Monthly Technical Report PROJECT TITLE

Environmental Chamber Experiments and CMAQ Modeling to Improve Mechanisms to Model Ozone Formation from HRVOCs

PROJECT # 12-006

PROJECT PARTICIPANTS

University of California at Riverside Texas A&M University

DATE SUBMITTED

9/8/2013

REPORTING PERIOD

From: August 1, 2013 To: August 31, 2013

REPORT # 7

University of California at Riverside

Texas A&M University

Invoice # 58294-006 #7

Amount $7,426.47 $4,421.51

A Financial Status Report (FSR) and Invoice will be submitted separately from each of the Project Participants reflecting charges for this Reporting Period. I understand that the FSR and Invoice are due to the AQRP by the 15th of the month following the reporting period shown above. Detailed Accomplishments by Task The activities in August, 2013 were for (1) synthesizing available information on kinetic and mechanistic reaction parameters and updating current reaction parameters for the 10 alkenes (1,3-butadiene, 1-butene, isobutene, trans-2-butene, and cis-2-butene (5 HRVOCs); 1-pentene, 1-hexene, trans-2-pentene, cis-2-pentene, and 2-methyl-2-butene (5 non-HRVOCs)) to improve mechanisms for Task 3 (Develop Mechanisms), (2) implementing two versions of SAPRC-11 for Task 4 (Implement Mechanisms into CMAQ ) and (4) preparing emissions data for CMAQ simulations for Task 5 (Perform CMAQ Modeling) . For Task 3, information on reaction parameters for the 10 alkenes was gathered and synthesized. We made progresses in incorporation of those updated reaction parameters into the SAPRC chemical mechanism framework. For this project, a detailed version of SAPRC-11(referred to as SAPRC-11D or S11D where “D” means “detailed”) is one of the five versions of the SAPRC chemical mechanism that will be used for CMAQ simulations. Emission-mapping rules for SAPRC-11D were finalized by fixing minor errors, and the program to generate mechanism files ready for use in implementation into CMAQ was also modified. Potentially improved reaction parameters were tested to generate an updated version of SAPRC-11D. For Task 4, two versions of SAPRC were implemented into CMAQ. The “standard lumped” version of SAPRC-11 (referred to as SAPRC-11L or S11L where “L” means “lumped”) was successfully implemented into CMAQv5.0.1. This version is an updated version of the standard lumped SAPRC-07. Implementation of the detailed SAPRC-11 (SAPRC-11D) in CMAQ was also completed. For Task 5, preparing emissions data for CMAQ simulations was carried out.

Preliminary Analysis Gathering, synthesizing and incorporating updated information on reaction parameters: The 10 alkenes studied for this project can be classified as five groups: (1) 1-butene, 1-pentene, 1-hexene (terminal alkenes, RCH=CH2 where R is alkyl); (2) cis-2-butene, trans-2-butene, cis-2-pentene, trans-2-pentene (internal alkenes; R1CH=CHR2 where R1 and R2 are alkyl); (3) isobutene ((CH3)2C=CH2, a branched terminal alkene); (4) 2-methyl-2-butene ((CH3)2C=CHCH3, a branched internal alkene); (5) 1,3-butadiene (CH2=CH-CH=CH2, an alkene with two C=C bonds). The fates of the alkoxy radicals (RO˙) formed from peroxy radicals (ROO˙ that are formed from addition of O2 to alkyl radicals (R˙) formed by reaction of the alkenes with OH) are (1) isomerization (involving H-migration and formation of a different alkyl radical), (2) reaction with O2 (forming HO2 and a hydroxycarbonyl compound (containing -OH and -C(=O)-)) and (3) decomposition into two smaller entities. New information on the branching of the alkoxy radicals (e.g., R. Atkinson, Atmos. Environ., 2007, 41, 8468–8485; L. Vereecken and J. Peeters, Phys. Chem. Chem. Phys., 2009, 11, 9062–9074) was used in updating mechanisms for 1,3-butadiene (e.g., decomposition of CH2(OH)CH(O˙)CHO (which is formed from acrolein (CH2=CHCHO), a major product of 1,3-butadiene) into HOCH2CHO (glycoaldehyde) and ˙CHO). Based on the literature review (e.g., B. Ghosh et al, Chemical Physics Letters, 2010, 494, 8-13; T. Berndt and O. Bӧge, J. Phys. Chem. A, 2007, 111, 12,099-12,105; J. Baker et al, Environ. Sci. Technol., 2005, 39, 4091-4099) and chamber simulation results for 1,3-butadiene, the mechanisms for 1,3-butadiene need to be updated. The yield for acrolein (CH2=CH-CHO) formed from reaction of 1,3-butadiene (CH2=CH-CH=CH2) with OH needs to be adjusted from 0.48 (the current yield under high-NOx conditions in SAPRC-11D) to ~0.55-0.65 (e.g., 0.58 based on Baker et al (2005)). The reaction of OH with CH2=CH-C(O)OONO2, an unsaturated peroxy acyl nitrate (unsaturated PAN) formed from acrolein, was also reviewed. The reaction of OH with CH2=CH-C(O)OONO2 by OH addition at the terminal C of the C=C bond) forms CH2(OH)-CH(OO.)-C(O)OONO2 which reacts with NO to form CH2(OH)-CH(O.)-C(O)OONO2 and subsequently decompose to HOCH2CHO + CO2 + NO3 (Orlando et al, Atmos. Environ., 2002, 36, 1895-1900; Orlando and Tyndall, J. Phys. Chem. A, 2002, 106, 12252-12259; Grosjean and Grosjean, International Journal of Chemical Kinetics, 1993, 25, 921-929). Kinetic parameters for multiple reactions (e.g., for the reaction of glycolaldehyde + OH, 8.0 x 10-12 cm3 molecule-1 s-1, independent of temperature over the range 240-370K (IUPAC, 2007, http://www.iupac-kinetic.ch.cam.ac.uk/datasheets/pdf/HOx_VOC17_HO_HOCH2CHO.pdf)) need updating. Newly obtained information will be further synthesized and incorporated into SAPRC in September, 2013. SAPRC-11D: A detailed version of SAPRC-11, SAPRC-11D, was prepared and implemented for use in CMAQ simulations for this project. SAPRC-11D uses ~330 model species to more explicitly represent reactive VOC emissions. Files for emission-mapping for SAPRC-11D are available at http://www.cert.ucr.edu/~carter/emitdb/SpecDB_Update_8_13.zip (which is an updated version of http://www.cert.ucr.edu/~carter/emitdb/SPEC-S11.zip). It contains files for SAPRC-11L and SAPRC-11D. Implementation of SAPRC-11L and SAPRC-11D: SAPRC-11L (standard lumped SAPRC-11, S11L) and SAPRC-11D (detailed SAPRC-11, S11D) were successfully implemented into

CMAQ 5.0.1. Steps of implementing these two chemical mechanisms are summarized below using SAPRC-11D as an example.

1. Create a directory under $M3HOME/scritps/chemmech/saprc11d. 2. Copy the mechanism file (so-called “B” version) to the directory and rename it to mech-

saprc11d.def. 3. Slightly modify the file to conform with CHEMMECH program requirements.* 4. Modify and run the csh script run.chemmech to generate RXCM.EXT and RXDT.EXT. 5. Create a sub-directory $M3HOME/models/mechs/release/saprc11d, copy the

RXCM.EXT and RXDT.EXT files into this directory. 6. Generate a GC_saprc11d.csv file. The dry and wet deposition surrogates of explicit

species that are not explicit in S11L are based on the surrogate species for the lumped species to which they will be lumped in S11L. Run csv2nml.csh to generate the corresponding nml file (a namelist file), which will be read by CMAQ in run time. The nml and csv files for AE and NR are copied from saprc07tc_ae5_aq. In regard to photolysis data (cross sections and quantum yields), CSQY_DATA_saprc11d is also created by copying from saprc07tc_ae5_aq

7. Build a CMAQ source code directory and an executable using sarpc11d. The SMVGEAR solver available in CMAQ is used to solve both S11L and S11D. Some changes are necessary.** The build options (and run options set in the run script) were chosen so that they best matches with the options used in CMAQ 4.7.1. Many online features, such as dust and biogenic emissions and plume rise calculation, were not used.

8. IC/BC files for 36km domain are currently generated using profiles for SAPRC-07T. We plan to add all VOCs in the SAPRC-07C (http://www.engr.ucr.edu/~carter/SAPRC/files.htm) IC/BC profiles and apply TOG profile 0000 to generated compatible S11L and S11D profiles.

* Changes include: add a title; remove HV from reactions; fix the problem with negative stoichiometric coefficients before XC; and add a constant section. Note that the standard lumped mechanism file does not have these problems. The tags for the photolysis reactions use “-” instead of “ _”, as used in other EPA mechanism files. This is changed so that photolysis data files in the standard CMAQ5.0.1 can be used without renaming. S11L uses the same set of photolysis reactions as SAPRC07. SAPRC11D includes three additional photolysis reactions for MITC (methyl isothiocyanate), CS2 (carbon disulfide) and CLIPICERI (chloropicrin). These three species do not exist in the current emission inventory and are removed from SAPRC11D. ** Parameter spc_dim on Line 147 in CGRID_SPCS.F needs to be modified from 200 to 500 and parameter MXARRAY on line 55 in GRVARS.F needs to be changed from 4200 to 25000 to incorporate the large number of species used in S11D. Calls to subroutine AQCHEM in convcld_acm.F and rescld.F are commented out so that wet deposition is calculated but aqueous chemistry in cloud droplets are not performed. Call to subroutine AERO is currently commented out as well. AERO will be enabled in production runs without an SOA module for this project.

Emission processing with speciation profiles: Speciation profiles for SAPRC-11L and SAPRC11-D (generated by William Carter) were applied in SMOKE to generate speciated model-ready emissions for the 36-km eastern US domain. Only 2005 National Emissions Inventory (NEI) v4.2 was used for 36km (and also 12km) resolution domains. For 4km and 2km

domains, TECQ point sources will be used to replace the NEI data.*** Changes to the SMOKE program are:

1. The underlying Input/Output Applications Programming Interface (I/O API) software used in CMAQ was modified to allow 5000 species per file to avoid generating multiple emission files for a single day. The chksetdesc.f file in the filesetapi (a component of SMOKE) was also modified to allow 5000 species per file as well. (5000 is not necessary as the total number of species is ~500. It is changed so that it can be used for other projects).

2. The gspro files in NEI v4.2 for CB05 were modified to use S11L and S11D profiles. 3. Spatial allocation surrogates for the domains have been generated in previous projects

using NEI v2, but spatial allocation surrogate US_165 was not used in 2005 NEI v2. Based on EPA documentation, it is the average of US_160 and US_300. A program is developed to average the two surrogates to generate US_160.

***We are still waiting for TCEQ’s response on whether it is possible to include TCEQ link based on-road mobile emissions.

Preliminary comparison of CMAQ simulation results with SAPRC-11L (S11L) and SAPRC-11D (S11D): Figure 1 shows comparison of S11L and S11D for O3, OH, HO2 and peroxy acetyl nitrate (PAN) at 1300-1400 CST on August 31, 2006. The two mechanisms predict very similar O3 concentrations while relative differences in OH, HO2 and PAN are somewhat larger compared to relative differences in O3 over certain areas.

Figure 1. Predicted O3, OH, HO2 and PAN concentrations (in units of parts per billion (ppb)) at 1300-1400 CDT and relative differences ((S11D-S11L)/S11D; in units of %) between S11D and S11L.

Data Collected No new data were collected. Identify Problems or Issues Encountered and Proposed Solutions or Adjustments Incorporating new information on reaction parameters into SAPRC: Updated information on kinetic and mechanistic reaction parameters needs to be implemented into SAPRC in a way compatible with the SAPRC chemical mechanism framework. To limit the size of the updated SAPRC-11D (which is the largest of the three updated versions of SAPRC-11 developed for this project), key stable products (e.g., acrolein formed from 1,3-butadiene) will be explicitly represented but unstable reaction intermediates will not be explicitly represented in most cases. Implementing mechanisms into CMAQ: Necessary changes for implementation of chemical mechanisms developed for this project were described above in section “Implementation of SAPRC-11L and SAPRC-11D”. We do not expect that we will have new time-consuming technical issues during implementation of other chemical mechanisms for this project. Preparing emissions data for CMAQ simulations: In regard to processing TCEQ point source emissions, we noticed some errors in our in-house code for temporal allocation and speciation of daily emissions and fixed the problems.

Goals and Anticipated Issues for the Succeeding Reporting Period In regard to Task 3 (Develop Mechanisms), the chamber experimental data newly generated for this project and information on reaction parameters obtained from the literature review and in March – August, 2013 will be used to develop and evaluate mechanisms. Updating mechanisms involves (1) synthesizing recently available information on reaction parameters, (2) incorporating the updated reaction parameters into reactions compatible with the SAPRC chemical mechanism framework, and (3) updating emission-mapping rules if necessary (e.g., when a new species is added to explicitly represent a compound directly emitted). The key constraint for Task 3 is the limited time available for this task. Therefore, we plan to move forward as follows: (1) focus on updating the reactions for the 10 alkenes studied in this project (particularly reactions for 1,3-butadiene for which chamber data showed relatively poor model performance) and use those updated reaction parameters in updating the detailed SAPRC-11 (SAPRC-11D), (2) evaluate and refine this updated SAPRC-11D, (3) derive two less-detailed versions from this updated SAPRC-11D, and (4) document the updates in the reaction parameters, lumping/condensation methods and emission mapping. In regard to Task 4 (Implement Mechanisms into CMAQ) and Task 5 (Perform CMAQ Modeling), the Texas A&M team will (1) implement three additional SAPRC mechanisms into CMAQ (2) continue to prepare emissions data for CMAQ simulations, and (3) continue discussion with TCEQ on getting help with reprocessing TCEQ mobile source emissions and incorporating that into the emission processing framework used for this project.

In regard to Task 5 (Perform CMAQ Modeling), particularly regarding the time needed for the simulations, CMAQ simulations for SAPRC-11D for one modeling day usually take about 3 hours (without aerosol chemistry) on our cluster (using 30 CPUs), and can be done on TAMU’s EOS computer in about 1 hour. Simulating 21 modeling days will take about 1-2 days to complete. For the entire nested simulation down to 2km for a single mechanism, we expect that less than 2 weeks are needed (based on simulations with SAPRC-11D). 2 and 4 km simulations will be much slower than 36 or 12 km simulations, but should be shorter for other mechanisms. Different mechanisms can run simultaneously; therefore, we should be able to complete all CMAQ runs by early October, 2013. Preparing emissions for SAPRC-11D and SAPRC-11L (for the remaining three nested domains) can be completed in a week. We will generate emissions for other SAPRC mechanisms by using emissions prepared for SAPRC-11D instead of calculating from raw inventory files. Emissions prepared for the already implemented SAPRC-11D can be used for the updated SAPRC-11D (without re-mapping model-ready emissions files) and two other versions to be derived from the updated SAPRC-11D (with re-mapping model-ready emissions files due to using different emission-mapping rules). Once a set of emissions are generated, we will start to run CMAQ simulations. Detailed Analysis of the Progress of the Task Order to Date The timeline of this project is shown in the table below. The approval of the work plan and QAPP for this project was given in February, 2013, and the start of this project is February 8, 2013. As stated in section 1.3 of the approved Work Plan and given below,* some delays (e.g., around ten days) in submitting the listed deliverables are expected. However, we will do our best to submit the deliverables as scheduled in the table below. Deliverable Original Due Date Actual Delivery DateTechnical memorandum on chamber experimental design (Task 1)

March 5, 2013 March 13, 2013

Technical memorandum on environmental chamber experiments (Task 2)

May 15, 2013 June 30, 2013

Technical memorandum on mechanism developments (Task 3)

July 30, 2013

Technical memorandum on implementing SAPRC mechanisms (Task 4)

August 30, 2013

Technical memorandum on CMAQ modeling with 5 versions of SAPRC (Task 5)

September 30, 2013

Draft Final Report (Task 6) October 21, 2013 Final Report acceptable to TX AQRP (Task 6) November 30, 2013

*: “This schedule assumes that we will receive approval to spend funds on this project by January 28, 2013. If such approval comes after January 28, 2013, each of the dates given on Table 3 will be pushed back by an equal amount of time as the number of days after January 28, 2013 that the necessary approval is received.” In regard to submitting Task 2 Report (technical memorandum on environmental chamber experiments), multiple extensions were requested to generate chamber experimental data to satisfy the requirements stated in Work Plan and Task 1 Report for this project, and the report was submitted on June 30, 2013 (original due: May 15, 2013).

A report for Task 3 will be submitted in September, 2013 (original due: July 30, 2013). The main reason that we have been taking time in wrapping up developing mechanisms (Task 3) is to prevent forcing the TAMU team to repeat CMAQ simulations due to late changes in the mechanisms already delivered to the TAMU team. Once mechanism files are sent to TAMU and implemented into CMAQ, changes to the mechanisms are practically not allowed due to time constraints. Therefore, it is important to make sure that improved and correct mechanism files and associated emission-mapping rules be prepared and sent to the TAMU team. Adjusted schedules are as follows:

1. Task 3 (develop mechanisms): Report 3 - original due (7/30/2013), adjusted due (9/16/2013)

2. Task 4 (implement mechanisms): Report 4 - original due (8/30/2013), adjusted due (9/25/2013) [Note: UCR team will assist TAMU team in solving issues in implementing mechanisms and mapping emissions]

3. Task 5 (perform CMAQ simulations): original due (9/30/2013), adjusted due (10/18/2013)

4. Task 6 Report: draft final report (10/21/2013), final report (11/30/2013) [Note: UCR and TAMU will coordinate writing reports so that a reasonably written draft final report can be submitted]

Submitted to AQRP by: Gookyoung Heo Principal Investigator: Gookyoung Heo