Merging space, time, chemistry and Merging space, time, chemistry and environmental media: Monitoring environmental media: Monitoring

challengeschallengesWRAP Monitoring Workshop

Chandler, ArizonaMay 15, 2008

Rich Scheffe, EPA-OAR

Acknowledgments

• Everyone• WRAP-RPO’s National Level Impact on

Environmental Assessments– Gap filling IMPROVE samplers in center of

CONUS– VIEWS and related TSS– NH3 emissions modeling– Accelerating SOA treatment in CMAQ

simply, Arithmetic injustice

• Greater than 95% of air pollutant mass is located above 100m, yet we (air program community) focus 95 % of our characterization on the bottom 10 meters{compromises both predictive and current characterization phenomena}

Topics• Integration drivers

– Themes from 2004 NAS study• Multiple-pollutant, - media; accountability

– Trend of lowed high volume air quality standards (O3, PM)– Relative economic growth distribution globally– Convergence of non-cancer causing health effect mechanisms

across pollutants– Increasing technology– Decreasing (relative) measurement resources– Climate-AQ interactions

• Information technology and data integration systems• Monitoring thoughts

Obstacles to improved observation operations and design

• Decaying(?) infrastructure• Reliance on compliance type

measurements and related FRM/FEMs• Lack of market incentives• Inadequate technology transfer from

research to operations

Emerging Challenges for Air Policy• Developing Multiple pollutant integrated management strategies• Assessing and Protecting Ecosystem Health• Multiple spatial scales of interest• Intercontinental and Cross-Border Transport• Maintaining AQM System Efficiency in the face of

Changing Climate• Ongoing Assessments and feedbacks of program progress

(accountability)

Air Toxics

• History of emissions standards setting processes

• General characterization of risk

Nexus of ozone, PM2.5 (2003-5) and air toxics (NATA 1999)

.

High Risk Counties often Coincide with Locations whereCriteria Pollutant Issues are Significant -

Draft

Multimedia Assessments

• Start with NAPAP (Acid rain, Title 4)– Interest waning as ozone, then PM2.5 emerged as

dominant air quality interests starting in the late 1980’s

• 2004 NAS AQ Report driving EPA, AQ community – Reorganization– Resource allocations– New NARSTO MP-MM-ACC assessment

• NASA participation requested

Integration across pollutants and media: tradeoffs and optimum strategies?Primary Sources

HgHAPmetals

VOC (HAPs)

COSVOC

NO2

O3O3

hν

NO SO2

OH

H2SO4HNO3

NH3OH Hgo,Hg2

OH,O3

OH

OrganicPM

RO2HO2

OH

hν

NitratePM

SulfatePM

ChemicalDeposition

gases

particles

ACCOUNTABILITY

Source emissionsDirect NO, SO2, VOC, CO, metals,

Ambient precursors and intermediatesNO, NOy, CO, VOC, SO2, metals, radicals, peroxides

Ambient target speciesO3, PM, HAPs

Health effectsAsthma, cardio-pulmonary ↓,Cancer, death

Ecosystem + effectsDefoliation, Visibility↓ biodiversity, Metals concentration

Perceived (measured?)Life quality

Increasing influence in confounding factors and perceived value to public policy

Increasing confidenceIn characterization

Secondary and deposition loadsVisibility, acidification, eutrophication, metals

ExposuresInhalation, digestion

Accountability and Indicators Pipeline

Feedback/correction

Largest decline in ozone occurs in and downwind of EGU NOx emissions reductions (2002-2004)

(analysis constrained by absence ambient NOx data)Decrease from 2002 to 2004 (Adjusted Data)

-3 ≤ D

-5 ≤ D < -3-8 ≤ D < -5

D < -8

Decrease in ppb

Decrease from 2002 to 2004 (Adjusted Data)

-3 ≤ D

-5 ≤ D < -3-8 ≤ D < -5

D < -8

-3 ≤ D

-5 ≤ D < -3-8 ≤ D < -5

D < -8

Decrease in ppb

The major EGU NOx emissions reductions occurs after 2002 (mostly NOx SIP Call)Average rate of decline in ozone between 1997 and 2002 is 1.1%/year. Average rate of decline in ozone between 2002 and 2004 is 3.1%/year.

Decline in “Seasonal Average” 8-Hour Daily Maximum Ozone

Met. Adj.Tons Reduction

-33,000 - 0

0 - 27,000

28,000 - 73,000

74,000 - 110,000

120,000

EGU NOx Tons Reduced

GOME Satellite NO2 Trends (1995-2002)

Richter et al., 2005

Courtesy NOAA, Kim et al.

Satellites provide best source of ambient NO2: Accountability and Trends

Figure 20. Left - superimposed Eastern U.S. emission and combined GOME and SCIAMACHY NO2 1997-2002 trends (Kim et al., 2006); right - GOME NO2 trends from 1995 – 2002 (after Richter, 2005). Clear evidence of reductions in midwest U.S. and European NOx emissions, and increased NOx generated in Eastern Asia.

Figure 21. 2004 OMI NO2 column images aggregated for all Fridays (left) and Sundays (right) indicating weekend/weekday patternsassociated with reduced Sunday emissions (source, Husar).

MANAGING MULTIPLE SPATIAL SCALES

Evolutional change in National Air Pollution Management

2050

20001970 1990 2010

Local/urbanRegionalHemispheric

Initial CAA BiogenicsRegional science

8-hr ozonePM2.5(annual driver)

Regional Rules

New PMStandardsDaily/annual drivers

Climate-AQHemisphericalTransport

Hemispheric > 1000 kmRegional > 200km

Urban 15–50 kmLocal< 5 km

O3

SecondaryPM2.5

PM2.5 dust

CO POPsHg

methane CO2

NOxVOCs

SecondaryPM2.5

PrimaryOC (fires)

PrimaryPM2.5

HAPs VOCO3 Hg

metals

UFs, SourceSpecificPM, gases

HNO3

PAN

PANCHC

Hg

International transport/climate interactions Scale: global/regional

April 2001 Dust Transport Event Observed from TOMS

April 9/8 April 10/9 April 11/10

April 12/11 April 13/12 April 14/13

Aug 17

Aug 18Aug 19Aug 20

Aug 21Aug 22Aug 23

Aug 25Aug 28

5 km3 km

2006 Dust Transport Event Observed from CALIPSO

David Winker

High exposure to ultrafineparticles, CO, other pollution near roadway

Increased risk near and on roadways

New findings on roadway pollution

Relative Particle Number, Mass, Black Carbon, CO Concentration near a major LA freeway

Example: New Haven, CT70% of block group centroids are within 500m from a major road

>10,000 ADT

Factors affecting a health outcome

Physical State Mental State

outcome

Pollution dose

Genetic Disposition

Diet

Moving toward

Multi-Pollutant Analytical FrameworkFuture = National Air Pollutant Assessment

Control Strategies

Criteria Pollutants

Benefits Assessment

Air Toxics

Benefits Assessment

Exposure/Risk AnalysisEcosystems

Benefits Assessment

Exposure/Risk Analysis

Spatial Surfaces

Emissions Inventory

Air Quality Modeling

Modeling Platform

Ambient Data

Regional Local

LegendIn Place

Requires development

e.g., PHASE

Exposure/Risk Analysis

Maximizing space/time/composition through systems integration

• Integration of systems to improve – air quality models

for forecast– Current and– Retrospective

assessments• Global-Regional

Air Quality Connections

• Climate-AQ connections

Land AQ Monitors

Total column depth(through Satellites)

AQ model results

Vertical Profiles

Integrated Observation- Modeling

Optimized air chemistry

Characterizations

Exposure/Health

Air managementecosystem

s

accountability

Simple integration of of Model outputs and observations; Eastern U.S.fused PM2.5 surface

Parallel Information Technology solutions to enable integrated assessments

Mercury Deposition from US Power Plants: 2020 with CAIR & CAMR

Mercury Deposition from US Power Plants: 2001

Mercury Deposition From All Sources: 2001

Mercury – a multiple scale, multiple media Assessment challenge

Questions• How can efficiencies across observation networks be

enabled?• What are reasonable roles of space-based and ground

based agencies?• How can GEOSS and related organizing structures

help?• How do we commit to the pain of integration?....

harmonization …beyond QA/QC..(across and within systems and time trends)

• What drives observation design? And other top-down, bottom-up conundrums…

Fine Particle Reductions Work

0 5 10 15 20 25 30 350.7

0.8

0.9

1

1.1

1.2

1.3

P

T W

HL

S

T

W

H

L

S

PM2.5 µg/m3

Rat

e R

atio

Steubenville

Topeka

Watertown

KingstonSt. Louis

Portage PM pollution (including sulfates) declines accompanied by reduced mortality risk

Layden et al (2006). Effect of Reduction in Fine Particulate Air Pollution and on Mortality: A extended follow-up in of the Harvard Six Cities Adult Cohort

relatively straightforward emissions strategy

0

5

10

15

20

1980 1985 1990 1995 2000 2005 2010 2015 2020

Mill

ion

Tons

SO2

NOx

Source: EPA

Projected, w/ CAIR

Health Effects: Symmetries in atmospheric and cellular level chemistries

·OH

O3

HONO

VOC

Radical PoolHO2·; RO2·

Carbonyls

NO

HNO3

FP

NO2

SOx

H2SO4

NH3

HOOH

hv

hv

CO

hv

SOx

Clouds/Aqueous

orgaer

Source

Secondary

Sink

PAN N2O5

Nighttime N2O5

·NO3

Chemistry

H O2

hv

O1

D

O3

P

hv

NH4NO3

·OH

O3

HONO

VOC

Radical PoolHO2·; RO2·

Carbonyls

NO

HNO3

FP

NO2

SOx

H2SO4

NH3

HOOH

hv

hv

CO

hv

SOx

Clouds/Aqueous

orgaer

Source

Secondary

Sink

PAN N2O5

Nighttime N2O5

·NO3

Chemistry

·OH

O3

HONO

VOC

Radical PoolHO2·; RO2·

Carbonyls

NO

HNO3

FP

NO2

SOx

H2SO4

NH3

HOOH

hv

hv

CO

hv

SOx

Clouds/Aqueous

orgaer

Source

Secondary

Sink

PAN N2O5

Nighttime N2O5

·NO3

Chemistry

H O2

hv

O1

D

O3

P

hv

NH4NO3

HOO

C

OC

NH2

NH2H 2N

O2-.

O2

L-Arg

.NO

O2-.

NADPHNADP+

L-Arg + O2

FMN

e-

FAD

FAD

FMNFMN

Heme

Fe2+ONOO-

L-ArgL-Arg

HemeFe

HemeFe

CaM CaM

Zn BH4BH4

e-

NADPH+ H+

FAD

O2 H+

Nox2Nox2

p67

p47rac

p22

HOO

C

OC

NH2

NH2H 2N

O2-.

O2

L-Arg

.NO

O2-.

NADPHNADP+

L-Arg + O2

FMN

e-

FAD

FAD

FMNFMN

Heme

Fe2+ONOO-

L-ArgL-Arg

HemeFe

HemeFe

CaM CaM

Zn BH4BH4

e-

NADPH+ H+

FAD

O2 H+

Nox2Nox2

p67

p47rac

p22

Source, Harrison, 2006

Source, Harrison, 2006

AtmosphericPathways

Reactive OxidantCell Chemistry Processes

Hypothesized effect

Consequences of new standards

New PM NAAQS 2006• Annual NAAQS 15 ug/m3• 24 hour 98th percentile NAAQS 35 µg/m3

– From 65 µ g/m3– Implications ….new definition for anomalous events

• Increased relevance of remote sensing information• PM10 remains• Requirements for PM10-2.5 monitoring

– focus on urban coarse PM resuspended by heavy traffic, industrial sources, and construction

• excludes rural dust uncontaminated by urban, industrial sources (excludes agriculture, mining, wind blown dust

Major Ozone Standard changes

• 1 hour to 8 hour standard (late 1990’s)– Transition from urban to regional

assessments• Recent 8 hour 80 (84) ppb to 75ppb

– Raises importance of background ozone, transport and climate-AQ interactions

Ozone revitalization after the PM onslaught

• Research $ exploded for PM in the late 90’s -2000’s

• What happened to fundamental oxidant research?

We need to re-respect the Center of the Environmental Assessment Universe…

Air Air ToxicsToxics

OzonOzonee

Acid Acid RainRain

VisibilitVisibilityy

PMPM2.52.5

Water Water QualitQualityy

..OHOH

..OHOH Role in Linking Pollutants Formation : Role in Linking Pollutants Formation : OneOne--AtmosphereAtmosphere

NOx + VOC + OH+ hv ---> O3

SOx [or NOx] + NH3 + OH---> (NH4)2SO4 [or

NH4NO3]

SO2 + OH ---> H2SO4NO2 + OH ---> HNO3

VOC + OH --->Orgainic PM

OH <---> Air Toxics

(POPs, Hg, etc.)

Fine PM(Nitrate, Sulfate,

Organic PM)

NOx + SOx + OH(Lake

Acidification, Eutrophication)

C. Jang

Monitoring

There is a wealth of measurements, but is it aligned for current drivers?

Deposition and surface water chemistry Networks

Scarcity of routine soil and surface water/chemistry

Consider importance of meteorological systems

e.g., Solar radiation networks

UV networksAeronet sun photometers

Air quality focused radar profilers

Comments on how satellite data really support air program management – ordered attempt

• Direct incorporation into emissions inventory process– 2002 NEI and 2005 fire components utilize

satellite data• Inverse modeling, top-down construction of emissions

– Generally for hemispheric scale applications• Accountability – (e.g., NOx EGU reductions)• Constraining air quality model evaluation (and EIs) by

providing consistent vertical column information• Direct Boundary condition Observations and conceptual

modeling of transport events• Spatial gap filling

– Most attractive marketing item

Recommendations(integration)

• In addition to speciated dry Hg

Sequencing Model Evaluation Steps

PBL development; Vertical/horizontal Mixing; Temperature radiation, water

Emissions evaluationand/or modification

Conserved speciesand precursor evaluation

Intermediateand fast reactingspecies

Transformed species

Wet and dry deposition

PBL development; Vertical/horizontal Mixing; Temperature radiation, water

Emissions evaluationand/or modification

Conserved speciesand precursor evaluation

Intermediateand fast reactingspecies

Transformed species

Wet and dry deposition

Recommendation 1: Support required deployment of 75 surface stationsdesigned to constrain regional model evaluation, link to satellites, serviceaccountability and epidemiological studies (not compliance sites)

NCore network: 75 Level 2 sites of collocated trace gases and aerosolcomponents in “representative” mix of urban and regional areas – included in

12/06 PM NAAQS revision

Level 2: ~ 75 Multi-pollutant (MP)

Sites,“Core Species”Plus Leveraging From

PAMS, Speciation Program,

Air Toxics

Level 1. 3-10 Master Sites Comprehensive

Measurements, Advance Methods

Serving Science and Technology Transfer

Needs

Level 3: Minimum Single Pollutant Sites (e.g.> 500 sites each for O3 and PM2.5 and related spatial

Mapping Support

L2

Level 3

L1

NCore Measurements

Minimum “Core” Level 2 MeasurementsContinuous NO,NOy,SO2,CO, PM2.5, PM10/PMc,O3,Meteorology (T,RH,WS,WD); Integrated PM2.5 FRM, HNO3, NH3,

Level 2: ~ 75 Multi-pollutant (MP)

Sites,“Core Species”Plus Leveraging From

PAMS, Speciation Program,

Air Toxics

Level 1. 3-10 Master Sites Comprehensive

Measurements, Advance Methods

Serving Science and Technology Transfer

Needs

Level 3: Minimum Single Pollutant Sites (e.g.> 500 sites each for O3 and PM2.5 and related spatial

Mapping Support

L2

Level 3

L2

Level 3

L1

NCore Measurements

Minimum “Core” Level 2 MeasurementsContinuous NO,NOy,SO2,CO, PM2.5, PM10/PMc,O3,Meteorology (T,RH,WS,WD); Integrated PM2.5 FRM, HNO3, NH3,

Recommendation 2: Improve surface based nitrogen characterizations

• Proposed NCore NOy – operational level issues remain ?

• True routine low cost NO2 instruments not available

• ambient NH3

Recommendation 3: VOCs - Ground based complement for satellite HCHO and possibly glyoxal• HCHO only provided in urban high ozone locations

(dating back to 1990 CAAA)– No routine program for regionally representative

HCHO (key surrogate for biogenic isoprene emissions, important diagnostic species for model evaluation)

• Glyoxal – recent importance of role in SOA formation and leveraging opportunity with total column values

Recommendation 4: Routinely available vertical air chemistry

• Adoption of a North American complement to MOZAIC/CARIBE (domestic flights)– Exploration through TAMDAR

Recommendation 5: Sustaining and enhancing “sentinel” fixed station sites for LR transport and background characterization support (source, HTAP interim report)

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Recommendation 6: Geostationary air chemistry mission – sustained through partnership with ground based agencies (EPA, USDA, NPS, NOAA) – LANDSAT model (Engel- Cox)chenistry

Recommendation 7: Harness or guide GEOSS and other“integration” umbrellas to create effective information

technology support to enable data retrieval, archiving, access, distribution and interpretation across disparate informations sources (Data Fed, ESIP,…rudyworld)

GEOSS

Eco-informaticTest beds

Accountability/indicators

SIPs, nat. rulesdesignations

PHASE

PM research

Risk/exposureassessments

AQ forecasting

EPA NOAA

NASA

NPS

USDA

DOE

PrivateSector

States/Tribes/RPO’sInterstate orgs.

Academia

NARSTO

NAS, CAAACCASAC, OMB

Enviros

Supersites

IMPROVE, NCorePM monit, PAMS

CASTNET

Lidarsystems

NADP Satellite data

Intensive studies

PM centers

Other networks:SEARCH, IADN..

OrganizationsPrograms

Data sources

CMAQGEOS-CHEM

EmissionsMeteorology

NAAQSsetting

CDC

Health/mort.records

CoordinationClusterMess

Extras

Key Gaps/Recommendations• Surface/soil chemistry

– Scarcity of routine, long term soil and water chemistry campaigns to associate changes in deposition with soil/surface water responses

– Sustainability of TIME/LTM• Spatial and temporal scales

– Leveraging satellite observations with key surface measurements and vertical profile systems

• e.g., HCHO, NO2, glyoxal, SO2, CO– Poorly covered rural areas

• Link to satellite observations• Support ecosystem assessments• Critical for integration models and observation systems

– Support for geostationary satellite campaigns• Enable near continuous streams of trace gas and aerosol observations, from current

(typically twice daily) “point in time” measurements– Routine aircraft campaigns for vertical profiles

• Trace gases and aerosols– Higher time resolved aerosol components

• Transition period between Supersites and implementation• Acknowledge SEARCH and RPO efforts

– Strategy for near roadway exposures?

Key Gaps/Recommendations, cont.

• Multiple pollutants (atmospheric view)– Air toxics conundrum (inhalable)

• Perceived and real significant measurement gaps– Especially beyond mobile source BTEX compounds

• Challenging variety of source- and local scale- specific attributes– Mercury

• Speciated “dry” (elemental gas, divalent gas, p-Hg) observation– Needed complement to precipitation MDN program– Initiative underway coordinated through NADP

– Nitrogen species• Elevated importance related to 3 major MP-MM-AC themes

– (note: national scale U.S emissions strategies are N and S dominated)• Critical need: continued lack of true NO2

– Central diagnostic specie imbedded in atmospheric reaction pathways– Compromises leveraging satellite obs.

• Noted scarcity of rural measurements• Slow deployment of NOy• Extremely scarce reduced N observations (NH3 and p-NH4)• Critical role of CASTNET

Key Gaps/Recommendations, cont.

• Multiple pollutants (atmospheric view), cont– Sulfur and CO

• Inadequate SO2 observations– Key to confirming treatment of modeled sulfate formation– Input in NH3 bi-directional parameterization schemes

• Very limited trace CO observations– demanded for model evaluation– Indicator for exhaust gas HAPs

– VOCs• Rethinking since PAMS of early 1990’s?• Lacking important rural indictors (e.g., HCHO)

– Collocated “representative” MP sites • enables increased probing of confounding associations and

constraining model evaluation• 75 site initiative through NCORE

– Central city and key rural areas» modest backbone, ideally catalyzing increased coverage

– Adds trace gases (CO, NOy, SO2, NH3*) to established aerosol speciation sites– Reasonable “starting” surface link for satellite systems

Key Gaps/Recommendations, cont.

• Other process/diagnostic species[based on evolving knowledge and priorities]– Glyoxal

• Precursor for cloud based heterogeneous SOA formation• Reasonable indicator of urban based VOC oxidation products• Surface link to satellites

– Nitrous acid, HONO• Important generator of OH (morning/evening)• Diagnostic for atmospheric N balance

– Nitrate ion• Important role in biogenic SOA formation

• Other Accountability indicators (atmospheric view)– N species, Hg

• N and Hg emissions reduction projections– Energy policies, e.g. shift in fuels

• Low sulfur diesel– Particle physical properties

• FOSSIL fuels to GRAIN based sources– Increased acetaldehyde and PAN

• Field campaigns– Challenge to communicating effectiveness and distributing information beyond

small circles– Occasional comprehensive model evaluation campaigns

Aug. 14 cloud experimentVertical Profile (courtesy, A. Carlton, EPA)

Base CMAQ CMAQ w/ AORGC

ICARTT PILS WSOC meas.

Vertical profile comparison of CMAQ-predicted OC and PILS WSOC measurements