1

Catalytic converters and checkerspot butterflies:

air quality impacts of vehicular ammonia

emissions

Stuart B. WeissStuart B. Weiss

Creekside Center for Earth Creekside Center for Earth

ObservationsObservations

NThe biggest global change The biggest global change

nobody (almost) has ever nobody (almost) has ever

heard ofheard of

The N-cycle is massively disrupted –proportionally more than the C-cycle

Tg

/ye

ar

Galloway et al 2003 Bioscience

The case of the Drive-by Extinction

Another episode of CSI Redwood CityAnother episode of CSI Redwood City

Mesocosm of NMesocosm of N--deposition Impactsdeposition Impacts

� Emissions

� Transport

� Chemical transformations

� Deposition

�Species composition change

�Loss of biodiversity� Management response

Serpentinite forms discrete patches of nutrient-poor soils

2

Charismatic meso-invertebrate

Hostplants and Nectar Sources Charismatic microflora

3

Charismatic mega-vertebrate

Well mapped,

Population biology of the butterfly well understood

Needs large areas with

diverse topography

(topoclimate, microclimate)

5000+ acres on Coyote Ridge

In absence of cattle grazing in South Bay, introduced annual grasses overrun habitat within several years (repeatable).

Dry Nitrogen Deposition

Smog is slow release N-fertilizer

Air Pollution ChemistryAir Pollution Chemistry

SimplifiedSimplified

O3

NO2

HNO3 +

hv

NH3

NO

[OH*]

NO3NH4(p)

Combustion

Fertilizer, Livestock, Vehicles, Soils, Vegetation, etc.

PAN

4

Metcalf Energy Center

124 tons NOx

per year

<116 tons NH3

per year

Worst-case scenario modeling, all emissions as HNO3

Former-future Cisco World HQ

230 tons NOx/year, ~20 tons ammonia

Incipient Coyote Valley Urbanization

Widening Highway 101

250 acres, Kirby Canyon Trust, long-term lease131 acres MEC, $1.4 million management endowment – SVLC540 acres (2005) for highway mitigation + ~$700,000 endowment, management by SCCOSA80 acres (2002-2004) strategic freeway frontage, ~$650,000 endowment from 2 other power plants - SVLCMitigation marketSanta Clara County HCP/NCCP

Coyote Valley Specific Plan

Conservation So Far

Dry deposition – Dominant in California

Operation Flower Power

5

Dry deposition – Dominant in California

CongressmanJerry McNerney (2005)

Edgewood Natural PreserveEdgewood Natural Preserve

Proposed for golf course

1981-1994 “Epic”battle to stop it

“Natural Preserve”status in 1994

Hands off management of serpentine grassland

9,000 larvae in 1997, 9,000 larvae in 1997, The last larva in 2002The last larva in 2002 Passive Sampling

Dr. Andrzej Bytnerowicz, USDA FS Riverside, CA

1-3 EW5 RCAQ

4 JRSJAQ

6 Tulare

7-8 KC

Nov-April wet season May-Oct dry season

6

EW400E

EWEastEWWest

Highway 280 carries 114,000 vehicles per day (2003)

Mostly LDV (includes SUV)

All results are completely compatible with known emissions sources, atmospheric transport and chemistry (come back to later)

July 2002 – June 2003 (monthly bars) July 9 2002 - Jul 1 2003

0

5

10

15

20

EW

-Wes

t

EW-E

ast

EW

-400

E JR

RCA

Q TH

KC-L

ow

KC-H

igh

kg

-N/h

a HNO3

NH3

NO2

Simple deposition model, monthly average deposition velocities for wet and dry season.

HNO3>NH3>>NO2>>>NONH3 deposition to Italian ryegrass canopy measured = 16.7 mm/s (Sommer, S. G. & Jensen, E. S. 1991. Journal of

Environmental Quality 20, 153-156.)

Transects

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

-200 0 200 400 600

W Meters from I-280 E

log(C

ove

r+1

)

Plantago

Lolium

Edgewood 2001Edgewood 2001� Lolium cover higher on thicker soils (more

nutrients/water available), Plantago opposite

3

10

30

100

7

0.25

0.3

0.35

0.4

0.45

0.5

0.55

0.6

0.65

0.7

Avg %

N (

Acid

ifie

d)

-400 -200 0 200 400 600

distance from center (est.)

-7

-6

-5

-4

-3

-2

-1

0

1

Avg

d1

5N

(A

cid

ifie

d)

-400 -200 0 200 400 600

distance from center (est.)

50

75

100

125

150

175

200

Avg C

:N R

atio (

Acid

ifie

d)

-400 -200 0 200 400 600

distance from center (est.)

% N Lolium

1.5

2

2.5

3

Avg %

C (

Acid

ifie

d)

-400 -200 0 200 400 600

distance from center (est.)

C/N Ratio Lolium

d15N Lolium

% C Soil

10 hectares of degraded habitat = 2.5 cows….

Restoration ExperimentsRestoration Experiments

�� SmallSmall--scale (700 mscale (700 m22), replicated), replicated

�� Fire Fire –– Three strikes and your outThree strikes and your out……spring spring

burns workburns work

�� Goat grazing Goat grazing –– Expensive, not selective Expensive, not selective

nor effectivenor effective

�� Mowing Mowing –– Effective, known costs and Effective, known costs and technologytechnology

�� Seeding Seeding PlantagoPlantago appears unnecessaryappears unnecessary

Well-timed weed whacking

Passes the “O-test”

0

5

10

15

20

25

Control Mowed

% c

ov

er

2001200220032004

0

10

20

30

40

50

60

70

Control Mowed

% c

ov

er

Plantago

Lolium

8

2003

2005

2006

Reintroduction in 2007

Regulatory ecosystem

White-rayed Pentachaeta at long-term risk? Only known occurrence west of 280 across from Edgewood Preserve, absent less than 75 meters from freeway except on rock lenses !

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0 100 200 300 40050Kilometers

.

T&E Taxa N−dep 5 kg−N ha−1 year−1

T&E Species Mean N-dep

0

50

100

150

200

250

0 5 10 15 20

kg-N ha-1

year-1

Co

un

t

99/225 listed T&E plant species > 5 kg-N ha-1 yr-1

�Weiss 2006 CEC PIER Report

Biogeochemical phenomenon

9

San Jose AQ NH3 5.9 ppb in December

July 2002 – June 2003 (monthly bars)

July 9 2002 - Jul 1 2003

0

5

10

15

20

EW

-Wes

t

EW-E

ast

EW-4

00E JR

RCA

Q TH

KC-L

ow

KC-H

igh

kg

-N/h

a HNO3

NH3

NO2

Chemical climateChemical climate

I = PAT

� Impact = Population X Affluence X Technology

� Population: Number of vehicles

� Affluence: speed and size of vehicles

� Technology: emissions systems

?

60

Grams NOx per km

Fleet Emissions

0.00

0.50

1.00

1.50

2.00

0 20 40 60 80 100 120kph

g N

Ox/k

m

603510

?

75

CARB Emissions Reduction MethodologyCARB Emissions Reduction Methodology

20002000--20052005

Ammonia from Cars?

� 1990+ catalytic converters over-reduce NOx when running fuel rich

� Function of Vehicle Specific Power

� 1.8 - 6+ Mg/km/year for Highway 280

� Highly variable from vehicle to vehicle, 10% of vehicles produce 50% of emissions

Baum et al. 2001 Env. Sci. Tech 35: 3635-3741

Roadside laser on freeway on ramp, 46-55 mph

94 +/- 8 mg-NH3 km-1

SoCAB tons/day Vehicles: 44 Livestock: 27-30All Sources: 165-218

10

VSP 0 grade

0

10

20

30

40

50

60

70

80

0 10 20 30 40 50 60 70 80 90

mph

VS

P

0

250

500

750

1000

1250

1500

0 10 20 30 40 50 60 70 80 90

mph

mg

NH

3/k

m

SULEV

ULEV

LEV

NOx vs NH3

0

0.5

1

1.5

2

2.5

3

3.5

4

0 0.05 0.1 0.15 0.2

NH3 grams/mile

NO

x g

ram

s/m

ile

Durbin et al. 2002 Atmos. Environ. 36: 1475-1482

Appendix A published online

CMAQ 4km California

Gail Tonnesen UCR

Can be queried for individual chemical species, monthly

average concentrations, and monthly deposition

Run with and without vehicular NH3 and see

effects on N-dep and PM

11

Chemical Climate Change

Total cumulative dose over 40 years =

hundreds of kg-N ha-1

More immediate than climate change, driving

weed invasions

4 km CMAQ map provides basis for

regional and subregional analyses

Is available

0 10 20 30 40 505

Kilometers

Dry deposition 2002 CMAQ

not for release08/2005

kg−N ha−1 year−1

0.1 − 2.5

2.6 − 5

5.1 − 7.5

7.6 − 10

10.1 − 12.5

Trends in NO2 Annual Average in Select California

Counties

0.00

0.02

0.04

0.06

0.08

1980

1982

1984

1986

1988

1990

1992

1994

1996

1998

pp

m N

O2

Santa Clara

San Mateo

San Francisco

Alameda

Los Angeles

Orange

SanBernardino

Fresno

Kern

Sacramento

2001 California Almanac of Emissions and Air Quality

EPA Standard

NOx Emissions

0

20

40

60

80

100

120

140

160

180

1975 1980 1985 1990 1995 2000 2005 2010

To

ns/d

ay Santa Clara

San Mateo

San Francisco

Problem is not going away soon

2001 California Almanac of Emissions and Air Quality

Agenda: Make it better

� CARB study – meeting with Jerry Hill

� How did we get here, what is current impact on health and welfare, and where are we going?

� EPA funding?

� Run CMAQ w/o vehicular ammonia, effect on N-deposition and PM

� Ammonia monitoring network (passive)

� Detailed freeway study along I-280, modeling, measurement, and calibration

� Other freeway sites, CAFOs, etc.