SPECIATE and Speciation Tool Training - VOC and PM for Air ...

SPECIATE and Speciation Tool Training - VOC and PM for Air ...

SPECIATE and Preparing VOC and PM chemical speciation profiles for air quality modeling Madeleine Strum, EPA/OAQPS; Marc Menetrez, EPA/ORD 1 Emission Inventory Training Workshop May 17, 2018 TRAINERS Marc Menetrez, EPA ORD Madeleine Strum, EPA OAQPS 2 Emission Inventory Training Workshop May 17, 2018 COURSE OUTLINE 1:00 SPECIATE, SPECIATE 101 1:45 Speciation Concepts 2:15 Break 2:30 SPECIATE Data Gaps and Future Plan 3:30 Preparing Profiles for SMOKE 4:30 End of Class 3 Emission Inventory Training Workshop May 17, 2018 CLASS OBJECTIVES To introduce you to SPECIATE, its content and use

To introduce you to the SPECIATE Web Browser and its use To provide an opportunity to ask questions about SPECIATE To present the how the SPECIATE weight percent information gets converted to the speciation inputs used in SMOKE (GSPRO) 4 Emission Inventory Training Workshop May 17, 2018 SPECIATE 101 What is Speciation? What is SPECIATE? The SPECIATE Data Browser 5 Emission Inventory Training Workshop May 17, 2018 WHAT IS SPECIATION? Speciation disaggregates inventory species (e.g. VOC, PM2.5) into more detailed species VOC PM2.5 6

propane ethylene formaldehyde acetaldehyde ethanol etc. elemental carbon organic carbon nitrate sulfate aluminum silicon iron etc. Emission Inventory Training Workshop May 17, 2018 SPECIATION IN GENERAL (STEPS) 100 tons of VOC Solvent Utilization; Surface Coating; Architectural Coatings; Total: All Solvent Types in Autauga County, AL (SCC = 2401001000) 7 Profile Code: 8744 Composite Profile - Architectural

Coatings: Solvent Borne and Waterborne Emission Inventory Training Workshop May 17, 2018 50 tons mineral spirits 9 tons texanol 9 tons propylene glycol 5 tons ethylene glycol etc. SPECIATION IN GENERAL (SPECIATE) Assign Speciation Profile to source based on process (SCC) SPECIATE is EPAs repository of speciation profiles. SPECIATE 4.5 is the current version. Several hundred literature citations to SPECIATE have been found. 8 Emission Inventory Training Workshop May 17, 2018 WHAT IS SPECIATE? DATA SOURCES Peer-reviewed literature Source testing of

speciated emissions Other SPECIATE DATA USERS Input to Air Quality Models -- NEI Modeling Platform NEI PM species (EC, OC, etc) Source Apportionment/ Source Receptor Models Black Carbon Report to Congress Air Toxics Inventories Feedback on Data Gaps 9 Emission Inventory Training Workshop May 17, 2018 WHAT IS SPECIATE? (2) A repository for speciated emissions profiles A searchable Microsoft Access database Profiles for three air pollution emission types: Particulate Matter (PM) Total Organic Gases (TOG) Other Gases [Hg, NO/NO2/HONO, semivolatile organic compounds

(SVOC)] Available on EPA Website: https://www.epa.gov/air-emissions-modeling/speci ate-version-45-through-40 10 Emission Inventory Training Workshop May 17, 2018 WHAT IS SPECIATE? (3) Species include metals, ions, elements, organic and inorganic compounds PM profiles are size-segregated (PM10, PM2.5) Lots of metadata (references, test methods, notes, geographic region) Profiles are rated for quality judgement (J), vintage (V), number of data points (D) 11 Emission Inventory Training Workshop May 17, 2018 KEY TABLES IN SPECIATE PM_PROFILE GAS_PROFILE PM_SPECIES GAS_SPECIES

List of profiles Weight percents by profile and species ID SPECIES_PROPERTIES REFERENCE 12 Species ID, name, molecular weight, other IDs, formula, whether it is a HAP, non-VOC Citation or source of data Emission Inventory Training Workshop May 17, 2018 KEY SPECIATE QUERIES 13 Emission Inventory Training Workshop May 17, 2018 EXAMPLES USING MS ACCESS 1. How do I find a VOC profile that has Oil and Gas in the title? (106 of them, example: 95420 Oil and Gas Production - Composite Profile Glycol Dehydrator, Uinta Basin) A. How do I find the latest profiles? B. How would I know if a profile is for a specific geographic region? (Look at Region field for where test was conducted ) C. How do I get out the weight percentages for any one

profile? (View gas profiles or view PM profiles, filter on profile ID) 2. How do I find a PM profile that has "Combustion" in the title? (There are 248 of them, example: 91105, Residential Wood Combustion -Composite) 14 Emission Inventory Training Workshop May 17, 2018 KEY METADATA COLUMNS NOTES REGION T_METHOD (Test method for profile) ANYLMETHOD (analytical method specific to species in profile) DOCUMENT (Reference) TEST_YEAR P_DATE (Profile date) QUALITY CONTROLS ORIG_COMPO (original or composite) MASTER_POL LOWER_SIZE (PM only) UPPER_SIZE (PM only) 15 Emission Inventory Training Workshop May 17, 2018 THE SPECIATE DATA BROWSER Provides database access for the non-MS Access user

URL: https://cfpub.epa.gov/speciate/ On-Line demo Key strength of the browser is the ability to search for profiles, View them, and Download them to MS Excel for further manipulation 16 Emission Inventory Training Workshop May 17, 2018 SPECIATE DATA BROWSER QUERY How do I find a VOC profile that has Oil and Gas in its title? [Use Keyword Search] How would I know if a profile is for a specific geographic region? [View profile information. See 4th row.] How do I download profiles to MS Excel? [Add to Shopping Cart (but note its free) from Search page. Download cart.] 17 Emission Inventory Training Workshop May 17, 2018 SPECIATE 4.5 HIGHLIGHTS New Profiles (September 2016)

182 new PM profiles for a total of 3,782 291 new TOG profiles for a total of 2,170 No new Other Gases profiles for a total of 249 2,602 unique species Composite profiles for 85 source categories SPECIATE4.5 Profiles being used in modeling: Oil and Gas (TOG) Prescribed/wildfires (TOG) Brake & Tire (PM) Nonroad gas & diesel (TOG) Onroad CNG transit buses (PM) Natural gas combustion (PM) 18 Emission Inventory Training Workshop May 17, 2018 Profiles for SPECIATE5.0 (Spring

2019 release) Gas combustion composite (already using) Consumer Product and architectural coatings More region-specific oil & gas profiles (WY) Residential wood combustion profiles Coal combustion Midwest soil and road dust 19 Emission Inventory Training Workshop May 17, 2018 SPECIATION CONCEPTS 1. TOG (VOC) Gas" Profiles Terminology 2. PM Profiles and AE6 3. Assigning Inventory Sources to Profiles 4. VOC Integration 5. Composite Profiles 6. Gap-Filling Profiles 7. On-Road Speciation 8. Nonroad Speciation 9. Combination Profiles 20 Emission Inventory Training Workshop May 17, 2018 VOC/TOG TERMINOLOGY Gas Profiles in SPECIATE can be based on VOC or TOG

(see MASTER_POL field) Inventories have VOC (regulatory definition) TOG is Total Organic Gases TOG =VOC + exempt compounds (e.g., methane, ethane, various chlorinated fluorocarbons, acetone, perchloroethylene, volatile methyl siloxanes, etc.) TOG profiles have a factor that allow you to convert VOC to TOG. Googled and got this from CARB fact sheet 21 Emission Inventory Training Workshop May 17, 2018 definitions Emission Inventory Training Workshop May 17, 2018 22 VOC EXEMPTION INFORMATION Electronic Code of Federal Register where the VOC information is available under Title 40 Chapter I Subchapter C Part 51 Subpart F 51.100

http://www.ecfr.gov/cgi-bin/text-idx?SID=b77fd17146a534c225c8 557b5ed4a469&node=40:2.0.1.1.2.3.8.1&rgn=div8 EPAs Regulatory Definition of VOC VOC means any compound of carbon, excluding carbon monoxide, carbon dioxide, carbonic acid, metallic carbides or carbonates, and ammonium carbonate, which participates in atmospheric photochemical reactions. This includes any such organic compound other than the following, which have been determined to have negligible photochemical reactivity: .. 23 Emission Inventory Training Workshop May 17, 2018 CURRENT STATUS OF VOC EXEMPTION A VOC is exempt based on O3 formation List of Exempt VOC: 1. http://www.ecfr.gov/cgi-bin/text-idx?SID=b77fd17146a5 34c225c8557b5ed4a469&node=40:2.0.1.1.2.3.8.1&rgn =div8 2. Currently, we have about 70 exempt chemicals including methane and ethane. 3. More chemicals could be added to the list in future assessments. 24

Emission Inventory Training Workshop May 17, 2018 PROCESS OF VOC EXEMPTION Interim Guidance of 2005 (70 FR 5404654051) is the guiding process to assess the viability of a VOC exemption based on: 1. KOH: Reactivity with OH 2. MIR: Maximum Incremental Reactivity to form O3 3. Toxicity and environmental fate 4. GWP: Global Warming Potential 5. ODP: Ozone Depletion Potential 6. Viability as a better substitute for the same end-uses of other chemicals 25 Emission Inventory Training Workshop May 17, 2018 CONVERTING VOC TO TOG Ideally, when modeling you want TOG so you get all the species. TOG profiles have a factor that allow you to convert VOC to TOG. You can compute it VOC-to-TOG = 100/(sum of VOC percent) These factors are in the GSCNV SMOKE ancillary file. 26

Emission Inventory Training Workshop May 17, 2018 EXAMPLE TOG SPECIATION PROFILE (selected fields from the Query View Gas Profiles) VER SPECIES_PR P_NUM GAS_PROF CONT TOTA SIO VOCtoTO SPECI OPERTIES.N WEIGH BER ILE.NAME ROLS P_DATE L N G ES_ID AME T_PER VOC 0051 Flares Uncon Natural Gas trolled 05-Jan89 0051 Flares Uncon Natural Gas trolled 05-Jan89

100 3.2 0051 Flares Uncon Natural Gas trolled 05-Jan89 0051 Flares Uncon Natural Gas trolled 05-Jan89 100 3.2 2 438 Ethane 30 2 465

Formaldehyd e 20 100 3.2 2 529 Methane 20 100 3.2 2 671 Propane 30 YES YES

Assume you have 100 lb VOC from Flare How much propane? Mass of Propane = 100 lb VOC x (30/100) [lb propane/lb TOG] x [2 lb TOG /1 lb VOC] = 60 lb Emission Inventory Training Workshop May 17, 2018 27 Profiles in SPECIATE are a part of what is needed for AQ modeling Develop chemical-mechanism specific profiles from profiles in SPECIATE Assign sources to profiles PM2.5 SPECIATION- MODELING PROFILE EXAMPLE Example modeling speciation profile AE6 Model species definitions species species name description AE5 AE6 POC PEC PSO4

PNO3 PMFINE PNH4 Y Y Y Y Y N Y Y Y Y N Y PNCOM PFE PAL PSI PTI PCA PMG PK PMN PNA PCL

organic carbon elemental carbon sulfate nitrate unspeciated PM2.5 ammonium non-carbon organic matter iron aluminum silica titanium calcium magnesium potassium manganese sodium chloride N N N N N N N N N N N

Y Y Y Y Y Y Y Y Y Y Y PH2O PMOTHR water unspeciated PM2.5 N N Y Y Prescribed Burning Composite (91109) pollutant species massfrac PM2_5 POC

0.5019 PM2_5 PEC 0.1093 PM2_5 PSO4 0.0033 PM2_5 PNO3 0.0107 PM2_5 PNH4 0.0034 PM2_5 PAL

0.0005 PM2_5 PCA 0.0007 PM2_5 PCL 0.0024 PM2_5 PFE 0.0004 PM2_5 PK 0.0014 PM2_5 PMN

0.0001 PM2_5 PMOTHR 0.0125 PM2_5 PNA 0.0014 PM2_5 PNCOM 0.3513 PM2_5 PM2_5 PSI PTI 0.0001 0.0007

Emission Inventory Training Workshop May 17, 2018 29 HOW DO YOU KNOW THE PM2.5 PROFILE HAS WHAT YOU NEED? Example1 95126 Gas-fired process heater exhaust This one does NOT have what you need for AE6. Example 2 95462 Composite - Brake Wear This one does. Hints Composite profiles from Emissions Inventory of PM2.5 Trace Elements across the United States, Environ. Sci. Technol., 43 (15), pp 57905796, 2009 will have what you need. But, we did add more recent profiles as well (search for PNCOM or PH20). 30 Emission Inventory Training Workshop May 17, 2018 SIMPLIFIED PROFILES PM2.5 ONLY These are legacy profiles. They were used from AE5. Their function was superceded by the Speciation Tool. 31

Emission Inventory Training Workshop May 17, 2018 ASSIGNING SOURCES TO PROFILES GSREF Nonpoint (area) & Mobile (county level) You can assign profiles based on SCC and/or country/state/county. Provides no sub-county variation - If you want this, you need your source to be inventoried as a point source. Point You can assign based on SCC and/or country/state/county and/or facility, unit, process, release point. NE SM WOK E4 .5 You can assign a combination of multiple profiles to the same source (10% profile A, 35% profile B, 55% profile C). 32 Emission Inventory Training Workshop May 17, 2018 Examples of Profile Assignments SCC 3999999 Industrial Process, NEC

Assigned to profile 0000 - Overall Average (the King of Defaults) SCC 2811015001 Prescribed Forest Burning; Smoldering County=Autauga, AL Assigned to profile 95421 Composite Profile Prescribed fire southeast conifer forest SCC 2811015001 Prescribed Forest Burning; Smoldering County=Gila, AZ Assigned to profile 95422 Composite Profile Prescribed fire southwest conifer forest 33 Emission Inventory Training Workshop May 17, 2018 COMPOSITE PROFILES Often, a single study may be too specific to apply to an

inventory category or that study has multiple test scenarios or different operators. A composite profile combines these data into something usable. When creating a composite of different profiles, one can take the mean or median of each species from the various profiles being composited. When compositing individual SPECIATE profiles, see NOTES for the P_NUMBERS used in the composite. 34 Emission Inventory Training Workshop May 17, 2018 GAP-FILLING PROFILES This is DIFFERENT from Compositing It is adding missing species to a profile. Why? Some profiles may be missing species that are expected. (Be aware of this when assigning profiles.) We can create new profiles by filling in these species (gapfilling) from another profile. Use G to indicate which profiles are gap-filled and the NOTES field to give details. 35 Emission Inventory Training Workshop May 17, 2018

VOC INTEGRATION - CONCEPT Integration Process of taking select VOC HAPs from the HAP inventory and speciating the remaining VOC because it is generally believed that the HAP inventory is a better source of HAP emissions than the speciated VOC Want to avoid double counting of HAPs Want to speciate the remaining VOC taking into account HAPs that were removed NBAFM chosen as integration HAPs in 2014 Modeling Platform Naphthalene, Benzene, Acetaldehyde, Formaldehyde, Methanol These are explicit VOC HAPs in the CB6-CMAQ chemical mechanism. NONHAPVOC Remaining VOC after removing explicit VOC HAPs NONHAPVOC = VOC - NBAFM 36 Emission Inventory Training Workshop May 17, 2018 Integration Steps 37 Emission Inventory Training Workshop May 17, 2018

EXAMPLE OF INTEGRATED PROFILE 38 Emission Inventory Training Workshop May 17, 2018 WHY NOT INTEGRATE A SOURCE Point sources The State reports HAPs at a different process level than where they reported VOCs. So HAP is at the facility but there is no VOC at that process level to do the subtraction. There is misalignment of VOC and HAP even though both are reported. Nonpoint sources There are no inventory NBAFM emissions at the source. If there really shouldnt be, then remove NBAFM from the profile. NBAFM mass > VOC 39 Emission Inventory Training Workshop May 17, 2018 TWO APPROACHES TO NO-INTEGRATE 1) Dont use any HAPs from the HAP inventory. Use the profile to generate all model species - HAPs and nonHAPs. 2) Assume HAP inventory is better than speciation:

Use the HAP inventory (NBAFM) for model species Create TOG profiles that drop the mass of NBAFM. TOG profiles will have less than 100% of mass if the profile has NBAFM. 40 Emission Inventory Training Workshop May 17, 2018 VOC INTEGRATION BY SECTOR 41 Platform Sector * Approach for Integrating ptegu ptnonipm ptfire othafdust othar othon ag afdust biog nonpt np_oilgas pt_oilgas

rwc nonroad c1c2rail othpt c3marine onroad No integration No integration No integration No integration No integration No integration N/A sector contains no VOC N/A sector contains no VOC N/A contains specific VOC model species Partial integration (NBAFM) Partial integration (NBAFM) No integration Partial integration (NBAFM) Full integration (calculated in MOVES) Partial integration (NBAFM) Partial integration (NBAFM) Partial integration (NBAFM) Full integration (calculated in the MOVES model)* *See Modeling Platform technical support document for sector descriptions Emission Inventory Training Workshop May 17, 2018 (https://www.epa.gov/air-emissions-modeling).

ONROAD SPECIATION MOVES2014 does speciation within MOVES for onroad sources Uses outputs from the Speciation Tool Different profiles for different vehicle model years, regulatory classes, fuel types, and emission processes Previously used COMBO files or weighted profiles to approximate, but was a coarse approach PM2.5 AE6 species come directly from MOVES (in mass). VOC 16 pollutants are explicit, i.e. integrated. Model species (moles) and inventory pollutants (mass) come directly from MOVES. Need to specify chemical mechanism in the MOVES run 42 Emission Inventory Training Workshop May 17, 2018 ONROAD SPECIATION IN MOVES OTAQ MOVES Speciation profiles with all measured species (e.g., based on EPAct data)

Acetaldehyde TOG Formaldehyde Benzene Other individual toxics to be integrated TOG integrated toxics (NONHAPTOG) Speciate Tool Chemical mechanism for lumping measured species into CMAQ model species speciation Mapping of each integrated toxic Speciation of NONHAPTOG with

renormalized profile New CMAQ model species profiles renormalized without integrated toxics OAQPS Summed CMAQ model species SMOKE 43 CMAQ Emission Inventory Training Workshop May 17, 2018 NONROAD SPECIATION MOVES2014a provides nonroad emissions that are semi- speciated. Also provides individual HAPs - benzene, toluene, etc. And provides the remainder along with the profile code e.g. NONHAPTOG95327 is the pollutant name NONHAPTOG is the difference between TOG and the sum of the HAPs. 95327 is the profile code to use for NONHAPTOG. Unlike onroad, the speciation is done in SMOKE. Approach allows application of new chemical mechanisms in SMOKE without re-running MOVES.

44 Emission Inventory Training Workshop May 17, 2018 COMBINATION PROFILES SMOKE now has a method of combining two or more speciation profiles for a specific SCC/FIPS. Examples: Combine E0 and E10 fuel profiles Combine flare profile with oil & gas process profile 45 Emission Inventory Training Workshop May 17, 2018 COMBINATION PROFILES (cont.) Combine flare profile with oil & gas process profile Based on output from the Oil and Gas Tool (software & data that is used to develop EPA Oil and Gas estimates for the NEI) SCC PROFILE CODE POLLUTANT FIPS

FACTOR 2310021010 (Oil & Gas:OnShore Gas Prod;Cond. Storage Tank) SWFLA_R (Oil and Gas -SW Wyoming Basin Flash Gas Composition for Condensate Tanks) NONHAPVOC 56045 0.0456 2310021010 FLR99 (Natural Gas Flare Profile with DRE >98%) NONHAPVOC 56045 0.9544

46 Emission Inventory Training Workshop May 17, 2018 SPECIATE DATA GAPS AND FUTURE PLANS 47 Emission Inventory Training Workshop May 17, 2018 DATA GAP ANALYSIS AN ONGOING PROCESS Goal: Every inventory source is assigned to a good profile that best fits its source category. Are assignments appropriate? How good are the available profiles? What research is needed to meet the goal? Past Efforts: Analyses leading toward 2011 NEI Modeling Platform improvements Current Efforts: Gaps and needs analysis 48 Emission Inventory Training Workshop May 17, 2018 PAST EFFORT: 2008 NEI (2013

VOLUNTEER) Found low-hanging fruit in the 2008 NEI Platform Reviewed VOC emission profiles applied to SCCs that are the largest sources of VOCs Identified opportunities for Pulp & Paper Over 200 source operations linked to generic profiles Profile 1185: Coal Fired Boiler Industrial linked to eight largest operations (43 of 144 kTpy) The 2008 NEI had > 500 kTpy of TOG speciated with the default profile (0000). 49 Emission Inventory Training Workshop May 17, 2018 IMPACT OF MISMATCHED PROFILES Chemical Composition: Coal-Fired Boiler - Industrial vs. Pulp & Paper Mills - Kraft Mill Bleach Plants (wt.%) 100 10 1 0.1 0.01 0 0 Coal-Fired Boiler - Industrial Pulp and Paper Mills - Kraft Mill Bleach Plants 50

Emission Inventory Training Workshop May 17, 2018 PAST EFFORTS: 2011 NEI MODELING PLATFORM IMPROVEMENTS EPA developed and applied appropriate composite source profiles for the Pulp & Paper and Chemical Manufacturing sectors from SPECIATE emissions profiles. Pulp and Paper: 97 of 121 kTpy (80%) reassigned from profiles 0000 and 1185 Chemical Manufacturing: 20 of 90 kTpy (22%) reassigned from profile 0000 Composite profiles were added to SPECIATE 4.5. 51 Emission Inventory Training Workshop May 17, 2018 Assessment of Important SPECIATE Profiles in EPAs Emissions Modeling Platform and Current Data Gaps Casey Bray, NC State & EPA/ORD Intern Goals Elucidate profiles/categories of most importance for air quality modeling purposes Evaluate current profiles Identify and articulate research needs 52

Emission Inventory Training Workshop May 17, 2018 Major PM2.5 Profiles (% of mass assigned in 2014 EPA modeling platform)* - from Brays work *excludes emissions from the onroad mobile sector 53 Emission Inventory Training Workshop May 17, 2018 VOC PROFILES REGIONAL DIFFERENCES* (From Bray) Southwest: UT, CO, AZ, NM 953,352 tons/year Northeast: ME, NH, VT, RI, CT, NY, NJ, DE, PA, MD 823,885 tons/year *excludes emissions from the onroad and nonroad mobile sectors 54 Emission Inventory Training Workshop May 17, 2018 THE SPECIATE WORKGROUP AND FUTURE PLANS EPAs SPECIATE Workgroup Modelers tell us what is important Ongoing literature searches

Peer-reviewed journal articles preferred The Master List of references Needs Analysis Project - data gaps Please let us know if youve got data that could be added! 55 Emission Inventory Training Workshop May 17, 2018 FUTURE SPECIATE PLANS Release SPECIATE5.0 Spring 2019 Develop Standard Operating Procedure (SOP) for SPECIATE Profile Selection, Collection, and Entry Allow In-House Processing of Profiles Improve Documentation of Metrics and Processes Identify Key Metrics for Quality Profiles Formalize Prioritization Process ACCESS database structure improvements (including use of forms to add to profiles) Add new profiles 56 Emission Inventory Training Workshop May 17, 2018 SPECIATION FOR AQ

MODELING Emission Inventory Training Workshop May 17, 2018 57 SPECIATION STEPS IN MODELING TOOLS Speciation Tool: creates SMOKE ancillary files GSPRO and GSCNV Uses SPECIATE profiles Uses mechanism-specific chemical mapping, e.g., CB6 different from CB05 SMOKE: Uses GSREF to assign profiles to sources and uses ancillary files GSPRO and GSCNV to compute AQM emission files Emissions Modeling Framework: can be used as an interface for managing inventories and related data (profiles), and interface for running the Speciation Tool and SMOKE International Emissions Inventory Conference Emission Inventory Training

Baltimore, Workshop MD, May August 17, 2018 15, 2017 58 SPECIATION TOOL SPTOOL SPTOOL is a stand-alone tool that was developed to generate the GSPRO and GSCNV ancillary data SMOKE uses for speciation SPTOOL implemented using open source PostgreSQL database and Perl interface The latest SPTOOL install and User Guide can be downloaded from the EPA/CMAS website https://www.cmascenter.org/help/documentation.cfm? MODEL=speciation_tool&VERSION=4.0 Emission Inventory Training Workshop May 17, 2018

59 How to get SPECIATION TOOL? You can also look at slides from Baltimore Emission Inventory conference training which lists the steps to take to run it Emission Inventory Training Workshop May 17, 2018 60 DEFINITIONS terms you will see in the Speciation Tool instructions AQM Air Quality Model CMAQ, CAMx, etc. Model Species - Model species are used in the AQM o e.g., OLE, PAR, etc. in CB mechanisms

Profile list of mass fractions (or wt. %) of compounds Organic Compounds Organic compounds included in SPECIATE profiles o e.g., 1-Methylcyclopentene, isomers of hexane, etc. SPECIATE EPAs SPECIATE database SPTOOL The stand-alone Speciation Tool Emission Inventory Training Workshop May 17, 2018 61 ATMOSPHERIC CHEMISTRY IN AQM Atmospheric chemistry consists of millions of reactions among many thousands of chemical compounds

AQMs use a condensed chemical mechanism with a manageable number of reactions and model species CB05, CB6 SAPRC99, SAPRC07, SAPRC11 RACM2 CRIv2r5 etc. Emission Inventory Training Workshop May 17, 2018 62 PREPARING EMISSIONS FOR MODELING GSPRO contains factors to speciate

Split Factor: numerator for mole-based speciation Divisor: denominator for the mole-based speciation Split Factor/Divisor = moles of model species per mass of TOG For PM, divisor = 1 GSCNV contains VOC-to-TOG conversion factors to convert inventory VOC (or ROG) to TOG to apply TOGbased speciation profiles Emission Inventory Training Workshop May 17, 2018 63 SMOKE GSPRO and GSCNV files GSPRO sample profile Speciation profile number Pollutant ID (name) Species ID

(name) Split factor Divisor Mass Fraction 0051 TOG CH4 0.2 16.042 0.2 0051 TOG ETHA 0.3 30.069

0.3 0051 TOG FORM 0.2 30.026 0.2 0051 TOG PRPA 0.3 44.096 0.3 GSCNV sample

Name of Name of pollutant pollutant converting converting to from VOC TOG profile Speciation profile code Conversion factor 0051 2 Emission Inventory Training Workshop May 17, 2018 64 Example GSPRO records Poll is TOG

GSPRO sample Speciation Pollutant ID profile (name) number profile Species ID (name) Split factor Divisor Mass Fraction 0051 TOG CH4

0.2 16.042 0.2 0051 TOG ETHA 0.3 30.069 0.3 0051 TOG FORM 0.2 30.026 0.2

0051 TOG PRPA 0.3 44.096 0.3 Poll is NONHAPTOG (remove formaldehyde) Speciation Pollutant ID profile (name) number Species ID (name) Split factor Divisor Mass Fraction

0051 NONHAPTOG CH4 0.25 16.042 0.25 0051 NONHAPTOG ETHA 0.375 30.069 0.375 0051 NONHAPTOG PRPA

0.375 44.096 0.375 Emission Inventory Training Workshop May 17, 2018 65 Example GSPRO records using Inventory HAPs that are explicit in the chemical mechanism Inventory HAP Maps to Explicit CB6 HAP SMOKE converts from pollutant code to NAME GSPRO Speciation profile number sample Pollutant ID (SMOKE name)

records Species ID (name) Split factor Divisor Mass Fraction 0000 ACETALD ALD2 1 16.042 1 0000 FORMALD FORM 1

30.026 1 0000 BENZENE BENZ 1 78.1118 1 0000 METHANOL MEOH 1 32.0419 1 0000

NAPHTH NAPH 1 128.1705 1 Emission Inventory Training Workshop May 17, 2018 66 Example GSPRO records using inventory HAPs that are not explicit in the mechanism Inventory HAP Maps to Lumped CB6 SMOKE converts from pollutant code to NAME GSPRO sample Speciation Pollutant ID profile (SMOKE name)

number records Species ID (name) Split factor Divisor Mass Fraction 0000 STYRENE OLE 0.125 26.0373 1 0000 STYRENE TOL

0.875 91.1305 1 0000 PROPIONAL ALDX 0.6667 38.7194 1 0000 PROPIONAL PAR 0.3333 19.3597 1

Emission Inventory Training Workshop May 17, 2018 67 Example GSPRO records using inventory HAPs that are part of the air toxics version of CMAQ Inventory HAP maps to non CB6 HAP that is in CMAQ (version5.2) GSPRO sample records Speciation profile number Pollutant ID (SMOKE name) Species ID (name)

Split factor Divisor Mass Fraction 0000 ACETALD ALD2_PRIMARY 1 30.069 1 30.026 1 0000 converts FORMALD FORM_PRIMARY 1 SMOKE from pollutant code to NAME

0000 ACROLEI ACROLEIN 1 56.0633 1 0000 BUTADIE BUTADIENE13 1 54.0904 1 Emission Inventory Training Workshop May 17, 2018 68 GSPRO PM2.5 example GSPRO

sample records Speciation profile number Pollutant ID (SMOKE name) Species ID (name) Split factor Divisor Mass Fraction 95475 PM2_5 PAL 0.0078

1 0.0078 95475 PM2_5 PCA 0.0105 1 0.0105 95475 PM2_5 PCL 0.0275 1 0.0275 95475

PM2_5 PEC 0.0666 1 0.0666 95475 PM2_5 PFE 0.0156 1 0.0156 95475 PM2_5 PK 0.0037

1 0.0037 95475 PM2_5 PMOTHR 0.0565 1 0.0565 95475 PM2_5 PNCOM 0.1786 1 0.1786 95475

PM2_5 PNH4 0.0444 1 0.0444 95475 PM2_5 PNO3 0.0238 1 0.0238 95475 PM2_5 POC 0.4465

1 0.4465 95475 PM2_5 PSI 0.0243 1 0.0243 95475 PM2_5 PSO4 0.0943 1 0.0943 Emission Inventory Training Workshop May 17, 2018

69 Calcs done by SPTOOL to go from SPECIATE profile to GSPRO profile Spreadsheet Example Calcs: Sample_VOC_profile_calcs_speciate_training.xlsx Emission Inventory Training Workshop May 17, 2018 70 SPTOOL SOFTWARE REQUIREMENTS PostgreSQL can be downloaded from http://www.postgresql.org Perl and the database drivers can be downloaded from http://www.perl.com User must have database create privileges in PostgreSQL to run the Speciation Tool Emission Inventory Training Workshop May 17, 2018 71

RUN PARAMETERS MECH_BASIS select chemical mechanism to use OUTPUT select which output profiles to generate. Options are VOC for gas species and PM for particulates RUN_TYPE - The RUN_TYPE options are: CRITERIA, INTEGRATE, NOINTEGRATE, HAPLIST, and VBS AQM this parameter selects model-correct species names for output files TOLERANCE specifies acceptable deviation from 100% for the sum of weight percentages (default is 5%) Emission Inventory Training Workshop May 17, 2018 72

SPTOOL Frequently asked questions (1) What happens when an organic compound used by a profile lacks a defined molecular weight? Any detailed organic compound with an undefined molecular weight is dropped from the profile because a molecular weight is required to compute splits factors. Dropped mass fraction due to missing molecular weights may takes the profile sum outside the selected tolerance, causing the profile to be dropped. This problem should be resolved by specifying missing molecular weights in the species properties. Emission Inventory Training Workshop May 17, 2018 73 SPTOOL Frequently asked questions (2) What happens when an organic compound used by a profile lacks an assignment in the mechanism mapping? SPTOOL issues a warning and the compound is assigned to UNK When does SPTOOL renormalize a profile?

If the sum of mass fractions for a profile is not 100%, and nothing is done to correct the profile, subsequent SMOKE processing will not conserve mass. SPTOOL renormalizes all gas profiles whose sum is within the tolerance thereby preserving VOC mass. Profiles outside the tolerance are dropped and a warning is issued. For the AE6 PM profiles, when sum of AE6 PM species is less than 100%, the remaining mass gets assigned to PMOTHR (=100% - sum of AE6). When the sum is greater than 100%, the profiles are dropped with a warning. Emission Inventory Training Workshop May 17, 2018 74

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