Pinal County Air Quality

Pinal County Air Quality
Speciation Study Final Report
Kale Walch
TEOM Comparison Studies
Joe Pisano
January 9, 2005

Speciation Project Description
Speciation Project Description
The project was designed to identify sources of particulate
matter in the Pinal County agricultural basin.
PM10 and PM2.5 Mini-Vol samplers utilizing Pallflex quartz
filters and Teflon filters were operated at five sites on a 1 in 3
schedule. (At least one FRM sampler was also located at each
site.)
Soil samples were collected from feedlots, dirt roads, and
agricultural fields.
Sampling took place from October 1, 2003 to November 10,
2003. The ten runs with the best data recovery were chosen for
analysis.
DRI performed speciation and source apportionment analysis
on the Mini-Vol filters.

Method Comparison
Figure 1: Hi-Vol vs M ini-Vol: PM 10
Conc. (ug/m3)
140
120
100
80
60
40
20
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
HiVol
MiniVol
Run #
Figure 2: Hi-Vol vs Mini-Vol: PM10
Min-Vol
120
100
80
60
40
20
FRM HiVol to MiniVol
PM10
Linear (FRM HiVol to
MiniVol PM10)
0
0 20 40 60 80 100 120
FRM Hi-Vol

Method Comparison
Figure 3: TEOM vs Mini-Vol: PM10
Conc. (ug/m3)
400
350
300
250
200
150
100
50
0
TE OM
MiniVol
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19
Figure 4: TEOM vs Mini-Vol: PM10
Run #
Mini-Vol
350
300
250
200
150
100
50
0
0 50 100 150 200 250 300 350
TEOM
TEOM vs MiniVol
PM10
Linear (TEOM vs
MiniVol PM10)

Method Comparison
Table 5: FRM PM 2.5
vs Mini-Vol PM 2.5
0.32
Date
FRM PM 2.5
Mini-Vol PM 2.5
10/18/2003
10/30/2003
11/5/2003
10.1
26.7
10.7
14.1
49.5
20.2
Table 6: Mini-Vol PM 2.5
/PM 10
ratios
Site
Avg. Mini-Vol
PM 10
µg/m 3
Avg. Mini-Vol
PM 2.5
µg/m 3
Avg. Mini-Vol
PM 2.5
/PM 10
Ratio
Casa Grande
44
18
0.41
Coolidge
47
25
0.53
Cowtown
127
67
0.53
Pinal County Housing
60
25
0.42
Stanfield
55
18

Iron
OC1
Iron
OC1
Iron
OC1
Calcium
Calcium
Calcium
Potassium
Potassium
Potassium
Silicon
Silicon
Silicon
40
30
20
10
0
Chemical Fingerprint - Agricultural Dust, PM10
OC2
OC3
OC4
OPT
EC1
EC2
EC3
TC
Aluminum
Chemical Fingerprint - Road Dust, PM10
OC2
OC3
OC4
OPT
EC1
EC2
EC3
TC
Aluminum
Chemical Species
Ammonium
Ammonium
Sulfate
Sulfate
Nitrate
Nitrate
40
30
20
10
0
40
30
20
10
0
Chemical Fingerprint - Feedlot Dust, PM10
OC2
OC3
OC4
OPT
EC1
EC2
EC3
TC
Aluminum
Chemical Species
Chemical Species
Ammonium
Sulfate
Nitrate
% Concentration
% Concentration
% Concentration

Iron
Iron
Iron
Calcium
Calcium
Calcium
Potassium
Potassium
Potassium
Silicon
Silicon
Silicon
40
30
20
10
0
Chemical Fingerprint - Feedlot Dust, PM2.5
OC2
OC3
OC4
OPT
EC1
EC2
EC3
TC
Aluminum
OC1
Chemical Species
Chemical Fingerprint - Agricultural Dust, PM2.5
OC2
OC3
OC4
OPT
EC1
EC2
EC3
TC
Aluminum
OC1
Ammonium
Ammonium
Sulfate
Sulfate
Nitrate
Nitrate
40
30
20
10
0
Chemical Species
Chemical Fingerprint - Road Dust, PM2.5
OC2
OC3
OC4
OPT
EC1
EC2
EC3
TC
Aluminum
OC1
Ammonium
Sulfate
% Concentration
% Concentration
40
30
20
10
0
Chemical Species
Nitrate
% Concentration

Casa Grande Source
Apportionment
Casa Grande PM 10
Casa Grande PM 2.5
1%
6%
0% 3% 3%
5%
Soil
Feedlot
MvEmi
4%
1%
13%
43%
VgBrn
20%
62%
ColPP
AmSulf
AmNitr
17%
Other
10%
12%
0%

Coolidge Source Apportionment
Coolidge PM 10
Coolidge PM 2.5
2%
9%
5%
3%
0% 0%
8%
Soil
Feedlot
MvEmi
VgBrn
ColPP
3%
1%
20%
40%
AmSulf
AmNitr
15%
73%
Other
9%
7%
5%

Cowtown Source Apportionment
Cowtown PM 10
32%
Cowtown PM 2.5
24%
0% 2% 4%
Soil
1%
1%
1%
59%
Feedlot
MvEmi
VgBrn
ColPP
AmSulf
AmNitr
Other
0%
9%
7%
3%
4% 4%
49%

Pinal County Housing Source
Apportionment
Pinal County Housing PM 10
0%
6%
0% 3%
2%
3%
Soil
Feedlot
MvEmi
Pinal County Housing PM 2.5
50%
0%
17%
3%
7%
19%
VgBrn
ColPP
AmSulf
7%
67%
AmNitr
Other
8%
8%

Stanfield Source Apportionment
Stanfield PM 10
Stanfield PM 2.5
0% 3% 7%
4%
4%
0%
Soil
Feedlot
MvEmi
VgBrn
5%
2%
17%
6%
48%
19%
63%
ColPP
AmSulf
AmNitr
Other
15%
7% 0%

Speciation Project Conclusions
Crustal Material emissions are a significant source of
PM10 and PM2.5 in Pinal County
Manure emissions are a significant source of PM10
and to a lesser extent PM2.5 in Pinal County
Chemically construction dust and agricultural dust are
identical in an urban interface environment
The Mini-Vol Samplers likely over estimated ambient
PM2.5 concentrations
It is still possible that Pinal County will have difficulty
meeting the proposed PM2.5 standard

TEOM Comparison Studies
Monitoring Site : Cowtown Road
4 miles SE of Maricopa, surrounded by active and
retired agricultural operations to the north, northeast,
and east, and three cattle feedlots and a grain
processing complex to the south southwest and
southeast.
Current Site Status: 1 R&P TEOM 1400ab sampler, 1
R&P FDMS sampler, 1 MET station, 2 FRM Andersen
47mm filter samplers (1 PM 10 & 1 PM 2.5 ), and a timelapse
video system.

2 Key Issues / Inaccuracies
In April 2005 the FDMS and TEOM 1400 were installed
side by side sampling PM 10 . TEOM was found to be
recording 24 hour average concentrations 30% higher
than the FDMS.
The first issue: TEOM 1400 was recording large 5
minute negative concentrations after an extremely large
positive number (1000 ug/m 3 )
The second issue: TEOM 1400 was recording elevated
noise levels during these same episodes.

2006 Cowtown PM 10 24-hour avg.
January February March April May June July August September October November December
1 12.1 14.2 42.6 79.1 419.6 41.6 393.2 769.6 341.5 308.8
2 15.6 26.0 49.3 210.0 342.4 166.6 197.6 742.6 259.9 266.3
3 4.5 21.7 47.1 255.3 314.0 282.2 177.5
4 9.3 23.3 66.6 228.2 32.4 199.8 166.8 218.5 170.0
5 11.6 36.7 8.8 640.2 196.1 201.8 213.3 170.5 208.0 358.5
6 19.2 29.6 9.8 297.0 198.6 205.6 68.0 392.2 189.8 268.1
7 42.7 15.7 291.4 225.8 342.0 62.3 367.8 219.3 275.6
8 24.7 55.6 26.1 272.1 167.5 325.6 35.7 132.8 233.4 257.8
9 20.3 90.8 36.7 270.3 49.9 192.8 287.9 302.3
10 28.5 55.2 40.2 273.2 340.8 382.9 321.2 215.8 245.2
11 81.5 59.8 320.2 215.8 323.9 45.5 304.0 125.0 260.7
12 40.9 9.1 52.8 581.5 414.7 66.8 343.1 162.8 261.6
13 34.3 10.4 46.9 391.0 45.0 249.6 278.2 211.3
14 56.9 13.2 55.9 243.2 326.1 84.2 219.6 196.2 213.7
15 43.6 16.7 32.3 326.9 328.4 235.5 94.2 431.7 343.2 172.2 151.2
16 40.7 24.6 115.6 229.5 335.2 303.8 129.9 299.9 379.5 110.3
17 115.4 32.7 80.2 373.9 308.9 315.2 350.8 163.7 356.7
18 111.7 8.4 93.3 517.0 323.7 297.3 337.1 156.5 379.1 164.1
19 108.8 4.5 44.6 284.3 368.3 279.1 179.7 126.8 606.9 405.0
20 7.9 55.4 455.7 226.1 352.1 171.1 316.0 251.6 101.5
21 16.2 99.2 371.9 264.3 470.0 234.2 279.3 250.5 90.7 384.2
22 11.0 60.9 368.8 306.5 167.8 211.8 277.8 90.0
23 13.1 111.0 281.5 269.7 142.7 153.0 341.4 79.1 294.6
24 13.9 60.8 346.6 118.6 533.4 132.8
25 19.7 97.4 439.6 392.1 142.1 197.3
26 17.5 31.4 122.9 138.5 183.5 456.9 108.6 158.5
27 13.3 28.8 100.1 164.3 377.5 160.0 151.4 395.1 118.4 228.6
28 12.8 34.5 165.3 179.7 193.1 415.6 353.8
29 24.5 175.6 155.3 113.3 107.9 585.2 95.7 225.6
30 10.9 209.3 133.8 300.3 58.7 222.2 653.8 141.0 252.3
31 22.0 67.6 378.0 14.2 288.6 207.0

TEOM PM 10 Hourly data w/ main flow at 3 LPM
1 HOUR AVG 24 HOUR AVG DATE TIME
45.7 353.7 5-Apr-05 12:00:05
21.6 338.6045455 5-Apr-05 13:00:05
12.2 324.4130435 5-Apr-05 14:00:05
38.2 296.1434783 5-Apr-05 15:00:05
30.7 270.5347826 5-Apr-05 16:00:05
37.3 233.7347826 5-Apr-05 17:00:05
35.2 214.9434783 5-Apr-05 18:00:05
191.2 201.4565217 5-Apr-05 19:00:05
6444.5 440.4043478 5-Apr-05 20:00:05
4381 600.4608696 5-Apr-05 21:00:05
829.6 626.2086957 5-Apr-05 22:00:05
413.4 640.226087 5-Apr-05 23:00:05
332 648.9478261 6-Apr-05 0:00:05
156.7 651.126087 6-Apr-05 1:00:05
178.1 652.9086957 6-Apr-05 2:00:05
277.7 659.1304348 6-Apr-05 3:00:05
265.6 665.6304348 6-Apr-05 4:00:05
175.2 668.1608696 6-Apr-05 5:00:05
381.1 661.1434783 6-Apr-05 6:00:05
400.2 656.626087 6-Apr-05 7:00:05
376.7 656.9521739 6-Apr-05 8:00:05
179.6 661.0217391 6-Apr-05 9:00:05
71.6 664.1347826 6-Apr-05 10:00:05
143.1 642.425 6-Apr-05 11:00:05

TEOM PM 10 Hourly data w/ main flow at 1 LPM
1 HOUR AVG 24 HOUR AVG DATE TIME
36.4 663.9478261 1-Oct-05 15:00:05
22.3 664.3347826 1-Oct-05 16:00:05
67 667.2478261 1-Oct-05 17:00:05
432.5 682.2391304 1-Oct-05 18:00:05
4272.4 860.3130435 1-Oct-05 19:00:05
4101.3 899.2130435 1-Oct-05 20:00:05
1397.8 835.1565217 1-Oct-05 21:00:05
493.3 801.4608696 1-Oct-05 22:00:05
591.1 769.6695652 1-Oct-05 23:00:05
455.8 728.3782609 2-Oct-05 0:00:05
989.8 725.1 2-Oct-05 1:00:05
474.4 711.4869565 2-Oct-05 2:00:05
110.3 681.973913 2-Oct-05 3:00:05
132 682.126087 2-Oct-05 4:00:05
73.5 667.4043478 2-Oct-05 5:00:05
388 672.826087 2-Oct-05 6:00:05
357 668.7478261 2-Oct-05 7:00:05
337.8 665.3478261 2-Oct-05 8:00:05
189.9 664.5913043 2-Oct-05 9:00:05

Before 1 LPM flow restrictor (PM 10 )
FDMS v.s. 1400ab
500
450
400
350
300
250
200
150
100
50
0
24 hr avg Mass Concentration (ug/m3)
04/23/2005
04/30/2005
05/07/2005
05/14/2005
05/21/2005
05/28/2005
06/04/2005
06/11/2005
06/18/2005
Days
FDMS
1400 ab

Troubleshooting TEOM 1400
After working with R&P to resolve the issues,
R&P recommended putting a 1.0 LPM flow
restrictor on the main line inlet. (August 2, 2005)
The assumption was that too much material was
entering into the sample line and disrupting the
microbalance. (Noise & Negative readings)

Result of 1.0 LPM Flow Restrictor
Reduction in large negative concentration
readings.
A dramatic noise reduction within the
microbalance.
Brought the TEOM 1400 and FDMS units to a
15% difference in recorded 24 hour
concentrations.

After 1 LPM flow restrictor (PM 10 )
After 1 LPM flow restrictor (PM 10 )
FDMS vs 1400 ab (After 1.0L)
450
400
350
300
250
200
150
100
50
0
24 hr avg. Mass Concentration
(ug/m3)
10/21/2005
10/28/2005
11/04/2005
11/11/2005
11/18/2005
11/25/2005
12/02/2005
12/09/2005
Run Days
FDMS
1400ab

Filter-based / TEOM Comparison
Installed 2 FRM Andersen 47mm filter-based
monitors (1 PM 10 and 1 PM 2.5 ) that operate on a
6-day schedule.
Began sampling on August 14, 2005.
The purpose or intent of these two monitors is to
be used as comparisons to TEOM / FDMS.

Cowtown PM 10 FRM (filter based)
RUN DATE PM 10 STATUS CODES
(µg/m3)
8/14/2005 82.6384 0
8/20/2005 271.4979 FILTER DAMAGED
8/26/2005 107.6425 0
9/1/2005 366.1906 0
9/7/2005 327.0518 0
9/13/2005 259.2250 0
9/19/2005 604.4240 0
9/25/2005 412.4626 0
10/1/2005 677.7994 0
10/7/2005 178.6250 0
10/11/2005 FIELD BLANK
10/13/2005 756.1905 0
10/19/2005 INVALID RUN - STOR
10/31/2005 223.5771 0
11/6/2005 197.4814 0
11/12/2005 181.5310 0
11/18/2005 152.1459 0
11/24/2005 138.0572 0
11/30/2005 266.4094 0
12/3/2005 150.0138 0
12/6/2005 276.5912 0
12/9/2005 333.0680 0
12/12/2005 284.9892 0

PM 10 Method Comparisons
1400ab v.s. 47mm v.s. FDMS
900
800
700
600
500
400
300
200
0
100
08/14/2005
08/28/2005
09/11/2005
09/25/2005
10/09/2005
10/23/2005
11/06/2005
11/20/2005
12/04/2005
Days
1400 ab
47 mm
FDMS
24 hr avg Mass Concentration
(ug/m3)

Cowtown PM 2.5 FRM (filter based)
RUN DATE PM 2.5 STATUS CODES
(µg/m3)
8/14/2005 9.7519 0
8/20/2005 20.7532 0
8/26/2005 16.0860 0
9/1/2005 25.6719 0
9/7/2005 29.7556 0
9/13/2005 23.3821 0
9/19/2005 57.3465 0
9/25/2005 50.8490 0
10/1/2005 144.8109 0
10/7/2005 22.3416 0
10/11/2005 FIELD BLANK
10/13/2005 78.9316 0
10/19/2005 INVALID RUN - STORM
10/31/2005 25.6279 0
11/6/2005 26.2138 0
11/12/2005 20.5045 0
11/18/2005 16.2133 0
11/24/2005 15.4200 0
11/30/2005 29.5949 0
12/3/2005 13.9608 0
12/6/2005 25.6447 0
12/9/2005 29.1029 0
12/12/2005 29.9331 0

FRM PM 10 / PM 2.5 / Coarse
Cowtown ~PM10-2.5
800
700
600
500
400
300
200
100
0
08/14/2005
08/21/2005
08/28/2005
09/04/2005
09/11/2005
09/18/2005
09/25/2005
10/02/2005
10/09/2005
10/16/2005
10/23/2005
10/30/2005
11/06/2005
Run Days
PM10 PM2.5 PM10-2.5
24 hr avg Mass Concentration
(ug/m3)

Future Plans
Change FDMS unit over PM 2.5 sampling.
Compare FDMS PM 2.5 to 47mm PM 2.5
Expanding other PCAQCD monitoring sites for
PM 2.5 and PM 10-2.5 .
Still working with R&P on the 15% difference and
troubleshooting FDMS. (R&P conclusion)