1 PAMS IN THE OZONE TRANSPORT REGION March 2, 2011 MEDEP Monitoring Meeting Tom Downs, CCM Chief Meteorologist Maine DEP-BAQ 207-287-7026 [email protected]

1

PAMS IN THE OZONE TRANSPORT REGION

March 2, 2011 MEDEP Monitoring Meeting

Tom Downs, CCMChief MeteorologistMaine [email protected]

2

Overview of NESCAUM PAMS Workgroup’s Efforts

Reviewed:• EPA guidance

– Focused on linking common species to emission sources.

– Anticipated that major sources would become SIP focused

• Past EPA PAMS Analyses– Often focused on

redundancies and

how the network

can be reduced

3

TYPE 1 – UPWIND/background site

TYPE 2 – MAXIMUM EMISSIONS site

TYPE 3 – MAXIMUM OZONE concentration site

TYPE 4 – Extreme DOWNWIND site

1or4?

1/3

1/3

1/4

1/3

1or4?

1/3

1/3

1/4

1/3

4

Overview of NESCAUM PAMS Workgroup’s Efforts

Also Reviewed:• Detection limits• Common species

–Are some species too often below MDL to be useful?–Are there species that should be added?

• Carbonyls – data quality, are they worth the cost?• Is the newer, more sensitive or less expensive analytical

techniques? (Synspec – gets more compounds including more biogenics)

• Data analyses by state

5

DATA PROCESSING

• Summary statistics calculated– Average concentrations (by site and by classification)– Percent of data below minimum detect levels– Percent data recovery rates

• QA checks– Check for qualifier flags and delete obvious invalid data– Check for units consistency and convert to correct units

if necessary– Box plots to identify outliers? – Concern with the frequency of below minimum detects?

6

Overview of NESCAUM PAMS Workgroup’s Preliminary FindingsConcluded:• Data analysis should also be done regionally• PAMS data critical for regional modeling efforts• State survey found that many (but not all) states

don’t know or trust their carbonyl data quality. States still submitted data to AQS as required.– Known problems with acrolein – EPA pulled data from AQS– Suspected quality problems with other carbonyls – OAQPS looking into.

• Will look at Regional Network Needs Under New Ozone NAAQS Implementation rule

7

Should we analyze all 54-57 VOC species in future data analyses?

• On the ftp site - analyses for each site comparing trends for the full suite of VOC’s vs. a reduced (“focused”) PAMS species list of 23 and 7 compounds http://www.maine.gov/dep/ftp/DEP_PAMS/NESCAUM_PAMS_ANALYSES/

• Preliminary analyses are also included– % unidentified VOC’s– Benzene/tolulene ratios– Ranking of VOC’s

http://www.maine.gov/dep/ftp/DEP_PAMS/NESCAUM_PAMS_ANALYSES/

8

Sub-Grouping of 54 Target PAMS Compounds

1. Propane 2. Ethane 3. Toluene 4. Isopentane 5. Isoprene 6. n-Butane 7. Ethylene 8. n-Pentane 9. Isobutane 10. 2,2,4-Trimethylpentane 11. m/p Xylene 12. 2-Methylpentane 13. Ethylbenzene 14. n-Hexane 15. Benzene 16. Propylene 17. Acetylene 18. o-Xylene 19. 1,2,4-Trimethylbenzne 20. n-Decane 21. Methylcyclohexane 22. n-Nonane 23. n-Octane

1. Ethane 2. Toluene 3. Isoprene 4. Ethylene 5. m/p Xylene 6. Benzene 7. Styrene

23 Target Compounds 7 Target Compounds

9

Propane 43204Isopentane 43221

Ethane 43202Toluene 45202n-Butane 43212

n-Pentane 43220Isoprene 43243Isobutane 43214Ethylene 43203

m/p Xylene 451092-Methylpentane 43285

n-Hexane 432312,2,4-Trimethylpentane 43250

Propylene 43205Benzene 45201

1,2,3-Trimethylbenzene 452253-Methylpentane 43230

Ethylbenzene 452033-Methylhexane 43249

Methylcyclopentane 43262Acetylene 43206n-Heptane 43232

1,2,4-Trimethylbenzene 45208o-Xylene 45204

m-Ethyltoluene 452122-Methylhexane 43263

2,3-Dimethylbutane 432841,3,5-Trimethylbenzene 45207

Methylcyclohexane 43261Styrene 45220

n-Undecane 43954n-Decane 43238

2,3,4-Trimethylpentane 43252p-Ethyltoluene 45213

n-Nonane 43235n-Octane 43233

2,3-Dimethylpentane 43291Cyclohexane 43248

trans-2-Butene 43216trans-2-Pentene 43226Cyclopentane 43242

2,2-Dimethylbutane 432442,4-Dimethylpentane 43247

o-Ethyltoluene 452112-Methylheptane 43960

1-Pentene 432241-Butene 43280

3-Methylheptane 43253cis-2-Butene 43217

p-Diethylbenzene 45219n-Propylbenzene 45209

cis-2-Pentene 43227Isopropylbenzene 45210m-Diethylbenzene 45218

ALL hourly sites TYPE 1 sites TYPE 2 sites TYPE 3 sites TYPE 4 sitesPropane 43204Ethane 43202

Isoprene 43243Isopentane 43221

Toluene 45202n-Butane 43212

n-Pentane 432201,2,3-Trimethylbenzene 45225

Benzene 45201Isobutane 43214

2-Methylpentane 43285m/p Xylene 45109n-Hexane 43231Ethylene 43203

2,2,4-Trimethylpentane 43250p-Ethyltoluene 45213

Propylene 432053-Methylpentane 43230m-Ethyltoluene 452123-Methylhexane 43249Ethylbenzene 45203

Methylcyclopentane 43262n-Heptane 43232Acetylene 43206o-Xylene 45204

trans-2-Butene 432162,3-Dimethylbutane 43284

2-Methylhexane 43263Cyclohexane 43248

2,3,4-Trimethylpentane 432521,2,4-Trimethylbenzene 45208

Methylcyclohexane 432612,2-Dimethylbutane 43244

n-Octane 43233Cyclopentane 43242

2,3-Dimethylpentane 432913-Methylheptane 43253

n-Nonane 432352,4-Dimethylpentane 43247

1-Pentene 432242-Methylheptane 43960

Styrene 45220o-Ethyltoluene 45211

1,3,5-Trimethylbenzene 452071-Butene 43280n-Decane 43238

n-Propylbenzene 45209trans-2-Pentene 43226

cis-2-Butene 43217n-Undecane 43954

m-Diethylbenzene 45218p-Diethylbenzene 45219

cis-2-Pentene 43227Isopropylbenzene 45210

Propane 43204Ethane 43202Toluene 45202

Isopentane 43221Isoprene 43243n-Butane 43212Ethylene 43203

n-Pentane 43220Isobutane 43214

1,3,5-Trimethylbenzene 452072,2,4-Trimethylpentane 43250


Ethylbenzene 45203n-Hexane 43231Benzene 45201

1,2,3-Trimethylbenzene 45225Propylene 43205Acetylene 43206o-Xylene 45204

3-Methylpentane 43230n-Undecane 43954n-Heptane 43232

1,2,4-Trimethylbenzene 452083-Methylhexane 43249

Methylcyclopentane 43262n-Decane 43238

m-Ethyltoluene 452122-Methylhexane 43263

Methylcyclohexane 432612,3,4-Trimethylpentane 43252

n-Nonane 43235o-Ethyltoluene 45211

2,3-Dimethylbutane 43284p-Diethylbenzene 45219

trans-2-Butene 432162-Methylheptane 43960n-Propylbenzene 45209

n-Octane 432332,3-Dimethylpentane 43291

Styrene 452202,2-Dimethylbutane 43244

Cyclohexane 43248Cyclopentane 43242p-Ethyltoluene 45213

trans-2-Pentene 43226m-Diethylbenzene 45218

1-Butene 432802,4-Dimethylpentane 43247

1-Pentene 432243-Methylheptane 43253Isopropylbenzene 45210

cis-2-Butene 43217cis-2-Pentene 43227

Rankings of VOC’s during 0500-0800 hours of an Ozone event day (8-hr > 70 ppb)

Isopentane 43221Propane 43204Ethane 43202Toluene 45202n-Butane 43212

n-Pentane 43220Isobutane 43214

2-Methylpentane 43285m/p Xylene 45109Ethylene 43203n-Hexane 43231

2,2,4-Trimethylpentane 43250Isoprene 43243

Propylene 432053-Methylpentane 43230

Benzene 45201Methylcyclopentane 43262

3-Methylhexane 43249n-Heptane 43232

1,2,4-Trimethylbenzene 45208Acetylene 43206

Ethylbenzene 452032-Methylhexane 43263

o-Xylene 452042,3-Dimethylbutane 43284

Styrene 452201,2,3-Trimethylbenzene 45225

m-Ethyltoluene 45212Methylcyclohexane 43261

2,3,4-Trimethylpentane 43252n-Decane 43238

trans-2-Pentene 432262,3-Dimethylpentane 43291

n-Octane 43233Cyclohexane 43248

trans-2-Butene 43216n-Nonane 43235

n-Undecane 439542,2-Dimethylbutane 43244

Cyclopentane 432422,4-Dimethylpentane 43247

1-Pentene 432241,3,5-Trimethylbenzene 45207

3-Methylheptane 43253cis-2-Butene 43217

1-Butene 43280p-Ethyltoluene 45213

2-Methylheptane 43960o-Ethyltoluene 45211cis-2-Pentene 43227

n-Propylbenzene 45209p-Diethylbenzene 45219Isopropylbenzene 45210m-Diethylbenzene 45218

Propane 43204Ethane 43202

Isoprene 43243Toluene 45202

Isopentane 432211,2,3-Trimethylbenzene 45225

n-Butane 43212n-Pentane 43220Ethylene 43203Isobutane 43214


Benzene 45201n-Hexane 43231

2,2,4-Trimethylpentane 43250Propylene 43205

m-Ethyltoluene 452123-Methylhexane 432493-Methylpentane 43230p-Ethyltoluene 45213

Acetylene 43206n-Heptane 43232

1,2,4-Trimethylbenzene 45208Methylcyclopentane 43262

o-Xylene 45204Ethylbenzene 45203

2-Methylhexane 432632,3-Dimethylbutane 43284Methylcyclohexane 43261

Cyclohexane 43248n-Octane 43233

2,3,4-Trimethylpentane 43252n-Decane 43238n-Nonane 43235Styrene 45220

2,3-Dimethylpentane 43291n-Undecane 43954

Cyclopentane 432421-Butene 43280

2,2-Dimethylbutane 43244trans-2-Butene 43216

1,3,5-Trimethylbenzene 452073-Methylheptane 43253

1-Pentene 432242-Methylheptane 43960

2,4-Dimethylpentane 43247o-Ethyltoluene 45211

trans-2-Pentene 43226p-Diethylbenzene 45219Isopropylbenzene 45210n-Propylbenzene 45209

cis-2-Butene 43217m-Diethylbenzene 45218

cis-2-Pentene 43227

Only in the 23 target compounds list

In both the 23 and 7 target compounds lists

Only in the 7 target compounds list

10

Cape Elizabeth, Maine PAMS SITE - Benzene

SAS JMP statistical software used

Annual Box and Whisker Plots by Site and Key Species

Philadelphia PAMS SITE - Benzene

Comparative line drawn at 2ppbC

11

TYPE 1 SITEType 1 (Upwind) Site TrendsArendtsville, PA PAMS 0500-0800 LST Non-event VOC Concentrations

0

5

10

15

20

25

30

1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

PP

BC

54 compounds

7 compounds

23 compounds

53 (w/o-isoprene)

6 (w/o-isoprene)

22 (w/o-isoprene)

Tom Downs, Maine DEP-BAQ - 11/9/2010

12

TYPE 1 SITE

Corbin, VA PAMS 0500-0800 LST Non-event VOC Concentrations

0

10

20

30

40

50

60

70

80

90

100

1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

PP

BC

54 compounds

7 compounds

23 compounds

53 (w/o-isoprene)

6 (w/o-isoprene)

22 (w/o-isoprene)


Type 1 (Upwind) Site Trends

13

TYPE 2 SITE

Essex, MD PAMS 0500-0800 LST Non-event VOC Concentrations

0

20

40

60

80

100

120

1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

PP

BC

54 compounds

7 compounds

23 compounds

53 (w/o-isoprene)

6 (w/o-isoprene)

22 (w/o-isoprene)


Type 2 (High Emission) Site Trends

14

NYC (Bronx & Pfizer Lab), NY PAMS 0500-0800 LST Non-event VOC Concentrations

0

20

40

60

80

100

120

140

1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

PP

BC

54 compounds

7 compounds

23 compounds

53 (w/o-isoprene)

6 (w/o-isoprene)

22 (w/o-isoprene)


TYPE 2 SITEType 2 (High Emission) Site Trends

15

TYPE 3 SITEType 3 (High Ozone) Site TrendsRider U, NJ PAMS 0500-0800 LST Non-event VOC Concentrations

0

10

20

30

40

50

60

1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

PP

BC

54 compounds

7 compounds

23 compounds

53 (w/o-isoprene)

6 (w/o-isoprene)

22 (w/o-isoprene)2004-2008 - no m- & p-

Ethyltoluene measurements


16

TYPE 3 SITEType 3 (High Ozone) Site TrendsNewbury, MA PAMS 0500-0800 LST Non-event VOC Concentrations

0

5

10

15

20

25

30

35

1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

PP

BC

54 compounds

7 compounds

23 compounds

53 (w/o-isoprene)

6 (w/o-isoprene)

22 (w/o-isoprene)2007 - no 1,2,4-Trimethylbenzene

measurements

2006 - Isopropylbenzene & 1,2,3-Trimethylbenzene measurements

missing for many hours


17

TYPE 4 SITEType 4 (Downwind) Site Trends

Cadillac Mt, ME PAMS 0500-0800 LST Non-event VOC Concentrations

0

2

4

6

8

10

12

14

1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010

PP

BC

54 compounds

7 compounds

23 compounds

53 (w/o-isoprene)

6 (w/o-isoprene)

22 (w/o-isoprene)


18

As VOCs Emissions are Reduced, There are More Below Detection Limits

Cape Elizabeth PAMS site Ozone Event Number of VOC's below Minimum Detect Levels (54 VOC's monitored)

0

3

6

9

12

15

18

21

24

27

30

33

36

39

42

45

48

51

54

1998

0528

1998

0713

1998

0716

1998

0807

1999

0530

1999

0716

1999

0723

1999

0825

2001

0503

2001

0615

2001

0630

2001

0724

2001

0908

2002

0702

2002

0708

2002

0811

2002

0814

2002

0909

2003

0626

2003

0703

2003

0821

2004

0810

2005

0625

2005

0808

2006

0710

2007

0423

2007

0627

2007

0803

2007

0926

2008

0726

2009

0817

Event Day

# b

elo

w M

DL

Peak Ozone

Morning

Linear (Peak Ozone)

Linear (Morning)

Created by Tom Downs, Maine DEP-BAQ - 4/23/10

19

NO/NOy Trends(?)

Cape Elizabeth PAMS Site Ozone Event NOy and NO Trends

0

2

4

6

8

10

12

14

16

18

20

22

24

1998

0528

1998

0713

1998

0716

1998

0807

1999

0530

1999

0716

1999

0723

1999

0825

2001

0503

2001

0615

2001

0630

2001

0724

2001

0908

2002

0702

2002

0708

2002

0811

2002

0814

2002

0909

2003

0626

2003

0703

2003

0821

2004

0810

2005

0625

2005

0808

2006

0710

2007

0423

2007

0627

2007

0803

2007

0926

2008

0726

2009

0817

Event Day

NO

y co

nce

ntr

atio

ns

(pp

b)

0.00

0.02

0.04

0.06

0.08

0.10

0.12

NO

co

nce

ntr

atio

ns

(pp

b)

Morning NOy Peak Ozone NOy Morning NO Peak Ozone NO

Linear (Peak Ozone NO) Linear (Morning NO) Linear (Peak Ozone NOy) Linear (Morning NOy)


20

Aging Ratios – Benzene/TolueneCadillac PAMS Site Event Days Benzene/Toluene Ratio

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

5.0

5.5

6.0

6.5

7.0

7.5

8.0

8.5

9.0

9.5

10.0

10.5

1998

0430

1998

0529

1998

0625

1998

0717

1998

0824

1999

0601

1999

0714

1999

0812

1999

0904

2000

0622

2000

0809

2001

0512

2001

0616

2001

0723

2001

0810

2002

0524

2002

0704

2002

0804

2002

0813

2002

0908

2003

0607

2003

0630

2003

0721

2004

0515

2004

0730

2005

0419

2005

0621

2005

0805

2005

0922

2006

0619

2006

0716

2007

0524

2007

0726

2007

0830

2008

0701

2009

0521

Event Day

ben

zen

e/to

luen

e ra

tio

Morning

Peak OzoneLow Volatility

Fuel Program in Southern Maine (May 1, 1999)

Tier II Vehicle and Heavy duty

engine Standards (Fed 2004)

Small Engine Standards

(Tier II Fed 2001)

2005 State Control Programs (Solvent Cleaning, Mobile

equipment repair and refinishing, Distributed

Generation, Portable Fuel Containers and Consumer Products


21

Wind Directions During High OzoneCape Elizabeth, ME (1000-1500 LST) Wind Direction Frequency During

1997-2007 Ozone events (8-hr Ozone max > 75 ppb)

0

10

20

30

40

50

60

70

80

90

100

010

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160170

180190

200

210

220

230

240

250

260

270

280

290

300

310

320

330

340350

1998-2002

2003-2007

1997-2007


22

23

24

NESCAUM PAMS Workgroup Data

NESCAUM PAMS ftp data archive:ftp://airbeat.org/PAMS/

MEDEP links to PAMS data sets and analyses files : http://www.maine.gov/dep/ftp/DEP_PAMS/NESCAUM_PAMS_DATA/ and


ftp://airbeat.org/PAMS/



http://www.maine.gov/dep/ftp/DEP_PAMS/NESCAUM_PAMS_DATA/

http://www.maine.gov/dep/ftp/DEP_PAMS/NESCAUM_PAMS_DATA/





Documents

1 PAMS IN THE OZONE TRANSPORT REGION March 2, 2011 MEDEP Monitoring Meeting Tom Downs, CCM Chief Meteorologist Maine DEP-BAQ 207-287-7026 [email protected]