Previous Project Information Page

Development of an Improved Chemical Speciation Database for Processing Emissions of Volatile Organic Compounds for Air Quality Models

By
William P. L. Carter
College of Engineering, Center for Environmental Research and Technology (CE-CERT)
University of California, Riverside, CA 92521

Database last updated April 1, 2013
Programs or input files last updated April 30, 2009
Database and documentation superceded on February, 2014. Click here for the current version.


NOTE: This has been superceded by a completely revised version of the database and its associated programs, which are available at http://www.cert.ucr.edu/~carter/emitdb. This page is provided as a link to the earlier programs and files

Contents
Project Description

Volatile organic compounds (VOCs) differ significantly in their effects on ozone formation, and these differences need to be represented appropriately in the airshed models used to predict the effects of changes of emissions on formation of ozone. This requires appropriate methods to specify the chemical compositions of the many types of VOCs that are emitted, and appropriate methods to represent the chemical differences of these compounds in the models. However, current models and emissions databases have significant problems in this regard:

To address these problems, the University of Houston (UH) funded us to begin the development of an improved chemical speciation database with assignments to the current SAPRC-99 mechanism, and the American Chemistry Council (ACC) funded us to further develop this database and develop the software and files needed to utilize this database to implement the SAPRC-99 and other chemical mechanisms into the SMOKE emissions processing system. The UH project has been completed, and the speciation database developed for this project is described below. The ACC project has also recently been completed and is also described below. The final report for this project, titled  "Integration of the SAPRC Chemical Mechanism in the SMOKE Emissions Processor for the CMAQ/Models-3 Airshed Model" is now available (PDF format).

More recently, we have been funded by Pecan and Associates to make model species classifications for species categories in the Speciate 4.0 database that is now under development. This has necessitated the addition of a number of additional categories, which are now included in the speciation database developed for the previous projects. As part of this effort, model speciation assignments were made for the new Carbon Bond '05 mechanism, so four mechanisms (SAPRC-99, RADM2, CB4, and CB05) are now supported by the current database.

The emissions speciation database assignments and profile data compiled for UH, ACC and Speciate 4.0 projects are given in Excel files that can be downloaded from the links below. However, ultimately we need the chemical assignments for the speciation profiles to be in a universally available, web accessible format that can be updated as needed using state-of-the-art database software.

Development of the Speciation Database for the University of Houston Project

The development of the speciation database carried out under contract with the University of Houston has involved the following components:

Summary and Progress to Date on the American Chemistry Council Project
Project Description and Objectives
Additional work on this speciation database has been initiated as part of a project being carried out by the University of North Carolina (UNC) and ourselves at CE-CERT to improve the integration of the SAPRC and other chemical mechanism into SMOKE modeling system within the Models-3 framework. This work is being funded by the ACC for the RRWG as described n the Project Description section, above. The specific objectives of this project are as follows: The following are optional tasks that may be carried out if funding is available. They would be carried out primarily by UNC. The latter tasks could not be carried out for this project because of limited resources and time. Given below is a brief summary of the progress to date on the tasks in this project being carried out at CE-CERT.
Profile Database
We obtained the profile data from Speciate 3.2 (Speciate 2002), and compiled it into an Excel database with updated profiles we obtained from the California ARB (CARB, 2003), and profiles we already had from the the EPA (Gipson, 2001), and for Texas (Yarwood, 2002). These are merged into an Excel file named profdb.xls, which also includes macros to output the profile data as ASCII files that can be read by the Profile Preprocessing program discussed below. We have also obtained updated Texas profiles from Gabriel Cantu of TCEQ, but have not yet incorporated them. Note that many of these profiles are the same, though we have not yet determined which are duplicates. This file is available for downloading and is described in more detail below.
Speciation Processing Programs
The work plan for this project calls for developing a series of FORTRAN programs so that the speciation database described above can be used when processing emissions with the SMOKE system. As presently formulated, these consist of four programs: the Profile Preprocessor (ProfPro), the Speciation Preprocessor (SpecPro), the Emissions Summary Processor (EmitSum), and the Mechanism Processor (MechPro). The relationships between these programs and relevant programs and files in the SMOKE and the CMAQ systems are shown in Figure 1, below. At the present time, the initial versions of all four programs have been written and preliminary documentation has been prepared, and preliminary versions of the programs and their input and output files are available (see below).  Work on implementing them into the SMOKE and CMAQ systems is underway. The files and programs discussed in the preliminary documentation are subject to change as this work proceeds.

Figure 1. Diagram showing relationships between SMOKE and the speciation database programs and files. Mechanism-dependent files are indicated by dashed borders. The programs completed thus far are indicated with bold ovals, and the program still to be completed for this project is shown with the dashed oval.

Description of the Speciation Assignment File

The current set of speciation assignments (which incorporates work on the ACC project that will be described later) is incorporated in an Excel 2000 file emitdb.xls, which can be downloaded as indicated below. The file includes a "documentation" sheet that describes in detail the format of all the other sheets, and also a number of Excel macros that can be used to process the data or output ASCII files with the mechanism assignments. Given below is a summary of all the sheets incorporated in the current database file.
 
Documentation Summarizes the purpose of each sheet and describes the columns or data fields they contain. Also gives the color conventions used throughout the file and reference citations for additional information on the mechanisms.
Parameters and Commands Gives the parameters or definitions used in the various sheets or macros, and also lists the macros used and gives controls that can be used to run them. See comments in the sheet for details.
Master List List of all the emissions classifications in my current database. Each class should be a unique compound or mixture.
Compounds Lists the emissions categories that refer to single compounds (or mixtures of isomers that are not distinguished, optical isomers), and gives their mechanistic assignments
Simple Mixes Lists the emissions categories that refer to mixtures of isomers, and summarizes their assignments to compounds. (Note that the assignments used are in a separate "Simple Mixes Asst's" sheet, and the assignments on this sheet are produced by the "CompileSimpMixAsnts" macro.)
Simple Mixes Asst's Used to give the assignments of compounds to the simple mixtures listed in the "Simple Mixes" sheet. One row is used for each assignment, so multiple rows will be used for mixtures assigned to more than one compound.
Complex Mixtures Gives summaries, compositional assignments, and other information about complex mixtures. Details of assignments and additional information about complex mixtures are given in separate sheets as indicated below.
Mix Profile Summary Gives summary information about the profiles used to specify the compositions of some of the complex mixtures. The profiles are associated with the complex mixtures in the "Assignment of Mwt" column in the "Complex Mixtures" sheet for the mixtures with assignment type given as "CMP". The composition of the profiles is given in the "Mix Profile Assignments" sheet, and additional documentation notes are given in the "Profile Documentation Notes" sheet.
Mix Profile Assignments Gives composition assigned to the profiles used to specify the compositions of some of the complex mixtures. One row is given for each component assigned to a profile, so in general a profile will have more than one column.
Profile Documentation Notes Footnotes corresponding to numbers given in the "notes" column of the mixture profile summary sheet, giving additional information about the derivation of the composition of the mixture profiles used.
Other Categories Lists and gives summary and other information about the emissions classifications that are poorly defined or inappropriate or have not yet been categorized. These include (1) compounds or mixtures that are not appropriate for VOC profiles; (2) Polymers, salts, or extremely high molecular weight materials; (3) categories that are not compounds or mixtures, such as elements or CB4 model species; (4) categories that are designated incorrectly or are too ambiguous to assign; (5) categories that may be compounds or mixtures of compounds but the compounds' structures could not be determined or have not yet been determined. (6) categories that have not yet been classified because they are not present or are extremely minor constituents in current profiles.
Emissions Groups Gives the table of SAPRC-99 and emissions groups and the SAPRC-99 and RADM-2 lumped model species associated with each.
DMS Lists SAPRC-99 detailed model species and gives relevant summary information, including lumped emissions groups assigned to each.
Master Assignments Gives the complete mechanism assignments for all of the emissions categories in the database. All data on the sheet except the headers are derived using the "MergeAllCmpds" macro. Multiple rows are given for categories represented by more than one compound, one per compound used.
SAROAD Assignments Assigns master emissions database categories to the SAROAD or chemical codes used in the EPA, California ARB, TNRCC, and Speciate 3.2 and 4.0 emissions databases. Also gives the complete mechanism assignments for these categories. The latter are derived by running the "ProcessSARmodelSpec" macro.
Emit Worksheet Can be used as an example to derive detailed and lumped model species assignments for an emissions profile given in terms of a given type of SAROAD or pseudo-SAROAD categories.

The file incorporates several macros to output the data in the spreadsheet into various ASCII files that can be read by the speciation database processing programs that are being developed for the ACC project discussed above.

The current version of the speciation assignment file can be downloaded from ../emitdb/emitdb.xls

Profile Database File

The profile database file contains the profiles in the Speciate 3.2 database (Speciate, 2002), the profiles used by the EPA for processing emissions for Models-3 (Gipson, 2001), the Texas Natural Resource Conservation Commission (TNRCC) (Yarwood, 2002), and the profiles provided by the California Air Resources Board (CARB, 2003). The file contains a "documentation" sheet that describes the data in the file. Given below is a summary of the sheets incorporated in the current file.
 
Documentation Summarizes the purpose of each sheet and describes the columns or data fields they contain.
Parameters Gives the parameters and controls for the macros in this file and also lists and documents the profile types incorporated in the database. Gives the locations of the profile data (.EMI) files to be output by the macro in this file and the control to run the macro.
Profile Descriptions Lists all the profiles and gives descriptive and documentation information available for them. Documentation consists of reference and note numbers that are associated with documentation text in the "Profile Reference" and "Profile Notes" sheets.
Profile Compositions Gives the mass fractions of the chemical categories in the profiles, and also the descriptions of the categories used in the profile databases as obtained. Note that the categorizations used are those of the database from which the profiles were obtained, and differ for each database. The assignments of compounds to these categories is made in the speciation database incorporated in emitdb.xls.
Profile References Gives the text associated with the reference numbers used in the "Profile Descriptions" sheet.
Profile Notes Gives the text associated with the note numbers used in the "Profile Descriptions" sheet.

This Excel file also incorporates a macro that outputs the profile composition data and available documentation information into the ASCII profile data (.EMI) files that are used as input to the speciation processing programs discussed above

The current version of the profile database file,can be downloaded from ../emitdb/profdb.xls

Additional Work Needed

Although portions of this new database have been provided to others, the complete database has not been externally reviewed by other groups or checked for general utility or other problems. However, the available funding for the project for the University of Houston has been spent, so the remaining work for this project must be restricted to correcting any problems or inconsistencies found in the database and completing the final documentation and report. Additional work to incorporate this into the SMOKE emissions processing system is underway as part  an ACC project for the RRWG as discussed above.

Even after the current ACC project is completed, this speciation database must be considered to be a work in progress. Ongoing work that is needed is summarized below:

The ultimate success of this project requires the widespread adoption and use of this database (or one developed from it) when emissions profiles are developed and updated in the future. This will require development of standard procedures to update and add to the database as needed, and central maintenance of the database by an appropriate and recognized authority. Otherwise, the database will either not be used or will soon become outdated and something resembling the current disorganized and inconsistent system will evolve again.

References

CARB (2003): Organic Gas Speciation Profiles provided by the California Air Resources Board at a web site that has been moved. Downloaded file named ORGPROF_03_19_03.xls and dated 3/19/2003.

Carter, W. P. L. (2000a): "Documentation of the SAPRC-99 Chemical Mechanism for VOC Reactivity Assessment," Report to the California Air Resources Board, Contracts 92-329 and 95-308, May 8. Available at ../reactdat.htm.

Carter, W. P. L. (2000b): "Implementation of the SAPRC-99 Chemical Mechanism into the Models-3 Framework," Report to the United States Environmental Protection Agency, January 29. Available at ../absts.htm#s99mod3.

Carter, W. P. L. (2007): "Development of the SAPRC-07 Chemical Mechanism and Updated Ozone Reactivity Scales," Final report to the California Air Resources Board Contract No. 03-318. August. Available at ../SAPRC.

Gipson (2001). PROFILE.VOC.DAT file, used for processing VOC emissions data for Models-3. Received from Gerald L. Gipson, EPA, Research Triangle Park, NC,. November, 2001

MCNC (2000): "Sparse Matrix Operator Kernel Emissions (SMOKE) Modeling System,"

SPECIATE (2001): Speciate 2.1 database was available at http://www.epa.gov/ttn/chief/software/speciate/ as of late 2001. Data in spreadsheet format provided by Ronald Ryan, EPA, Research Triangle Park, NC, November 2001. It has now been superseded by the Speciate 3.2 database, which is now what is available at that website.

Speciate (2002). Speciate 3.2 database available at http://www.epa.gov/ttn/chief/software/speciate/ as of early 2004. Dated November 3, 2002.

Yarwood (2002). Texas Natural Resource Conservation Commission emissions species data file "compound.database.eps2x.17May02", provided by Greg Yarwood, Environ corporation, Novato, CA, Latest version provided June 18, 2002

Allen (2001). California Air Resources Board chemical species data file provided by Paul Allen, CARB, Sacramento, CA, November 26, 2001. Superseded by the CARB (2003) profiles.


Update History
 
2/10/14
4/1/13
  • Assignments for MCM added to emitdb.xls.
  • Errors in RACM2 assignments for nonvolatile mixtures were corrected.
3/26/13
  • The assigments for RACM2 have been updated to reflect the published version of the mechanism. The assignments were reviewed and approved by Wendy Goliff and Bill Stockwell, the developers of RACM2.
  • Several minor corrections were made and a few minor new categories added to represent current SAPRC detailed model specie
12/18/11
  • The assigments for RACM2 have been updated to reflect the current version of the mechanism. The assignments were reviewed and approved by Bill Stockwell, one of the RACM2 developers..
  • Revisions were made to Carbon Bond 05 assignments for several alkenes as recommended by the CB05 developers
4/28/11
  • The "Emit Worksheet" sheet of emitdb.xls was modified to allow processing of additional mechanisms. No assignments were changed and the normal processing procedures are not affected
7/23/02
  • Some corrections made to SAROAD assignments and a few mixture assignments
  • "Denaturant" returned to a category by itself, and is again unassigned.
  • CO is removed from the list of SAPRC-99 lumped VOC categories, based on the assumption that CO emissions are generally processed separately from VOCs.
  • Option implemented to lump non-volatile compounds with unassigned compounds, as requested by Greg Yarwood
  • Option implemented to output names of database categories assigned to SAROAD classes in output file giving lumped model species assignments to SAROAD categories
7/2/02
  • Some SAPRC-99 lumped model species names changed to conform to requirements for some models that they be no more than 4 characters
  • "Denaturant" assigned to methanol
  • TAME given Texas SAROAD number of 99997 and CB4 splits for it changed as Greg Yarwood recommended.
6/28/02
  • Output format of the lumped mechanism assignments for SAROAD categories was modified. Now a molecular weight is assigned for each category where that information is available, and the assignments are given in terms of moles of model species per mole of category. (The molecular weight of mixtures is defined as 1 gram / total number of moles of compounds assigned to the mixture per gram, and the number of moles of the category is defined as the number of moles of assigned compounds.) The ASCII file that can be produced to give the lumped species assignments also now includes the molecular weights assigned to the lumped classes.
  • Some minor corrections were made for some categories, and unused mixture categories were removed.
  • A brief discussion of the formats of the mechanism assignment ASCII files output by the macros was added to the "Documentation" sheet.
1/8/04
  • Many changes made to the speciation assignments as part of work carried out during the previous 1 1/2 years, including work for the ongoing ACC project. A number of errors corrected and other improvements made to the assignments.
  • Macros were incorporated to output the assignment data into ASCII files that can be read by the Fortran speciation processing programs being prepared for the ACC project.
The profile database file was added to the distribution.
4/7/04
  • Changes made to the speciation assignments as part of the ongoing projects. Several errors corrected and some additions made to the assignments.
  • Significant progress was made in preparing the emissions processing programs for the ACC project. The preliminary documentation for these programs was updated accordingly.
4/23/04
  • Assignments for RADM-2 mechanism added to the database file
  • Changes made to the SAPRC-99 emissions groups to accomodate future RACM assignments
  • Corrections made to assignments for a few compounds.
5/17/04
  • Minor corrections made to "unknown" and "unassigned" profiles in profdb.xls
6/1/04
  • Corrected profile documentation for "base ROG" and "total emissions" profiles in profdb.xls
6/7/04
  • Corrected bug in emitdb.xls macro ProcessSarEmit.
7/21/04
  • Profiles added to represent mixtures used in SAPRC-99 evaluation experiments and for SAPRC-99 reactivity scales. Speciation and mixture categories used in these profiles were added.
  • Errors were found in the SAPRC-99 mechanism files in the preliminary program files (dated June 1, 2004) that affected reactions generated by MechPro in the CMAQ (.MEC) format. (The names ISOPROD, METHACRO, and PROD2 was used for IPRD, MACR, and PRD2 in some places in the generated mechanism files.)  These have been corrected. Mechanisms generated using files downloaded previously should not be used.
12/22/04
  • Additional profiles added. These include petroleum distillate compositions from the study of Cencullo et al (2002) and versions of EPA profiles currently used by the University of Houston in Texas modeling studies.
  • Assignments were made to Texas "contaminant" code categories used in Texas point source profiles.
  • Updates, corrections, and additions made to speciation processing programs.
  • Programs and examples prepared for processing EPS profiles in the Texas database (preliminary)
1/17/05
  • The MechPro program updated to output a species table .CSV file for compiling mechanisms for CMAQ. The program documentation was updated accordingly.
2/21/05
  • EMITROG1 profile added to serve as a base ROG mixture based on EPA emissions data for relative reactivity calculations.
8/24/05
  • Speciation assignments were added to support profiles and new categories in a preliminary version of the Speciate 4.0 database.
  • Carbon Bond 4 assignments were modified for some compounds to improve self-consistency among assignments. 
  • Assignments were added for the new Carbon Bond '05 mechanism.
  • Model species assignments were made to a number of previously unassigned compounds. Compounds are now either assigned for all supported mechanisms or assigned for none.
  • A few additional profiles added to permit assignments of several complex mixture categories.
  • Some modifications were made to the emitdb.xls spreadsheet. 
  • The capability was added for the spreadsheet to assign model species to unknown mixtures or unassigned compounds using profiles designed for this purpose.
  • Some minor modifications were made to the programs. The major changes were that the dimensions had to be increased to support the increased number of speciation categories.
  • Molecular weights were modified slightly to be consistent with IUPAC atomic weights. The largest atomic weight change is about 0.006%.
8/30/05
  • Minor corrections made to speciation assignments
7/26/06
  • Carbon Bond 4 and Carbon Bond '05 assignments were modified based on recommendations by Uarporn Nopmongcol, Greg Yarwood and Gary Z. Whitten of Environ to Mark Houyoux of the EPA dated May 9, 2006
  • A NVOL (nonvolatile) model species added for all lumped mechanisms and used to represent non-volatile compounds. For CB4 and CB05 this is number of non-volatile carbons. For Lumped Molecule mechanisms this kg non-volatile mass (i.e., as if NVOL has a molecular weight of 1000). (Note that this assignment is not made for uncharacterized non-volatile mixtures.)
  • The Carbon number and molecular weight for the SAPRC-99 INERT model species were modified to reflect the mixture of inert compounds in the EMITBAS1 mixture (Profile representing total anthropogenic emissions obtained from EPA Models-3 emissions databases (EPA, 1998), with methane, unknowns, nonvolatiles and negligible contribution compounds removed.)
  • Went back to using Access internal ID numbers for Speciate 4 categories
  • References to Emitdb macros whose accuracy could not be assured, and cells that they update, have been removed. Model species assignments are no longer given on the "Master List" and "Saroad Assignments" spreadsheet. Model species assignments for compounds are given on the "compounds" and "Master Assignments" sheets. Model species assignments for other categories are given only on the "Master Assignments" list. (Most of these were replaced in the 8/4/06 version.)
  • This version of EmitDB.xls was found to have errors in the "Master Assignments" sheet and should be replaced by the 8/4 or a later version.
8/4/06
  • Errors in macros used to produce assignments the "Master Assignments" sheet have been corrected.
  • Macros used to produce model species assignments in the "Master List" and "Saroad Assignments" sheets have been restored because the errors have been fixed. No change in the primary compound or mixture assignments.
8/5/06
  • Macros modified so that model species assignments in the "Saroad Assignments" sheet are updated at the same time those in the "Master List" sheet are calculated. No change in the assignment data.
8/7/06
  • Three new Speciate 4 categories added to the "Saroad Assignments" sheet.
8/10/06
  • Several previously unassigned Speciate 4 categories given compound, molecular weight, and mechanism assignments.
8/12/06
  • Category type codes now indicate whether complex mixtures have been assigned to known compounds or not.
  • Some new compounds added to the database on 8/10 to define simple mixtures were not on the "master list" sheet in the previous database. This has been corrected. Some other minor corrections made. 
8/31/07
  • Assignments for the SAPRC-07 mechanism added to emitdb.xls. However, the speciation programs have not been updated, nor have all the files needed by MechPro been created for this mechanism. See ../SAPRC for information about SAPRC-07.
  • Some new compounds added to compounds list. These are primarily compounds added as part of the SAPRC-07 mechanism update.
  • Several new unspeciated mixture profiles, which are included in the reactivity tabulation for SAPRC-07, have been added to profdb.
12/31/07
  • Emissions assignments and model species revised for modified SAPRC-07 amine mechanism.
1/3/08
  • Error in SAPRC-99 assignment files caused with the SAPRC-07 (August 31, 2007) update corrected. (This affects only the the macros in emitdb.xls and the ASCII files they create, not the assignments in emitdb.xls).
2/4/08
  • Error in assignment for propene in the RADM-2 mechanism has been corrected.
5/27/08
  • Some minor corrections made to some assignments and a few new compounds added
  • Hydrocarbon volatility cutoff for hydrocarbons now strictly set at C20 for consistency.
  • Added assignments for a preliminary version of a "Toxics" SAPRC07 mechanism, SAPRC07T, that is still under development
  • Added assignments for a preliminary version of a condensed SAPRC07 mechanism, CS07, that is still under review
8/25/08
  • Preliminary assignments added for the RACM2 mechanism of Goliff and Stockwell. This required adding new sheets for assignment data. These need to be checked by the RACM2 mechanism developers and are therefore subject to change.

10/6/08
  • Emissions categories added to cover all current SAPRC-07 detailed model species
  • Mixture used to represent aloft VOCs in reactivity scale calculations added to profdb.xls
  • Emitdb.xls now outputs condensed mechanism lumping (LCC) files used by SAPRC modeling software.
10/15/08,
10/29/08
  • Added several chemical categories new in Speciate 4.2
4/30/09
  • Added MechPro input files for SAPRC-07 mechanism and updated SAPRC-07 to the 3/09 version. Corrected an error in MechPro in formating RXN output files.


Database files
 
  • Profdb.xls (dated October 8, 2008) (Link deleted: out of date. Does not reflect updates for Speciate 4).
  • SpTool.zip Speciation Tool assignment files (CSV format). Link deleted; out of date. See home page for current assignment files.


Program files, Documentation, and Reports
 
  • Final report to the ACC project titled "Integration of the SAPRC Chemical Mechanism in the SMOKE Emissions Processor for the CMAQ/Models-3 Airshed Model", dated mid-2005.
  • specpgms.zip Version of programs and input and output files as of updated April 30, 2008). See the README.TXT file for more information. Superceded by SpecDB.zip.
  • This also includes files for processing SAPRC-99 with benzene and 1,3-butadiene explicit. 


Related links
 

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