An Alternative Approach To Ambient Ozone Monitoring

An Alternative Approach To Ambient Ozone Monitoring

Presenter: Patrick KingTeledyne 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 C2 - 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 BenzeneAcetylene Butane TolueneEthane Isopentane StyrenePropylene 1-Pentene Ethylbenzene

Propane n-PentaneMethyl-tert-Butyl-Ether

Isobutane n-Hexanetrans-2-Butene

1-Butene Isoprene cis-2-Butene

Interference Study Results

10/27/2010 16:33 10/27/2010 17:45 10/27/2010 18:57 10/27/2010 20:09

-40

-20

0

20

40

60

80

100

1202010 VOC Interference Study

Houston Regional Monitoring Network

TE 49CAPI 265EDasibi 1008API 400

Date / Time

Ozo

ne (

ppb)

Addition of HC Mixture

Removal of HC Mixture

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

0 15 30 45 60 75 90 1050

15

30

45

60

75

90

105265E 100 ppb Range Linearity

703E Calibrator Output (ppb)

265E

Out

put (

ppb)

Correlation Coeff = 1.0000

0 75 150 225 300 375 450 5250

75

150

225

300

375

450

525

265E 500 ppb Range Linearity

703E Calibrator Output (ppb)

265E

Out

put (

ppb)

Correlation Coeff = 1.0000

0 300 600 900 1200 1500 18000

300

600

900

1200

1500

1800

265E 2000 ppb Range Linearity

703E Calibrator Output (ppb)

265E

Out

put (

ppb)

Correlation Coeff = 1.0000

Comparison Data

10/1 10/2 10/3 10/4 10/5 10/6 10/70

50

100

150

200

250

300

350

400

450Subpart C Overlaid Graphs M265E_SN51 M400EBendix

Date

Con

c(pp

b)

Group 1 Group 2 Group 3

Noise And Drift Data Test #1

Std DEV Test #2

Std DEV Test #3

Std DEV Test #4

Std DEV Test #5

Std DEV Test #6

Std DEV Test #7

Std DEVZero Span Span Zero Span Span Zero Span Span Zero Span Span Zero Span Span Zero Span Span Zero Span Span0.04 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

Zero

16% Rang

e 80% Range

Zero

16% Rang

e 80% Range Zero

16% Rang

e 80% Range Zero

16% Rang

e 80% Range Zero

16% Rang

e 80% Range Zero

16% Rang

e 80% Range Zero

16% Rang

e 80% 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 80.19404.4

8 0.03 80.28405.8

6 -0.07 80.34405.9

0 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 79.55404.5

0 0.08 80.71405.8

5 0.03 80.45406.2

8 0.02 80.54 405.75 0.14 80.53 407.47 0.01 80.65 406.66 -0.07 80.24 405.30

Field Comparison Data8/

25/2

010

0:00

8/26

/201

0 0:

008/

27/2

010

0:00

8/28

/201

0 0:

008/

29/2

010

0:00

8/30

/201

0 0:

008/

31/2

010

0:00

9/1/

2010

0:0

09/

2/20

10 0

:00

9/3/

2010

0:0

09/

4/20

10 0

:00

9/5/

2010

0:0

09/

6/20

10 0

:00

9/7/

2010

0:0

09/

8/20

10 0

:00

9/9/

2010

0:0

09/

10/2

010

0:00

9/11

/201

0 0:

009/

12/2

010

0:00

9/13

/201

0 0:

009/

14/2

010

0:00

9/15

/201

0 0:

009/

16/2

010

0:00

9/17

/201

0 0:

009/

18/2

010

0:00

9/19

/201

0 0:

009/

20/2

010

0:00

9/21

/201

0 0:

009/

22/2

010

0:00

9/23

/201

0 0:

009/

24/2

010

0:00

9/25

/201

0 0:

009/

26/2

010

0:00

9/27

/201

0 0:

009/

28/2

010

0:00

9/29

/201

0 0:

009/

30/2

010

0:00

10/1

/201

0 0:

0010

/2/2

010

0:00

10/3

/201

0 0:

0010

/4/2

010

0:00

10/5

/201

0 0:

0010

/6/2

010

0:00

10/7

/201

0 0:

0010

/8/2

010

0:00

10/9

/201

0 0:

0010

/10/

2010

0:0

010

/11/

2010

0:0

010

/12/

2010

0:0

010

/13/

2010

0:0

010

/14/

2010

0:0

010

/15/

2010

0:0

010

/16/

2010

0:0

010

/17/

2010

0:0

010

/18/

2010

0:0

010

/19/

2010

0:0

010

/20/

2010

0:0

010

/21/

2010

0:0

010

/22/

2010

0:0

0

0

20

40

60

80

100

120Comparison Data: Model 265E Analyzer And TECO 49C

Houston Regional Monitoring Network August 25, 2010 to October 22, 2010 1-Hour Ozone Values (ppbv)

TE 49C TAPI 265E

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?