An Alternative Approach To

Ambient Ozone Monitoring

Presenter: Patrick King
Teledyne Advanced Pollution Instrumentation
O3 Measurement Methods
 Dasibi came out with the first EPA approved
equivalent photometric ozone analyzer in
1977.
 Before that, the EPA Reference Method was,
and still is, a chemiluminescence analyzer
using Ethylene as the reagent.
 Obvious issue with Reference Method –
Ethylene is highly flammable, potential for
serious injury.
What Is A 265 Ozone Analyzer?
 Through close communication with our
customers a need for an alternate
measurement approach was identified.
 Why not replace Ethylene with Nitric Oxide?
Basically, the premise is based on a reverse
NOx analyzer. Low cost, high precision
bottles of Nitric Oxide are readily available.
 Used continuously, standard cylinders of
Nitric Oxide should last approximately one
year, due to the low flow rate of 5 cm3/min.
265 Pneumatic Design
265 Sample Flow Path
265 Azero Flow Path
265 Nitric Oxide Flow Path
Why A Chemi-Ozone Analyzer?
Known Photometric Interferants:
Many compounds absorb photons as well or
better than ozone at 254 nm.
◦ ClO2
◦ Mercury
◦ Tetrahydrofuran
◦ Turpines
◦ Other VOC’s
 UV photometric analyzers experience large
wet dry episodes, especially when switching
between wet sample and dry calibration gases.
Prospective Customers
 Example 1: Customers who are marginal in
their ozone attainment.
 Example 2: In pine forests.
◦ Pine trees emit turpines at night
 Example 3: In natural gas fields.
◦ Gas wells have large amounts of mercury
 Example 4: In welding operations.
◦ Arc welding makes both O3 as well as fine particulates.
 Example 5: In areas with high VOC
backgrounds.
 Example 6: Near polyvinyl chloride (PVC)
plants.
◦ The solvent for PVC is tetrahydrofuran
Interference Study
 Houston TCEQ Study:
A hydrocarbon spike experiment was carried out to examine how organic
compounds might interfere with ozone monitors. A mixture of 21 C 2 - C8
hydrocarbons was used to challenge the instruments being compared by our study,
as well as two TCEQ UV ozone monitors. The total hydrocarbon concentration was
1.4 ppmV, and the individual species concentrations were 66 ppbV each. All
instruments were first zeroed and then spanned at 100 ppb. The input ozone
concentration was then set to 30 ppb, and the hydrocarbon mixture was used to
challenge the ozone monitors.
 Species Contained In Mixture:
Ethylene 1,3-Butadiene Benzene
Acetylene Butane Toluene
Ethane Isopentane Styrene
Propylene 1-Pentene Ethylbenzene
Methyl-tert-Butyl-
Propane n-Pentane Ether
trans-2-
Isobutane n-Hexane Butene
1-Butene Isoprene cis-2-Butene
 Interference Study Results
2010 VOC Interference Study
120
Houston Regional Monitoring Network
100

Addition of HC Mixture
80
TE 49C
API 265E
60
Ozone (ppb)

Dasibi 1008
API 400
40

20

Removal of HC Mixture
0
1 0 /2 7 /2 0 1 0 1 6 :3 3 1 0 /2 7 /2 0 1 0 1 7 : 4 5 1 0 /2 7 /2 0 1 0 1 8 :5 7 1 0 /2 7 /2 0 1 0 2 0 : 0 9

-20
Date / Time
-40
Product Specifications
 Ranges: 0-100 ppb to 0-2000 ppb
 Zero Noise: <0.3 ppb (RMS)
 Span Noise: <0.5% of reading above 100 ppb
 Linearity: <1% of Full Scale
 Precision: <0.5% of reading
 Rise/Fall time: < 20 Seconds to 95%
 Sample Flow: 500 cm3/min
 Reagent Flow: 5 cm3/min
 Linearity Data

265E 100 ppb Range Linearity 265E 500 ppb Range Linearity 265E 2000 ppb Range Linearity
105 525

Correlation Coeff = 1.0000 Correlation Coeff = 1.0000

Correlation Coeff = 1.0000
265E Output (ppb)

265E Output (ppb)

265E Output (ppb)
1800
90 450

1500
75 375

1200
60 300

900
45 225

150 600
30

75 300
15

0 0 0
0 15 30 45 60 75 90 105 0 75 150 225 300 375 450 525 0 300 600 900 1200 1500 1800
703E Calibrator Output (ppb) 703E Calibrator Output (ppb) 703E Calibrator Output (ppb)
Comparison Data
Subpart C Overlaid Graphs
450
M265E_SN51 M400E
Bendix
400
Conc(ppb)

350

300

250

200

150

100

50
Group 1 Group 2 Group 3
0
10/1 10/2 10/3 10/4 10/5 10/6 10/7

Date
 Noise And Drift Data
Test #1 Test #2 Test #3 Test #4 Test #5 Test #6 Test #7
Std DEV Std DEV Std DEV Std DEV Std DEV Std DEV Std DEV
Zero Span Span Zero Span Span Zero Span Span Zero Span Span Zero Span Span Zero Span Span Zero Span Span
0.04 0.35 1.98 0.05 0.45 1.95 0.09 0.47 1.76 0.09 0.56 0.32 0.05 0.47 1.20 0.07 0.35 1.03 0.06 0.15 1.16
16% 80% 16% 80% 16% 80% 16% 80% 16% 80% 16% 80% 16% 80%
Zero Range Range Zero Range Range Zero Range Range Zero Range Range Zero Range Range Zero Range Range Zero Range Range
-0.08 80.03 395.71 0.15 80.64 397.92 0.28 79.55 399.30 0.34 79.76 406.34 -0.02 81.86 401.44 0.22 81.55 402.35 0.15 80.49 400.02

-0.02 80.39 398.89 0.11 82.27 401.20 0.16 81.53 400.84 0.17 81.98 406.16 -0.04 81.24 405.89 0.16 81.55 405.68 -0.02 80.45 403.41

-0.04 79.44 403.39 0.08 80.83 405.32 0.10 80.61 405.23 0.16 81.03 405.68 0.07 80.13 407.02 0.15 80.18 407.28 -0.06 80.61 405.15

-0.04 79.19 404.38 0.10 80.26 405.91 0.09 80.01 405.90 0.12 79.72 405.44 0.09 80.14 407.00 0.16 80.06 407.73 -0.07 80.33 405.30

-0.03 79.35 404.19 0.06 79.90 406.34 0.07 79.59 406.27 0.10 79.49 405.84 -0.02 80.32 407.14 0.15 80.38 407.56 -0.06 80.56 405.33

-0.01 79.35 404.35 -0.01 79.94 406.29 0.06 79.39 406.51 0.08 79.20 406.43 0.01 79.98 407.48 0.07 80.51 407.20 -0.02 80.25 405.17

-0.05 79.44 404.66 0.06 80.25 406.24 0.03 79.66 406.35 0.11 79.55 406.46 0.00 79.79 407.54 0.00 80.35 406.67 0.02 79.99 405.33

-0.09 79.22 404.35 -0.01 80.34 406.57 0.02 79.88 406.39 0.11 80.07 406.04 0.04 79.65 407.32 0.03 80.16 406.69 0.07 80.28 405.57

-0.11 79.38 403.93 -0.02 80.37 405.88 0.04 79.80 406.36 0.10 79.96 406.13 0.05 79.91 407.45 0.01 80.33 406.83 0.03 80.29 405.08

-0.05 79.44 404.06 0.03 80.74 406.39 -0.03 79.95 406.32 0.12 80.00 406.30 0.04 80.25 407.38 0.02 80.87 406.56 0.05 80.16 405.17

-0.04 79.64 404.01 0.04 80.48 407.23 -0.06 80.24 406.38 0.12 80.06 406.68 0.06 80.36 407.07 0.04 80.62 407.44 0.01 80.36 406.04

-0.04 79.95 404.30 0.00 80.24 406.70 -0.08 80.19 406.23 0.07 80.02 406.55 0.07 80.18 406.76 0.06 80.30 407.40 0.03 80.24 405.99

-0.01 80.19 404.48 0.03 80.28 405.86 -0.07 80.34 405.90 0.09 80.32 406.20 0.08 80.29 406.97 0.02 80.52 407.16 0.08 80.19 405.83
-0.06 80.12 403.88 0.09 80.24 405.97 -0.03 80.46 406.93 0.10 80.56 406.74 0.04 80.33 406.88 0.04 80.58 406.79 0.12 80.47 405.31

-0.01 79.74 404.30 0.13 80.53 406.42 -0.07 80.49 405.91 0.07 80.66 405.85 0.10 80.52 406.49 0.03 80.44 406.85 0.04 80.49 405.04

0.00 79.62 404.07 0.06 80.36 405.84 -0.04 80.64 405.46 0.09 80.17 405.98 0.10 80.94 407.08 0.03 80.49 406.63 0.06 80.35 404.95

0.01 79.69 404.07 0.04 79.94 405.69 -0.05 80.58 406.15 0.03 80.34 405.80 0.04 80.23 407.25 0.02 80.48 406.39 0.08 80.35 405.22

-0.08 79.98 404.20 0.10 80.39 405.69 -0.11 80.65 406.17 -0.03 80.47 405.85 0.02 79.95 407.48 0.09 80.73 406.49 0.08 80.45 405.31

-0.01 80.02 404.08 0.08 80.65 405.99 -0.07 80.70 406.92 -0.11 80.54 405.86 0.00 80.40 407.62 0.11 80.76 406.84 0.04 80.46 405.52

0.08 79.90 404.22 0.07 80.79 406.62 0.03 80.71 406.24 -0.06 80.56 406.16 0.01 80.30 407.41 0.06 80.65 407.17 -0.01 80.30 405.61

0.02 80.01 403.95 0.11 80.52 406.69 0.04 80.52 405.85 0.00 80.62 406.07 0.09 80.45 407.21 0.00 80.55 407.52 0.04 80.19 405.29

-0.02 80.12 403.75 0.11 80.31 406.66 0.04 80.34 406.41 0.05 80.65 405.86 0.10 80.75 407.29 -0.07 80.64 407.44 0.06 80.12 405.30

-0.09 80.32 404.54 0.08 80.31 406.46 0.02 80.53 406.92 0.04 80.47 406.05 0.10 80.76 407.22 -0.07 80.48 407.17 0.00 80.46 405.25

-0.06 79.92 404.66 0.11 80.65 406.19 0.05 80.45 406.21 0.02 80.52 405.96 0.11 80.63 406.76 -0.05 80.61 406.78 -0.02 80.24 405.47

-0.02 79.55 404.50 0.08 80.71 405.85 0.03 80.45 406.28 0.02 80.54 405.75 0.14 80.53 407.47 0.01 80.65 406.66 -0.07 80.24 405.30
 0
20
40
60
80
100
Houston
8/25/2010 0:00

8/27/2010 0:00

8/29/2010 0:00

8/31/2010 0:00

9/2/2010 0:00

TE 49C
9/4/2010 0:00

9/6/2010 0:00

9/8/2010 0:00

9/10/2010 0:00

9/12/2010 0:00

9/14/2010 0:00
TAPI 265E

9/16/2010 0:00

9/18/2010 0:00

9/20/2010 0:00

9/22/2010 0:00

9/24/2010 0:00

9/26/2010 0:00

9/28/2010 0:00
Field Comparison Data

9/30/2010 0:00

10/2/2010 0:00

10/4/2010 0:00

10/6/2010 0:00

10/8/2010 0:00
Comparison Data: Model 265E Analyzer And TECO 49C

10/10/2010 0:00

10/12/2010 0:00

10/14/2010 0:00

10/16/2010 0:00

10/18/2010 0:00

10/20/2010 0:00

10/22/2010 0:00
120 Regional Monitoring Network August 25, 2010 to October 22, 2010 1-Hour Ozone Values (ppbv)
What’s Next?
 Supart C submission in place, awaiting USEPA
equivalency approval.
 Discussing possible submission as an
alternate reference method.
 Currently CE certification compliant.

 Questions?