Monitoring of ozone ground concentration at temperature inversions in the atmosphere Egor Iasenko1, Vladimir Chelibanov1, Alexander Marugin2

geoyasenko@gmail.com

1 National Research University ITMO Saint-Petersburg

Russian Federation

1 JSC OPTEC Saint-Petersburg

Russian Federation

11th Annual International Symposium on Environment 23-26 May 2016, Athens, Greece

Temperature inversion, a reversal of the normal behavior of temperature in the troposphere (the region of the atmosphere nearest the Earth’s surface), in which a layer of cool air at the surface is overlain by a layer of warmer air. (Under normal conditions air temperature usually decreases with height.)

Introduction 1

Temperature Inversion

Pollutants (NO2, SO2, CnHx, CO and O3) become concentrated as more are added by everyday activities

1) Laboratory comparison studies of tree Analyzers: Thermo Electron Model TE49i (FEM based on UV-photometry), Bendix Model 8002 (FRM, based on homogeneous chemiluminescence) and Optec Model 3-02P-A, based on solid-state heterogeneous chemiluminescence.

2) Comparison field studies Monitoring of ozone ground concentration at temperature inversions in the atmosphere UV- photometry and solid-state heterogeneous chemiluminescence methods in Saint-Petersburg

2 Mission and Goals of work

Mission of our investigation: Provide correct monitoring of ozone ground concentration at temperature inversions in the atmosphere

3 O3 measurements methods

Homogeneous chemiluminescent (FRM)

Schematic illustration of the Bendix Model 8002

Method based on the chemiluminescence reaction of ethylene in gas phase (gas-phase titration) with O3:

accuracy, selectivity, sensitivity, danger, bulky, no portable

4 O3 measurements methods

Homogeneous chemiluminescent (FRM, Bendix Model 8002)

5 O3 measurements methods

UV-photometry (FEM)

Schematic illustration of the Thermo Electron Model TE49i

6 O3 measurements methods

UV-photometry (FEM, Thermo Electron Model TE49i)

The method uses the intensive band of O3 absorption in UV emission which maximum coincides with well-marked emission line of Hg vapors under low pressure at 253,7 nm:

quick, sensitivity, range, expensive

7 O3 measurements methods

Solid-State Chemiluminescent

Schematic illustration of the Model 3.02P-A O3 analyzer.

1. Valve 2. Chemiluminescent reactor 3. Calibrator 4. Photomultiplier tube 5. Analog-to-digital transformer 6. Processor 7. Digital indicator 8. Pump 9. Calibrator power supply 10.Control buttons (control keyboard) 11.Rotameter 12.Zero-gas filter

8 O3 measurements methods

Solid-State Chemiluminescent (Optec mod. 302P-A)

Method based on the solid-state chemiluminescence:

Accuracy Selectivity Sensitivity Portable Reasonable price

9 Experimental section

Comparability Model Optec 3.02 P-A with FEM and FRM

10 Experimental section

Comparability Model Optec 3.02 P-A with FEM and FRM

11

Mixing ChamberOptec Model

3.02P-A

PC

Scrubber

Exhaust

Model TE49i or Model 8002

Ozone GeneratorGS-024

Ambient Air80%

20%

Experimental section

Comparability Model Optec 3.02 P-A with FEM and FRM

Impurities of The ambient air: H2S, H2O, CO2

This comparability test was performed according to the procedures described in 40 Code Federal Regulation (CFR) Part 53.32

12

-0,10

0,00

0,10

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Co

nce

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pm

Time

OPTEC Model 3.02

Thermo Electron Model TE49i

Difference (ppm)

Experimental section

Comparability Model Optec 3.02 P-A with Thermo Electron Model TE49i (FEM)

-0,10

0,00

0,10

0,20

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Co

nce

ntr

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n, p

pm

Time

OPTEC Model 3.02Thermo Electron Model TE49iDifference (ppm)

-0,10

0,00

0,10

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on

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trat

ion

, pp

m

Time

OPTEC Model 3.02Thermo Electron Model TE49iDifference (ppm)

13

Concentration

Range, ppm № Date Time

Concentration,

ppm

Pass/

Fail

JSC

OPTEC

Model

3.02P-A

Thermo

Electron

Inc. Model

TE49i

Low

0.06-0.10

1 7/12/10 11:30-12:30 0.09 0.10 Pass

2 7/12/10 16:02-17:01 0.08 0.09 Pass

3 7/13/10 10:00-10:59 0.09 0.08 Pass

4 7/13/10 15:04-16-03 0.09 0.08 Pass

5 7/14/10 10:44-11:42 0.09 0.09 Pass

Med.

0.15 – 0.25

1 7/12/10 14:07-15:06 0.20 0.20 Pass

2 7/12/10 17:05-17:59 0.20 0.21 Pass

3 7/13/10 11:00-11:59 0.20 0.18 Pass

4 7/13/10 13:03-14:02 0.19 0.18 Pass

5 7/14/10 9:40-10:39 0.19 0.20 Pass

High

0.35 – 0.45

1 7/12/10 13:07-14:05 0.39 0.38 Pass

2 7/12/10 15:08-16:00 0.38 0.38 Pass

3 7/13/10 12:03-13:01 0.38 0.36 Pass

4 7/13/10 14:03-15:02 0.37 0.36 Pass

Experimental section

Comparability Model Optec 3.02 P-A with Thermo Electron Model TE49i (FEM)

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0

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9:00 10:00 11:00 12:00 13:00 14:00 15:00

Co

nce

ntr

atio

n, p

pm

Time

Bendix Model 8002 FRM

Optec Model 3.02 P-A

Experimental section

Comparability Model Optec 3.02 P-A with Bendix Model 8002 (FRM)

0

0,1

0,2

0,3

0,4

0,5

8:00 9:00 10:00 11:00 12:00 13:00

Co

nce

ntr

atio

n, p

pm

Time

Bendix Model 8002 FRM

Optec Model 3.02 P-A

0

0,1

0,2

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0,5

12:00 13:00 14:00 15:00 16:00 17:00

Co

nce

ntr

atio

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Time

Bendix Model…Optec Model…

15

Concentration

Range, ppm № Date Time

Concentration,

ppm

Pass/

Fail

JSC

OPTEC

Model

3.02P-A

Bendix

Model

8002

Low

0.06-0.10

1 12/29/10 12:06-13:05 0.079 0.080 Pass

2 12/29/10 16:25-17:24 0.081 0.083 Pass

3 12/30/10 10:47-11:45 0.091 0.093 Pass

4 12/31/10 09:50-10:49 0.087 0.089 Pass

5 12/31/10 12:11-13:10 0.092 0.094 Pass

Med.

0.15 – 0.25

1 12/29/10 14:15-15:14 0.205 0.207 Pass

2 12/29/10 09:42-10:41 0.195 0.197 Pass

3 12/30/10 11:49-12:48 0.190 0.193 Pass

4 12/31/10 14:00-14:59 0.195 0.195 Pass

5 12/31/10 11:00-11:59 0.197 0.198 Pass

High

0.35 – 0.45

1 12/29/10 13:11-14:10 0.404 0.406 Pass

2 12/29/10 15:20-16:19 0.406 0.409 Pass

3 12/30/10 12:56-13:53 0.395 0.398 Pass

4 12/31/10 08:45-09:43 0.403 0.403 Pass

Experimental section

Comparability Model Optec 3.02 P-A with Bendix Model 8002 (FRM)

16 Experimental section

Comparability Model 3.02 P-A with FEM under condition of temperature inversion

17 Experimental section

Comparability Model 3.02 P-A with FEM under condition of temperature inversion

Temperature inversion that was observed in lower troposphere on March 28-29, 2016 (http://www.flymeteo.org).

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0,04

0,05

0,06

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0,09

0,1

-0,001

0,004

0,009

0,014

0,019

18:28 20:52 23:16 1:40

O3 ,

pp

m

Time, min

NO

2 ,

pp

m

Optec Model 3.02 P-AThermo Electron Model TE49iNO2

Experimental section

Comparability Model 3.02 P-A with FEM under condition of temperature inversion

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0

0,05

0,1

0,15

0,2

-0,001

0,004

0,009

0,014

0,019

18:28 20:52 23:16 1:40

O3

, p

pm

Time, min

Du

st (

PM

1),

mg/

m3

Optec Model 3.02 P-A

Thermo Electron Model TE49i

Dust (PM1)

Experimental section

Comparability Model 3.02 P-A with FEM under condition of temperature inversion

20

• The laboratory comparison of solid-state heterogeneous chemiluminescence analyzer OPTEC Model 3-02P-A with UV-photometry analyzer Thermo Electron mod.49i (FEM) and homogeneous chemiluminescence analyzer Bendix Model 8002 (FRM) was done successfully.

• The comparison of Model 3.02 P-A with Model 49i in real urban air in Saint-Petersburg under conditions of temperature inversion also was done. The obtained experimental data demonstrate the significant influence of atmospheric air components (NO2 and dust PM1.0) on the measurement of ozone concentration by UV-photometry method.

Due to all the above it can be concluded that ozone ground concentration at temperature inversion in the atmosphere

could be correctly identified by using the method of chemiluminescence only.

Conclusion

Our thanks to Gordyushkin Vitaly (engineer researcher) for carrying out environmental measurements.

21 Acknowledgments