SARP2012: Introduction to Air Quality

Barry Lefer, James Flynn, and Nicole Grossberg University of Houston

Mark Jacobson via the Los Angeles Public Library - 1964

| DAOF 211| Wednesday 20 June 2012 |

SARP2012: Introduction to Air Quality

I. II. III. IV.

UH Measurement Payload What to expect in the Air Quality Group Basics of Ozone Photochemistry and Air Quality Project Ideas

Mark Jacobson via the Los Angeles Public Library - 1964

| DAOF 211| Wednesday 20 June 2012 |

UH Measurement Payload SARP 2012

Data System and Power Supplies Ozonizer BLC NOx and CO calibration system O3 (Dual Beam UV absorbance) O3 Calibrator

NO (O3 chemiluminescence) NOx (Blue Light Converter and O3 chemiluminescence)

CO (VUV Flourescence)

Aerolaser 5001 CO Monitor

Aerolaser 5001 CO Monitor

Measuring range: < up to 100,000.00 ppbV Detection limit: < 1.0 ppbV at T = 10 s Sensitivity: about 10 c/ppbV Time constants: about 1 sec (10-90%), signal delay 3 sec Background check: External Catalytic CO zero converter Calibration: CO-gas-standard Digital Signal output RS 232 interface

Thermo Electron 49C Ozone Monitor

Thermo Electron 49C Ozone Monitor

Measuring range: < up to 500 ppbv Detection limit: < 1.0 ppbv at T = 10 s Precision: 1.0 ppbv Time constants: about 20 sec (10-90%), signal delay 10 sec Zero drift: <1.0 ppbv (24 hr) Span Drift: <1% (per month) Calibration: O3 generator / calibrator Digital Signal output RS 232 interface

Air Quality Design NO and NOx Monitor

O2

Chemilumeninescence NO + O3 NO2 * + O2 NO2 * NO2 + hv

Unexpected Results

O2

Unexpected Results
600

400

NO (pptv)
O 2002
0 12/19

12/20

12/21

12/22

12/23

Date and Time (GMT)

Air Quality Design NO and NOx Monitor

Sensitivity : 3-5 counts/pptv NO in 1 second Detection Limit: 10 pptv in 1 second 2 pptv in 60 second Response Speed : 2 Hz Auto-Zero with prereaction chamber Range: linear from detection limit through >500 ppbv Mass flow sample control Photon counting detection system Precise temperature control Peltier-cooled PMT High performance dry scroll vacuum pump

Air Quality Design Blue Light Converter

NO2 + hv -> NO + O

High efficiency (~50% NO2 conversion/second) Highly specific for NO2 Negligible radiant heating of the sample gas 1 second residence time for 1 SLPM at low pressure (200 Torr) Integrated lamp control circuit and remote on/off

Metcon j-NO2 Filter Radiometer

NO2 + hv -> NO + O (j-NO2)

Metcon j-NO2 Filter Radiometer

NO2 + hv -> NO + O (j-NO2)

1e+15

1.5

Actinic Flux (quanta cm nm sec )

-1 -1

1e+14 1.0 1e+13

1e+12 0.5 Flux 1e+11 j-O(1D) j-NO2 1e+10 280 0.0 420

300

320

340

360

380

400

Wavelength [nm]

j -values (arbitary units)

-2

What to expect in Lefer/Yang Group: Insitu Real-Time Trace Gas Group: Ozone Photochemistry Investigators (OPI)

What to expect for the next few days:

Today (Wednesday): PM P-3 Arrives Palmdale UH Truck arrives from Houston Tomorrow (Thursday): Unpack Instruments Install in Rack (Front of the Aircraft) Connect everything up Smoke Test
Day after Tomorrow (Friday): Calibrations, Testing, Calibrations, Testing

Good ozone and Bad ozone

UH Ozonesonde Program

What is a safe level of ozone?

FEV1 10% Decrement

http://www.epa.gov/ttn/naaqs/standards/ozone/s_o3_cr_sp.html

Inflammation of lung tissue

Healthy Lung

Inflamed Lung

EPA

Why is ozone bad?

Bell et al. (2004) Ozone and Short-term Mortality in 95 US Urban Communities, 1987-2000, JAMA, 292:2372-2378.

Ozone Pollution Facts

More than 4 in 10 people in the United States live in areas with unhealthful levels of ozone. Counties that were graded F for ozone levels have a combined population of almost 116.7 million. Unhealthy ozone places them at risk for premature death, coughing, wheezing, asthma attacks, decreased lung function, respiratory infection, lung inflammation and worsened lung diseases. Deaths from respiratory diseases, such as chronic obstructive pulmonary disease, emphysema and pneumonia, account for about 8.5% of all U.S. deaths, an estimated 240,000 each year. Worldwide, such conditions account for 7.7 million deaths each year.
ALA State of the Air Report 2012

Where is ozone a problem?

EPA

ALA State of the Air Report 2012

1-hr Ozone Exceedances (Houston & LA)

200
Number of ozone days above 125 ppbv (1 hr average)

180 160 140 120 100 80 60 40 20 0 1986 Los Angeles Houston

1988

1990

1992

1994

1996

1998

2000

2002

2004

2006

2008

Source: TCEQ, CARB

Recent Houston Ozone Trend

Source: EPA

Recent Los Angeles Ozone Trend

Ave = 87.6 d

Source: EPA

LA Ozone Season

Source: EPA

Photostationary State Ozone

NO(g) + O 3(g) Nitric Ozone oxide
NO2 (g) + hn Nitrogen dioxide
O(g) + O 2(g) Ground- Molecular state atomic oxygen oxygen

NO2 (g) + O 2(g) Nitrogen Molecular dioxide oxygen

NO(g) + O(g) Nitric Atomic oxide oxygen
M O3(g) Ozone

l < 420 nm

(1) (3)
Source: Jacobson 2012

Photostationary State Ozone

cO =( J/Nd k1)(cNO (g)/cNO(g))
3 2
(4)

J = photolysis rate coefficient of NO2 + hn --> NO + O k1 = rate coefficient of NO + O3 --> NO2 + O2

Estimate ozone mixing ratio when Pd = 1013 mb T = 298 K cNO(g) = 5 pptv cNO (g) = 10 pptv 2 -14 cm3 molec.-1 s-1 k1 = 1.8x10 J = 0.01 s-1
---->

Nd = 2.46 x 1019 molec. cm-3 ----> c O (g) = 45.2 ppbv

3
Source: Jacobson 2012

Daytime Nitrogen Oxide Removal

NO2(g) + OH(g) Nitrogen Hydroxyl dioxide radical M HNO3(g) Nitric acid

(5)
Source: Jacobson 2012

Hydroxyl Radical Production

O3(g) + hn Ozone O2 (g) + O(1D)(g) Molecular Excited oxygen atomic oxygen
2OH(g) Hydroxyl radical

l < 310 nm

O(1D)(g) + H 2O(g) Excited Water atomic vapor oxygen

(6) (7)
Source: Jacobson 2012

Ozone From Carbon Monoxide

CO(g) + OH(g) Carbon Hydroxyl monoxide radical M H(g) + O2(g) Atomic Molecular hydrogen oxygen NO(g) + HO2(g) Nitric Hydroperoxy oxide radical NO2 (g) + hn Nitrogen dioxide CO2(g) + H(g) Carbon Atomic dioxide hydrogen HO2(g) Hydroperoxy radical NO2(g) + OH(g) Nitrogen Hydroxyl dioxide radical l < 420 nm

Source:

NO(g) + O(g) Nitric Atomic oxide oxygen M O(g) + O 2(g) O3(g) Ground- Molecular Ozone state atomic oxygen oxygen Jacobson 2012

(11) (15)

Ozone From Methane

CH4(g) + OH(g) Methane Hydroxyl radical M CH3(g) + O 2(g) Methyl Molecular radical oxygen CH3(g) + H2O(g) Methyl Water radical vapor CH3O2 (g) Methylperoxy radical

NO(g) + CH 3O2(g) Nitric Methylperoxy oxide radical

NO2 (g) + hn Nitrogen dioxide

NO2(g) + CH 3O(g) Nitrogen Methoxy dioxide radical

l < 420 nm

NO(g) + O(g) Nitric Atomic oxide oxygen M O(g) + O 2(g) O3(g) Ground- Molecular Ozone state atomic oxygen oxygen

(16) (20)

Source: Jacobson 2012

Ozone From Ethane

C2H6(g) + OH(g) Ethane Hydroxyl radical
C2H5(g) + O 2(g) Ethyl Molecular radical oxygen M

C2H5(g) + H2O(g) Ethyl Water radical vapor

C2H5O2 (g) Ethylperoxy radical

NO(g) + C 2H5O2(g) Nitric Ethylperoxy oxide radical

NO2 (g) + hn Nitrogen dioxide

NO2(g) + C 2H5O(g) Nitrogen Ethoxy dioxide radical

l < 420 nm

NO(g) + O(g) Nitric Atomic oxide oxygen M O(g) + O 2(g) O3(g) Ground- Molecular Ozone state atomic oxygen oxygen

(4.26) - (4.30)

Source: Jacobson 2012

Formaldehyde and Acetaldehyde Formation

Formaldehyde

CH3O(g) + O2(g) Methoxy Molecular radical oxygen

Acetaldehyde

HCHO(g) + HO2 (g) Formal- Hydroperoxy dehyde radical

C2H5O(g) + O 2(g) Ethoxy Molecular radical oxygen

CH3CH(=O) + HO2 (g) Acetaldehyde Hydroperoxy radical

(21), (31)

Source: Jacobson 2012

NO2 (g) + hn Nitrogen dioxide

NO(g) + O(g) Nitric Atomic oxide oxygen

l < 420 nm

Source: Jacobson 2012

Photochemical Smog Formation

NO(g) + O 3(g) Nitric Ozone oxide
NO(g) + RO2(g) Nitric Organic oxide peroxy radical

NO2 (g) + O 2(g) Nitrogen Molecular dioxide oxygen

NO2 (g) + RO(g) Nitrogen Organic dioxide oxy radical

NO2 (g) + hn Nitrogen dioxide

NO(g) + O(g) Nitric Atomic oxide oxygen M O(g) + O 2(g) O3(g) Ground- Molecular Ozone state atomic oxygen oxygen

l < 420 nm

Source: Jacobson 2012

NOAA Ozone Forecast - Today

NOAA Ozone Forecast - Today

Source/Receptor Regions in Los Angeles

Volume mixing ratio (ppmv) Volume mixing ratio (ppmv)

0.3
Central Los Angeles August 28, 1987

0.3
San Bernardino August 28, 1987 O3(g)

0.2

NO(g) NO2(g) O3(g)

0.2
NO2(g)

0.1

0.1
NO(g)

0 0 6 12 18 Hour of day 24

0 0

12 18 Hour of day

24

Source: Jacobson 2012

Impact of clouds and aerosols on O3 production

Source: Flynn et al. 2011

Ozone production rate variation with NO

Source: Cazorla et al. 2012

Sensitivity of O3 production to NOx and VOCs

Source: Ren et al. 2012

Ozone Isopleths
0.25
0.4
0.32 0.16

0.2
NOx(g) (ppmv)

0.1 0.05 0 0

0.5

0.24

0.15

0.08 = O3(g), ppmv

1 ROG (ppmC)

1.5

Contours are ozone (ppmv)

Source: Jacobson 2012

Comparison to CALNEX-2010 Data

Source: Pollack et al., 2011

Comparison to CALNEX-2010 Data CO/CO2

Source: Pollack et al., 2011

Comparison to CALNEX-2010 Data Ethene/NOx and Benzene/CO

Source: Pollack et al., 2011

Comparison to CARB Ground-based Trends

Source: Pollack et al., 2011

Comparison to Airborne (and roadside) observations

Source: Pollack et al., 2011

Changes in VOC/NOx ratio

Source: Pollack et al., 2011

What can you do with our data?

- Comparison of Ozone Forecast to Observed (why different)
- Impact of clouds and aerosols on photochemistry (photochemical box modeling, radiative transfer modeling) - Determination of ozone production rates in LA and at downwind locations (pbm) - Relative importance of mobile and point source emissions of NOx - Air mass characterization and transport source regions to Southern California (trajectory modeling) - Combustion efficiency of mobile and point sources - Comparison with previous aircraft and roadside studies - Long-term trends in LA and Central Valley - Importance of long range transport and vertical mixing on free tropospheric ozone - Analysis of best control policies for LA basic and/or Central Valley

Source: EPA

Acknowledgments:

SARP Emily, Rick, Adam, Jane, TCEQ, EPA, NSF