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Donald H. Stedman 50 Years of Air Quality Instrument Inventions and Measurements Haagen-Smit Clean Air Awards Sacramento, California May 18, 2016 Gary A. Bishop for Donald H. Stedman Department of Chemistry and Biochemistry University of Denver, Denver, CO 80208 www.feat.biochem.du.edu

Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

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Page 1: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

Donald H. Stedman 50 Years of Air Quality Instrument

Inventions and Measurements

Haagen-Smit Clean Air AwardsSacramento, California

May 18, 2016

Gary A. Bishop for Donald H. StedmanDepartment of Chemistry and Biochemistry

University of Denver, Denver, CO 80208www.feat.biochem.du.edu

Page 2: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

Acknowledgments

• Bishop(s)• State of Colorado• State of California• National Science Foundation• University of Denver• OPUS inspection• Coordinating Research Council, R.D. Shell,

Hirsch Foundation for Inspection Maintenance Review Committee and many other agencies and persons.

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Page 3: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

Chemistry Breakthrough• Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953.• LA smog is not London Smog (SO2 and soot), it is highly

oxidizing• Mainly with OZONE• It is counter intuitive to produce photochemically a strong

oxidizing agent by adding two reducing agents, NO and VOCs to air.

• It is counter intuitive to create an interesting free radical chain reaction by adding two free radical quenchers, NO and VOCs to air

• It is counter intuitive that when the sun shines, the UV absorbing agent, NO2, far from going away, actually increases with time.

3

Page 4: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

4

Don• Educated at Cambridge and met and married Hazel• M.Sc./Ph.D., Univ. of East Anglia with Michael Clyne• Post-Doc in Atmospheric Chemistry at K-State with Don

Setser, 1967• Ford Motor Company• Professor University of Michigan, 1970• Brainard Phillipson Professor University of Denver, 1983

• Popular Science, The Best of What’s New, 1991• Denver University Lecturer, 1994• AWMA Frank Chambers Award, 1996• ACS Advances in Environmental Science, 1996• ACS Colorado Professional Achievement, 1997• John Evans Professor 2000• ACS Thomas Midgley award, 2002

• Avid hiker and bird watcher / Singer / Woodworker / Beer maker / Watercolor painter / Poet

Page 5: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

5

50 Years of EducatingReactions of Atomic Hydrogen with Hydrogen Chloride and NitrosylChloride, M.A.A. Clyne and D.H. Stedman, Transactions of the Faraday Society, 62:2164, 1966.

High-mileage Light-duty Fleet Vehicle Emissions: Their Potentially Overlooked Importance, G.A. Bishop, D.H. Stedman, D.A. Burgardand O. Atkinson, Environmental Science & Technology, DOI:10.1021/acs.est.6b00717 , 2016.

• 300+ refereed publications• 35 patents to date• 40+ M.Sc. And Ph.D. degree students• Many more sabbatical faculty, post-doctoral students and

undergraduates• American Chemical Society traveling lecturer in retirement

Page 6: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

6

50 Years of Inventing Instruments for Real World Measurements

• Involved in the early development of chemiluminescent NO detector.• Published a measurement system for the photochemical rate of NO2

dissociation j(NO2).• Invented a chemical amplifier for HO2/RO2 detection.• Helped to develop a technique to measure ClO free radicals.

(Atomic Chlorine and the Chlorine Monoxide Radical in the Stratosphere: Three in-situ Observations, J.G. Anderson, J.J. Margitan and D.H. Stedman, Science, 198, 501-503, 1977)

• Subsequent measurements by this technique provided the “smoking gun” that helped decipher the Antarctic ozone hole

• Invented and commercialized chemiluminescence Nickel Carbonyl detector.• Invented and commercialized chemiluminescence NO2 detector.• Invented and commercialized flame chemiluminescent Sulfur detector.• Invented and commercialized on-road remote sensor for vehicle emissions• Invented an on-road heavy-duty truck measurement system

Page 7: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

7

Apparatus for detection of certain nitrogen-containing gases using chemiluminescence.US Patent No. 4,765,961, H.I. Schiff & D.H. Stedman, 1988.

The Airliner Cabin EnvironmentAir Quality and Safety Committee on Airliner Cabin Air Quality National Research Council, 1986.

Don felt the work of this committee was his most important contribution to society.

Page 8: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

8

On-road Remote Vehicle Exhaust Sensor (FEAT)

Speed and acceleration

detectors Calibration cylinders

Light Source

Detectors

Page 9: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

How FEAT Measures Tailpipe Emissions

0.20

0.15

0.10

0.05

0.00

%H

C

1.51.00.50.0%CO2

349gHC/kg of Fuel

0.4

0.3

0.2

0.1

0.0

%C

O

1.51.00.50.0%CO2

180gCO/kg of Fuel

1.5

1.0

0.5

0.0

Perc

ent

0.50.40.30.20.10.0Time (sec.)

COCO2HC

2003 Ford Expedition

Page 10: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

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Page 11: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

11

Ocean going VesselsLion’s Gate Bridge Vancouver BCBridge-based sensing of NOx and SO2emissions from ocean-going shipsDaniel A. Burgard and Carmen R.M. Bria

Page 12: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

12

West Los Angeles HC Emission Comparison

40

30

20

10

0

Mea

n gH

C/k

g of

Fue

l

20 15 10 5 0

Vehicle Age

19992015

Page 13: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

13

West Los Angeles Percentage of HC Contributed by the 99th Percentile

1999 201583%

54%

17%46%

Page 14: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

14

Four City Historical HC 99th Percentiles100

80

60

40

20

0

gHC

/kg

of F

uel 9

9th P

erce

ntile

201620122008200420001996

Measurement Year

DenverChicagoWest Los AngelesTulsa

Page 15: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

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The Public Does Not Always Cooperate

On-Road Remote Sensing of CO and HC Emissions in California, D.H. Stedman, G.A. Bishop, S.P. Beaton, J.E. Peterson, P.L. Guenther, I.F. McVey and Y. Zhang, Final Report, Contract No. A032-093, California Air Resources Board, Feb., 1994.

Page 16: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

16

Regulations Don’t Always Turn out as Envisioned2013 LD Diesel Data from Denver, LA and Tulsa

50

40

30

20

10

0

gNO

x/kg

of F

uel

201220102008200620042002

Model Year

2L Pass. EnginesTrucks All Engines

Bishop and Stedman, Reactive Nitrogen Species Emission Trends in Three Light-/Medium- Duty United States Fleets. Environ. Sci. Technol. 2015, 49, 11234-11240.

Page 17: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

17

How one of Don’s Ideas got Funding

System and method for quantifying the presence of components in the exhaust of commercial and/or heavy‐duty vehicles. US Patent 8,429,957, D.H. Stedman, 2013.

Page 18: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

18

On-road Heavy-duty Measurement System

Bishop et al., On-road Heavy-duty Vehicle Emissions Monitoring System. Environ. Sci. Technol. 2015, 49, (3), 1639-1645.

Page 19: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

19

OHMS Measurements from the Port of Los Angeles

0.20

0.15

0.10

0.05

0.00

gPM

/kg

of fu

el

2008 2009 2010 2011 2012 2013

Chassis Model Year

2013 2015

Page 20: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

20

Don and Hazel, March 2016

Page 21: Donald H. Stedman 50 Years of Air Quality …...Chemistry Breakthrough • Haagen-Smit, Bradley and Fox, Ind. Eng. Chem, 1953. • LA smog is not London Smog (SO 2 and soot), it is

References• Bishop, G. A.; Starkey, J. R.; Ihlenfeldt, A.; Williams, W. J.; Stedman, D. H., IR

long-path photometry, A remote sensing tool for automobile emissions. Anal. Chem. 1989, 61, 671A-677A, DOI: 10.1021/ac00185a746.

• Bishop, G. A.; Stedman, D. H., A decade of on-road emissions measurements. Environ. Sci. Technol. 2008, 42, (5), 1651-1656, DOI: 10.1021/es702413b.

• Burgard, D. A.; Bishop, G. A.; Stadtmuller, R. S.; Dalton, T. R.; Stedman, D. H., Spectroscopy applied to on-road mobile source emissions. Appl. Spectrosc. 2006, 60, 135A-148A, DOI: 10.1366/000370206777412185.

• Chaney, L. W., The remote measurement of traffic generated CO. Journal of the Air Pollution Control Association 1983, 33, 220-222. DOI:10.1080/00022470.1983.10465568

• Vehicle Inspection Instrumentation, H. Hoshizaki, A. D. Wood and D. D. Kemp, Lockheed Palo Alto Research Laboratory, Final report to the California Air Resources Board, June 1973. http://www.feat.biochem.du.edu/assets/reports/LockHeed_ARB_1973.pdf

• Bishop, G. A.; Schuchmann, B. G.; Stedman, D. H.; Lawson, D. R., Multispecies remote sensing measurements of vehicle emissions on Sherman Way in Van Nuys, California. J. Air Waste Manage. Assoc. 2012, 62, (10), 1127-1133, DOI: 10.1080/10962247.2012.699015.

• Bishop, G. A.; Stedman, D. H., The recession of 2008 and it impact on light-duty vehicle emissions in three western US cities. Environ. Sci. Technol. 2014,48, 14822-14827, DOI: 10.1021/es5043518.