A-1



## Appendix A: Methodology to Revise VOC from Reside ntial Wood Combustion

Purpose: Calculate corrected VOC emissions for EPA and State/local supplied sources with SCC=2104008001 which is Fireplaces (FP) and SCC=210 4008000 (total RWC; i.e. it includes fireplaces AND woodstoves) because we have evidence that with the exception of Calif., an erroneously high emission factor (229 lb/ton) was u sed.

Note that the 229 lb/ton was the EF in AP-42, but n umerous studies have shown it to be too high by approximately an order of magnitude. We chose t o use the emission factor from the MidAtlantic Regional Air Management Association (MARAM A) study of 18.9 lbs VOC/ton.

The evidence for the State/local supplied data usin g the 229 lb/ton EF is the ratio of VOC to PM2.5 which is much greater than what is expected w hen computed at the state and/or county level. Using the the erroneous VOC emission factor of 229 lb/ton EPA factors, the VOC-toPM2.5 ratio should be 9.7 ( VOC = 229 lb/ton and PM25 = 23.6 lb/ton). But this ratio can vary if States use different PM2.5 ratios.

Because the RWC data is provided in different ways (one example is that states provide the data aggregated for fireplace and woodstove SCCs rather than use the separate SCCs) and we don’t know what particular emission factors States used, we ha d to develop different adjustments for different ca ses. The caes are described below.A-2

CASE 1: Adjustment of VOC from 2104008001 for counties that have VOC emissions for BOTH fireplace SCCs (2104008001) and woodstove SCCs (any combination of 21040080XX, where XX not equal to 01 or 00)

Except for California (which we don’t change), reco mpute VOC from 2104008001 as follows:

VOCcorrected=VOCold*(EFcorrected/EFold) Where EFcorrected= 18.9 lbs VOC/tons of wood burned. And EFold=229 lbs VOC/tons of wood burned.

Leave VOC from woodstove SCCs as is.

Apply FP VOC change to the following 35 States base d on the value of their VOC to PM2.5 ratio for SCC=2104008001. State Comment regarding VOC to PM2.5 ratio AZ CO DC FL GA IA KS KY LA MN MO MT NC ND NE NM NV OK OR(#1) PA RI SD TN WI(#2) WY States appear to use the 229 EF (based on their VOC -toPM2.5 ratio of 9.7). For these States, this corre ction is most accurate. Note that the top 2 VOC emitting st ates are in this list.

IL IN MI WV have a VOC-to-PM2.5 ratio of 19.4, which may mean that they use a lower PM2.5 EF (11.8 lbs/ton?) or higher VOC EF (not likely). The calculation may be less accurate for these states, since we are unsure of t he VOC EF that they used. TX – EPA provided data Ratio is 3.55. Wood stove E Fs different (but not that far off) of EPA data for Colorado. TX – State submitted data Ratio is 10.73. Wood stove EFs different (but not that far off) of EPA data for Colorado. VT Ratio is 7.12. Other woodstove VOC to PM ratios ar e slightly higher than for the EPA data, but are not that far

away. NY Ratio is 7.88. Same ratio for outdoor wood burning but woodstove ratio is on the order of the EPA WA – local data only Counties 53-033, -035, -053, -061 ratio is 12.32. Wood stove ratios slightly higher than for the EPA data, but are not that far away.

MS Ratio is 33.68. ratios for 2104008002, 2104008003, 2104008004 are also pretty different (higher) than EPA, but VOC emissions from these are not nearly as larg e as 21040080001.A-3

CASE 2. Adjustment of VOC from 2104008000 from MA RAMA states

State Comment CT DE MA MD ME NH Ratio of VOC to PM2.5 is 4.7

They did not break out fireplace emissions from woo dstove emissions. Need to know what EFs they used for fireplaces.

Madeleine contacted Marama on Friday June 27 ( Julie R. McDill Mid-Atlantic Regional Air Management Association 8900 LaSalle Road Suite 636 Baltimore, MD 21286

P. 443-901-1882

F. 443-901-1886 Email: jmcdill@marama.org

www.marama.org ) to find out what they used so we know if/how to cor rect VOC. She indicated that for the 2002v3 nonpoint, they ha d not used corrected VOC.

THUS USE CASE3 DIRECTIONS FOR CASE2

CASE 3. Adjustment of VOC from 2104008000 from non -MARAMA states and where 2104008000 is the only SCC used.

Approach: Divide out the VOC from the broad into f ireplaces, uncontrolled woodstoves & controlled woodstoves using PM2.5 and then compute VOC from VOC/PM2.5 EFs, correcting the VOC EF for fireplaces.

Step 1. break out PM2.5 into fireplaces (FP), unco ntrolled-woodstoves, controlledwoodstoves using the following factors: 0.194, 0.7 15, 0.091 (respectively)

Step 2. multiply fireplaces PM2.5 by (18.9/23.6) to get corrected FP VOC (numerator is corrected VOC EF for fireplaces, denominator is EF used for PM2.5 for fireplaces, NEI documentation, Table 4) multiply uncontrolled-woodstoves PM2.5 by *( 53/30.6 ) to get uncontrolled-woodstoves VOC (numerator is VOC EF for the uncontrolled-woods tove SCCs: 2104008002 and 2104008010. Denominator is PM2.5 EF for the uncon trolled woodstoves. These values are from the NEI documentation, table 5) multiply controlled-woodstoves PM2.5 by *(12/19.6) to get controlled-woodstoves VOC (numerator/denominator are VOC&PM2.5 EFs for contro lledwoodstove SCCs : 2104008003 and 8050 from NEI documentation, table 6 – assume m ost emissions are from 2104008003 and 8050 since other controlled-woodstoves SCC: 21 04008004, has different ratios – (15/20.4) )

Step 3. Sum up VOC and use that as the corrected V OC for 2108004000A-4

Step 4. compute corrected ratio VOC to PM2.5 (NOT E THAT PM2.5 doesn’t change from the original value) just to check. Should be about 1.4 5

Sample Calculation for AR is shown below.

Apply to: State Comment AR Ratio is 2.49. AR pm2.5 from broad SCC is 2485 tons. Example calc shows how to derive corrected VOC. Statewide VOC goes from 6177 tons to 3605

tons. ID PM2.5 has different data source code than VOC. PM2.5 total from ID is 2263 tons. Data source code for PM2.5 is S-02-X-PR. Shouldn’t be a problem to do that calc. Statewide VOC goes from 15K to 3300. AZ local data (Maricopa county only ) Pm2.5 is 409, VOC was 2912. corrected VOC is 593

NJ – EPA data ratio is 6.62 based on bad VOC and AP-42 PM2.5 for fireplaces PM= 4419. VOC was 29K corrected VOC is 6405

NJ state data ratio is 1.73. PM = 4392. VOC was 76 07. corrected VOC is 6366. Ohio VOC to PM2.5 ratio is 1.67 PM=8936. VOC was 14962 corrected VOC is 12952

TN local data VOC to PM2.5 ratio is 6.62 UT state data. ratio is 3.05 WA state data. Ratio is 3.9

AR example calc: 2485 tons of PM2.5 and presumably bad VOC of 6177 tons .194 *2485=482 PM2.5 from FP .715 *2485=1779.6 from uncontrolled-woodstoves 210400800 2, 2104008010, or 2104008051

. 091 *2485=223.69 from controlled-wood stoves. 210400800 3, 2104008004, 2104008030, 2104008050, 2104008052 or 2104008053

Apply VOC to PM2.5 factor for FP: 482 *(18.9/23.6) =386 tons VOC Apply VOC to PM2.5 factor for uncontrolled-woodstov es (8002): 1779.6 *( 53/30.6 ) = 3082 tons VOC Apply VOC to PM2.5 factor for controlled-wood stove s (8003): 223.69 *(12/19.6) =136.95 tons Sum of VOC = 3605 tons  -------this is the corrected VOC for 2104008000.

So corrected ratio is 3605/2485=1.45 looks good.A-5

CASE 4. Virginia, which has no VOC for wood stoves , but there is PM. And has VOC (but no PM for broad SCC). state_a bbr Scc data_sour

ce PM2_5 VOC

VA 2104008000 S-02-X 53825.14 VA 2104008001 E-01-G 831.2484 VA 2104008002 E-01-G 3632.713 VA 2104008003 E-01-G 144.1626 VA 2104008004 E-01-G 60.54522 VA 2104008010 E-01-G 4937.689 VA 2104008030 E-01-G 82.29481 VA 2104008050 E-01-G 195.95

VA: remove all records with 2104008000 and compute VOC for all other SCCs using VOC to PM2.5 ratios.

For 210400 8001 (fireplaces) use: (18.9/23.6) For uncontrolled woodstoves: 2104008002, 2104008 010, or 2104008051 use ( 53/30.6 ) because both 2104008002, 2104008010 use that and there are no fa ctors for 2104008051 For controlled wood stoves use the following based on SCC: 2104008003 (12/19.6)

, 2104008004 (15/20.4 using Table 7), 2104008030 (15/20.4 using Table 7), 2104008050 (12/19.6)

, 2104008052: not there, so use same as 2104008050 (12/19.6)

, Same for 2104008053

CASE 5: Alabama for which there is both broad and detailed woodstove SCCs

This case is unique because VOC is only in 21040080 00 but PM2.5 (and HAPs) are in that SCC and numerous others

state_abbr Scc data_source PM2_5 VOC

AL 2104008000 S-02-X 216.46 54987.12 AL 2104008002 S-02-X 1505.05 AL 2104008003 S-02-X 59.76 AL 2104008004 S-02-X 25.1 AL 2104008010 S-02-X 2085.44 AL 2104008030 S-02-X 34.67 AL 2104008050 S-02-X 82.8

I examined county-level inventory and it looks like the above is the pattern in very county.

Examples:A-6

fips Scc poll ann_emis pm ratio 1001 2104008000 PM2_5 2.05 0.089716 1001 2104008002 PM2_5 10.55 0.461707 1001 2104008003 PM2_5 0.42 0.018381 1001 2104008004 PM2_5 0.18 0.007877 1001 2104008010 PM2_5 9.13 0.399562 1001 2104008030 PM2_5 0.15 0.006565 1001 2104008050 PM2_5 0.37 0.016193

fips Scc poll ann_emis PM ratio 1013 2104008000 PM2_5 0.77 0.028742 1013 2104008002 PM2_5 8.42 0.314296 1013 2104008003 PM2_5 0.33 0.012318 1013 2104008004 PM2_5 0.14 0.005226 1013 2104008010 PM2_5 16.22 0.60545 1013 2104008030 PM2_5 0.27 0.010078 1013 2104008050 PM2_5 0.64 0.02389 26.79

Approach is to remove current VOC from all counties and replace with VOC based on PM2.5 and the following PM2.5 to VOC ratios The ratios to use: (by SCC) are in column 5 scc Ratio based on PM2_5 factor num and denom Factor sum

AL 2104008000 FP: NEI documentation 2

Table 1 for PM2.5 and corrected VOC EF of 18.9 lb/ton 216.46 (18.9/23.6) 0.80084746 173.3514

AL 2104008002 NEI documentation Table

5 1505.05 ( 53/30.6 ) 1.73202614 2606.786

AL 2104008003 NEI documentation Table

6 59.76 (12/19.6) 0.6122449 36.58776

AL 2104008004 NEI documentation Table

7 25.1 15/20.4 0.73529412 18.45588

AL 2104008010 NEI documentation Table

5 2085.44 ( 53/30.6 ) 1.73202614 3612.037

AL 2104008030 NEI documentation Table

7 34.67 15/20.4 0.73529412 25.49265

AL 2104008050 NEI documentation Table

6 82.8 12/19.6 0.6122449 50.69388

Grand total 6523.404

2 ftp://ftp.epa.gov/EmisInventory/2002finalnei/docume ntation/nonpoint/2002nei_final_nonpoint_documentati on0206 version.pdf

Appendix A. Residential Heating Using WoodA-7

Case 6. SC, where VOC mass missing from some SCCs.

State SCC Data source code PM2.5 VOC SC 2104008001 S-02-X 157.93 43268.9 2104008002 S-02-X 1667.88

2104008003 S-02-X 66.21

2104008004 S-02-X 27.79

2104008010 S-02-X 3163.31 5478.91

2104008030 S-02-X 52.73 38.74 2104008050 S-02-X 125.57 76.85

Compute VOC from 2104008002, 2104008003 & 210400800 4 Using VOC to PM2.5 factors as follows:

For 2104008002, use ( 53/30.6 ) For 2104008003 use (12/19.6)

, For 2104008004 use (15/20.4)

Recompute VOC from 2104008001 as follows (case 1) VOCcorrected=VOCold*(EFcorrected/EFold) Where EFcorrected= 18.9 lbs VOC/tons of wood burned. And EFold=229 lbs VOC/tons of wood burned.



### Case 7 -- SCC=2104008053 from Oregon and Washoe C ounty (Nevada ) Multiply PM2.5 by (12/19.6)

Case 8 -- Selected New Jersey Counties For counties of Bergen, Essex, Hudson, Middlesex an d Union , VOC corrected = (18.9/229) * VOC old ie, treat these as Case 1 counties.

Case 9 -- Selected Washington Counties For counties of King (53-033), Kitsap(-035), Pierce (-053), and Snohomish (-061), calculate new VOC as in Case 3 .B-1



## Appendix B: Methodology to Speciate Partially-Spe ciated MOVES PM2.5 Emissions

Approach to adapt partially-speciated gasoline emis sions from the draft MOVES model to air quality modeling species needed for CMAQ.

The MOVES output provided three components of PM2.5 : two pre-speciated components of PM2.5 which are: 1) PEC , and 2) PSO4 , and a a non-speciated component termed “ PM25OC ”, which is defined as the difference between total PM 2.5 and PEC.

It is important to note that PM25OC is not organic carbon, but is defined as the follo wing:

MOVES total PM 2.5 = PEC + PM25OC (1)

The CMAQ PM2.5 species were computed from (1) the M OVES output pollutants: PEC, PSO4 and PM25OC, and (2) the speciation profile for tota l PM2.5 exhaust. The equations used are presented below. Since we had to adjust the PEC an d POC emissions at 72 F to reflect the impact of colder actual temperatures prior to compu ting all of the species, the implementation of the equations does not follow the order presented. The order is described after the list of equations is presented.

MOVES total PM 2.5 is the sum of the two pre-speciated components of P M2.5 and a remainder term, R

. MOVES total PM 2.5 = PEC + PSO4 + R (2)

The remainder term can be computed from the MOVES o utputs of PM25OC and PSO4 as

R = PM25OC - PSO4 (3)

The R term includes POM, which consists of POC and the h ydrogen and oxygen atoms attached to the carbon as part of the organic matter, PNO3, soil oxides and metals (also known as “crustal” and called METAL here), ammonium, and wat er, and thus can be also written as:

R = POM + PNO3 + METAL + NH4 + H 2 0 (4)

To correctly calculate the five PM 2.5 species needed for CMAQ, we first needed to break out the POC, PNO3, and PMFINE from R . We used the proportional relationship of known s pecies to unknown species from the speciation profile for exh aust PM2.5 for gasoline vehicles. All gasoline vehicles (e.g., Light Duty and Heavy Duty) use the same speciation profile for exhaust PM2.5, 92050: “Onroad Gasoline Exhaust – Simplifie d”. This simplified profile is based on Composite profile 91022. Fractions of PNO3 and PEC can be obtained from either the detailed or composite profile (they are the same). The deta iled composite profile is required in order to determine the METAL component in equation (4) since metal fractions are not included in theB-2

simplified profile. Profiles 92050 and 91022 are i n version 4.0 of SPECIATE (Hsu et al., 2006), which can be downloaded at www.epa.gov/ttn/chief/software/speciate/

We computed the primary nitrate based on the ratio of nitrate to elemental carbon from speciation profile 91022 using equation (5) shown b elow.

PNO3 = PEC × F NO3 / F EC (5)

where, F EC = Fraction of elemental carbon in speciation prof ile 91022= 20.801136% F NO3 = Fraction of nitrate in speciation profile 91022 = 0.1015%

Since CMAQ’s PMFINE species is the sum of soil oxid es, metals, ammonium, and water, we needed to calculate all of its components. First, t he metals and ammonium are computed using equations (6) and (7). Equation (7) is based on st oichiometric calculations.

METAL = PEC× F metal / F

EC (6)

NH4 = (PNO3/

MW NO3 +2 × PSO4/

MW SO4 ) × MW

NH4 (7)

where, F metal = Fraction of metals in speciation profile 91022 = ( 2.2256 % 3 ) F EC = Fraction of elemental carbon in speciation prof ile 91022= 20.801136%

MW SO4 = Molecular weight of sulfate ( 96.0576 ) MW NO3 = Molecular weight of nitrate ( 62.0049 ) MW NH4 = Molecular weight of ammonium ( 18.0383 )

The final component of PMFINE is the non-carbon mas s of organic carbon. To calculate the non-carbon mass, we first needed to compute organic carbon from the remainder term, R

.

A key assumption is that POM is a factor of 1.2 gre ater than the mass of primary organic carbon, which is also used in the CMAQ postprocessing softw are at EPA.

POM = 1.2 × POC (8)

Using this assumption and assuming that the H 2 0 is negligible, the equation needed for the calculation of POC is shown in equation (9) below.

POC = 5/6 × ( R – METAL – NH4 – PNO3) (9)

From equation (8), the non-carbon portion of the or ganic carbon matter is 20%, of the POC. By definition, PMFINE is the sum of the non-carbon por tion of the mass, METAL and NH4.

3 To obtain this, all metals and other ions (e.g., C hlorine) with the exceptions of nitrate and ammoni um were identified in the profile and the percentages were summed to give a total “METAL” percentage.B-3

PMFINE = METAL + NH4 + 0.2 × POC (10)

For mobile sources, we assumed that PMC is 8.6% of the PM 2.5 mass.

PMC = 0.086 × (PMFINE + PEC + POC + PSO4 + PNO3 ) (11)

Order of Computations due to Temperature Adjustment s

Due to the need to account for the impact of temper ature on exhaust PEC and POC, some of the equations above were not implement ed until after the temperature-adjusted PEC and POC were computed (aft er the spatial allocation and temporal allocation steps in SMOKE).

The input emissions to SMOKE and equations or MOVES outputs used to create them from the MOVES data are listed below. The po llutant name in SMOKE inventory file is italicized.

The following PM2.5 inventory “pollutants” were com puted for input into SMOKE. 1. PEC_72 (not computed, this is directly output from MOVES) 2. PSO4 (not computed, this is directly output from MOVES) 3. PNO3 (computed from Equation 5) 4. POC_72 (computed from Equation 9) 5. OTHER = NH4 + METAL (computed from Equations 6 and 7)

Temperature adjustments were applied by hour and gr id cell to the PEC_72 and POC_72 in the SMOKE intermediate files (prior to th e final merge) using a Lookup Table (see Table A-1). Note that the same lookup table was used to adjust PEC_72 and POC_72.

The other CMAQ PM2.5 species at actual temperatures were created as follows:

PMFINE = OTHER + 0.2 × POC (computed from Equation 10) PMC = 0.86 x (PMFINE + PEC + POC + PSO4 + PNO3) (computed from Equation 11)

A final merge of all sectors was then done.B-4

Table A-1. Correction Factors to Adjust 72 F PM OC and EC Emissions for colder temperatures (supplied by Harvey Michaels, OTAQ, 9/ 5/2008)

Year Temperature

(degrees F) Correction Factor for Running

Exhaust Correction Factor for Start Exhaust 2005 -20 18.6454 70.7816 2005 -19 18.0618 67.5797 2005 -18 17.4965 64.5218 2005 -17 16.9488 61.6025 2005 -16 16.4183 58.8153 2005 -15 15.9045 56.1542 2005 -14 15.4067 53.6136 2005 -13 14.9244 51.1878 2005 -12 14.4573 48.8719 2005 -11 14.0048 46.6607 2005 -10 13.5665 44.5495 2005 -9 13.1418 42.5339 2005 -8 12.7305 40.6095 2005 -7 12.332 38.7722 2005 -6 11.9461 37.018 2005 -5 11.5721 35.3431 2005 -4 11.2099 33.744 2005 -3 10.8591 32.2173 2005 -2 10.5192 30.7596 2005 -1 10.1899 29.3679 2005 0 9.87099 28.0392 2005 1 9.56203 26.7706 2005 2 9.26275 25.5594 2005 3 8.97281 24.4029 2005 4 8.69197 23.2988 2005 5 8.41992 22.2447 2005 6 8.15638 21.2382 2005 7 7.90109 20.2773 2005 8 7.65378 19.3599 2005 9 7.41422 18.484 2005 10 7.18216 17.6477 2005 11 6.95736 16.8492 2005 12 6.73959 16.0868 2005 13 6.52865 15.359 2005 14 6.3243 14.6641 2005 15 6.12635 14.0006 2005 16 5.9346 13.3672 2005 17 5.74885 12.7624 2005 18 5.56891 12.1849 2005 19 5.39461 11.6337 2005 20 5.22576 11.1073 2005 21 5.06219 10.6048 2005 22 4.90375 10.125 2005 23 4.75026 9.66683 2005 24 4.60158 9.22946 2005 25 4.45755 8.81189 2005 26 4.31803 8.41321 2005 27 4.18288 8.03256 2005 28 4.05196 7.6691 2005 29 3.92513 7.32215 2005 30 3.80228 6.99088 2005 31 3.68327 6.67456B-5

Table A-1. Correction Factors to Adjust 72 F PM OC and EC Emissions for colder temperatures (supplied by Harvey Michaels, OTAQ, 9/ 5/2008)

2005 32 3.56798 6.37257 2005 33 3.4563 6.08424 2005 34 3.34812 5.80897 2005 35 3.24333 5.54614 2005 36 3.14181 5.29521 2005 37 3.04347 5.05563 2005 38 2.94821 4.82689 2005 39 2.85593 4.6085 2005 40 2.76655 4.39999 2005 41 2.67995 4.20091 2005 42 2.59607 4.01085 2005 43 2.51481 3.82938 2005 44 2.4361 3.65612 2005 45 2.35985 3.4907 2005 46 2.28599 3.33277 2005 47 2.21444 3.18198 2005 48 2.14513 3.03801 2005 49 2.07799 2.90055 2005 50 2.01295 2.76932 2005 51 1.94994 2.64403 2005 52 1.88891 2.5244 2005 53 1.82979 2.41018 2005 54 1.77252 2.30114 2005 55 1.71704 2.19702 2005 56 1.66329 2.09762 2005 57 1.61123 2.00271 2005 58 1.5608 1.9121 2005 59 1.51195 1.82559 2005 60 1.46463 1.74299 2005 61 1.41878 1.66413 2005 62 1.37438 1.58883 2005 63 1.33136 1.51695 2005 64 1.28969 1.44832 2005 65 1.24932 1.38279 2005 66 1.21022 1.32022 2005 67 1.17234 1.26049 2005 68 1.13564 1.20346 2005 69 1.1001 1.14901 2005 70 1.06567 1.09703 2005 71 1.03231 1.04739 2005 72 1 1B-6