1 pams in the ozone transport region march 2, 2011 medep monitoring meeting tom downs, ccm chief...
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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
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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
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
m/p Xylene 451092-Methylpentane 43285
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
m/p Xylene 451092-Methylpentane 43285
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
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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
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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)
Tom Downs, Maine DEP-BAQ - 11/17/2010
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)
Tom Downs, Maine DEP-BAQ - 11/1/2010
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)
Tom Downs, Maine DEP-BAQ - 10/26/2010
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
Tom Downs, Maine DEP-BAQ - 9/23/2010
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
Tom Downs, Maine DEP-BAQ - 9/23/2010
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)
Tom Downs, Maine DEP-BAQ - 12/20/2010
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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
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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)
Created by Tom Downs, Maine DEP-BAQ - 4/23/10
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
Created by Tom Downs, Maine DEP-BAQ - 4/23/10
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
Created by Tom Downs, Maine DEP-BAQ - 02/16/2008
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
http://www.maine.gov/dep/ftp/DEP_PAMS/NESCAUM_PAMS_ANALYSES/