Characterizing Source Emissions

John G. Watson (johnw@dri.edu)

Judith C. Chow
Desert Research Institute
Reno, NV, USA
Presented at

The Workshop on Air Quality Management,

Measurement, Modeling, and Health Effects
University of Zagreb, Zagreb, Croatia
24 May 2007

Objectives
Review past and current source
sampling methods for PM
emission rates and source
profiles
Illustrate recent testing
protocols for dilution sampling
systems

Important Emissions Sources

Fugitive dust from wind erosion, agricultural activities,
construction, storage piles, and vehicle traffic on paved and
unpaved roads.
Ducted exhaust from industrial facilities (e.g., coal- and oilfired power stations, smelting, cement plants, chemical
plants, petroleum extraction and refining, glass
manufacturing, paper making, shipping).
Vehicle exhaust from cars, trucks, motorcycles, and buses.
Burning and cooking from stoves, charbroilers, trash, forest
fires, and agricultural burning.
Ammonia from animal husbandry and fertilization.

Important Emissions Characteristics

Emissions Rate:
Amount emitted per unit time or unit of activity.
Particle Size:
Determines transport and deposition properties.
Chemical Composition:
Fractional abundance of gaseous and particulate chemical
components in emissions. Used to speciate inventory and to
apportion ambient concentrations to sources.
Temporal Variation:
Emissions change on daily, weekly, seasonal, and annual
cycles. Timing of emissions affects atmospheric transport
and dilution as well as human exposure to outdoor air
pollution.

Emissions are Measured for Different

Purposes
Certification:

Verify that a process design is capable of achieving

emissions below a regulated limit. (e.g., FTP engine tests)

Compliance:
Determine that in-use processes are within permitted
values (e.g., vehicle smog tests, periodic stack tests,
opacity tests)
Emissions trading:
Relate actual emissions to allowances (e.g., continuous
SO2 monitors).
Emission inventories:
Real-world emissions for pollution planning.
Source apportionment:
Speciated emissions for source and receptor modeling.

 Emissions measured for one

purpose are typically
inaccurate for other
purposes!

Emissions Model
Component i emissions fluxes =
ij fraction of component i in source j
x
j

emission factor (mass/activity) for source

activity of source j

[particle size fraction]

[control efficiency]

[temporal profile]

0.001

Chemical Compound

100

Coal-firedPowerPlant

0.1

0.01

0.1

Abundance(%)

0.01

0.001

0.001

Chemical Compound

Chemical Compound

Chloride
Nitrate
Sulfate
Ammonium
Sol. Potas
OrganicCarbon
Ele.Carbon
Aluminum
Silicon
Phosporus
Sulfur
Chlorine
Potassium
Calcium
Titanium
Vanadium
Chromium
Manganese
Iron
Nickel
Copper
Zinc
Arsenic
Selenium
Bromine
Strontium
Lead

Lead

Strontium

Bromine

Selenium

Arsenic

Zinc

Copper

Nickel

Iron

Manganese

Chromium

Vanadium

Titanium

Calcium

Potassium

Chlorine

Sulfur

Phosporus

Silicon

A luminum

Ele. Carbon

Organic Carbon

Sol. Potas

Ammonium

Sulfate

Nitrate

Chloride

10

Vehicle Exhaust

10

10

0.001
Chloride
Nitrate
Sulfate
Ammonium
Sol.Potas
OrganicCarbon
Ele.Carbon
Aluminum
Silicon
Phosporus
Sulfur
Chlorine
Potassium
Calcium
Titanium
Vanadium
Chromium
Manganese
Iron
Nickel
Copper
Zinc
Arsenic
Selenium
Bromine
Strontium
Lead

Abundance(%)

10

Chloride
Nitrate
Sulfate
Ammonium
Sol.Potas
OrganicCarbon
Ele. Carbon
Aluminum
Silicon
Phosporus
Sulfur
Chlorine
Potassium
Calcium
Titanium
Vanadium
Chromium
Manganese
Iron
Nickel
Copper
Zinc
Arsenic
Selenium
Bromine
Strontium
Lead

Abundance(%)

Abundance (%)
100

PM Source Profiles
100

WoodBurning

0.1

0.01

100

RoadDust

0.1

0.01

ChemicalCompound

Emissions Rates/Factors
(PM10, PM2.5, SO2, NOX, NH3)
Existing gridded inventories:
specialized modeling studies
Emissions factor models:
http://www.epa.gov/OMSWWW/models.htm
http://www.epa.gov/ttn/chief/
Continuous emission monitors:
http://www.epa.gov/acidrain/edata.html
Large point sources:
http://www.epa.gov/airsweb/

Inventory GIS Activity Layers

Land use and terrain:
geological survey, satellite
Population:
Census
Roadways:
Census, mapping companies
Soil and coal types:
Soil Conservation Service
Fuel volumes and
composition:
sales records, taxes, certification
tests

Light-medium
commercial/industrial:
Census, stock listings
Large point sources:
Census, production records

Important Sources of Primary PM

and Secondary Precursors
PM Fugitive dust from wind erosion, agricultural activities,
construction, storage piles, and vehicle traffic on paved and unpaved
roads.
PM, NOx, VOC, SO2 Ducted exhaust from industrial facilities (e.g.,
coal- and oil-fired power stations, smelting, cement plants, chemical
plants, petroleum extraction and refining, glass manufacturing,
paper making, shipping).
PM, NOx, VOC, SO2 Vehicle exhaust from cars, trucks,
motorcycles, and buses.
PM, VOC Burning and cooking from stoves, charbroilers, trash,
forest fires, and agricultural burning.
NH3

Animal husbandry and fertilization.

Source Characterization
Measurement Methods

Laboratory suspension:
Dust or residue samples resuspended in laboratory chamber.
Source-dominated sampling:
Samples taken at locations and times when a single source
dominates ambient concentrations.
Vehicle dynamometer testing:
Simulate driving cycles on fixed roller.
Vehicle on-road testing: Roadside or tunnel, integrated or
individual vehicle samples
Diluted duct sampling:
Samples drawn into aging chamber and cooled with clean air.

Laboratory Dust Resuspension

Source-Dominated Sampling
Unpaved Road Dust Emissions

Road Dust Emissions

Use TRAKER (Testing Reentrained Aerosol Kinetic
Emissions from Roads) vehicle
to map road dust emissions.
Calibrate TRAKER with
unpaved road dust emissions.

TRAKER Measurements

Location of inlets
(right side and
background shown).

Generator and pumps

are mounted on a
platform on the back
of the van.

TRAKER Measurements (continued)

Two sampling plenums,

DustTrak and GRIMM particle
monitors, and rotameters.

GPS logs the TRAKERs

position every 1
second.

Results from the Treasure Valley,

Idaho, Road Dust Study

Source-Dominated Sampling
(Cooking)

Real-World Cooking

Simulated Cooking

New Vehicle Emissions Testing

Methods
Remote Sensing of Vehicle Emissions:

Allows emission rates to be determined for certain chemical

components (VOC, NOX, CO, PM).

Fast Response VOC and NOX Speciation Measurements

and Normalizing to CO2:
Can determine individual on-road vehicle emissions with
respect to fuel consumption. Can be applied to other sources
with high emissions of other gases.
Dense Spatial Monitoring:
Battery-powered PM monitors as well as passive VOC, NO2, and
CO absorbers are located within and around source complexes.
Emissions are inferred from complex dispersion models or
spatial receptor models.
Tunnel Studies:
Measurements are taken in tunnels to minimize contamination
from other sources (VOC, NOX, CO, PM).

Source-Dominated Sampling
(Vehicle Exhaust)

Roadside sampling

Diesel exhaust
sampling

Estimate Emissions of Vehicle

Exhaust
Sample real-time CO2 and pollutants in a
source-dominated environment to obtain
fuel-based emissions factors.
Use road tube counters to classify
vehicles.
Use area fuel sales to estimate emissions.
Compare results with MOBILE6 emissions
factors.

Estimate Vehicle
Exhaust Emission Rate
Fourier Transform Infrared
Spectroscope measures CO2,
CO, NO2, NO, and propane.
Correlation of pollutants
with CO2 yields fuel-based
emissions factors.
Real-time particle counters
(e.g., Grimm 1.108) can
quantify particles between
0.3 to 1.8 m at 1-sec
resolution.

Remote Sensing of In-Use Vehicle

Exhaust
~10-15 m

TRANSMITTER
Lic #

Backscattered
Light

Exhaust
Plume

RECEIVER

DATA
ACQUISITION

Absorption and Backscatter

Terminus
Plate

LORAX: Lidar On-Road Aerosol Experiment

In-Plume Vehicle Emission Sampling

Ducted Emissions: Hot sample

Total Suspended Particulate (TSP)
EPA Method 17: in-stack filter (at stack temperature)
EPA Method 5: heated out-of-stack filter (at 120 or 160
C)
EPA Method 5, 5A, 5B, 5C, 5D, 5F, 5G, 5H, 5I

PM10 and PM2.5, including condensable PM

Method 201A: combines Method 17 with in-stack 10 m
cyclone to collect PM10
Method PRE-004: combines Method 201A with in-stack 2.5
m cyclone to collect PM2.5
EPA Method 202: collect condensable PM as those which
pass through filter and are captured in water-filled bubblers
(impingers) in an ice bath

Method 201/202 Filter/Impinger Methods

PM10 and PM2.5 Glass or
Teflon
Condensable PM
cyclones and
probe liner
filter
(heated)Teflon
(in-stack)
(<1 m)
tubing Filter
Analysis:
(heated

Organic extraction

Filterable PM

Titration of inorganic
fraction

Analysis:
Evaporation of rinses
Gravimetric analysis
Range of chemical
speciation techniques
is limited due to high
temperatures,
moisture, interfering
particles & gases
EPA Methods PRE4 & 202

T T

Dry and weigh

organic and
inorganic residue
SO4= and ClPost Test Purge with N2 or Air

Sample gas is cooled to

60-70F in iced impingers

Method 202 Artifact

Findings
Condensable PM2.5 may be overestimated using
impinger-based methods
Sulfate artifacts significant even for gas-fired sources
If Method 202 is performed, a post-test nitrogen purge
should always be done
Further investigation of artifacts and differences between
impinger and dilution sampling methods is needed

Dilution sampling allows broader speciation of PM2.5

for improved speciation profiles

Difference in PM2.5 Mass

between In-Stack and Dilution Sampling
Gas-Fired Boiler - Field Data
0.018
0.016

lb/MMBtu

0.014

In-Stack
Methods

inorganic condensable (M202)

organic condensable (M202)
Filterable PM (M201A)
PM2.5 (dilution)

0.012
0.01
0.008
0.006
0.004

Dilution Method

0.002
0
Run 1

Run 2

Run 3

Run 1

Run 2

Run 3

AP42

Dilution Sampling of
Emissions from Meat Cooking

Dilution Sampling System

Ambient
Air

PM10
Cyclone
Probe

Stack
Gas

HEPA
Filter
Carbon
Filter

Flow Control

Sample gas is cooled to

ambient temperature by
dilution with ambient air

Flow meter
Rotameter
Pump

Venturi

PM2.5
Cyclones

Residence
Time
Chamber

Stainless steel
Cross-flow jet mixing

RH
To Sample
Collection
Trains

Dilution Ratio 10-40:1

Residence time 80-90 sec

Particle Characteristics Often Vary

During Emissions Tests
(ELPI and Grimm OPC Size
Distributions)
Number concentration

Dp (um) Mass concentration

2.5
Loose
sand mass

dp
1.0

Nucleation/
reactions from
binder

Shakeout (15min)

Pouring

0.1

Shakeout (15min)

Recently Developed DRI/BEI Dilution System

26

12.5
B
7
3

A
28

Inner Diameter
A: 1.875 in
B: 5.875 in
C: 8.375 in
8.5
C

Recently Developed DRI/BEI Dilution System

(continued)

Thermocouple Positions on each Collar

Red points are
measurement
points
0.5, 1.25, 1.75,
2.25 and 2.875
(center) from
inner wall.
Grey rods indicate
thermocouple
locations and
typical starting
points for each
thermocouple

Characterizing the DRI/BEI Dilution

System
Temperature profile at different depths
and along various distances from inlet.
Determine loses and mixing characteristic
as a function of particle size, dilution
ratios, and distance from inlet for
polystyrene latex sphere (PSL) particles
from 0.06 30 m.
Determine optimum range of dilution
ratios and aging time using a diesel
generator at idle and full load.

Diluted Stack Test Findings

Residence time and dilution ratio do not
change particulate mass emission rate, but
do affect size distribution and total
number of particles emitted. Longer
residence times shift particulate mass to
larger size and decrease total number
concentration.
Higher dilution rates increase ultrafine
particle concentrations.

Conclusions
Road dust emission potential can be measured
continuously.
Mobile emissions are more accurate from onroad sensing of many vehicles than from
dynamometer testing of a few vehicles.
Dilution sampling provides more accurate
estimates of PM stack emission rates than hot
stack and impinger samples.
Chemical source profiles should be measured
with emission rates.