECIE2(4,j).EQ.'3') JFLAG=j write(*,'(a,i2)') 'found some HNO3. Speies = ',jflag ENDIF end do iiflag=4 do ii=1,numspe IF((MSPECIE2(1,ii).EQ.'P')) then IIFLAG=ii write(*,'(a,i2)') 'found some PAN. Speies = ',iiflag ENDIF end do jjflag=0 do jj=1,numspe IF((MSPECIE2(1,jj).EQ.'N'.AND.MSPECIE2(2,jj).EQ.'X'.AND. $ MSPECIE2(3,jj).EQ.'O')) then JJFLAG=jj write(*,'(a,i2)') 'found some NXOY. Speies = ',jjflag ENDIF end do kkflag=0 do kk=1,numspe IF((MSPECIE2(1,kk).EQ.'H'.AND.MSPECIE2(2,kk).EQ.'O'.AND. $ MSPECIE2(3,kk).EQ.'N')) then KKFLAG=kk write(*,'(a,i2)') 'found some HONO. Speies = ',kkflag ENDIF end do 123

136 llflag=0 do ll=1,numspe IF((MSPECIE2(1,ll).EQ.'N'.AND.MSPECIE2(2,ll).EQ.'T'.AND. $ MSPECIE2(3,ll).EQ.'R')) then LLFLAG=ll write(*,'(a,i2)') 'found some NTR. Speies = ',llflag ENDIF end do iiiflag=0 do iii=1,numspe IF((MSPECIE2(1,iii).EQ.'N'.AND.MSPECIE2(2,iii).EQ.'O'.AND. $ MSPECIE2(3,iii).NE.'2')) then IIIFLAG=iii write(*,'(a,i2)') 'found some NO. Speies = ',iiiflag ENDIF end do jjjflag=0 do jjj=1,numspe IF((MSPECIE2(1,jjj).EQ.'N'.AND.MSPECIE2(2,jjj).EQ.'O'.AND. $ MSPECIE2(3,jjj).EQ.'2')) then JJJFLAG=jjj write(*,'(a,i2)') 'found some NO2. Speies = ',jjjflag ENDIF end do READ in headers from seond reord. & READ(12) MFILETYPE, MFILENAME, SEG, NUMSPE2, BEGD, BEGT, ENDD, ENDT READ(12) REFORX, REFORY, ZONE, XLOC, YLOC, XSIZE &, YSIZE, NUMXCELL, NUMYCELL, NUMZCELL, SD, DT, SHGT, MINSD &, MINDT READ(12) SEGX, SEGY, SCELLX, SCELLY READ(12) ((MSPECIES(M,L),M=1,10),L=1,NUMSPE2) diff=numspe-numspe2 Read hourly stuff. DO 9 H = 1,24 READ(11) BEGD, BEGT, ENDD, ENDT READ(12) BEGD, BEGT, ENDD, ENDT 124

137 Read the two files, heking to see if the speie is either O3 or HNO3. If the speie is Ozone, read it into CONC arrays. & & DO 12 S=1,NUMSPE2 if (S.EQ.IFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELO3(I,J,Z,H)=DUMM(I,J,Z,H) ENDDO ENDDO READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELO3(I,J,Z,H)=DELO3(I,J,Z,H)-DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is Nitri Aid, read it into DELNA arrays. & & elseif (S.EQ.JFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELNA(I,J,Z,H)=DUMM(I,J,Z,H) ENDDO ENDDO READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL DELNA(I,J,Z,H)=DELNA(I,J,Z,H)-DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is PAN, read it into dummy arrays. & elseif (S.EQ.IIFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), 125

138 & ENDDO J=1,NUMYCELL) If the speie is NTR, read it into dummy arrays. & & elseif (S.EQ.LLFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) ENDDO If the speie is part of NOz, read it into dummy arrays elseif ((S.EQ.JJFLAG).OR.(S.EQ.KKFLAG)) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) ENDDO If the speie is NOx (NO or NO2), read it into a dummy array. elseif ((S.EQ.IIIFLAG).OR.(S.EQ.JJJFLAG)) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) ENDDO If the speie is none of these things, read it into a dummy array. else DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) READ(12) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & ENDDO endif 126 J=1,NUMYCELL)

139 Loop through all of the Layers 12 CONTINUE if (diff.gt.0) then do k=1,diff DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & ENDDO enddo endif Loop through all of the Hours J=1,NUMYCELL) write(*,'(a,2i)') 'Done reading Hour # ',H 9 CONTINUE write(*,'(a)') 'done reading files' Now, we wish to find the differene in ozone and the differenes in nitri aid or NOz for the two runs. These values, when ombined, an give us an estimate for OPE. write(13,"(6(',',a))")'cell','o3','hno3','molo3', & 'maxo3','ellmax' maxo3=0. DO H=18,18 gridmax=0 hrmass=0. DO Z=1,NUMZCELL layo3(z)=0. ount(z)=0 DO J=1,NUMYCELL DO I=1,NUMXCELL lprint=.false. GRIDCELL=I*100+J If we're not in the "plume," set all values = 0. Note, also, that the flag for printing the values to the output files defaults to.false. if ((1000.*(delna(i,j,z,h))).le.THRESH) then delo3(i,j,z,h)=0. delna(i,j,z,h)=0. 127

140 If we are in the "plume," meaning there is at least THRESH delta HNO3 between the two runs being proessed, then store the following values: else lprint=.true. The number of grid ells in the urrent layer ount(z)=ount(z)+1 layo3(z)=layo3(z)+delo3(i,j,z,h) if (delo3(i,j,z,h).gt.maxo3) then maxo3=delo3(i,j,z,h) gridmax=i*100+j endif endif Then print the data for this ell, this layer. if (lprint) then write(13,"(',',i5,2(',',f6.3),',')") & gridell, & (1000.*delo3(i,j,z,h)), & (1000.*delna(i,j,z,h)) endif Now go bak and hek the next ell. ENDDO ENDDO & if(ount(z).gt.0) then masso3=layo3(z)*(16000.**2)*height(z) /(1.E6*.0224) kount(h)=kount(h)+ount(z) hrmass=hrmass+masso3 else masso3=0. endif C This is the end of the layer loop...go bak and start a new layer. & write(13,"(a,i2,4(','),f12.3,',',f6.3,',',i5)") 'LAYER ',Z,masso3,(maxo3*1000.),gridmax print*,'finished writing layer',z ENDDO 128

141 C This is the end of the hourly loop...go bak and start a new hour. hr=h-1 write(13,"(a,i2,',',i3,3(','),f12.3,',',f6.3,',',i5)") & 'HOUR ',hr,kount(h),hrmass,(maxo3*1000.),gridmax print*,'finished writing hour',h ENDDO END WRITE(*,'(A)')' COMPLETE ' 129

142 7. Airraft Data Comparison Code (6 pages) PROGRAM airomp This program reads a UAM format.avrg file and writes an ASCII format file for one hour, whih reports the utm oordinates (entroid of a grid ell) and ozone values for eah grid ell, whih is useful for analyzing point soure data. Dyron Hamlin, November Define Variables integer SEG, NUMSPE, BEGD,ENDD,ZONE,NUMXCELL,NUMYCELL,M integer NUMZCELL, SD, DT, SEGX, SEGY, SCELLX, SCELLY,I,J,L,Z,H integer NUMCELLS, kount(24), SPECMOD, GRIDCELL,k,ount(9),hr,X,Y real BEGT, ENDT, REFORX, REFORY, XLOC, YLOC, XSIZE, YSIZE real SHGT, MINSD, MINDT, THRESH real hropenoz(24),hravope real O3(82,106,9,24),NOZ(82,106,9,24) real DUMM(82,106,9,24) real dx,utmx dimension MFILETYPE(10), MFILENAME(60) dimension MDUMMY(10), MSPECIES(10,30), MSPECIE2(10,30) integer SPECIE(10) harater*100 IPATH Open files and make new output file WRITE(*,'(A)')' Enter the.avrg file to extrat from:' READ (*,'(20x,A)') IPATH open (unit=11, file=ipath, status='old',form='unformatted') WRITE(*,'(A)')' Enter the O3 OUTPUT file to be reated: ' READ (*,'(20x,A)') IPATH 130

143 open (unit=13, file=ipath, status='unknown',form='formatted') WRITE(*,'(A)')' Enter the NOz OUTPUT file to be reated: ' READ (*,'(20x,A)') IPATH open (unit=14, file=ipath, status='unknown',form='formatted') ' WRITE(*,'(A)')' Enter the grid resolution of the.avrg file: READ (*,'(20x,f3.1)') dx print*, 'dx =',dx DO H=1,24 DO Z=1,NUMZCELL DO I=1,NUMXCELL DO J=1,NUMYCELL O3(I,J,Z,H)=0. NOZ(I,J,Z,H)=0. DUMM(I,J,Z,H)=0. ENDDO ENDDO ENDDO ENDDO & READ(11) MFILETYPE, MFILENAME, SEG, NUMSPE, BEGD, BEGT, ENDD, ENDT READ(11) REFORX, REFORY, ZONE, XLOC, YLOC, XSIZE &, YSIZE, NUMXCELL, NUMYCELL, NUMZCELL, SD, DT, SHGT, MINSD &, MINDT READ(11) SEGX, SEGY, SCELLX, SCELLY READ(11) ((MSPECIES(M,L),M=1,10),L=1,NUMSPE) Put the speies list into a dummy array that an be hanged for reading. do L=1,NUMSPE do M=1,10 MSPECIE2(M,L)=MSPECIES(M,L) enddo enddo C Bswap the name and number of speies to allow the flag index to read the C "integer" MSPECIE2 as haraters when onverted to big endian 131

144 all bswap(mspecie2,10,30) do l=1,numspe WRITE(*,'(I5,A,10A1)') L,' ',(MSPECIE2(M,L),M=1,10) enddo C Flag indies of O3, HNO3, PAN, and NXOY. C - These will be used later to ensure that orret data is read. iflag=0 do i=1,numspe IF(MSPECIE2(1,i).EQ.'O'.AND.MSPECIE2(2,i).EQ.'3') then IFLAG=i write(*,'(a,i1)') 'found some O3. Speies = ',iflag ENDIF end do then jflag=0 do j=1,numspe IF(MSPECIE2(1,j).EQ.'H'.AND.MSPECIE2(2,j).EQ.'N' $.AND.MSPECIE2(3,j).EQ.'O'.AND.MSPECIE2(4,j).EQ.'3') JFLAG=j write(*,'(a,i2)') 'found some HNO3. Speies = ',jflag ENDIF end do Currently, for some reason, I an't reognize PAN using this same bswap tehnique. Thus, one should make sure that PAN is indeed speies #4. iiflag=4 do ii=1,numspe IF((MSPECIE2(1,ii).EQ.'P')) then IIFLAG=ii write(*,'(a,i2)') 'found some PAN. Speies = ',iiflag ENDIF end do jjflag=0 do jj=1,numspe IF((MSPECIE2(1,jj).EQ.'N'.AND.MSPECIE2(2,jj).EQ.'X'.AND. $ MSPECIE2(3,jj).EQ.'O')) then JJFLAG=jj write(*,'(a,i2)') 'found some NXOY. Speies = ',jjflag ENDIF end do kkflag=0 do kk=1,numspe IF((MSPECIE2(1,kk).EQ.'H'.AND.MSPECIE2(2,kk).EQ.'O'.AND. $ MSPECIE2(3,kk).EQ.'N')) then 132

145 KKFLAG=kk write(*,'(a,i2)') 'found some HONO. Speies = ',kkflag ENDIF end do llflag=0 do ll=1,numspe IF((MSPECIE2(1,ll).EQ.'N'.AND.MSPECIE2(2,ll).EQ.'T'.AND. $ MSPECIE2(3,ll).EQ.'R')) then LLFLAG=ll write(*,'(a,i2)') 'found some NTR. Speies = ',llflag ENDIF end do iiiflag=0 do iii=1,numspe IF((MSPECIE2(1,iii).EQ.'N'.AND.MSPECIE2(2,iii).EQ.'O'.AND. $ MSPECIE2(3,iii).NE.'2')) then IIIFLAG=iii write(*,'(a,i2)') 'found some NO. Speies = ',iiiflag ENDIF end do jjjflag=0 do jjj=1,numspe IF((MSPECIE2(1,jjj).EQ.'N'.AND.MSPECIE2(2,jjj).EQ.'O'.AND. $ MSPECIE2(3,jjj).EQ.'2')) then JJJFLAG=jjj write(*,'(a,i2)') 'found some NO2. Speies = ',jjjflag ENDIF end do Read hourly stuff. DO 9 H = 1,24 READ(11) BEGD, BEGT, ENDD, ENDT Read the two files, heking to see what the speie is. DO 12 S=1,NUMSPE If the speie is Ozone, read it into O3 array. & if (S.EQ.IFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((O3(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) ENDDO 133

146 If the speie is Nitri Aid, read it into an NOz array. & elseif (S.EQ.JFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((NOZ(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) ENDDO If the speie is PAN, read it into a dummy array. elseif (S.EQ.IIFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL NOZ(I,J,Z,H)=NOZ(I,J,Z,H)+DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is NTR, read it into a dummy array. & elseif (S.EQ.LLFLAG) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL NOZ(I,J,Z,H)=NOZ(I,J,Z,H)+DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is part of NOz, read it into a dummy array elseif ((S.EQ.JJFLAG).OR.(S.EQ.KKFLAG)) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) DO I=1,NUMXCELL DO J=1,NUMYCELL NOZ(I,J,Z,H)=NOZ(I,J,Z,H)+DUMM(I,J,Z,H) ENDDO ENDDO ENDDO If the speie is NOx (NO or NO2), read it into a dummy array. 134

147 elseif ((S.EQ.IIIFLAG).OR.(S.EQ.JJJFLAG)) then DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & J=1,NUMYCELL) ENDDO If the speie is none of these things, read it into a dummy array. else DO Z = 1,NUMZCELL READ(11) SEG,SPECIE,((DUMM(I,J,Z,H),I=1,NUMXCELL), & ENDDO endif Loop through all of the Layers 12 CONTINUE Loop through all of the Hours 135 J=1,NUMYCELL) write(*,'(a,2i)') 'Done reading Hour # ',H 9 CONTINUE write(*,'(a)') 'done with all the reading stuff' We wish to print only the ozone or NOz values for eah gridell, and report the orresponding lat/lon oordinates. write(13,"(4(a,','))")'utmx','utmy','o3','gridcell' write(14,"(4(a,','))")'utmx','utmy','noz','gridcell' DO H=15,15 DO Z=1,NUMZCELL DO J=54,80 DO I=57,83 GRIDCELL=J*100+I Define the UTM oordinate as the entroid of the urrent grid ell. Base the formula upon the grid resolution. if (dx.eq.4) then utmx=(i-1)*dx utmy=(j-1)*dx elseif (dx.eq.16) then

148 utmx=(i-1)*dx utmy=(j-1)*dx elseif (dx.eq.32) then utmx=(i)*dx utmy=(j)*dx endif write(13,"(2(f12.3,','),f6.2,',',i5)") & utmx,utmy, & (1000.*o3(i,j,z,h)), & gridell write(14,"(2(f12.3,','),f6.2,',',i5)") & utmx,utmy, & (1000.*noz(i,j,z,h)), & gridell Now go bak and hek the next ell. ENDDO ENDDO This is the end of the layer loop...go bak and start a new layer. print*,'finished writing layer',z ENDDO This is the end of the hourly loop...go bak and start a new hour. print*,'finished writing hour',h ENDDO WRITE(*,'(A)')' COMPLETE ' END 136

149 APPENDIX B: Airraft Data Comparison Airraft Data from 09/10/2000; DOE G1 flight Table B-1. Loations and Distanes of G-1 Transets From FPP Figure B-1. NOz/NOy relationship Figure B-2. NOx/NOy relationship Figure B-3. Loss of NOx in FPP plume Figure B-4. NOz/NOy orreted relationship Figure B-5. Wind Speed and Trajetory from FPP flight data Figure B-6. Temperature Comparison Figure B-7. Modeled O 3 onentrations 137

150 Date Time Time Lat Long Alt Stati P P altitude GPS GPS GPS yyyy-mm-dd hh:mm:ss.shh:mm:ss.ss(deg) (deg) (m) (mb) (m) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** 9/10/2000 2:54 PM 19:54: /10/2000 2:55 PM 19:55: /10/2000 2:55 PM 19:55: /10/2000 2:55 PM 19:55: /10/2000 2:55 PM 19:55: /10/2000 2:55 PM 19:55: /10/2000 2:55 PM 19:55: /10/2000 2:56 PM 19:56: /10/2000 2:56 PM 19:56: /10/2000 2:56 PM 19:56: /10/2000 2:56 PM 19:56: /10/2000 2:56 PM 19:56: /10/2000 2:56 PM 19:56: /10/2000 2:57 PM 19:57: /10/2000 2:57 PM 19:57: /10/2000 2:57 PM 19:57: /10/2000 2:57 PM 19:57: /10/2000 2:57 PM 19:57: /10/2000 2:57 PM 19:57: /10/2000 2:58 PM 19:58: /10/2000 2:58 PM 19:58: /10/2000 2:58 PM 19:58: /10/2000 2:58 PM 19:58: /10/2000 2:58 PM 19:58: /10/2000 2:58 PM 19:58: /10/2000 2:59 PM 19:59: /10/2000 2:59 PM 19:59: /10/2000 2:59 PM 19:59: /10/2000 2:59 PM 19:59: /10/2000 2:59 PM 19:59: /10/2000 2:59 PM 19:59: /10/2000 3:00 PM 20:00: /10/2000 3:00 PM 20:00: /10/2000 3:00 PM 20:00: /10/2000 3:00 PM 20:00: /10/2000 3:00 PM 20:00: /10/2000 3:00 PM 20:00: /10/2000 3:01 PM 20:01: /10/2000 3:01 PM 20:01:

151 Date Time T amb Theta Dew Pt RH H2O MR Wind Spee Wind Dir GPS GPS yyyy-mm-dd hh:mm:ss.s(c) (C) (C) (%) (g/kg) (m/s) (deg) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Onl 9/10/2000 2:54 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:01 PM /10/2000 3:01 PM

152 Date Time UV sky UV gnd PCASP tot FSSP total bap O3 CO GPS GPS yyyy-mm-dd hh:mm:ss.s(w/m^2) (W/m^2) (m^-3) (m^-3) (m^-1) (ppbv) (ppbv) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** 9/10/2000 2:54 PM E /10/2000 2:55 PM E /10/2000 2:55 PM E /10/2000 2:55 PM E /10/2000 2:55 PM E /10/2000 2:55 PM E /10/2000 2:55 PM E /10/2000 2:56 PM E /10/2000 2:56 PM E /10/2000 2:56 PM E /10/2000 2:56 PM E /10/2000 2:56 PM E /10/2000 2:56 PM E /10/2000 2:57 PM E /10/2000 2:57 PM E /10/2000 2:57 PM E /10/2000 2:57 PM E /10/2000 2:57 PM E /10/2000 2:57 PM E /10/2000 2:58 PM E /10/2000 2:58 PM E /10/2000 2:58 PM E /10/2000 2:58 PM E /10/2000 2:58 PM E /10/2000 2:58 PM E /10/2000 2:59 PM E /10/2000 2:59 PM E /10/2000 2:59 PM E /10/2000 2:59 PM E /10/2000 2:59 PM E /10/2000 2:59 PM E /10/2000 3:00 PM E /10/2000 3:00 PM E /10/2000 3:00 PM E /10/2000 3:00 PM E /10/2000 3:00 PM E /10/2000 3:00 PM E /10/2000 3:01 PM E /10/2000 3:01 PM E

153 Date Time SO2 NO NO2 NOy DelO3 NOz DelO3 GPS GPS onstant bg by yyyy-mm-dd hh:mm:ss.s(ppbv) (ppbv) (ppbv) (ppbv) bg transet ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Onl 9/10/2000 2:54 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:01 PM /10/2000 3:01 PM

154 Date Time OPE %OX %OX NOy NOz %OX GPS GPS (inst) no bg or norm by *1.3(byNOx) by Noy hange yyyy-mm-dd hh:mm:ss.ss 76% ***Seleted Data*** ***Seleted Data*** ***FPP Only*** ***FPP Only*** 9/10/2000 2:54 PM % % /10/2000 2:55 PM % % /10/2000 2:55 PM % % /10/2000 2:55 PM % % /10/2000 2:55 PM % % /10/2000 2:55 PM % % /10/2000 2:55 PM % % /10/2000 2:56 PM % % /10/2000 2:56 PM % % /10/2000 2:56 PM % % /10/2000 2:56 PM % % /10/2000 2:56 PM % % /10/2000 2:56 PM % % /10/2000 2:57 PM % % /10/2000 2:57 PM % % /10/2000 2:57 PM % % /10/2000 2:57 PM % % /10/2000 2:57 PM % % /10/2000 2:57 PM % % /10/2000 2:58 PM % % /10/2000 2:58 PM % % /10/2000 2:58 PM % % /10/2000 2:58 PM % % /10/2000 2:58 PM % % /10/2000 2:58 PM % % /10/2000 2:59 PM % % /10/2000 2:59 PM % % /10/2000 2:59 PM % % /10/2000 2:59 PM % % /10/2000 2:59 PM % % /10/2000 2:59 PM #DIV/0! #VALUE! % 1 9/10/2000 3:00 PM #DIV/0! #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:00 PM #DIV/0! #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:00 PM #DIV/0! #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:00 PM #DIV/0! #VALUE! % /10/2000 3:00 PM % % /10/2000 3:00 PM % % /10/2000 3:01 PM % % /10/2000 3:01 PM % %

155 Date Time NOy NOz %OX GPS GPS bg orret bg orret bg orret yyyy-mm-dd hh:mm:ss.ss ***Seleted Data*** ***FPP Only*** 9/10/2000 2:54 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:55 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:56 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:57 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:58 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM /10/2000 2:59 PM #VALUE! #VALUE! 9/10/2000 3:00 PM #VALUE! #VALUE! #VALUE! 9/10/2000 3:00 PM #VALUE! #VALUE! #VALUE! 9/10/2000 3:00 PM #VALUE! #VALUE! #VALUE! 9/10/2000 3:00 PM #VALUE! #VALUE! 9/10/2000 3:00 PM /10/2000 3:00 PM /10/2000 3:01 PM /10/2000 3:01 PM

156 Date Time Time Lat Long Alt Stati P P altitude GPS GPS GPS yyyy-mm-dd hh:mm:ss.shh:mm:ss.ss(deg) (deg) (m) (mb) (m) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** FIRST TRANSECT FIRST TRANSECT FIRST TRANSECT FIRST TRA 9/10/2000 3:01 PM 20:01: /10/2000 3:01 PM 20:01: /10/2000 3:01 PM 20:01: /10/2000 3:01 PM 20:01: ######## ######## ######## 9/10/2000 3:02 PM 20:02: /10/2000 3:02 PM 20:02: /10/2000 3:02 PM 20:02: /10/2000 3:02 PM 20:02: /10/2000 3:02 PM 20:02: /10/2000 3:02 PM 20:02: /10/2000 3:03 PM 20:03: /10/2000 3:03 PM 20:03: /10/2000 3:03 PM 20:03: /10/2000 3:03 PM 20:03: SECOND TRANSECT SECOND TRANSECT SECOND TRANSECT SECOND T 9/10/2000 3:03 PM 20:03: /10/2000 3:03 PM 20:03: /10/2000 3:04 PM 20:04: /10/2000 3:04 PM 20:04: /10/2000 3:04 PM 20:04: /10/2000 3:04 PM 20:04: /10/2000 3:04 PM 20:04: /10/2000 3:04 PM 20:04: /10/2000 3:05 PM 20:05: /10/2000 3:05 PM 20:05: /10/2000 3:05 PM 20:05: /10/2000 3:05 PM 20:05: /10/2000 3:05 PM 20:05:

157 Date Time T amb Theta Dew Pt RH H2O MR Wind Spee Wind Dir GPS GPS yyyy-mm-dd hh:mm:ss.s(c) (C) (C) (%) (g/kg) (m/s) (deg) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Onl FIRST TRANSECT FIRST TRANSECT FIRST TRANSECT FIRST TRANSECT 9/10/2000 3:01 PM /10/2000 3:01 PM /10/2000 3:01 PM /10/2000 3:01 PM ######## ######## ######## 9/10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:03 PM /10/2000 3:03 PM /10/2000 3:03 PM /10/2000 3:03 PM SECOND TRANSECT SECOND TRANSECTSECOND TRANSECT SECOND TRANSECT 9/10/2000 3:03 PM /10/2000 3:03 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:05 PM /10/2000 3:05 PM /10/2000 3:05 PM /10/2000 3:05 PM /10/2000 3:05 PM

158 Date Time UV sky UV gnd PCASP tot FSSP total bap O3 CO GPS GPS yyyy-mm-dd hh:mm:ss.s(w/m^2) (W/m^2) (m^-3) (m^-3) (m^-1) (ppbv) (ppbv) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** FIRST TRANSECT FIRST TRANSECT FIRST TRANSECT FIRST TRANSECT 9/10/2000 3:01 PM E /10/2000 3:01 PM E /10/2000 3:01 PM E /10/2000 3:01 PM E ######## ######## ######## 9/10/2000 3:02 PM E /10/2000 3:02 PM E /10/2000 3:02 PM E /10/2000 3:02 PM E /10/2000 3:02 PM E /10/2000 3:02 PM E /10/2000 3:03 PM E /10/2000 3:03 PM E /10/2000 3:03 PM E /10/2000 3:03 PM E SECOND TRANSECT SECOND TRANSECT SECOND TRANSECT SECOND TRANSECT 9/10/2000 3:03 PM E /10/2000 3:03 PM E /10/2000 3:04 PM E /10/2000 3:04 PM E /10/2000 3:04 PM E /10/2000 3:04 PM E /10/2000 3:04 PM E /10/2000 3:04 PM E /10/2000 3:05 PM E /10/2000 3:05 PM E /10/2000 3:05 PM E /10/2000 3:05 PM E /10/2000 3:05 PM E

159 Date Time SO2 NO NO2 NOy DelO3 NOz DelO3 GPS GPS onstant bg by yyyy-mm-dd hh:mm:ss.s(ppbv) (ppbv) (ppbv) (ppbv) bg transet ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Onl FIRST TRANSECT 9/10/2000 3:01 PM /10/2000 3:01 PM /10/2000 3:01 PM /10/2000 3:01 PM ######## ######## ######## 9/10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:03 PM /10/2000 3:03 PM /10/2000 3:03 PM /10/2000 3:03 PM SECOND TRANSECT 9/10/2000 3:03 PM /10/2000 3:03 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:05 PM /10/2000 3:05 PM /10/2000 3:05 PM /10/2000 3:05 PM /10/2000 3:05 PM

160 Date Time OPE %OX %OX NOy NOz %OX GPS GPS (inst) no bg or norm by *1.3(byNOx) by Noy hange yyyy-mm-dd hh:mm:ss.ss 76% ***Seleted Data*** ***Seleted Data*** ***FPP Only*** ***FPP Only*** FIRST TRANSECT 9/10/2000 3:01 PM #DIV/0! #VALUE! % /10/2000 3:01 PM #DIV/0! #VALUE! % /10/2000 3:01 PM % % /10/2000 3:01 PM % % ######## 44% ######## ######## 9/10/2000 3:02 PM % % /10/2000 3:02 PM % % /10/2000 3:02 PM % % /10/2000 3:02 PM % % /10/2000 3:02 PM % % /10/2000 3:02 PM % % /10/2000 3:03 PM % % /10/2000 3:03 PM % % /10/2000 3:03 PM % % /10/2000 3:03 PM % % SECOND TRANSECT 9/10/2000 3:03 PM % % /10/2000 3:03 PM % % /10/2000 3:04 PM 0.00 #VALUE! % /10/2000 3:04 PM % % /10/2000 3:04 PM % % /10/2000 3:04 PM % % /10/2000 3:04 PM % % /10/2000 3:04 PM % % /10/2000 3:05 PM % % /10/2000 3:05 PM % % /10/2000 3:05 PM % % /10/2000 3:05 PM % % /10/2000 3:05 PM % %

161 Date Time NOy NOz %OX GPS GPS bg orret bg orret bg orret yyyy-mm-dd hh:mm:ss.ss ***Seleted Data*** ***FPP Only*** FIRST TRANSECT /10/2000 3:01 PM /10/2000 3:01 PM /10/2000 3:01 PM /10/2000 3:01 PM ######## ######## ######## /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:02 PM /10/2000 3:03 PM /10/2000 3:03 PM /10/2000 3:03 PM /10/2000 3:03 PM SECOND TRANSECT 9/10/2000 3:03 PM /10/2000 3:03 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:04 PM /10/2000 3:05 PM /10/2000 3:05 PM /10/2000 3:05 PM /10/2000 3:05 PM /10/2000 3:05 PM

162 Date Time Time Lat Long Alt Stati P P altitude GPS GPS GPS yyyy-mm-dd hh:mm:ss.shh:mm:ss.ss(deg) (deg) (m) (mb) (m) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** 9/10/2000 3:05 PM 20:05: /10/2000 3:06 PM 20:06: /10/2000 3:06 PM 20:06: /10/2000 3:06 PM 20:06: /10/2000 3:06 PM 20:06: /10/2000 3:06 PM 20:06: /10/2000 3:06 PM 20:06: /10/2000 3:07 PM 20:07: /10/2000 3:07 PM 20:07: /10/2000 3:07 PM 20:07: /10/2000 3:07 PM 20:07: /10/2000 3:07 PM 20:07: /10/2000 3:07 PM 20:07: /10/2000 3:08 PM 20:08: /10/2000 3:08 PM 20:08: /10/2000 3:08 PM 20:08: /10/2000 3:08 PM 20:08: /10/2000 3:08 PM 20:08: /10/2000 3:08 PM 20:08: /10/2000 3:09 PM 20:09: /10/2000 3:09 PM 20:09: /10/2000 3:09 PM 20:09: /10/2000 3:09 PM 20:09: /10/2000 3:09 PM 20:09: /10/2000 3:09 PM 20:09: THIRD TRANSECT THIRD TRANSECT THIRD TRANSECT THIRD TRA 9/10/2000 3:10 PM 20:10: /10/2000 3:10 PM 20:10: /10/2000 3:10 PM 20:10: /10/2000 3:10 PM 20:10: /10/2000 3:10 PM 20:10: /10/2000 3:10 PM 20:10: /10/2000 3:11 PM 20:11: /10/2000 3:11 PM 20:11: /10/2000 3:11 PM 20:11: /10/2000 3:11 PM 20:11: /10/2000 3:11 PM 20:11: /10/2000 3:11 PM 20:11: /10/2000 3:12 PM 20:12: /10/2000 3:12 PM 20:12:

163 Date Time T amb Theta Dew Pt RH H2O MR Wind Spee Wind Dir GPS GPS yyyy-mm-dd hh:mm:ss.s(c) (C) (C) (%) (g/kg) (m/s) (deg) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Onl 9/10/2000 3:05 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM THIRD TRANSECT THIRD TRANSECT THIRD TRANSECT THIRD TRANSECT 9/10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:12 PM /10/2000 3:12 PM

164 Date Time UV sky UV gnd PCASP tot FSSP total bap O3 CO GPS GPS yyyy-mm-dd hh:mm:ss.s(w/m^2) (W/m^2) (m^-3) (m^-3) (m^-1) (ppbv) (ppbv) ***Seleted Data*** ***FPP Only*** 9/10/2000 3:05 PM E /10/2000 3:06 PM E /10/2000 3:06 PM E /10/2000 3:06 PM E /10/2000 3:06 PM E /10/2000 3:06 PM E /10/2000 3:06 PM E /10/2000 3:07 PM E /10/2000 3:07 PM E /10/2000 3:07 PM E /10/2000 3:07 PM E /10/2000 3:07 PM E /10/2000 3:07 PM E /10/2000 3:08 PM E /10/2000 3:08 PM E /10/2000 3:08 PM E /10/2000 3:08 PM E /10/2000 3:08 PM E /10/2000 3:08 PM E /10/2000 3:09 PM E /10/2000 3:09 PM E /10/2000 3:09 PM E /10/2000 3:09 PM E /10/2000 3:09 PM E /10/2000 3:09 PM E THIRD TRANSECT THIRD TRANSECT THIRD TRANSECT THIRD TRANSECT 9/10/2000 3:10 PM E /10/2000 3:10 PM E /10/2000 3:10 PM E /10/2000 3:10 PM E /10/2000 3:10 PM E /10/2000 3:10 PM E /10/2000 3:11 PM E /10/2000 3:11 PM E /10/2000 3:11 PM E /10/2000 3:11 PM E /10/2000 3:11 PM E /10/2000 3:11 PM E /10/2000 3:12 PM E /10/2000 3:12 PM E

165 Date Time SO2 NO NO2 NOy DelO3 NOz DelO3 GPS GPS onstant bg by yyyy-mm-dd hh:mm:ss.s(ppbv) (ppbv) (ppbv) (ppbv) bg transet ***Seleted Data*** ***FPP Only*** /10/2000 3:05 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM THIRD TRANSECT /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:12 PM /10/2000 3:12 PM

166 Date Time OPE %OX %OX NOy NOz %OX GPS GPS (inst) no bg or norm by *1.3(byNOx) by Noy hange yyyy-mm-dd hh:mm:ss.ss 76% ***Seleted Data*** ***FPP Only*** /10/2000 3:05 PM % % /10/2000 3:06 PM % % /10/2000 3:06 PM % % /10/2000 3:06 PM % % /10/2000 3:06 PM % % /10/2000 3:06 PM % % /10/2000 3:06 PM % % /10/2000 3:07 PM % % /10/2000 3:07 PM % % /10/2000 3:07 PM % % /10/2000 3:07 PM % % /10/2000 3:07 PM % % /10/2000 3:07 PM % % /10/2000 3:08 PM % % /10/2000 3:08 PM % % /10/2000 3:08 PM % % /10/2000 3:08 PM % % /10/2000 3:08 PM % % /10/2000 3:08 PM % % /10/2000 3:09 PM % % /10/2000 3:09 PM % % /10/2000 3:09 PM % % /10/2000 3:09 PM #VALUE! % 1 9/10/2000 3:09 PM 9/10/2000 3:09 PM THIRD TRANSECT #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:10 PM % % /10/2000 3:10 PM % % /10/2000 3:10 PM % % /10/2000 3:10 PM % % /10/2000 3:10 PM % % /10/2000 3:10 PM % % /10/2000 3:11 PM % % /10/2000 3:11 PM % % /10/2000 3:11 PM % % /10/2000 3:11 PM % % /10/2000 3:11 PM % % /10/2000 3:11 PM % % /10/2000 3:12 PM % /10/2000 3:12 PM %

167 Date Time NOy NOz %OX GPS GPS bg orret bg orret bg orret yyyy-mm-dd hh:mm:ss.ss ***Seleted Data*** ***FPP Only*** /10/2000 3:05 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:06 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:07 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:08 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM /10/2000 3:09 PM #VALUE! #VALUE! 9/10/2000 3:09 PM /10/2000 3:09 PM THIRD TRANSECT #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:10 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:11 PM /10/2000 3:12 PM 9/10/2000 3:12 PM 155

168 Date Time Time Lat Long Alt Stati P P altitude GPS GPS GPS yyyy-mm-dd hh:mm:ss.shh:mm:ss.ss(deg) (deg) (m) (mb) (m) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** 9/10/2000 3:12 PM 20:12: /10/2000 3:12 PM 20:12: /10/2000 3:12 PM 20:12: /10/2000 3:12 PM 20:12: /10/2000 3:13 PM 20:13: /10/2000 3:13 PM 20:13: /10/2000 3:13 PM 20:13: /10/2000 3:13 PM 20:13: /10/2000 3:13 PM 20:13: /10/2000 3:13 PM 20:13: /10/2000 3:14 PM 20:14: /10/2000 3:14 PM 20:14: /10/2000 3:14 PM 20:14: /10/2000 3:14 PM 20:14: /10/2000 3:14 PM 20:14: /10/2000 3:14 PM 20:14: /10/2000 3:15 PM 20:15: /10/2000 3:15 PM 20:15: /10/2000 3:15 PM 20:15: FOURTH TRANSECT FOURTH TRANSECT FOURTH TRANSECT FOURTH T 9/10/2000 3:15 PM 20:15: /10/2000 3:15 PM 20:15: /10/2000 3:15 PM 20:15: /10/2000 3:16 PM 20:16: /10/2000 3:16 PM 20:16: /10/2000 3:16 PM 20:16: /10/2000 3:16 PM 20:16: /10/2000 3:16 PM 20:16: /10/2000 3:16 PM 20:16: /10/2000 3:17 PM 20:17: /10/2000 3:17 PM 20:17: /10/2000 3:17 PM 20:17: /10/2000 3:17 PM 20:17: /10/2000 3:17 PM 20:17: /10/2000 3:17 PM 20:17: /10/2000 3:18 PM 20:18: /10/2000 3:18 PM 20:18: /10/2000 3:18 PM 20:18:

169 Date Time T amb Theta Dew Pt RH H2O MR Wind Spee Wind Dir GPS GPS yyyy-mm-dd hh:mm:ss.s(c) (C) (C) (%) (g/kg) (m/s) (deg) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Onl 9/10/2000 3:12 PM /10/2000 3:12 PM /10/2000 3:12 PM /10/2000 3:12 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:15 PM /10/2000 3:15 PM /10/2000 3:15 PM FOURTH TRANSECT FOURTH TRANSECT FOURTH TRANSECT FOURTH TRANSECT 9/10/2000 3:15 PM /10/2000 3:15 PM /10/2000 3:15 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:18 PM /10/2000 3:18 PM /10/2000 3:18 PM

170 Date Time UV sky UV gnd PCASP tot FSSP total bap O3 CO GPS GPS yyyy-mm-dd hh:mm:ss.s(w/m^2) (W/m^2) (m^-3) (m^-3) (m^-1) (ppbv) (ppbv) ***Seleted Data*** ***FPP Only*** 9/10/2000 3:12 PM E /10/2000 3:12 PM E /10/2000 3:12 PM E /10/2000 3:12 PM E /10/2000 3:13 PM E /10/2000 3:13 PM E /10/2000 3:13 PM E /10/2000 3:13 PM E /10/2000 3:13 PM E /10/2000 3:13 PM E /10/2000 3:14 PM E /10/2000 3:14 PM E /10/2000 3:14 PM E /10/2000 3:14 PM E /10/2000 3:14 PM E /10/2000 3:14 PM E /10/2000 3:15 PM E /10/2000 3:15 PM E /10/2000 3:15 PM E FOURTH TRANSECT FOURTH TRANSECT FOURTH TRANSECT FOURTH TRANSECT 9/10/2000 3:15 PM E /10/2000 3:15 PM E /10/2000 3:15 PM E /10/2000 3:16 PM E /10/2000 3:16 PM E /10/2000 3:16 PM E /10/2000 3:16 PM E /10/2000 3:16 PM E /10/2000 3:16 PM E /10/2000 3:17 PM E /10/2000 3:17 PM E /10/2000 3:17 PM E /10/2000 3:17 PM E /10/2000 3:17 PM E /10/2000 3:17 PM E /10/2000 3:18 PM E /10/2000 3:18 PM E /10/2000 3:18 PM E

171 Date Time SO2 NO NO2 NOy DelO3 NOz DelO3 GPS GPS onstant bg by yyyy-mm-dd hh:mm:ss.s(ppbv) (ppbv) (ppbv) (ppbv) bg transet ***Seleted Data*** ***FPP Only*** /10/2000 3:12 PM /10/2000 3:12 PM /10/2000 3:12 PM /10/2000 3:12 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:15 PM /10/2000 3:15 PM /10/2000 3:15 PM FOURTH TRANSECT 2.2 1/1/ /10/2000 3:15 PM /10/2000 3:15 PM /10/2000 3:15 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:18 PM /10/2000 3:18 PM /10/2000 3:18 PM

172 Date Time OPE %OX %OX NOy NOz %OX GPS GPS (inst) no bg or norm by *1.3(byNOx) by Noy hange yyyy-mm-dd hh:mm:ss.ss 76% ***Seleted Data*** ***FPP Only*** /10/2000 3:12 PM % % /10/2000 3:12 PM % % /10/2000 3:12 PM % % /10/2000 3:12 PM % % /10/2000 3:13 PM % % /10/2000 3:13 PM % % /10/2000 3:13 PM % % /10/2000 3:13 PM % % /10/2000 3:13 PM % % /10/2000 3:13 PM % % /10/2000 3:14 PM % % /10/2000 3:14 PM % % /10/2000 3:14 PM % % /10/2000 3:14 PM % % /10/2000 3:14 PM % % /10/2000 3:14 PM % % /10/2000 3:15 PM % % /10/2000 3:15 PM % % /10/2000 3:15 PM % % % % FOURTH TRANSECT % % % % /10/2000 3:15 PM #VALUE! % 1 9/10/2000 3:15 PM 9/10/2000 3:15 PM 9/10/2000 3:16 PM 9/10/2000 3:16 PM #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:16 PM #VALUE! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:16 PM % % /10/2000 3:16 PM % % /10/2000 3:16 PM % % /10/2000 3:17 PM % % /10/2000 3:17 PM % % /10/2000 3:17 PM % % /10/2000 3:17 PM % % /10/2000 3:17 PM % % /10/2000 3:17 PM % % /10/2000 3:18 PM % % /10/2000 3:18 PM % % /10/2000 3:18 PM % %

173 Date Time NOy NOz %OX GPS GPS bg orret bg orret bg orret yyyy-mm-dd hh:mm:ss.ss ***Seleted Data*** ***FPP Only*** /10/2000 3:12 PM /10/2000 3:12 PM /10/2000 3:12 PM /10/2000 3:12 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:13 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:14 PM /10/2000 3:15 PM /10/2000 3:15 PM /10/2000 3:15 PM FOURTH TRANSECT /10/2000 3:15 PM #VALUE! #VALUE! 9/10/2000 3:15 PM /10/2000 3:15 PM /10/2000 3:16 PM /10/2000 3:16 PM #VALUE! #VALUE! #VALUE! 9/10/2000 3:16 PM #VALUE! #VALUE! #VALUE! 9/10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:16 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:17 PM /10/2000 3:18 PM /10/2000 3:18 PM /10/2000 3:18 PM

174 Date Time Time Lat Long Alt Stati P P altitude GPS GPS GPS yyyy-mm-dd hh:mm:ss.shh:mm:ss.ss(deg) (deg) (m) (mb) (m) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** 9/10/2000 3:18 PM 20:18: /10/2000 3:18 PM 20:18: /10/2000 3:18 PM 20:18: /10/2000 3:19 PM 20:19: /10/2000 3:19 PM 20:19: /10/2000 3:19 PM 20:19: /10/2000 3:19 PM 20:19: /10/2000 3:19 PM 20:19: /10/2000 3:19 PM 20:19: FIFTH TRANSECT FIFTH TRANSECT FIFTH TRANSECT FIFTH TRA 9/10/2000 3:20 PM 20:20: /10/2000 3:20 PM 20:20: /10/2000 3:20 PM 20:20: /10/2000 3:20 PM 20:20: /10/2000 3:20 PM 20:20: /10/2000 3:20 PM 20:20: /10/2000 3:21 PM 20:21: /10/2000 3:21 PM 20:21: /10/2000 3:21 PM 20:21: /10/2000 3:21 PM 20:21: /10/2000 3:21 PM 20:21: /10/2000 3:21 PM 20:21: /10/2000 3:22 PM 20:22: ######## Hi/Lo LAT Hi/Lo LON Hi/Lo UTMxHi/Lo UTMy ######## DELTAX ######## /10/2000 3:22 PM 20:22: /10/2000 3:22 PM 20:22: /10/2000 3:22 PM 20:22: /10/2000 3:22 PM 20:22: /10/2000 3:22 PM 20:22: /10/2000 3:23 PM 20:23: /10/2000 3:23 PM 20:23: /10/2000 3:23 PM 20:23: /10/2000 3:23 PM 20:23: /10/2000 3:23 PM 20:23: /10/2000 3:23 PM 20:23: /10/2000 3:24 PM 20:24: /10/2000 3:24 PM 20:24: /10/2000 3:24 PM 20:24: /10/2000 3:24 PM 20:24:

175 Date Time T amb Theta Dew Pt RH H2O MR Wind Spee Wind Dir GPS GPS yyyy-mm-dd hh:mm:ss.s(c) (C) (C) (%) (g/kg) (m/s) (deg) ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted Data*** ***Seleted ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Only*** ***FPP Onl 9/10/2000 3:18 PM /10/2000 3:18 PM /10/2000 3:18 PM /10/2000 3:19 PM /10/2000 3:19 PM /10/2000 3:19 PM /10/2000 3:19 PM /10/2000 3:19 PM /10/2000 3:19 PM FIFTH TRANSECT FIFTH TRANSECT FIFTH TRANSECT FIFTH TRANSECT 9/10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:22 PM ######## ######## DELTAY ######## km aross the stinkin plume 9/10/2000 3:22 PM /10/2000 3:22 PM /10/2000 3:22 PM /10/2000 3:22 PM /10/2000 3:22 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:24 PM /10/2000 3:24 PM /10/2000 3:24 PM /10/2000 3:24 PM

176 Date Time UV sky UV gnd PCASP tot FSSP total bap O3 CO GPS GPS yyyy-mm-dd hh:mm:ss.s(w/m^2) (W/m^2) (m^-3) (m^-3) (m^-1) (ppbv) (ppbv) ***Seleted Data*** ***FPP Only*** 9/10/2000 3:18 PM E /10/2000 3:18 PM E /10/2000 3:18 PM E /10/2000 3:19 PM E /10/2000 3:19 PM E /10/2000 3:19 PM E /10/2000 3:19 PM E /10/2000 3:19 PM E /10/2000 3:19 PM E FIFTH TRANSECT FIFTH TRANSECT FIFTH TRANSECT FIFTH TRANSECT 9/10/2000 3:20 PM E /10/2000 3:20 PM E /10/2000 3:20 PM E /10/2000 3:20 PM E /10/2000 3:20 PM E /10/2000 3:20 PM E /10/2000 3:21 PM E /10/2000 3:21 PM E /10/2000 3:21 PM E /10/2000 3:21 PM E /10/2000 3:21 PM E /10/2000 3:21 PM E /10/2000 3:22 PM E ######## ######## ######## 9/10/2000 3:22 PM E /10/2000 3:22 PM E /10/2000 3:22 PM E /10/2000 3:22 PM E /10/2000 3:22 PM E /10/2000 3:23 PM E /10/2000 3:23 PM E /10/2000 3:23 PM E /10/2000 3:23 PM E /10/2000 3:23 PM E /10/2000 3:23 PM E /10/2000 3:24 PM E /10/2000 3:24 PM E /10/2000 3:24 PM E /10/2000 3:24 PM E

177 Date Time SO2 NO NO2 NOy DelO3 NOz DelO3 GPS GPS onstant bg by yyyy-mm-dd hh:mm:ss.s(ppbv) (ppbv) (ppbv) (ppbv) bg transet ***Seleted Data*** ***FPP Only*** 9/10/2000 3:18 PM /10/2000 3:18 PM /10/2000 3:18 PM /10/2000 3:19 PM /10/2000 3:19 PM /10/2000 3:19 PM /10/2000 3:19 PM /10/2000 3:19 PM /10/2000 3:19 PM FIFTH TRANSECT 9/10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:20 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:21 PM /10/2000 3:22 PM ######## ######## ######## 9/10/2000 3:22 PM /10/2000 3:22 PM /10/2000 3:22 PM /10/2000 3:22 PM /10/2000 3:22 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:23 PM /10/2000 3:24 PM /10/2000 3:24 PM /10/2000 3:24 PM /10/2000 3:24 PM

178 Date Time OPE %OX %OX NOy NOz %OX GPS GPS (inst) no bg or norm by *1.3(byNOx) by Noy hange yyyy-mm-dd hh:mm:ss.ss 76% ***Seleted Data*** ***FPP Only*** 9/10/2000 3:18 PM #DIV/0! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:18 PM % /10/2000 3:18 PM % /10/2000 3:19 PM % /10/2000 3:19 PM % /10/2000 3:19 PM % /10/2000 3:19 PM % /10/2000 3:19 PM % /10/2000 3:19 PM #DIV/0! 0.05 #VALUE! #VALUE! #DIV/0! % FIFTH TRANSECT #DIV/0! % #DIV/0! % 9/10/2000 3:20 PM #DIV/0! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:20 PM #DIV/0! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:20 PM #DIV/0! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:20 PM #DIV/0! 2.98 #VALUE! #VALUE! 9/10/2000 3:20 PM % % 9/10/2000 3:20 PM % % 9/10/2000 3:21 PM % % 9/10/2000 3:21 PM % % 9/10/2000 3:21 PM % /10/2000 3:21 PM % /10/2000 3:21 PM % /10/2000 3:21 PM % /10/2000 3:22 PM % % % ######## #DIV/0! % ######## #DIV/0! % ######## #DIV/0! % #DIV/0! % 9/10/2000 3:22 PM % /10/2000 3:22 PM % /10/2000 3:22 PM #DIV/0! #VALUE! #VALUE! 9/10/2000 3:22 PM #DIV/0! #VALUE! #VALUE! #VALUE! #VALUE! 9/10/2000 3:22 PM % /10/2000 3:23 PM % /10/2000 3:23 PM % /10/2000 3:23 PM % /10/2000 3:23 PM % /10/2000 3:23 PM % /10/2000 3:23 PM % /10/2000 3:24 PM % /10/2000 3:24 PM % /10/2000 3:24 PM % /10/2000 3:24 PM %

179 Date Time NOy NOz %OX GPS GPS bg orret bg orret bg orret yyyy-mm-dd hh:mm:ss.ss ***Seleted Data*** ***FPP Only*** 9/10/2000 3:18 PM 9/10/2000 3:18 PM 9/10/2000 3:18 PM 9/10/2000 3:19 PM 9/10/2000 3:19 PM 9/10/2000 3:19 PM 9/10/2000 3:19 PM 9/10/2000 3:19 PM 9/10/2000 3:19 PM FIFTH TRANSECT 9/10/2000 3:20 PM 9/10/2000 3:20 PM 9/10/2000 3:20 PM 9/10/2000 3:20 PM 9/10/2000 3:20 PM 9/10/2000 3:20 PM 9/10/2000 3:21 PM 9/10/2000 3:21 PM 9/10/2000 3:21 PM 9/10/2000 3:21 PM 9/10/2000 3:21 PM 9/10/2000 3:21 PM 9/10/2000 3:22 PM ######## ######## ######## 9/10/2000 3:22 PM 9/10/2000 3:22 PM 9/10/2000 3:22 PM 9/10/2000 3:22 PM 9/10/2000 3:22 PM 9/10/2000 3:23 PM 9/10/2000 3:23 PM 9/10/2000 3:23 PM 9/10/2000 3:23 PM 9/10/2000 3:23 PM 9/10/2000 3:23 PM 9/10/2000 3:24 PM 9/10/2000 3:24 PM 9/10/2000 3:24 PM 9/10/2000 3:24 PM 167

180 Table B-1. Loations and Distanes of G-1 Transets From FPP (based on flight data taken 9/10/2000 during TEXAQS). Item Latitude (degrees) Longitude (degrees) UTMx (m) UTMy (m) Distane from FPP (m) FPP N W Transet 1 N W ,680 Transet 2 N W ,700 Transet 3 N W ,540 Transet 4 N W ,590 Transet 5 N W ,980 Transet 6 N W ,

181 7 Transet 2 Transet 3 Transet 4 Transet 5 6 y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = NOz NOy Figure B-1. Correlation of NOz and NOy for FPP G-1 Data 09/10/ Transet 1 Transet 2 Transet 3 Transet 4 Transet 5 y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = NOx NOy Figure B-2. Correlation of NOx and NOy for FPP G-1 Data 09/10/

182 y = x R 2 = Slope of NOx/NOy Regression Plume Age (hr) Figure B-3. Cumulative Loss of NOx in FPP Plume (G-1 Data 09/10/2000). Transet 2 Transet 3 Transet 4 Transet 5 Transet y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = y = x R 2 = NOz [(NOy orreted )-NOx] NOy (Correted by NOx/NOy) Figure B-4. NOz/NOy (NOy Correted Based Upon Initial NOx/NOy Ratio of 1.3) 170

183 250 Meas-diretion Meas-speed Mod-diretion Mod-speed Wind diretion (deg) (from) Wind speed (m/s) :52 PM 3:00 PM 3:07 PM 3:14 PM 3:21 PM Fig Figure B-5. Wind Speed and Trajetory Comparison for July 9, 1995 (Mod) and FPP G-1 Data 09/10/2000 (Meas) Airraft Model 34 Wind diretion (deg) :52 PM 3:00 PM 3:07 PM 3:14 PM 3:21 PM Time (Airraft basis) Figure B-6. Temperature Comparison near FPP (July 9, 1995, and FPP G-1 Data 09/10/2000). 171

184 Figure B-7. Modeled Ozone; 3 p.m. on July 9,

185 Transet 1 Transet 2 Transet 3 Transet 4 Transet 5 Transet 6 15 y = 0.738x R 2 = 1 y = x y = x R 2 = y = x y = x R 2 = y = 7.022x R 2 = Delta O3 (Bakground orreted by Transet), ppb R 2 = R 2 = NOz, ppb Figure B-8. OPE by Transet for FPP Data Colleted 09/10/

186 APPENDIX C: Diurnal Sensitivity Figures and Spreadsheet Data Methods for Temporal Sensitivity Modeling 1. Find the time-resolved emission rate for the soure of interest. use ptsumpig.f, referene a CAMx-ready point soure emission file to print out data 2. Determine how you wish to normalize the emissions, and reate a spreadsheet whih will alulate fators to hange the emission rates in the CAMx-ready point soure file to the normalized value. The spreadsheet fator.generator.xls is available on disk; the only requirement for the fator file is that it be text tab delimited. 3. Compile and run ptmodpig.f to reate a new emissions file, using the fator file you have reated. Save the file under a name in your diretory. 4. Change a CAMx runsript to referene the new point soure file. 5. Rename the runsript so that it reflets the goal of the run (i.e., pssafull implies full, normalized emissions for the City Publi Servie plant in San Antonio.) 6. Run CAMx. (at the prompt, nohup./[runsript name]) 7. You will need to reate the following runs: Normalized, full emissions ase. Half of the above emissions rate. Emissions inrease bak to full for 2-hr periods 174

187 8. The data from these runs an be analyzed by ompiling and running psettemp.f (C-shell runsripts for various timeslots are available on disk) 9. The output of psettemp.f should be ompiled into a spreadsheet, suh as the ones inluded on disk (psettemp.xls, psettemp3pm.xls, and psettemp5pm.xls). This spreadsheet allows generation of impat assessments. Bar harts, as in Chapter IV Spatial analysis, as in Figure 4-7. Generated using Arview. 10. Additional omparison of modeled output to airraft data: use the On-Off CAMx runs; proess the data using pset.f, and send the output to a file suh as pset_all3good.xls, inluded on disk. 11. Plot the O 3 vs the NOz that is reported in the output of pset.f, the slope is the OPE of the soure. Other analysis an be done to orrelate OPE with Plume Chemial Age. 12. If wishing to ompare the data to airraft data from the base ase, simply run airomp.f. This program assigns O 3 and NOz to UTM oordinates. These onentrations an then be ompared to airraft data taken at similar points in spae using Golden Surfer software. 175

188 Figure C hour Ozone Puff at 3pm on Day 3 due to 100% Emissions Inrease from Base Case (Base Case = 50% Redution per SB7). Figure C-2. Noon-2pm Ozone Puff at 3pm on Day 3 due to 100% Emissions Inrease from Base Case (Base Case = 50% Redution per SB7). 176

189 Figure C-3. 2am-4am Ozone Puff at 3pm on Day 3 due to 100% Emissions Inrease from Base Case (Base Case = 50% Redution per SB7). Figure C-4. 4am-6am Ozone Puff at 3pm on Day 3 due to 100% Emissions Inrease from Base Case (Base Case = 50% Redution per SB7). 177

190 Figure C-5. 8am-10am Ozone Puff at 3pm on Day 3 due to 100% Emissions Inrease from Base Case (Base Case = 50% Redution per SB7). 178

191 psettemp 2pm Total Moles Ozone in Plume Fration of Total Day 3 Day 4 Day 5 Day 6 Day 3 Day % -1% % 0% % 0% % 1% % 7% % 8% % 7% % 3% 24hr hr 100% 100% Moles O3 formed per Moles Original NOx emitted Emission Rate (tons/hr) Day 3 Day 4 Day 5 Day 6 Day 2 Day 3 Day hr **Emission Rate is 85.5%NO, 14.5 OPE in Plume Emission Rate (moles/hr) Day 3 Day 4 Day 5 Day 6 Day 2 Day 3 Day hr OPE in Plume Day 3 Day 4 Day 5 Day hr **OPEs are the slopes of the o3/hno3 plots for their respetive days. **Slopes were taken from OPE plots (ontained in this worksheet) 179

192 For Sinusoid Graph Moles O3 formed per Moles Original NOx emitted Day 5 Day 6 Day 3 Day 4 Day 5 Day 6 0% -1% % 1% % 8% % 9% % 8% % 4% % 6% % 4% % 100% 24hr Day 5 Day %NO2 for all days Day 5 Day

193 Puff position (defined by max O3) MaxO3 Gridell Data For Surfer Day X Y O3(mol) OPE Day Day Day Day Day Day Day Day Day 3 0 n/a Day Day 4 0 n/a Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day Day 3 0 Day Day Day 4 0 Day Day Day 5 0 Day Day Day hr 24hr Day Day Day Day Day Day Day Day

194 In UTM (for Arview): X Y MAXO3 OPE Day Day Day Day X Y MAXO3 OPE Day Day Day Day X Y MAXO3 OPE Day Day Day Day X Y MAXO3 OPE Day Day Day Day X Y MAXO3 OPE Day Day Day Day X Y MAXO3 OPE Day Day Day Day X Y MAXO3 OPE Day Day Day Day X Y MAXO3 OPE Day Day 3 0 Day Day 4 0 Day Day 5 0 Day Day hr X Y MAXO3 OPE Day Day Day Day

195 APPENDIX D: Episode Base Case Tables and Figures. D1-D6. D7-D12. D13-D18. Fayette Power Projet Emission Rates (Pre- and Post- Normalized) Maximum Ozone Conentration by Day (Spatial Plots). Maximum Ozone Contribution of Fayette Power Projet by Day 183

196 Figure D-1. Atual (top) and Normalized (bottom) Emission Rate for the Fayette Power Projet (July 7, 1995). Emission rate-1st day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day Emission rate-1st day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day 184

197 Figure D-2. Atual (top) and Normalized (bottom) Emission Rate for the Fayette Power Projet (July 8, 1995). Emission rate-2nd day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day Emission rate-2nd day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day 185

198 Figure D-3. Atual (top) and Normalized (bottom) Emission Rate for the Fayette Power Projet (July 9, 1995). Emission rate-3rd day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day Emission rate-3rd day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day 186

199 Figure D-4. Atual (top) and Normalized (bottom) Emission Rate for the Fayette Power Projet (July 10, 1995). Emission rate-4th day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day Emission rate-4th day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day 187

200 Figure D-5. Atual (top) and Normalized (bottom) Emission Rate for the Fayette Power Projet (July 11, 1995). Emission rate-5th day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day Emission rate-5th day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day 188

201 Figure D-6. Atual (top) and Normalized (bottom) Emission Rate for the Fayette Power Projet (July 12, 1995). Emission rate-6th day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day Emission rate-6th day Emission rate (tons NOx/hr) :00 4:00 8:00 12:00 16:00 20:00 0:00 Time of Day 189

202 Figure D-7. Maximum Modeled O 3 onentration for July 7,

203 Figure D-8. Maximum Modeled O 3 onentration for July 8,

204 Figure D-9. Maximum Modeled O 3 onentration for July 9,

205 Figure D-10. Maximum Modeled O 3 onentration for July 10,