Exposure
Protocol
and
Study
Plan
for
the
Section
211(
B)
Tier
2
High
End
Exposure
Screening
Study
of
Baseline
and
Oxygenated
Gasoline
Prepared
for
AMERICAN
PETROLEUM
INSTITUTE
1220
L
Street
Washington,
DC
20005­
4070
Prepared
by
Barbara
Zielinska,
Eric
M.
Fujita,
John
C.
Sagebiel,
and
David
E.
Campbell
Desert
Research
Institute
2215
Raggio
Parkway
Reno,
NV
89512
Jacob
D.
McDonald
Lovelace
Respiratory
Research
Laboratory
P.
O.
Box
5890
Albuquerque,
NM
87185
Lawrence
R.
Smith
Southwest
Research
Institute
6220
Culebra
Road
San
Antonio,
TX
78228­
0510
Ted
Johnson
TRJ
Environmental,
Inc.
713
Shadylawn
Road
Chapel
Hill,
NC
27514
Revised:
September
30,
2002
ii
ACKNOWLEDGMENT
This
work
is
supported
by
the
American
Petroleum
Institute.
We
gratefully
acknowledge
the
administrative
and
technical
support
provide
by
Dr.
Will
Ollison
of
API.
We
acknowledge
Darryl
Joseph
and
Thomas
Kelly
of
Battelle
for
their
assistance
with
the
continuous
formaldehyde
measurements
during
the
pilot
study
phase
of
the
project.
iii
TABLE
OF
CONTENTS
Acknowledgment
........................................................................................................................
ii
Table
of
Contents.......................................................................................................................
iii
List
of
Tables.............................................................................................................................
iv
List
of
Figures............................................................................................................................
iv
1.
INTRODUCTION
...............................................................................................................
1­
1
2.
PROPOSED
MEASUREMENT
METHODS
AND
PROTOCOLS
......................................
2­
1
2.1
Proposed
Exposure
Measurement
Methods
................................................................
2­
1
2.2
Proposed
Biomarker
Measurements
...........................................................................
2­
3
2.2.1
Urine
and
Breath
Sample
Collection
.................................................................
2­
4
2.2.2
VOC
Analysis
in
Breath
and
Urine
Samples
.....................................................
2­
4
2.3
Proposed
Measurement
Protocol
................................................................................
2­
5
2.3.1
Kore
MS200
.....................................................................................................
2­
5
2.3.2
CO
Instruments.................................................................................................
2­
6
2.3.3
Continuous
Formaldehyde
Monitor..................................................................
2­
8
2.3.4
BTEX
and
MTBE
by
Solid
Phase
Microextraction
(
SPME)..............................
2­
8
2.3.5
Time­
Integrated
Air
Sample
Collection
and
Analysis........................................
2­
9
3.
EXPERIMENTAL
PLAN....................................................................................................
3­
1
3.1
Controlled
In­
Cabin
and
Residential
Garage
Exposure
Measurements
(
Task
2)..........
3­
1
3.1.1
Procurement
of
Test
Fuels
from
Houston,
Chicago
and
Atlanta
(
Task
2a).........
3­
1
3.1.2
Determination
of
Tailpipe
and
Evaporative
Emissions
of
Test
Vehicles
(
Task
2b)
..........................................................................................................
3­
7
3.1.3
Relationship
Between
Exhaust
Emission
Rates
and
In­
Cabin
Exposure
(
Task
2c).........................................................................................................
3­
11
3.1.4
Relationship
Between
Evaporative
Emission
Rates
and
Exposure
in
a
Residence
With
an
Attached
Garage
(
Task
2d)
...............................................
3­
12
3.2
Microenvironmental
Exposure
Measurements
in
Atlanta,
Chicago,
and
Houston
(
Task
3).............................................................................................................
3­
13
3.2.1
Exposure
Diary
and
Script
Development
(
Task
3a)
.........................................
3­
14
3.2.2
In­
cabin
Exposures
in
Urban
Microenvironments
(
Task
3b)............................
3­
14
3.2.3
Outdoor
and
Indoor
Exposure
in
Urban
Microenvironments
(
Task
3c)............
3­
15
3.2.4
Technician
Biomarker
Analysis
(
Task
4)
........................................................
3­
15
3.2.5
Approach
for
Selecting
High
End
Microenvironments
....................................
3­
15
3.3
Meteorology
(
Task
5)...............................................................................................
3­
20
3.4
Data
Analysis
(
Task
6).............................................................................................
3­
20
3.5
Reporting
.................................................................................................................
3­
23
4.
PROJECT
SCHEDULE
AND
DELIVERABLES
................................................................
4­
1
5.
REFERENCES
....................................................................................................................
5­
1
iv
LIST
OF
TABLES
Table
No.
Page
No.

Table
2­
1.
Proposed
Measurement
Method........................................................................
2­
2
Table
3­
1.
Collection
of
Time­
Integrated
Samples
for
Chemical
Analysis
.........................
3­
4
Table
3­
2.
Suggested
Test
Plan
for
Each
Vehicle
...............................................................
3­
9
Table
3­
3.
Summary
of
FTP
Driving
Cycle......................................................................
3­
10
Table
3­
4
API
Trailing
Vehicle
Protocol
                  ..
3­
11
Table
3­
5
API
Garage
Study
Protocol
                   ...
3­
13
LIST
OF
FIGURES
Figure
No.
Page
No.

Figure
2­
1.
Variability
of
CO
Electrochemical
Cell
Response
with
Temperature.................
2­
7
Figure
3­
1.
Overall
Structure
of
211
(
b)
Monitoring
Requirements
.....................................
3­
2
Figure
3­
2.
Monitoring
Requirements
for
San
Antonio
Study..............................................
3­
3
Figure
3­
3.
FTP
Driving
Cycle..........................................................................................
3­
10
LIST
OF
APPENDICES
Appendix
A
Summer
2002
Sampling
Plan
for
Houston         
A1
Appendix
B
Sampling
Plan
for
Atlanta
               .
B1
Appendix
C
Sampling
Plan
for
Chicago
               
C1
Appendix
D
Example
of
a
Diary
                      .
D1
1­
1
1.
INTRODUCTION
The
U.
S.
Environmental
Protection
Agency
(
EPA)
has
recently
issued
requirements
for
a
test
program
in
accordance
with
the
Alternative
Tier
2
provisions
of
the
fuels
and
fuel
additives
(
F/
FA)
health
effects
testing
regulations,
which
are
required
pursuant
to
Section
211(
b)
of
the
Clean
Air
Act.
In
response
to
these
requirements,
the
American
Petroleum
Institute
(
API)
contracted
with
a
research
team
consisting
of
the
Desert
Research
Institute
(
DRI),
Southwest
Research
Institute
(
SwRI),
Lovelace
Respiratory
Research
Institute
(
LRRI),
and
TRJ
Environmental,
Inc
(
TRJ)
to
conduct
a
screening
study
of
the
high­
end
distribution
of
inhalation
exposures
to
evaporative
and
combustion
emissions
of
baseline­
and
oxygenated
gasoline.
This
study
plan
describes
the
exposure
protocols
and
specifies
the
measurement
methods,
sampling
&
analytical
procedures,
and
quality
assurance
protocols
that
will
be
used
in
the
study.

The
goal
of
this
research
program
is
to
screen
potential
high­
end
inhalation
exposure
microenvironments
dominated
by
evaporative
and
exhaust
emissions
of
baseline­
and
oxygenated­
gasoline.
The
specific
objectives
are
to
provide
information
allowing
the
Agency
to:

 
Quantify
personal
exposures
to
motor
vehicle
oxygenated
and
non­
oxygenated
gasoline
evaporative
and
exhaust
emissions
in
microenvironments
(
MEs)
representing
the
upper
end
of
the
exposure
frequency
distribution
of
such
exposures;

 
Determine
the
quantitative
relationships
between
personal
exposures
in
selected
MEs
with
fixed
site
measurements
in
these
MEs
and
at
nearby
air
monitoring
stations;

 
Determine
how
personal
exposures
differ
in
cities
and
seasons
in
which
MTBEoxygenated
,
EtOH­
oxygenated,
and
baseline
gasolines
are
in
use;

 
Extrapolate
to
other
sites
and,
if
possible,
other
oxygenated
fuels;

 
Determine
the
relative
contributions
of
vehicle
fuel
exhaust
and
evaporative
emissions
to
personal
exposures
from
oxygenated
and
non­
oxygenated
gasoline.

The
overall
approach
for
the
exposure
study
is
based
upon
the
draft
S211b
Tier
2
Exposure
Study
Protocol
that
was
developed
in
May
2001
by
the
API
Section
211(
b)
Research
Group
and
reviewed
by
the
U.
S.
Environmental
Protection
Agency
(
EPA).
DRI
and
LRRI
conducted
a
five­
day
pilot
study
(
Task
1)
in
Reno,
NV
during
February
2002
to
test
alternative
measurement
approaches
in
the
field
under
conditions
that
are
similar
to
those
that
will
be
encountered
in
the
main
study.
TRJ
and
API
provided
input
in
the
design
of
the
pilot
study
and
reviewed
the
results
and
findings.
The
evaluations
included
available
measurement
methods
for
continuous
and
time­
integrated
measurements
of
carbon
monoxide
(
CO),
total
volatile
organic
compounds
(
TVOC),
and
designated
VOC
species.
DRI
and
LRRI
also
evaluated
the
stability
of
the
designated
VOC
species
in
breath
and
urine
samples
during
the
pilot
study.
Results
of
the
pilot
study
are
summarized
in
Appendix
A.
The
draft
exposure
protocols
were
appropriately
modified
based
upon
the
results
of
the
pilot
study.
Section
2
1­
2
describes
the
proposed
exposure
measurement
approaches
and
calibration
and
other
quality
control
procedures.

Two
approaches
are
proposed
for
the
main
exposure
study.
First,
DRI
and
SwRI
will
conduct
exposure
measurements
under
controlled
conditions
in
order
to
establish
quantitative
relationships
between
vehicle
tailpipe
and
evaporative
emissions
to
exposure
levels
in
two
specific
microenvironments,
a
trailing
vehicle
cabin
and
an
attached
residential
garage.
In
the
second
approach,
DRI
and
LRRI
will
monitor
microenvironmental
and
personal
exposures
in
various
potential
high­
end
microenvironments
in
Houston,
Chicago,
and
Atlanta
during
summer
(
July
to
September
2002)
and
winter
(
January
to
March
2003).
These
cities
have
ongoing
ambient
monitoring
programs
and
have
MTBE­
RFG,
EtOH­
RFG,
and
baseline
gasoline
formulations,
respectively.
A
number
of
key
variables
will
be
measured
in
ambient
air
within
microenvironments,
in
subjects'
personal
breathing
zones,
and
urine.
Section
3
specifies
the
microenvironments
and
exposure
protocols.
The
results
of
this
study
will
provide
information
that
would
permit
quantification
of
the
upper­
end
personal
exposure
to
gasoline
and
oxygenated
gasoline
emissions
and
extrapolations
to
other
cities
using
oxygenated
fuels.
The
information
from
this
study
will
permit
sensitivity
analyses
to
determine
the
range
of
these
exposures,
especially
during
heavy
traffic,
in
residential
and
public
parking
garages
and
during
refueling.
2­
1
2.
PROPOSED
MEASUREMENT
METHODS
AND
PROTOCOLS
This
section
describes
the
measurement
methods
that
are
proposed
for
the
exposure
study
and
provides
the
rationale
for
their
selection.
Results
of
the
evaluation
of
the
methods
during
the
pilot
study
are
summarized
in
the
Pilot
Study
Report,
which
is
attached
to
this
study
plan.

2.1
Proposed
Exposure
Measurement
Methods
The
methods
we
propose
to
use
to
measure
the
exposures
in
the
various
microenvironments
(
MEs)
are
summarized
in
Table
2­
1
and
will
be
discussed
below.

Three
continuous
methods
will
be
employed
to
monitor
1)
the
aromatic
hydrocarbons
benzene,
toluene,
ethylbenzene
and
the
xylenes
(
BTEX),
2)
carbon
monoxide,
and
3)
formaldehyde.
These
methods
will
be
also
combined
with
component
concentration
ratios
from
contemporaneous
time­
integrated
samples
to
reconstruct
the
expected
time
series
for
species,
e.
g.,
1,3
butadiene
(
BD),
ethanol
(
EtOH),
and
methyl
tert­
butyl
ether
(
MTBE),
for
which
we
do
not
have
continuous
instruments.

The
Kore
MS200
will
be
used
to
monitor
BTEX
on
a
one­
minute
basis.
This
instrument
uses
a
time­
of­
flight
mass
spectrometer
to
separate
compounds
of
interest.
Rather
than
using
a
gas
chromatograph,
this
instrument
uses
a
software
solution
to
apportion
the
contribution
of
each
component
of
interest
to
the
time­
of­
flight
(
TOF)
mass
spectrum
seen
by
the
instrument.
The
software
does
not
distinguish
between
specific
isomers,
thus
xylenes
are
reported
together.
The
inlet
uses
a
polydimethylsiloxane
membrane
preferentially
to
allow
non­
polar
organic
compounds
into
the
analyzer
while
maintaining
the
vacuum
inside
the
analyzer
chamber.
This
membrane
inlet
does
limit
the
types
of
compounds
that
can
be
analyzed,
however.
Common
air
constituents
and
polar
orgainic
molecules
do
not
pass
the
membrane
quickly.
The
instrument
performed
well
during
the
pilot
study,
comparing
favorably
with
the
canister
measurements
for
most
samples.
Part
of
the
challenge
during
the
pilot
study
was
that
the
instrument
had
not
fully
recovered
from
the
long
delay
it
was
held
in
customs
prior
to
the
study.
Once
the
vacuum
system
had
fully
recovered,
we
had
no
problems
with
the
instrument.
Since
the
pilot
study
we
have
been
further
researching
this
instrument
and
are
confident
that
this
instrument
will
perform
well.
In
addition,
we
have
secured
the
availability
of
another
Kore
MS200,
which
is
maintained
by
Horiba
Instruments,
Inc.
in
Irvine,
CA.
In
the
event
there
are
further
difficulties
with
our
MS200,
we
can
get
this
one
on
loan
very
quickly.

Carbon
monoxide
will
be
monitored
by
the
Langan
T15
CO
monitor
and
by
the
API
300
CO
NDIR
instrument
(
courtesy
of
the
US
EPA).
Langan
T15
is
an
electrochemical
monitor
for
CO.
The
response
time
of
this
instrument
is
somewhat
slower
than
infrared­
based
instruments.

Since
Battelle
was
unable
to
construct
a
Continuous
Formaldehyde
Monitor
for
DRI,
we
purchased
this
instrument
from
Alpha­
Omega
Power
Technology,
Ltd.
(
Albaquerque,
NM).
The
Alpha­
Omega
instrument
utilizes
the
same
reaction
as
the
Battelle
monitor
­
it
absorbs
formaldehyde
in
acidified
water,
reacting
it
with
2,4­
pentanedione
and
ammonia
to
form
a
cyclized
product,
3,5­
diacetyl­
1,4­
dihydrolutidene,
which
is
continuously
detected
by
fluorescence.
The
method
is
highly
specific
for
formaldehyde
and
very
sensitive.
2­
2
Table
2­
1
Proposed
Measurement
Methods
Method
Species
Continuous
BTEX
1,3­
BD
MTBE
EtOH
HCHO
Acetaldehyde
NMHC
CO
Time
MS200
X
1
min
T15
CO
X
1
min
API
300
CO
X
Seconds
HCHO
X
1
min
ppbRAE
X
Seconds
Surrogate
A
B
C
D
E,
F
Semi­
Cont.
SPME
X
X
X(?)
15
min
Integrated
Can
X
X
X
X(?)
X
X
60
min
DNPH
X
X
60
min
Solid
Adsob.
X
X
X
60
min
Notes:
A.
Time
series
will
be
reconstructed
from
the
canister/
CO
ratio
for
exhaust­
dominated
samples.
B.
Time
series
will
be
reconstructed
from
the
canister/
CO
ratio
for
exhaust­
dominated
samples.
C.
Time
series
will
be
reconstructed
from
the
solid
adsorbent/
CO
ratio
for
exhaust­
dominated
samples.
D.
Time
series
will
be
reconstructed
from
CH3CHODNPH/
HCHOContinuous
ratio
for
exhaustdominated
samples.
E.
Time
series
will
be
reconstructed
from
the
canister/
CO
ratio
for
exhaust­
dominated
samples.
F.
Time
series
will
be
reconstructed
from
the
canister/
MS200
ratio
of
BTEX
for
evaporativedominated
samples.

It
would
be
preferable
to
have
continuous
measurement
methods
for
several
other
compounds;
however,
there
are
no
acceptable
methods
for
1,3­
butadiene,
MTBE,
ethanol,
acetaldehyde
or
NMHC,
which
could
be
used
in
portable
modes
of
operation
with
the
necessary
sensitivity.
There
are
methods
that
will
allow
us
to
correlate
the
integrated
values
with
a
continuous
method
in
order
to
reconstruct
a
time
series.
For
example,
both
1,3­
butadiene
and
MTBE
can
be
determined
from
the
canister.
We
will
also
determine
the
integrated
CO
value
from
the
canister.
We
will
start
from
the
assumption
that
the
MTBE/
CO
and
1,3­
butadiene/
CO
ratios
will
be
constant
in
MEs
that
are
exhaust
dominated
over
the
hour
integrated
by
the
canister
measurement.
Thus,
by
ratioing
to
the
continuous
trace
of
CO,
we
can
reconstruct
the
time
series
of
MTBE
and
1,3­
butadiene.
The
same
method
will
be
used
for
ethanol
and
NMHC.
In
the
case
of
microenvironments
that
are
dominated
by
evaporative
emissions
(
for
example,
refueling)
we
would
not
expect
the
ratio
of
hydrocarbons/
CO
to
be
consistent.
In
these
ME's
we
will
use
the
MS200
time
series
values
and
correlate
these
with
the
BTEX
concentrations
from
the
integrated
samples.
The
assumption
is
that
the
MTBE/
BTEX
ratio
will
be
constant
and
we
can
thus
reconstruct
the
time
series
for
MTBE,
ethanol
and
NMHC
in
this
manner.
Neither
should
1,3­
2­
3
butadiene
be
present
in
evaporative
emissions.
In
addition,
we
will
collect
SPME
samples
over
a
shorter
time
period
(
10­
20
min)
to
measure
the
concentrations
of
MTBE
and
BTEX.
These
data
can
also
be
used
to
derive
the
time
series
for
various
pollutants.

In
a
similar
manner,
acetaldehyde
and
formaldehyde
should
be
correlated
in
exhaust
dominated
samples
and
we
will
reconstruct
the
time
series
for
acetaldehyde
from
the
continuous
formaldehyde
data
and
the
ratio
of
acetaldehyde
to
formaldehyde
from
the
contemporaneous
hourly
integrated
DNPH
samples.

In
addition
we
will
be
monitoring
total
BTEX
using
hand­
held
portable
PID
monitor.
A
new
instrument,
ppbRAE
from
Pine
Environmental
Services,
is
highly
sensitive
with
ppb
detection
level.
The
ppbRAE
measures
continuously
total
volatile
compounds
excluding
methane
and
C2
 
C4
saturated
hydrocarbons.
We
will
use
this
device
also
as
a
"
pollutant
sniffer"
to
help
us
selecting
the
microenvironments
with
the
highest
pollutant
levels.

2.2
Proposed
Biomarker
Measurements
During
the
pilot
study
both
urinary
and
breath
concentrations
of
MTBE
and
the
BTEX
compounds
were
measured
in
two
subjects
after
three
separate
scripted
exposures.
Breath
measurements
showed
an
exposure
effect
(
post­
exposure
concentration
in
breath
higher
than
preexposure
concentration)
when
samples
were
collected
soon
after
exposure
(
within
~
2­
3
minutes).
Breath
samples
collected
after
longer
post­
exposure
durations
showed
no
increase
relative
to
preexposure
breath
concentrations,
most
likely
due
to
the
short
1­
3
minute
half
lives
of
these
compounds
in
breath
(
Lindstrom
and
Pleil,
1996).
The
short
half­
life
of
absorbed
volatile
vapors
such
as
BTEX
in
breath
is
a
limitation
in
terms
of
its
use
as
a
biomarker
of
exposure.
Unless
breath
samples
are
collected
throughout
the
scripted
exposure,
a
breath
sample
at
the
end
of
the
exposure
will
only
measure
what
the
subject
is
exposed
to
during
the
last
few
minutes
before
sampling.

Urinary
measurements
from
the
pilot
study
also
showed
little
exposure
effect
from
most
compounds
for
2
of
the
three
exposures.
In
all
cases
the
urinary
concentrations
of
MTBE,
toluene,
ethyl
benzene,
and
xylene
were
below
detection
limits.
In
most
cases
the
concentrations
of
benzene
(
the
only
observed
compound)
post­
exposure
were
similar
to
pre­
exposure
due
to
the
fact
that
the
exposure
concentrations
were
low
in
most
cases.
After
the
highest
exposure
in
the
pilot
study
(
refueling
a
vehicle
­
hourly
canister
average
of
about
10
ppbv
benzene)
there
was
a
relatively
strong
exposure
effect
observed
in
one
subject
and
a
lesser
exposure
effect
observed
in
a
second
subject.
There
was
a
time
course
in
the
elimination
of
benzene
that
showed
urinary
benzene
concentrations
increasing
with
time.
This
is
similar
to
the
results
reported
by
Lee
and
Weisel
(
1998)
on
the
behavior
of
MTBE
in
urine.
During
the
pilot
study
urinary
concentrations
were
only
measured
3
hours
post
exposure,
so
we
were
not
able
to
observe
what
may
have
been
a
peak
concentration
of
the
compound
or
the
start
of
elimination
from
the
body.
Because
of
an
inability
to
see
the
decay
of
urinary
benzene
after
exposures,
and
the
slight
inconsistency
in
the
two
subjects
(
one
showed
much
higher
urinary
benzene),
we
conducted
another
scripted
refueling
exposure
in
Reno,
NV,
to
repeat
this
peak
exposure
and
see
if
the
urinary
VOC
concentration
data
can
be
linked
strongly
to
an
exposure
effect
at
these
levels
and
to
follow
the
full
time
course
of
elimination.
This
experiment
was
conducted
on
June
4,
2002,
in
Reno
and
the
results
are
described
in
the
Pilot
Study
Report.
2­
4
Since
the
additional
measurements
of
urinary
MTBE/
BTEX
from
the
second
refueling
experiment
were
promising,
we
propose
to
use
this
measurement
as
the
biomonitoring
technique
of
choice.
Since
we
were
not
able
to
discriminate
urinary
benzene
concentrations
in
low
level
exposures
(
e.
g.
walking
down
street),
we
propose
to
only
conduct
biomonitoring
experiments
from
projected
"
high­
end"
exposures
such
as
refueling.
Monitoring
will
be
conducted
similar
to
the
pilot
study,
with
pre
and
post
exposure
collections
of
the
subject's
urine.
The
complete
time
course
of
collection
will
be
lengthened
based
on
the
results
of
the
additional
experiments
that
will
be
conducted.
Collection
and
analysis
will
be
conducted
as
described
below.

In
addition,
we
will
include
breath
measurements
for
the
two
microenvironments
judged
to
be
the
highest:
refueling
and
underground
garage.
We
propose
to
collect
three
1
liter
canister
samples
for
each
experiment:
before
the
exposure,
immediately
after
the
peak
of
the
exposure,
and
after
the
1­
hr
exposure
scenario
measurement
period.

2.2.1
Urine
and
Breath
Sample
Collection
Urine
will
be
collected
from
technicians
who
participate
in
a
scripted
exposure.
Since
this
study
requires
the
use
of
human
subjects,
the
final
protocol
was
reviewed
by
an
Institutional
Review
Board
that
is
certified
with
the
National
Institute
of
Health.

Technicians
will
be
instructed
to
avoid
exposure
to
material
that
may
compromise
the
exposure
assessment
prior
to
and
during
the
scripted
exposures.
This
will
include
avoiding
alcohol
ingestion
(
ethanol)
and
first­
hand
or
second­
hand
cigarette
smoke
for
at
least
3
days
prior
to
the
scripted
exposures.
Urine
samples
(
voids)
collected
before
the
exposure
will
be
used
to
assess
background
levels
in
the
technician.
Urine
biomarker
samples
are
taken
immediately
before
and
after
completion
of
the
exposure
scenario
and
at
hourly
intervals
thereafter
until
substantial
declines
in
oxygenate
and
BTEX
species
were
noticed
(
about
6­
8
hours)
in
pilot
studies.

All
voids
will
be
encoded
for
confidentiality.
During
and
after
exposures,
voids
will
be
collected
every
hour
for
a
time
course
based
on
additional
measurements
described
above.

Urine
samples
will
be
collected
in
100
ml
polyethylene
collection
containers.
Immediately
after
collection,
a
50
ml
portion
of
the
sample
will
be
transferred
via
disposable
pipette
to
a
glass
storage
vial
with
an
airtight
Teflon
seal.
Samples
will
then
be
immediately
placed
on
dry
ice
or
in
a
freezer
prior
to
shipment
to
LRRI.
Samples
will
be
shipped
priority
overnight
to
LRRI
on
dry
ice,
where
they
will
be
immediately
placed
in
a
freezer
at
 
80
°
C
prior
to
analysis.

The
breath
measurements
will
be
accomplished
by
having
the
technician,
immediately
after
completing
the
exposure,
take
a
1­
liter
canister,
place
the
tube
in
his
mouth,
waste
the
first
half
of
a
breath,
turn
the
valve
to
allow
the
evacuated
cylinder
to
suck
the
second
half
into
the
canister,
and
close
the
valve
(
Pleil
and
Lindstrom
2002).

2.2.2
VOC
Analysis
in
Breath
and
Urine
Samples
The
analysis
of
VOCs
in
urine
will
be
conducted
according
to
the
methods
derived
from
Fustinoni
et
al.
(
1999).
This
technique
will
meet
the
analytical
detection
limits
required
to
2­
5
measure
the
target
analytes
at
concentrations
that
would
be
present
after
environmental
exposure.
The
analysis
of
VOC
in
breath
samples
will
be
conducted
as
described
by
Pleil
and
Lindstrom
(
2002).
The
approach
for
these
analyses
is
described
below.

Sample
Preparation.
The
VOCs
of
interest
here
are
stable
in
urine
for
up
to
2
months
(
Fustinoni
et
al.,
1999).
All
extractions
and
analyses
will
be
conducted
within
1
month
after
receipt
at
LRRI.
Frozen
urine
samples
will
be
left
at
room
temperature
until
completely
thawed.
After
mixing,
an
aliquot
of
the
urine
will
be
transferred
to
an
analysis
vial
containing
1
g
of
NaCl.
The
vial
will
then
be
sealed
after
addition
of
approximately
1
µ
g/
ul
of
benzene­
d6,
toluene­
d8,
xylened10
and
ethyl
alcohol­
d6
that
will
serve
as
internal
standards
for
the
analysis.

Head
Space­
Solid
Phase
Microextraction.
The
sample
will
be
heated
to
approximately
40
º
C
and
held
at
this
temperature
to
allow
analytes
to
reach
equilibrium
between
the
headspace
(
HS)
gas
and
aqueous
solution.
Analytes
will
then
be
sampled
from
the
HS
by
use
of
a
polydimethylsiloxane
SPME
fiber.
During
sampling,
the
fiber
will
be
exposed
directly
to
the
HS
for
about
15
minutes.
At
the
end
of
this
period,
the
sample
will
be
directly
injected
into
the
gas
chromatograph
(
GC).

Gas
Chromatography­
Mass
Spectrometry.
HS
fiber
extracts
will
be
thermally
desorbed
onto
a
GC
(
Hewlett
Packard,
5890)
coupled
to
a
Hewlett
Packard
5972
mass
selective
detector
(
GCMS).
Desorption
will
occur
at
approximately
200
º
C
for
3
minutes.
An
Agilent
DB­
624
column
(
30
m
x
0.25
mm)
will
be
applied
to
attain
the
necessary
chromatography
in
order
to
selectively
analyze
MTBE,
ethanol,
and
the
BTEX
compounds
in
the
scan
mode.
The
compounds
will
be
quantified
by
comparing
the
response
of
the
analytes
and
spiked
internal
standards
to
those
of
calibration
curves
created
from
authentic
analytical
standards.
The
limit
of
detection
for
this
analysis
is
approximately
15
ng/
µ
l
for
BTEX
(
Fustinoni
et
al.,
1999).
The
specific
limits
of
detection
for
MTBE
and
ethanol
are
expected
to
be
in
the
same
range
and
will
be
evaluated
during
method
development.

Breath
Samples
Analysis.
The
analysis
of
VOC
in
breath
samples
will
be
conducted
as
described
below
in
Section
2.3.5
for
canister
VOC
analysis.

2.3
Proposed
Measurement
Protocol
This
section
describes
the
protocols
that
will
be
applied
for
each
method
and
applicable
quality
assurance
procedures.

2.3.1
Kore
MS200
The
Kore
MS200
will
be
used
to
measure
BTEX
in
the
MEs.
The
protocol
for
use
includes
the
following
calibration
and
operational
procedures.

Calibration
Procedures:

1.
Start
instrument
and
establish
zero.
2.
Apply
span
gas
and
allow
2
minutes
to
stabilize
response.
3.
Collect
at
least
5
spectra
2­
6
4.
Using
calibration
section
in
software,
confirm
calibration
response
or
enter
new
calibration
values
as
needed.

Daily
Startup
Procedures:

1.
Check
Battery
Status
(
or
plug
in).
2.
Inlet
valve:
Middle
position
(
heater).
3.
Inlet
pump:
On
4.
Wait
until
inlet
vacuum
is
less
than
3x102
pa
and
inlet
temperature
led
is
green
5.
Sample
pump
On
6.
TOF
MS:
On
7.
TDC:
On
(
unless
you
are
on
battery,
then
wait
as
this
draws
a
lot
of
current.)

Once
you
are
ready
to
sample:

1.
Inlet
Valve
Down
position
(
confirm
that
vacuum
is
ok
and
heat
is
still
ok)
2.
Apply
zero
air
and
allow
it
to
flow
for
at
least
1
minute.
3.
Collect
5
spectra
of
background
air
to
assess
variability.
4.
Begin
sampling
If
possible,
during
a
run
perform
a
zero
check
as
follows:
Apply
zero
air
for
15
to
30
seconds,
allowing
the
instrument
to
collect
1
spectra.
After
a
sampling
run,
perform
a
zero
check
as
follows:
Apply
zero
air
and
immediately
collect
at
least
5
spectra.
Allow
the
zero
air
to
remain
on
the
instrument
for
5
minutes
and
collect
another
5
spectra.

During
sampling
runs,
keep
track
of
the
main
analyzer
chamber
vacuum.
If
the
vacuum
is
regularly
getting
above
20
x10­
6
Pa,
the
instrument
may
need
baking
out.
Follow
the
written
procedures
for
bakeout.

2.3.2
CO
Instruments
Two
CO
monitoring
instruments
will
be
used
for
the
field
study:
a
high
sensitivity,
fast
response
gas­
correlation
unit
(
API
300
and
Monitor
Labs
9830)
as
a
reference
device,
and
a
portable,
battery­
powered
passive
electrochemical
unit
(
Langan
T15)
for
exposure
measurements.

Prior
to
each
period
of
field
measurements
both
instruments
will
be
calibrated
using
a
zero­
air
generator
and
span
gas
to
provide
two
reference
points
encompassing
the
expected
range
of
concentrations
anticipated
during
actual
testing.
The
two­
point
calibration
procedure
is
as
follows:

1.
Collocate
both
instruments
and
allow
to
stabilize
for
a
minimum
of
15
minutes.
2.
Record
ambient
concentration
as
determined
by
each
instrument.
3.
Connect
inlet
lines
from
both
instruments
to
a
zero­
air
source
(
for
passive
sampler
use
flooder
cap
provided
by
manufacturer)
and
check
for
positive
flow
rate
of
>
1
lpm
with
rotometer.
4.
Let
instruments
stabilize,
record
current
baseline,
then
adjust
zero.
2­
7
5.
Connect
inlet
lines
to
a
tank
of
span
gas
with
appropriate
CO
concentration
for
anticipated
range
and
verify
flow
rate
6.
Let
instruments
stabilize,
record
current
reading,
and
adjust
span
to
correct
value.
7.
Re­
connect
zero­
air
source,
let
stabilize
and
check
baseline
zero
readings.
8.
Repeat
steps
4­
7
if
necessary.
9.
Check
third
concentration
level
with
span
gas
if
available.

During
field
measurement
periods
the
passive
sampler
will
be
checked
against
the
reference
unit,
which
has
an
automatic
baseline
stabilization
and
internal
zero­
air
source,
at
the
beginning
and
end
of
each
sampling
day
and
baseline
readings
will
be
recorded.
If
any
significant
deviations
are
observed
a
re­
calibration
will
be
performed.

The
electrochemical
cell
in
the
Langan
instruments
exhibits
a
significant
response
to
temperature
variations
as
shown
in
Figure
2.2­
1.
Note
that
these
variations
are
due
to
changes
in
the
temperature
of
the
electrolyte
in
the
cell,
not
in
the
ambient
air
temperature.
Prior
to
field
use,
we
will
attempt
to
characterize
this
temperature
response
at
realistic
CO
levels
in
the
laboratory.
If
the
response
appears
to
be
sufficiently
reproducible,
the
resulting
concentration
data
will
be
adjusted
based
on
the
units
internal
temperature
sensor,
which
has
been
observed
to
be
sufficiently
accurate
(+/­
2
C).

If
the
temperature
compensation
approach
does
not
appear
feasible,
the
instrument
will
be
thermally
isolated
and
maintained
as
close
to
calibration
temperature
(
typically
20
C)
as
possible
during
use.
The
reference
unit
will
be
kept
in
a
climate­
controlled
environment
(
mobile
laboratory)
so
temperature
response
is
not
a
concern
in
that
case.

In
addition,
the
Langan
T15
monitor
encounters
an
artifact
under
low
vent
conditions
inside
the
vehicle
cabin.
We
suspect
that
there
is
an
interference
that
is
vented
out
under
the
high
ventilation
conditions.
Our
initial
evaluation
indicated
that
the
lead­
acid
batteries
are
a
source
of
hydrogen
that
interferes
with
the
Langan
CO
monitor.
This
was
confirmed
by
observing
the
Langan
CO
monitor
in
the
presence
of
the
batteries
when
both
were
removed
from
the
vehicle.
In
order
to
help
eliminate
possible
sources
of
interference,
we
have
eliminated
the
wet­
cell
lead
acid
batteries
and
replaced
them
with
AGM
batteries
that
are
sealed
and
hence
do
not
outgas.
We
have
currently
installed
4
large
AGM
batteries
and
two
new
battery
chargers
in
the
van
along
with
two
new
power
inverters
providing
a
total
of
approximately
3000
Watts
of
continuous
power
at
110V
AC.
The
power
system
will
be
permanently
installed
so
that
we
will
not
need
to
remove
the
batteries
to
charge
them,
they
will
simply
be
plugged
in
to
charge.
To
handle
the
additional
load,
we
have
installed
overload
springs
on
the
van.
We
will
continue
to
use
the
other
batteries
for
the
cart
experiments
since
the
lack
of
a
trapped
space
means
we
will
not
encounter
interferences.
We
will
also
use
only
the
NDIR­
based
CO
instrument
inside
the
vehicle
cabin
which
does
not
suffer
from
the
same
artifact
as
the
Langan.
2­
8
Figure
2­
1.
Variability
of
CO
Electrochemical
Cell
Response
with
Temperature.

2.3.3
Continuous
Formaldehyde
Monitor
The
continuous
monitor
for
gaseous
formaldehyde
analyzer
was
purchase
from
Alpha­
Omega
Power
Technologies.
This
instrument
uses
Hantzsch
reaction
to
produce
a
fluorescent
derivative
from
HCHO
that
is
monitored
with
a
fluorescent
detector.
An
aqueous
calibration
standard
in
the
10­
7
to
10­
6
M
range
made
by
serial
dilution
of
37%
formalin
solution
in
the
0.1
N
H2SO4
scrubber
solution
is
used
for
the
daily
instrument
calibration
(
Kelly
and
Fortune,
1994).
This
daily
calibration
standard
is
compared
with
the
gaseous
formaldehyde
standard,
purchased
from
Apel­
Riemer
Environmental,
Inc.
The
monitor
is
zeroed
by
supplying
high­
purity
air
to
the
inlet.
Span
and
zero
samples
are
provided
to
the
monitor
at
regular
intervals
using
automated
valving.
We
are
presently
working
on
re­
engineering
the
Alpha
Omega
HCHO
instrument
to
make
it
more
field­
rugged
and
reliable.

2.3.4
BTEX
and
MTBE
by
Solid
Phase
Microextraction
(
SPME)

Based
on
the
results
of
our
pilot
study,
we
propose
to
use
75
µ
m
Carboxen/(
poly)
dimethylsiloxane
(
CAR/
PDMS)
fibers
for
BTEX,
MTBE,
and
possibly
ethanol.
The
fibers
are
exposed
for
15
to
30
min,
depending
on
the
specific
microenvironment,
and
are
analyzed
by
injection
into
a
model
8610C
gas
chromatograph
(
SRI),
which
will
be
housed
in
the
mobile
laboratory.
The
analysis
is
performed
immediately
after
collection
in
most
cases,
but
the
fibers
can
be
stored
on
dry
ice
in
a
cooler
for
a
period
of
several
hours
(
Chai
and
Pawliszyn,
2­
9
1995),
if
necessary.
The
gas
chromatograph
is
configured
with
FID
and
PID
detectors
and
a
60
m
capillary
column
(
CPSil
5,
0.32
mm
i.
d.,
1
µ
m
film
thickness,
Varian,
Inc.)
optimized
for
quantification
of
BTEX
and
MTBE.

Calibration.
The
GC
is
calibrated
in
the
laboratory
prior
to
deployment
in
the
field,
using
a
method
described
by
Martos
and
Pawliszyn
(
1997).
Briefly,
we
constructed
a
standard
gas
mixture
generating
device
that
consisted
of
a
20
L
stainless
steel
chamber,
Hamilton
syringe
pump,
and
an
air
dilution
system.
The
outside
of
the
chamber
is
covered
with
a
heating
blanket,
allowing
for
controlling
and
maintaining
constant
temperature
in
the
chamber.
A
20
µ
l
gas­
tight
Hamilton
syringe
is
used
to
deliver
the
analyte
mixture
with
a
controlled
speed.
An
ultra­
high
purity
air
is
mixed
with
the
upcoming
liquid
in
a
mixing
tee
and
delivered
to
the
chamber.
By
controlling
the
air
and
liquid
mixture
delivery
speed,
the
desired
concentration
of
the
analytes
can
be
achieved
in
the
chamber
(
ranged
from
low
ppb
to
ppm
levels).
The
chamber
is
allowed
to
reach
a
steady
state
after
a
minimum
of
10
volume
exchanges
after
each
alteration
of
gas
concentration.
The
concentrations
of
standard
compounds
in
the
calibration
mixture
is
verified
by
collecting
a
canister
sample
and
analyzing
it
by
our
standard
GC/
FID
method.
The
SPME
fibers
are
exposed
to
the
mixture
in
the
chamber
for
an
appropriate
time
and
then
thermally
desorbed
in
the
injector
of
the
GC/
PID/
FID
unit
for
2
minutes
at
200
C.
Each
fiber
is
exposed
to
the
same
mixture
at
least
three
times
to
ensure
the
desired
repeatability
of
measurements
and
three
different
calibration
mixture
concentrations
are
used
for
the
GC/
PID/
FID
system
calibration.
Using
the
SRI
software
system,
the
calibration
curve
is
constructed
for
each
analyte.

Daily
calibration
check.
For
the
daily
calibration
check,
the
SPME
fiber
will
be
exposed
to
one
concentration
of
the
calibration
mixture.
We
will
collect
several
canister
samples
from
the
dilution
chamber
to
take
these
mixtures
on
the
road
in
the
mobile
laboratory.
A
small
aliquot
of
the
mixture
will
be
placed
in
a
1
L
Tedlar
bag
to
allow
for
the
fiber
exposure.
The
canisters
could
be
shipped
back
to
the
DRI
laboratory
for
refilling
them
with
a
new
calibration
mixture,
when
the
pressure
in
the
canister
becomes
too
low.

2.3.5
Time­
Integrated
Air
Sample
Collection
and
Analysis
Time­
integrated
monitoring
methods
are
used
primarily
for
verification
of
the
responses
of
continuous
instruments.
The
methods
include
canister
sampling
for
VOC
(
BTEX,
1,3­
butadiene,
MTBE),
solid
adsorbent
sampling
(
for
ethanol
and
MTBE)
and
DNPH­
coated
Sep
Pak
cartridges
sampling
for
carbonyl
compounds.
These
methods
are
routinely
used
by
the
DRI
Organic
Analytical
Laboratory
(
OAL)
and
DRI
standard
operating
procedures
(
SOPs)
for
sampling
and
analysis
are
available
upon
request.
One­
hour
samples
will
be
collected.

Sampling.
The
DRI
custom
built
sampler
that
can
sample
simultaneously
a
canister,
solid
adsorbent
cartridges
(
two
in
parallel)
and
DNPH­
impregnated
Sep­
Pac
cartridge,
is
used
for
this
study.
The
sampler
is
compact;
it
can
be
set­
up
in
a
vehicle
cabin
and
run
from
the
battery.
Prior
to
use
the
sampler
is
checked
for
cleanliness
by
sampling
zero
air
through
the
canister
inlet.
If
the
concentration
of
any
targeted
compound
exceeds
0.1
ppb,
the
sampler
is
thoroughly
cleaned
and
re­
tested.
2­
10
The
canister
sampler
uses
a
differential
pressure
flow
controller
to
supply
air
to
the
sampler
canister.
The
flow
rate
will
be
checked
by
a
calibrated
mass
flow
controller.
Since
the
actual
flow
rate
is
less
important
than
the
fact
that
the
flow
rate
remains
constant,
additional
quality
assurance
checks
on
the
flow
controllers
is
not
necessary.

Both
the
solid
adsorbent
and
DNPH
samplers
use
the
same
vacuum
pump
controlled
by
mass
flow
controllers.
These
controllers
will
be
calibrated
at
the
start
of
the
field
program
by
using
a
primary
flow
device
(
e.
g.
Gillibrator)
and
then
will
be
periodically
checked
while
in
the
field
to
confirm
that
the
flow
rates
are
accurate.

Canister
samples.
Prior
to
sampling,
the
canisters
are
cleaned
by
repeated
evacuation
and
pressurization
with
humidified
zero
air,
as
described
in
the
EPA
document
"
Technical
Assistance
Document
for
Sampling
and
Analysis
of
Ozone
Precursors"
(
October
1991,
EPA/
600­
8­
91/
215).
Six
repeatable
cycles
of
evacuation
to
~
0.5
mm
Hg
absolute
pressure,
followed
by
pressurization
with
ultra­
high­
purity
(
UHP)
humid
zero
air
to
~
20
psig
are
used.
The
differences
between
the
DRI
procedure
and
the
EPA
recommended
method
are
that,
in
the
DRI
method,
canisters
are
heated
to
140
°
C
during
the
vacuum
cycle
and
more
cycles
of
pressure
and
vacuum
are
used.
According
to
our
experience
and
that
of
others
(
Rasmussen,
1992),
heating
is
essential
to
achieve
the
desired
canister
cleanliness.
Also,
the
canisters
are
kept
longer
under
vacuum
cycles,
about
one
hour
in
the
DRI
method,
as
opposed
to
half
an
hour
in
the
EPA
method.
At
the
end
of
the
cleaning
procedure,
one
canister
out
of
12
in
a
lot
is
filled
with
humidified
UHP
zero
air
and
analyzed
by
the
gas
chromatograph/
flame
ionization
detection
(
GC/
FID)
method.
The
canisters
are
considered
clean
if
the
total
non­
methane
organic
compound
(
NMOC)
concentration
is
less
than
20
ppbC.
The
actual
concentrations
of
blank­
check
canisters
are
typically
below
10
ppbC.

Canister
samples
are
analyzed
for
speciated
VOC
concentrations
promptly
upon
receipt
of
samples
from
the
field,
using
gas
chromatography
with
flame
ionization
detection
(
GC/
FID,
Hewlett
Packard)
according
to
guidance
provided
by
the
EPA
Method
TO­
15.
The
GC/
FID
response
is
calibrated
in
ppbC,
using
NIST
Standard
Reference
Materials
(
SRM)
1805
(
254
ppb
of
benzene
in
nitrogen).
Based
on
the
uniform
carbon
response
of
the
FID
to
hydrocarbons,
the
response
factors
determined
from
these
calibration
standards
are
used
to
convert
area
counts
into
concentration
units
(
ppbC)
for
every
peak
in
the
chromatogram.
Identification
of
individual
compounds
in
an
air
sample
is
based
on
the
comparison
of
linear
retention
indices
(
RI)
with
those
RI
values
of
authentic
standard
compounds.
A
DB­
1
column
(
60
m
long
0.32
mm
i.
d.,
1
µ
m
film
thickness)
is
used
for
these
analyses.

Blanks
are
performed
once
daily,
while
performance
standards
are
executed
three
times
per
week.
Our
analysis
plan
and
data
processing
standards
call
for
the
replicate
analysis
of
approximately
20%
of
the
samples.
For
canisters
the
replicate
analysis
is
conducted
at
least
24
hours
after
the
initial
analysis
to
allow
re­
equilibration
of
the
compounds
within
the
canister.
The
replicate
analyses
are
flagged
in
our
database
and
the
programs
we
have
for
data
processing
extract
these
replicates
and
determine
a
replicate
precision.
Replicate
analysis
is
important
because
it
provides
us
with
a
continuous
check
on
all
aspects
of
each
analysis,
and
indicates
problems
with
the
analysis
before
they
become
significant.

Solid
adsorbent
samples.
Ethanol
and
MTBE
will
be
quantified
using
solid
adsorbent
cartridges,
in
addition
to
canister
method.
Although
MTBE
is
stable
in
SUMMA
canisters
and
2­
11
can
be
quantified
with
high
precision
and
accuracy,
ethanol
is
rather
unstable
and
the
replicate
analysis
of
canister
samples
show
high
degree
of
scatter
(
Goliff
and
Zielinska,
2001).
Thus,
the
solid
adsorbent
samples
are
only
necessary
for
quantification
of
ethanol.
MTBE
and
BTEX
data
will
be
obtained
from
the
solid
adsorbent
samples
to
serve
as
a
comparison
with
canister
data
for
QA
purpose.
For
sample
collection
we
will
use
multibed
adsorbent
cartridges
consisting
of
Tenax
TA,
Carbotrap
(
or
Carboxen)
and
Carbosieve
(
Shire
et
al.,
1996;
Tsai
and
Weisel.,
2000;
Vayghani
et
al.,
1999).
Prior
to
use,
the
Tenax­
TA
solid
adsorbent
is
cleaned
by
Soxhlet
extraction
with
hexane/
acetone
mixture
(
4/
1
v/
v)
overnight,
and
dried
in
a
vacuum
oven
at
~
80
°
C.
The
dry
Tenax
is
packed
into
Pyrex
glass
tubes
together
with
Carbotrap
and
Carbosieve
and
thermally
conditioned
for
four
hours
by
heating
in
an
oven
at
300
°
C
under
nitrogen
purge.
Approximately
10%
of
the
precleaned
cartridges
are
tested
by
GC/
FID
for
purity
prior
to
sampling.
After
cleaning,
the
cartridges
are
capped
tightly
using
clean
Swagelok
caps
(
brass)
with
graphite/
vespel
ferrules,
placed
in
metal
containers
with
activated
charcoal
on
the
bottom,
and
kept
in
a
clean
environment
at
room
temperature
until
use.

After
sampling,
cartridge
samples
are
analyzed
by
the
thermal
desorption­
cryogenic
preconcentration
method,
followed
by
high
resolution
gas
chromatographic
separation
and
Fourier
transform
infrared/
mass
spectrometric
detection
(
IRD/
MSD)
of
individual
compounds.
The
Chrompack
Thermal
Desorption­
Cold
Trap
Injection
(
TCT)
unit
is
used
for
the
purpose
of
sample
desorption
and
cryogenic
preconcentration.
The
compounds
are
quantified
by
MS,
using
the
response
factors
of
authentic
standards,
prepared
at
five
different
concentrations
with
a
static
dilution
bulb.

Carbonyl
compounds.
Formaldehyde
and
acetaldehyde
will
be
collected
with
Sep­
Pak
cartridges
that
have
been
impregnated
with
an
acidified
2,4­
dinitrophenylhydrazine
(
DNPH)
reagent
(
Waters,
Inc),
according
to
the
EPA
Method
TO­
11A.
When
ambient
air
is
drawn
through
the
cartridge,
carbonyls
in
the
air
sample
are
captured
by
reacting
with
DNPH
to
form
hydrazones,
which
are
separated
and
quantified
using
HPLC
in
the
laboratory
(
Fung
and
Grosjean,
1981).
Depending
on
the
type
of
sorbent
(
C18
or
silica
gel)
in
the
cartridge,
the
ambient
measurement
results
are
subject
to
various
artifacts
due
to
interaction
with
ozone,
thus
the
ozone
denuder
is
recommended
for
sample
collection.
We
will
use
a
honeycomb
denuder
coated
with
sodium
carbonate/
sodium
nitrite/
glycerol
mixture
(
method
developed
by
Dr.
Koutrakis
from
Harvard
School
of
Public
Health).
After
sampling,
the
cartridges
will
be
eluted
with
acetonitrile.
An
aliquot
of
the
eluent
will
be
transferred
into
a
1­
ml
septum
vial
and
injected
with
an
autosampler
into
a
high
performance
liquid
chromatograph
(
Waters
Alliance
System)
for
separation
and
quantitation
of
the
hydrazones
(
Fung
and
Grosjean
1981).
3­
1
3.
EXPERIMENTAL
PLAN
This
section
specifies
the
tasks
required
to
meet
the
objectives
for
the
S211(
b)
Tier
2
Exposure
Study
and
how
each
element
of
the
proposed
testing
protocol
will
be
carried
out.
Details
of
the
methods
and
procedures
and
quality
assurance
program
are
described
in
Section
2.
The
proposed
exposure
study
consists
of
two
parts.
First,
Desert
Research
Institute
(
DRI)
and
Southwest
Research
Institute
(
SwRI)
will
conduct
exposure
measurements
in
San
Antonio
under
controlled
conditions
in
order
to
establish
quantitative
relationships
between
vehicle
tailpipe
and
evaporative
emissions
to
exposure
levels
in
a
trailing
vehicle
cabin
and
in
a
residence
with
an
attached
garage.
In
the
second
approach,
DRI
and
LRRI
will
monitor
microenvironmental
and
personal
exposures
in
various
potential
high­
end
exposure
microenvironments
in
Atlanta,
Chicago,
and
Houston
during
summer
and
winter
conditions.
Figures
3­
1
and
3­
2
show
the
monitoring
requirements
for
the
overall
study
and
for
Task
2,
respectively.
Table
3­
1
shows
the
planned
exposure
matrix
and
the
number
of
samples
and
hours
of
measurements
for
each
microenvironment.

3.1
Controlled
In­
Cabin
and
Residential
Garage
Exposure
Measurements
(
Task
2)

DRI
and
SwRI
will
determine
the
quantitative
relationships
between
evaporative
and
tailpipe
emission
from
characterized
test
vehicles
to
exposure
in
(
1)
a
cabin
of
a
trailing
vehicle
under
normal
operation
and
with
induced
malfunctions
and
(
2)
a
residence
with
an
attached
garage.
The
exposure
measurements
will
be
made
in
San
Antonio
during
June
2002
for
summer
fuels
and
during
January
2003
for
winter
fuels
according
to
the
following
protocol.

3.1.1
Procurement
of
Test
Fuels
from
Houston,
Chicago
and
Atlanta
(
Task
2a)

With
API
and
DRI
guidance,
SwRI
will
procure
six
test
fuels
(
a
summer
regular
grade
and
winter
regular
grade
fuels
in
each
of
the
three
cities
 
Houston,
Atlanta,
and
Chicago)
for
the
study.
SwRI
will
procure
two
55­
gallon
drums
of
each
fuel
from
a
major
supplier
in
each
city
to
conduct
the
work
in
San
Antonio.
Three
summer
fuels
will
be
procured
and
evaluated
during
May/
June
of
2002
and
the
three
winter
fuels
during
December
2002.
SwRI
will
test
fuels
for
bulk
properties
and
DRI
will
speciate
the
chemical
composition
of
each
of
the
six
blended
fuels.
3­
2
Figure
3­
1:
Overall
Structure
of
211(
b)
Monitoring
Requirements
Scenario
1
Scenario
2
...
Scenario
N
Summer
Winter
Houston
RFG­
MTBE
Atlanta
Baseline
Chicago
RFG­
EtOH
San
Antonio
(
Chart
B)

Section
211(
b)

Exposure
Study
Scenarios
In
vehicle:
commuter
rush
hour
(
stop­
and­
go)

In
vehicle:
urban
street
canyons
In
vehicle:
refueling*

In
vehicle:
parking
garage
In
vehicle:
toll
plaza
In
vehicle:
tunnel
Outdoors:
refueling
vehicle*

Outdoors:
sidewalk
near
high­
density
traffic
Outdoors:
bus
stop
Indoors:
underground
parking
garage
Indoors:
toll
booth
Indoors:
auditorium
with
auto
show
or
similar
event
MEASUREMENTS
Continuous
(
1­
5
min)
Langan
­
CO,
MS200
­
BTEX,
Battelle
­
HCHO
Semi­
continuous
(
15­
20
min):
SPME
­
MTBE,
EtOH,
BTEX
Integrated
(
60
min):
canister
­
1,3
BD,
MTBE,
EtOH,
BTEX,
TVOC
DNPH
cartridge
­
HCHO,
CH3CHO
Tenax
tube
­
MTBE,
EtOH,
BTEX
OTHER
DATA
Diary
(
ME/
event)

Location:
GPS
(
lat/
long,
min)

Biomarkers*:
urine
(
MTBE,
BTEX)

Meteorology:
WS/
WD,
RH,
T
(
min);
surface
roughness;
stability
class
Local
air
quality:
sampling
day
monitoring
station
data
(
60
min)
3­
3
Figure
3­
2.
Monitoring
Requirements
for
San
Antonio
Study
Segment
N
Leading
vehicle
Trailing
vehicle
Segment
1
Cabin
Tests
FTP
Emission
Tests
Garage
Adjacent
room
Test
1
Test
N
Garage
Tests
Normal
Malfunctioning
Sedan
Truck
RFG­
MTBE
RFG­
EtOH
Baseline
Summer
Winter
San
Antonio
MEASUREMENTS
Continuous
(
1­
5
min)
Langan
­
CO,
KORE
­
BTEX,
Battelle
­
HCHO
Semi­
continuous
(
15­
20
m
in):
SPME
­
MTBE,
EtOH,
BTEX
Integrated
(
60
m
in):
canister
­
1,3
BD,
M
TBE,
E
tOH,
BTEX,
TVOC
DNPH
cartridge
­
HCHO,
CH3CHO
Tenax
tube
­
MTBE,
E
tOH,
BTEX
OTHER
DATA
Diary
(
ME/
event)

Location:
GPS
(
lat/
long,
m
in)

Meteorology:
W
S/
WD,
RH,
T
(
min);
surface
roughness;
stability
c
lass
Local
air
quality:
sampling
day
m
onitoring
station
data
(
60
m
in)

MEASUREMENTS
Semi­
continuous
(
15­
20
m
in):
SPME
­
MTBE,
EtOH,
BTEX
OTHER
DATA
Diary
(
ME/
event)

Location:
GPS
(
lat/
long,
m
in)

Meteorology:
W
S/
WD,
RH,
T
(
min);
surface
roughness;
stab.
c
lass
Local
air
quality:
sampling
day
m
onitoring
station
data
(
60
m
in)

Segm
ents
for
Cabin
Tests
1
Initial
background
­­
no
test
vehicles
2
Idling,
c
lose
spacing
3
Moderate
speed,
m
oderate
spacing
4
High
speed,
greater
spacing
5
F
inal
background
­
no
test
vehicles
Garage
Tests
1
Background,
garage
em
pty
2
Car
in
garage,
kitchen
door
open
f
or
1
m
in
3
Car
in
garage,
kitchen
door
open
for
entire
test
4
Car
in
garage,
kitchen
door
closed
­­
window
open
5
Car
in
garage
idling,
garage
door
open,
kitchen
door
open
for
1
min
6
Back
car
out
and
close
ga
rage
door
3­
4
Table
3­
1
Collection
of
Time­
Integrated
Samples
for
Chemical
Analysis
Number
of
Samples
Per
Exposure
Period
Total
Durat
ion
of
Measurement
and
Samples
Test
Duration
(
min)
Sample
t
ime
SPME
(
min)
SPME1
SPME2
Cans
DNPH
Solid
Adsorb.
a
No.
of
Tests
Test
Durat
ion
(
hrs)
SPME1
SPME2
Cans
DNPH
Solid
Adsorb.

Task
1
Lab
evaluation
and
Pilot
Study
Pilot
­
In­
cabin,
Freeway
am
&
pm
60
30
2
2
1
1
1
2
2.0
4
4
2
2
2
Pilot
­
In­
cabin,
surface
street
60
30
2
2
1
1
1
2
2.0
2
2
1
1
1
Pilot
­
In­
cabin,
refueling
60
30
2
1
1
1
1
2
2.0
2
2
1
1
1
Pilot
­
Refueling
at
pump
60
30
2
1
1
1
1
2
0.5
2
2
1
1
1
Pilot
­
Parking
Garage
60
30
2
2
1
1
1
2
0.5
2
2
1
1
1
Pilot­
Residential
Garage
180
30
6
6
4
4
4
1
180.0
6
6
4
4
4
Pilot
­
Pedestrian
Walk
360
30
12
12
1
1
1
2
12.0
2
2
1
1
1
Subtotal
840
28
26
10
10
10
199
20
20
11
11
11
Task
2b:
FTP
Dynamometer
Tests
(
Optional
Measurements
by
DRI)

FTP
composite
exhaust
emissions
22.86
NA
NA
1
1
1
NA
NA
24
24
4
Diurnal
Evap
Test
NA
NA
1
0
1
NA
NA
24
0
4
Subtotal
0
0
2
1
2
0
0
48
24
8
Task
2c:
Controlled
Exposures
­
Trailing
medium/
high
emitters
(
Table
3­
4)

Initial
background
10
10
1
1
1
1
24
4.0
24
0
24
24
4
Exposure
Measurements
(
Table
3­
4)
140
10
15
2
2
2
24
56.0
360
0
48
48
8
In­
cabin
exposure
in
lead
car
(
b)
3
0
0
0
24
72
0
0
0
0
Subtotal
150
19
0
3
3
3
60.0
456
0
72
72
12
Task
2d:
Controlled
Exposure
­
Residential
Garage
Exposure
(
Table
3­
5)

In­
garage
(
background)
30
30
1
1
1
1
24
12.0
24
0
24
24
4
In­
garage
(
during
exposure)
150
30
5
1
1
1
24
60.0
120
0
24
0
adjcent
room
(
background)
(
b)
30
1
1
1
1
24
(
b)
24
0
24
24
4
adjcent
room
(
during
exposure)
(
b)
5
1
1
1
24
(
b)
120
0
24
0
Subtotal
180
30
12
4
4
4
72.0
288
0
96
48
8
3­
5
Table
3­
1
(
Continued)

Collection
of
Time­
Integrated
Samples
for
Chemical
Analysis
Number
of
Samples
Per
Exposure
Period
Total
Duration
of
Measurement
and
Samples
Test
Duration
(
min)
Sample
time
SPME
(
min)
SPME1
SPME2
Cans
DNPH
Solid
Adsorb.
a
No.
of
Tests
Test
Duration
(
hrs)
SPME1
SPME2
Cans
DNPH
Solid
Adsorb.

Task
3a:
Urban
Exposures
in
Vehicle
Cabin
Commuter
Rush
Hour
(
stop­
n­
go)
60
15
3
1
1
1
18
18.0
54
18
18
3
Urban
canyons
60
15
3
1
1
1
18
18.0
54
18
18
3
Refueling
­
in
cabin
60
15
3
1
1
1
18
18.0
54
18
18
3
Parking
garage
60
15
3
1
1
1
18
18.0
54
18
18
3
Toll
Plaza
60
15
3
1
1
1
18
18.0
54
18
18
3
Tunnel
60
15
3
1
1
1
18
18.0
54
18
18
3
Subtotal
360
18
0
6
6
6
108
324
0
108
108
18
Task
3b:
Urban
Exposures
in
Outdoor
and
Indoor
Microenvironments
Refueling
at
pump
60
15
3
1
1
1
18
18.0
54
18
18
3
Sidewalk
near
high­
density
traffic
60
15
3
1
1
1
18
18.0
54
18
18
3
Underground
parking
garage
60
15
3
1
1
1
18
18.0
54
18
18
3
Bus
Stop
60
15
3
1
1
1
18
18.0
54
18
18
3
Toll
Booth
60
15
3
1
1
1
18
18.0
54
18
18
3
Auditorium
with
Auto
Show
60
15
3
1
1
1
18
18.0
54
18
18
3
Subtotal
360
18
0
6
6
6
108
324
0
108
108
18
3­
6
Table
3­
1
(
Continued)
Collection
of
Time­
Integrated
Samples
for
Chemical
Analysis
Test
Duration
(
hrs)
SPME1
SPME2
Cans
DNPH
Solid
Adsorb.
Totals
Task
1
199.0
20
20
11
11
11
Task
2b
0.0
0
0
48
24
8
Task
2c
60.0
456
0
72
72
12
Task
2d
72.0
288
0
96
48
8
132.0
744
0
216
144
28
Task
3a
108.0
324
0
108
108
18
Task
3b
108.0
324
0
108
108
18
216.0
648
0
216
216
36
All
Tasks
547
1412
20
443
371
75
a.
Collected
for
ethanol­
containing
fuels
only.
b.
Combined
with
initial
background.
c.
Two
out
of
three
runs.

Notes
Controlled
Exposure
All
Fuels
EtOH
only
Fuels
(
Houston,
Chicago,
Atlanta)
3
1
Seasons
(
summer,
winter)
2
1
Vehicle
Condition
(
normal,
malfunction)
2
2
Vehicles
(
car,
truck)
2
2
Total
Combinations
24
4
Grand
Total
24
4
Urban
Exposure
in
Vehicle
Cabin
Fuels
(
Houston,
Chicago,
Atlanta)
3
1
Seasons
(
summer,
winter)
2
1
Number
of
runs
3
3
Default
condition
on
weekday
Low
ventilation
on
weekday
Total
Combinations
18
3
Other
Microenvironments
and
Scripts
Fuels
(
Houston,
Chicago,
Atlanta)
3
1
Seasons
(
summer,
winter)
2
1
Replicates
for
each
ME
3
2
Total
Combinations
18
2
Pilot
Test
Number
of
replicates
2
3­
7
3.1.2
Determination
of
Tailpipe
and
Evaporative
Emissions
of
Test
Vehicles
(
Task
2b)

SwRI
will
procure
two
test
vehicles
and
determine
evaporative
and
tailpipe
emissions
for
the
vehicles
with
and
without
malfunctions
using
the
six
test
fuels.
The
two
test
vehicles
will
be
1993
to
1996
model
year
vehicles
with
90
to
110K
odometer
miles.
One
vehicle
will
be
a
sedan,
and
the
second
a
full
sized
pickup
truck
with
a
V­
8
engine.
The
SWRI
will
measure
the
vehicle's
exhaust
emissions
on
a
dynamometer
according
to
the
Federal
Test
Procedures
(
FTP).
SwRI
will
modify
these
vehicles
so
that
emission
control
system
components
(
e.
g.,
ECU,
O2
sensor,
catalyst)
can
be
reversibly
disconnected
to
represent
normal
and
reasonable
high­
end
approximations
(
e.
g.,
 
2
gm
HC/
mile
exhaust)
of
real
world
exhaust
emissions.
SwRI
will
determine
exhaust
emission
rates
for
the
two
test
vehicles,
with
and
without
malfunction,
using
three
regional
fuels
during
each
of
two
seasons
(
with
seasonal
fuels).
This
will
result
in
12
combinations
for
each
season.
SwRI
also
will
measure
evaporative
emissions
using
the
same
test
vehicles
with
and
without
induced
malfunction
(
e.
g.,
disconnecting
fuel
line
to
carbon
canister).
Hydrocarbon
samples
will
be
collected
in
canisters
and
analyzed
by
DRI
for
complete
hydrocarbon
speciation.
The
data
will
be
used
to
apportion
the
relative
contributions
of
exhaust
and
evaporative
emissions
by
applying
these
source
composition
profiles
to
the
microenvironmental
measurements
from
the
three
cities
using
Chemical
Mass
Balance
(
CMB)
receptor
modeling.

The
emission
tests
will
be
coordinated
with
the
trailing
vehicle
tests
described
in
Section
3.1.3
and
the
residential
garage
exposure
tests
describes
in
Section
3.1.4.
SwRI
will
install
the
reversible
malfunction
on
the
two
test
vehicles
and
perform
all
emission
testing
prior
to
start
of
the
exposure
measurements.
Two
days
will
be
required
for
the
trailing
vehicle
and
residential
garage
exposure
measurements
described
in
Tasks
2c
and
2d
for
each
of
six
combinations
of
vehicle
and
test
fuel
per
season.
The
trailing
vehicle
exposure
measurements
would
be
scheduled
in
the
morning,
followed
by
garage
exposure
measurements
in
the
afternoon.
Measurements
will
be
made
on
the
first
day
with
normal
emissions
and
on
the
second
day
with
induced
malfunctions.
During
the
exposure
tests
of
one
vehicle,
SwRI
will
switch
the
fuel
in
the
other
vehicle
and
condition
the
vehicles
with
the
new
fuel
prior
to
the
exposure
measurements.

For
the
dynamometer
FTP
exhaust
emissions
testing,
regulated
exhaust
emissions
(
total
hydrocarbons,
THC;
non­
methane
hydrocarbons,
NMHC;
carbon
monoxide,
CO;
and
oxides
of
nitrogen,
NOx),
carbon
dioxide,
CO2;
and
speciated
VOC
emissions
(
to
include
MTBE,
ethanol,
benzene,
toluene,
ethylbenzene,
xylene,
1,3­
butadiene,
formaldehyde,
and
acetaldehyde)
will
be
determined
for
each
test.
During
hot
soak
SHED
tests,
total
hydrocarbon
and
VOC
emissions
(
as
above
except
without
aldehyde/
ketone
measurements)
will
be
determined.
Table
3­
2
presents
a
suggested
test
plan
for
the
emissions
testing
at
SwRI.

The
exhaust
emission
portion
of
the
FTP
utilizes
the
Urban
Dynamometer
Driving
Schedule
(
UDDS),
which
is
1372
seconds
in
duration.
The
UDDS
is
divided
into
two
segments;
the
first
consisting
of
505
seconds,
and
the
second
consisting
of
867
seconds.
An
FTP
is
composed
of
a
505­
second
cold­
transient
(
bag
1)
portion
and
a
867­
second
cold
stabilized
(
bag
2)
portion,
followed
by
a
ten­
minute
soak
and
then
a
505­
second
hot­
transient
(
bag
3)
portion.
A
summary
of
the
cycle
duration,
driving
distance,
and
average
speed
is
given
in
Table
3­
3.
The
3­
8
FTP
driving
schedule
with
the
cold­
and
hot­
transient
test
segments
identified
is
given
in
Figure
3­
1.

The
evaporative
emission
portion
of
the
FTP
will
consist
of
a
one­
hour
Diurnal
Heat
Build
(
DHB)
and
a
one­
hour
Hot
Soak
Loss
Test
(
HSL).
Total
hydrocarbons
and
VOC
emissions
will
be
recorded
only
during
the
HSL
segment
of
the
test.
Prior
to
the
cold­
start
exhaust
portion
of
the
FTP,
the
DHB
evaporative
segment
of
the
FTP
will
be
conducted
by
fueling
the
test
vehicle
to
40
percent
of
tank
capacity
with
test
fuel
at
a
temperature
below
55
°
F.
A
heating
blanket
will
be
attached
to
the
outside
of
the
fuel
tank,
and
a
thermocouple
placed
in
the
fuel
inside
the
fuel
tank
will
be
connected
to
the
computer
controller.
The
fuel
inside
the
tank
will
be
raised
to
a
nominal
temperature
of
60
°
F,
at
which
point
the
DHB
segment
of
the
test
will
begin.
The
fuel
temperature
will
be
raised
at
a
linear
rate
of
0.4
°
F
per
minute
for
the
60­
minute
test.
The
final
nominal
temperature
will
be
84
°
F.

The
HSL
segment
of
the
evaporative
emission
test
will
be
conducted
immediately
following
exhaust
emission
testing.
For
the
HSL
segment,
the
vehicle
will
be
driven
into
the
evaporative
emission
enclosure
immediately
after
the
exhaust
emission
portion
of
the
FTP
has
been
completed.
The
vehicle
will
be
allowed
to
"
soak"
in
the
enclosure
for
one
hour.
Total
hydrocarbon
and
VOC
emissions
will
be
measured
at
the
beginning
and
end
of
the
one
hour
segment
to
permit
calculation
of
hot
soak
evaporative
emissions.
3­
9
Table
3­
2
Suggested
Test
Plan
for
Each
Vehicle
STEP
DESCRIPTION
1
Obtain
test
vehicle.
Verify
proper
mechanical
operation.

2
Determine
malfunction
condition
to
achieve
2
or
more
grams/
mile
total
hydrocarbons.

3
Equip
vehicle
to
allow
switching
between
normal
and
malfunction
conditions.
Return
vehicle
to
normal
operating
condition.

4
Remove
canister
from
test
vehicle.

5
Purge
canister
with
300
°
F
zero
nitrogen
at
20L/
min
for
five
hours,
reattach
canister.

6
Drain
fuel
tank
and
fill
to
40
percent
capacity
with
test
fuel.

7
Perform
a
2­
hour
diurnal
heat
build
from
70
to
120
°
F
at
a
ramp
rate
of
0.4
°
F/
min.

8
Operate
vehicle
on
chassis
dynamometer
over
one
UDDS
cycle.

9
Turn
engine
off
for
five
minutes.

10
Start
engine
and
idle
for
one
minute.

11
Turn
engine
off
for
one
minute.

12
Start
engine
and
idle
for
one
minute.

13
Remove
canister
from
vehicle
and
purge
canister
with
zero
air
for
60
minutes.

14
Reattach
canister,
drain
fuel
from
tank,
and
fill
to
40
percent
capacity
with
chilled
test
fuel.

15
Conduct
one
hour
DHB
(
no
emission
measurements).

16
Operate
vehicle
on
chassis
dynamometer
over
one
UDDS.

17
Soak
vehicle
overnight.

18
Next
day
prior
to
the
cold­
start
exhaust
portion
of
the
FTP,
conduct
one­
hour
Diurnal
Heat
Build
(
DHB).
No
emission
measurements.

19
Conduct
3­
bag
FTP
exhaust
emission
test.
Measure
regulated
gaseous
emissions
and
VOC
emissions.

20
Conduct
the
Hot
Soak
segment
of
the
SHED
test
immediately
following
the
exhaust
emissions
testing.
Measure
total
hydrocarbons
and
VOC
emissions
(
same
as
with
exhaust
except
no
aldehyde
emissions).

21
Switch
vehicle
to
malfunction
per
Step
2,
and
disconnect
evaporative
canister.

22
Repeat
Steps
8
through
12
and
Steps
16
through
20.

23
Repeat
Steps
3
through
22
for
each
of
the
remaining
five
test
fuels.
3­
10
Table
3­
3
Summary
of
the
FTP
Driving
Cycle
F
Figure
3­
3.
FTP
Driving
Cycle.
Duration,
Distance,
Average
Speed,

Segment
Seconds
Miles
Miles/
Hr.

Transient
Phase
505
3.6
25.7
Stabilized
Phase
867
3.9
16.2
UDDS
1372
7.5
19.7
3­
11
3.1.3
Relationship
Between
Exhaust
Emission
Rates
and
In­
Cabin
Exposure
(
Task
2c)

DRI
and
SwRI
will
use
the
two
test
vehicles
in
normal
operation
and
with
induced
malfunction
to
determine
exposure
in
a
cabin
of
a
third
vehicle
that
is
trailing
the
test
vehicles.
In
addition
to
the
two
test
vehicles,
SwRI
will
procure
a
third
vehicle
which
will
be
used
as
the
trailing
vehicle.
DRI
will
install
the
instrument
and
sampling
systems
on
board
the
trailing
vehicle.
This
trailing
vehicle
will
be
towed
to
the
three
cities
and
used
to
conduct
the
exposure
measurements
described
in
Tasks
Section
3.2.
The
trailing
vehicle
tests
will
be
conducted
on
a
remote
road
upwind
of
San
Antonio,
Texas.
The
test
matrix
will
mirror
the
dynamometer
tests
­
two
test
vehicles
with
and
without
malfunction,
three
regional
fuels,
and
two
seasonal
fuels
for
12
combinations
per
season.
Tests
using
summer
and
winter
fuels
will
be
conducted
in
June
2002
and
January
2003,
respectively.

During
each
test,
the
trailing
vehicle
will
be
driven
behind
the
test
vehicle
over
a
travel
loop
of
several
miles
for
a
period
of
up
to
3
hours.
Measurements
will
be
made
during
the
first
10
minutes
without
the
test
vehicles
in
order
to
establish
background
exposure
levels.
The
trailing
vehicle
study
will
implement
three
scenarios
(
far,
near,
and
passing)
for
each
speed
(
30
and
60
mph)
as
scheduled
in
the
table
below.
During
each
'
far'
scenario,
the
trailing
vehicle
will
follow
continuously
at
the
conventional
'
safe'
following
distance
for
the
indicated
speed,
defined
as
one
car
length
(
about
10
feet)
for
each
10
mph.
During
the
'
near'
scenario,
the
vehicle
will
'
tailgate'
the
leading
vehicle
continuously
following
at
a
closer
distance
deemed
'
safe'
for
professional
drivers
under
low­
traffic
density
and
prevailing
meteorological
conditions
by
SwRI
and
DRI
staff.
During
the
"
passing"
scenario,
the
trailing
vehicle
will
spend
5
min
at
"
tailgating"
distance,
i.
e.,
as
close
as
safety
permits,
and
5
min
at
"
passing"
distance
at
an
adjacent
lane
position
that
maximizes
potential
cabin
penetration
(
based
on
maximal
hood
TVOC).
Table
3­
4
details
the
trailing
vehicle
protocol.
We
are
continuously
monitoring
total
VOC
(
with
ppbRAE
PID)
inside
the
cabin
during
the
entire
test.
In
the
future
experiments
we
will
also
monitor
TVOC
on
the
hood
of
the
vehicle.
In
addition,
we
measure
TNMHC
from
timeintegrated
canister
samples.

Table
3­
4.
Protocol
for
trailing
vehicle
tests
Time
min.
Speed
mph
Ventilation
Setting
Distance
Notes
Continuous
Instruments
SPME
Time
Integrated
10
high
high
background
Y
1
1
10
low
high
far
Y
1
10
low
high
near
Y
1
10
low
high
passing
Y
1
10
high
high
far
Y
1
10
high
high
near
Y
1
10
high
high
passing
Y
1
10
low
low
far
Y
1
10
low
low
near
Y
1
10
low
low
passing
Vehicles:
Toyota
Camry
and
Pick­
up
truck,
in
normal
and
malfunction
mode.

Fuels:
Y
1
1
3­
12
10
high
low
far
Y
1
10
high
low
near
Y
1
10
high
low
passing
Y
1
10
idle
low
adjacent
Y
1
10
idle
high
adjacent
baseline,
MTBE,
ethanol
Y
1
1
3.1.4
Relationship
Between
Evaporative
Emission
Rates
and
Exposure
in
a
Residence
With
an
Attached
Garage
(
Task
2d)

The
two
test
vehicles
(
with
and
without
malfunctions)
will
be
used
to
determine
indoor
exposures
in
homes
with
attached
residential
garages.
The
same
test
vehicles
will
be
used
to
measure
indoor
exposures
in
a
residence
with
an
attached
garage
using
the
following
testing
matrix.
The
vehicles
will
be
parked
in
a
closed
residential
garage
also
containing
a
gasoline
powered
lawnmower
and
gas
container
with
in­
garage
and
adjacent
room
monitoring
conducted
before,
during
and
after
the
vehicle
cool­
down
period.
Door
openings
between
the
garage
and
adjacent
room
and
room
window
openings
will
be
monitored.
The
vehicle
will
also
be
`
warmed
up',
idling
in
the
garage
(
with
the
garage
door
open)
during
a
period
of
the
3­
hour
monitoring
process.
The
measurements
will
be
made
in
San
Antonio
at
the
residence
of
a
SWRI
employee
who
has
agreed
to
provide
access
to
the
house
during
the
study.
The
test
procedure
will
be
similar
to
those
described
by
Tsai
and
Weisel
(
2000).
We
propose
to
collect
two
time­
integrated
samples
of
each
kind
per
test
(
one
in
the
garage
and
one
in
the
adjacent
room).
A
set
of
continuous
and
semi­
continuous
methods
will
be
operated
during
the
vehicle
exposure
period
of
approximately
two
hours.
The
attached
garage
study
will
implement
six
scenarios
as
described
in
the
Table
3­
5.
Measurements
will
be
taken
alternatively
over
10­
minute
periods
with
the
sampling
inlet
located
at
breathing
height
at
least
three
feet
away
from
nearby
walls
in
both
the
unvented
garage
and
adjacent
indoor
room.
A
half­
filled
two
gallon
standard
plastic
gasoline
storage
container
with
vent
open
will
be
placed
with
a
lawnmower
with
gas
tank
half
filled
against
the
center
of
the
garage
wall
common
to
the
adjacent
room.
The
appropriate
fuel
(
i.
e.
from
Houston,
Atlanta
or
Chicago)
will
be
placed
in
the
garage
one
day
before
the
series
of
tests
for
this
fuel
and
left
there
over
the
duration
of
these
tests.
Scenario
conditions
will
be
changed
every
30
minutes
over
the
3­
hour
protocol
as
described
in
the
table.
The
ambient
garage
temperature
will
be
recorded
every
30
min
during
each
experiment.
We
will
measure
total
VOC
in
the
garage
[
with
ppbRAE
photoionization
(
PID)
detector]
before
the
test
and
the
tests
will
be
conducted
every
day
(
excluding
weekends)
over
the
period
of
two
weeks.

For
all
tests
the
inlet
for
portable
and
time­
integrated
instruments
will
be
placed
at
breathing
zone
height
(
i.
e.
1.5
m
above
the
floor).
3­
13
Table
3­
5.
Protocol
for
attached
garage
experiments.
The
same
vehicles
and
fuels
as
for
trailing
vehicle
experiment
are
used.

Condition
Time
(
min)
Garage
Door
Kitchen
Door
Kitchen
Window
Inlet
Location
Continuous
SPME
Integrated
Samples
10
closed
closed
closed
garage
y
10
kitchen
y
Background
10
garage
y
2
2
10
closed
open
1min
closed
kitchen
y
10
&
closed
garage
y
Hot
soak
10
kitchen
y
2
10
closed
closed
closed
garage
y
10
kitchen
y
Maximal
AER
to
indoors
10
garage
y
2
10
closed
closed
open
kitchen
y
10
garage
y
Maximal
AER
to
outdoors
10
kitchen
y
2
10
open
open
1
min
closed
garage
y
10
&
closed
kitchen
y
Cold
start
10
garage
y
2
2
3.2
Microenvironmental
Exposure
Measurements
in
Atlanta,
Chicago,
and
Houston
(
Task
3)

DRI
will
determine
in­
cabin
exposure
in
urban
roadway
and
other
high­
end
exposure
microenvironments
in
Houston,
Chicago,
and
Atlanta
over
several
weeks
in
each
city
and
season
during
July­
September
2002
(
summer
test)
and
January­
March
2003
(
winter
test).
Exposure
measurements
will
be
made
for
up
to
twelve
different
microenvironments
with
three
replicate
measurements
for
each
microenvironment.
Measurements
in
each
of
the
microenvironments
will
be
taken
over
a
period
of
one
hour
beginning
at
the
top
of
the
hour.
Continuous
measurements
of
carbon
monoxide,
benzene,
toluene,
ethylbenzene,
xylenes
and
formaldehyde
will
be
taken
during
the
entire
hour.
Time­
integrated
canister,
DNPH
cartridge,
and
solid
adsorbent
(
in
city
with
ethanol­
containing
fuel)
samples
will
also
be
collected
over
the
full
hour
unless
the
next
sample
will
be
collected
during
a
consecutive
hour.
In
such
cases,
the
sample
will
be
collected
during
the
first
50
minutes
to
allow
time
for
replacement
of
sampling
media.
In
addition,
four
SPME
samples
(
for
MTBE
and
BTEX)
will
be
collected
during
four
consecutive
15­
minute
periods
during
each
one­
hour
exposure
period.
Table
3­
1
shows
the
planned
exposure
matrix
and
the
number
of
samples
and
hours
for
each
microenvironment.
3­
14
3.2.1
Exposure
Diary
and
Script
Development
(
Task
3a)

Scripted
activities
will
be
used
during
the
exposure
measurements.
This
methodology,
referred
to
as
the
indirect
approach,
has
the
advantage
of
providing
estimates
of
exposure
over
a
range
of
scenarios
based
on
a
limited
sample
size
(
Kleipas,
1999).
This
approach
involves
the
following
steps:
(
1)
microclimate
identification,
(
2)
quantification
of
time
spent
performing
activities
in
a
given
microclimate,
and
(
3)
measurements
of
pollutant
concentrations
during
a
specified
activity.
By
multiplying
the
total
time
spent
during
each
activity
by
the
pollutant
concentrations,
activity­
specific
exposure
can
be
estimated.
Using
EPA
human
activity
patterns
(
EPA,
1996),
exposure
from
these
activities
can
be
estimated
for
the
total
population.

One
of
the
key
aspects
of
the
indirect
approach
is
an
accurate
measure
of
the
time
spent
performing
a
specified
activity.
In
order
to
define
exposure
time
in
a
reproducible
manner,
scripted
activities
are
developed
for
this
study
by
Ted
Johnson
of
TRJ
Environmental
Inc.
for
various
high­
end
exposure
microenvironments.
In
this
manner,
different
subjects
can
reproduce
the
total
time
required
for
a
specified
activity
and
an
accurate
estimate
of
exposure
time
can
be
determined.
Scripted
activity
diaries
are
developed
and
completed
by
field
personnel
during
the
exposure
measurements
to
document
more
detailed
information
about
the
sampling
location
and
activities
during
each
monitoring
period.
The
example
of
a
diary
is
included
in
Appendix
D.

We
also
will
compare
personal
exposures
with
ambient
measurements
from
nearby
local
and
state
monitoring
sites.
This
can
be
accomplished
by
scheduling
activities
to
begin
on
the
hour
and
end
on
the
hour,
enabling
a
direct
comparison
with
ambient
network
data.

3.2.2
In­
cabin
Exposures
in
Urban
Microenvironments
(
Task
3b)

The
trailing
vehicle
from
the
controlled
exposure
tests
in
San
Antonio
will
be
transported
to
each
of
the
three
cities
and
used
for
the
in­
cabin
exposure
measurements
in
each
of
the
three
cities
in
both
summer
and
winter.
A
driving
route
will
be
developed
for
each
city,
which
includes
the
urban
roadway
microenvironments.

1.
Parking
garage
(
60
minutes).

2.
Downtown
surface
street
loop
characterized
by
an
urban
canyon
effect
(
60
minutes).

3.
Toll
plaza
or
crowded
inspection
station
(
60
minutes).

4.
Freeway
traffic
under
stop­
and­
go
conditions
(
60
minutes)

5.
Tunnel
or
covered
roadway
(
60
min)

6.
Refueling
(
60
min)

In
addition
to
continuous
measurements,
one
integrated
sample
will
be
collected
during
each
one­
hour
exposure.
Table
2­
1
shows
the
proposed
exposure
matrix.
We
will
use
GPS
on
board
the
vehicle
to
record
the
location
and
time
during
the
entire
test.
Testing
over
the
driving
route
will
be
made
three
times
for
each
city
and
season
on
rush­
hour
weekdays
with
both
high
ventilation
(
e.
g.,
window
and
vent
open
during
the
summer)
and
lower
ventilation
(
i.
e.,
windows
3­
15
and
vent
closed
with
AC
or
heater
on
during
the
summer/
winter).
Carbon
monoxide
will
be
measured
in
the
mobile
laboratory,
which
will
trail
the
test
vehicle
in
order
to
compare
the
outdoor
(
roadway)
ambient
CO
mixing
ratios
to
in­
cabin
CO
for
each
of
the
three
runs.
The
effect
of
varying
ventilation
will
be
normalized
to
this
ratio.

3.2.3
Outdoor
and
Indoor
Exposure
in
Urban
Microenvironments
(
Task
3c)

We
will
use
scripted
technicians
with
"
luggage
cart"
sampling
stations
to
measure
breathing
zone
and
ME
air
levels
in
the
following
outdoor
and
indoor
microenvironments:
selfservice
refueling
stations,
sidewalks
near
high­
density
traffic,
underground
parking
garage,
bus
stop,
toll
booth,
and
an
above
ground
parking
garage.
Technicians
will
follow
the
activity
scripts
developed
by
Ted
Johnson
and
will
use
diaries
and/
or
GPS
monitors
to
document
actual
exposure
locations
and
conditions.

The
exposures
in
each
microenvironment
will
be
monitored
for
approximately
one
hour.
We
propose
to
repeat
the
measurements
in
each
microenvironment
three
times
and
collect
timeintegrated
canister,
DNPH
and
solid
adsorbent
(
for
ethanol
only)
samples
during
each
exposure
period
(
see
Table
3­
1).
For
all
tests
the
inlet
for
portable
and
time­
integrated
instruments
will
be
placed
at
breathing
zone
height
(
i.
e.
1.5
m
above
the
ground)
and
in
the
breathing
zone
of
the
technician
as
appropriate.

3.2.4
Technician
Biomarker
Analysis
(
Task
4)

Urinary
MTBE/
BTEX
as
well
as
breath
measurements
will
be
used
as
the
biomarkers
of
choice.
Since
we
were
not
able
to
distinguish
background
benzene
concentrations
from
low­
level
exposures
(
e.
g.
walking
down
street),
we
propose
only
to
conduct
bio­
monitoring
experiments
for
projected
"
high­
end"
exposures
such
as
refueling
or
underground
parking
garage.
Urine
sampling
will
be
conducted
similar
to
the
pilot
study,
with
pre­
and
post­
exposure
collections
of
the
subject's
urine.
The
complete
time
course
of
collection
will
be
lengthened
based
on
the
results
of
additional
experiments
that
was
conducted
on
June
4.
Samples
will
be
collected
and
analyzed
according
to
the
protocol
described
in
Section
2.

3.2.5
Approach
for
Selecting
High
End
Microenvironments
One
of
the
overall
goals
of
the
project
is
to
sample
high­
end
microenvironments
(
MEs),
plausibly
characterized
in
the
upper
90th
centiles
of
exposure,
that
result
from
the
impacts
of
exhaust/
evaporative
emissions
from
gasoline­
fueled
vehicles.
Two
approaches
to
selecting
highend
MEs
would
include
urban
rush­
hour
sampling
of
high­
density
traffic
patterns
(
e.
g.,
congested
roadways)
and
concentrations
of
vehicles
in
enclosed
spaces
(
e.
g.,
underground
parking
garages).
Twelve
categories
of
high­
end
MEs
listed
below
(
and
in
Tasks
3a
&
b
of
the
protocol)
include
bulleted
selection
criteria
that
should
lead
to
sampling
ME
locations
with
higher
levels
of
accumulated
emissions.
Survey
technicians
will
also
use
pollutant
sniffers
(
e.
g.,
hand­
held
CO/
BTEX
monitors)
to
sense
relative
peak
pollutant
levels
within
and
among
these
candidate
locations,
choosing
the
MEs
with
the
highest
levels
in
each
category
for
inclusion
in
the
city­
specific
sampling
scripts.

1.
Congested
(
stop­
n­
go)
commuter
roadway
(
vehicle
cabin)
 
Rush
hour
sampling
on
roadway
parallel
to
wind
direction
3­
16
 
Locally
known
choke
points
&
signaled
intersections
on
high
density
routes
 
Locations
most
shielded
from
air
dispersion
by
local
topography
 
Lane
reductions
due
to
ongoing
construction
or
breakdowns/
accidents
 
Downwind
direction
from
traffic
density
centroid
Protocol:
Prior
to
test,
identify
roadway
segment
that
satisfies
above
conditions
and
confirm
high
potential
concentrations
using
sniffer.
Drive
back
and
forth
on
the
segment
continuously
during
the
60­
minute
rush­
hour
test
period.
Drive
in
most
congested
(
slowest)
lane.
Maintain
a
safe
following
distance,
about
one
car
length
(
10
feet)
per
10
mph
speed,
closing
to
within
3
feet
during
stopped
conditions.
Sample
alternative
30­
minute
periods
under
high­
and
lowventilation
(
vehicle
windows
&
vents
open
and
windows
&
vents
closed).

2.
Urban
canyon
(
vehicle
cabin)
 
Rush
hour
sampling
on
roadway
perpendicular
to
wind
direction
 
Greatest
contiguous
length
&
height
of
high­
rise
buildings
 
Narrowest
canyon
width
 
Highest
traffic
density
 
Mid­
block
sampling
most
shielded
from
air
dispersion
Protocol:
Prior
to
test,
identify
roadway
segment
that
satisfies
above
conditions
and
confirm
high
potential
concentrations
using
sniffer.
Drive
back
and
forth
on
the
segment
continuously
during
the
60­
minute
rush­
hour
test
period
(
an
around­
the­
block
downtown
loop
may
be
used
if
entire
loop
is
associated
with
high
canyon
concentrations).
Drive
in
most
congested
(
slowest)
lane.
Maintain
a
safe
following
distance,
about
one
car
length
(
10
feet)
per
10
mph
speed,
closing
to
within
3
feet
during
stopped
conditions.
Sample
alternative
30­
minute
periods
under
high­
and
low­
ventilation
(
vehicle
windows
&
vents
open
and
windows
&
vents
closed).

3.
Refueling
(
vehicle
cabin)
 
Lack
of
pump
nozzle
vapor
controls,
if
available
 
Peak
refueling
period
for
station
 
Largest
number
of
pumps
 
Downwind
direction
from
centroid
of
pump
locations
 
Location
most
shielded
from
air
dispersion
by
topography
Protocol:
Prior
to
test,
identify
service
station
that
satisfies
above
conditions
and
use
sniffer
to
locate
refueling
area
associated
with
highest
concentrations.
Park
car
at
refueling
location
and
sample
alternative
30­
minute
periods
under
high­
and
low­
ventilation
(
vehicle
windows
&
vents
open
and
windows
&
vents
closed).
Refuel
car
over
a
1
to
2­
minute
active
refueling
period
at
mid­
point
of
high­
ventilation
sampling
period.

4.
Parking
garage
(
vehicle
cabin)
above
ground
 
Rush
hour
sampling
 
High
capacity
&
usage
 
Near
internal
entrance/
exit
lanes
3­
17
 
Location
with
smallest
external
openings
&
most
shielded
from
air
dispersion
by
topography
 
Downwind
direction
from
centroid
on
most
occupied
parking
level
Protocol:
Prior
to
test,
identify
aboveground
parking
lot
that
satisfies
above
conditions
and
use
sniffer
to
locate
parking
area
within
lot
associated
with
highest
concentrations.
Park
car
at
the
location
and
sample
alternative
30­
minute
periods
under
high­
and
low­
ventilation
(
vehicle
windows
&
vents
open
and
windows
&
vents
closed).

5.
Toll
plaza
apron
(
vehicle
cabin)
 
Rush
hour
sampling
 
General
location
of
idling
traffic
queue
(
e.
g.,
at
road
toll,
parking
garage
entrance/
exit,
emissions
testing
facility,
controlled
on­
ramp,
multi­
road
signalcontrolled
intersection)
 
Location
most
shielded
from
air
dispersion
by
topography
 
High
use
location
 
Downwind
direction
from
centroid
of
traffic
mass
Protocol:
Prior
to
test,
identify
toll
plaza
apron
that
satisfies
above
conditions
and
use
sniffer
to
locate
parking
area
within
plaza
associated
with
highest
concentrations.
Park
car
at
the
location,
if
feasible,
and
sample
alternative
30­
minute
periods
under
high­
and
low­
ventilation
(
vehicle
windows
&
vents
open
and
windows
&
vents
closed).
If
not,
repeatedly
traverse
the
plaza
queue
during
the
60­
minute
test
period,
sampling
as
above.

6.
Tunnel/
Covered
Roadway
(
vehicle
cabin)
 
Rush
hour
sampling
 
Stop­
n­
go
traffic
flow
 
Highest
traffic
density
 
Lack
of
mechanical
ventilation,
if
available
 
Smallest
enclosed
volume
Protocol:
Prior
to
test,
identify
tunnel
or
covered
roadway
that
satisfies
above
conditions
and
use
sniffer
to
confirm
high
concentrations.
Drive
back
and
forth
on
enclosed
roadway
during
the
60­
minute
test
period
maximizing
minimizing
time
spent
in
the
enclosed
environment.
Drive
in
slowest,
most
congested
lane.
Maintain
a
safe
following
distance,
about
one
car
length
(
10
feet)
per
10
mph
speed,
closing
to
within
3
feet
during
stopped
conditions.
Sample
alternative
30­
minute
periods
under
high­
and
low­
ventilation
(
vehicle
windows
&
vents
open
and
windows
&
vents
closed).

7.
Refueling
(
self­
service)
 
Lack
of
pump
nozzle
vapor
controls,
if
available
 
Peak
refueling
period
for
station
 
Largest
number
of
pumps
 
Downwind
direction
from
centroid
of
pump
locations
 
Location
most
shielded
from
air
dispersion
by
topography
3­
18
Protocol:
Prior
to
test,
identify
service
station
that
satisfies
above
conditions
and
use
sniffer
to
locate
refueling
area
associated
with
highest
concentrations.
Park
car
at
refueling
location
and
sample
alternative
30­
minute
periods
under
high­
and
lowventilation
(
vehicle
windows
&
vents
open
and
windows
&
vents
closed).
With
sampling
inlet
in
the
breathing
zone,
refuel
the
vehicle
over
a
1
to
2­
minute
active
refueling
period
at
the
mid­
point
of
the
high­
ventilation
sampling
period.
Return
to
the
vehicle
cabin
for
the
rest
of
the
60­
minute
sampling
period.
During
refueling,
maintain
manual
control
of
the
nozzle
(
i.
e.,
use
an
unlatched
nozzle)
and
stand
downwind
of
the
vehicle
fuel
tank
inlet.
Once
per
week,
biomarker
samples
will
be
collected
from
the
technician
performing
this
self­
service
refueling
task.

8.
Sidewalk/
crosswalk
near
high
density
traffic
 
Rush
hour
sampling
on
roadway
parallel
to
wind
direction
 
Downwind
direction
from
traffic
mass
centroid
 
Location
most
shielded
from
air
dispersion
by
topography
 
Highest
traffic
density
 
In
urban
canyon
Protocol:
Prior
to
test,
identify
roadway
segment
with
sidewalks
that
satisfies
above
conditions
and
identify
high
concentration
area
using
sniffer.
With
cart
sampler
inlet
in
breathing
zone,
walk
along
loop
route
on
both
sides
of
roadway
using
crosswalks
to
cross
roadway
during
the
60­
minute
sampling
period.
Walk
within
three
feet
of
curb.

9.
Parking
garage
(
underground)
 
Rush
hour
sampling
 
High
capacity
&
usage
 
Near
internal
entrance/
exit
lanes
 
Lowest
level
with
high
capacity
usage
 
Lack
of
mechanical
ventilation,
or
away
from
fans
&
vents
if
present
Protocol:
Prior
to
test,
identify
underground
parking
lot
that
satisfies
above
conditions
and
use
sniffer
to
locate
parking
area
within
garage
associated
with
highest
concentrations.
Park
car
at
location
during
60­
minute
rush­
hour
test
with
front
windows
down
and
vents
open.
Sample
10
minutes
in
cabin
during
entry
and
parking
of
vehicle.
Close
vehicle
windows.
With
cart
inlet
in
breathing
zone,
sample
next
10­
minute
period
exiting
vehicle
and
making
way
to
street
level
exit;
repeating
sampling
in
the
reverse
direction
for
the
next
10­
minute
period.
Return
to
closed
vehicle
cabin
for
next
10­
minute
period.
Open
vehicle
windows
and
sample
during
final
10­
minute
period
exiting
the
garage
and
paying
toll.

10.
Bus
stop
 
Rush
hour
sampling
on
roadway
parallel
to
wind
direction
 
High
traffic
density
route
 
Located
on
traffic
island/
median
strip
 
Downwind
direction
near
high
density
traffic
intersection
3­
19
 
In
urban
canyon
Protocol:
Prior
to
test,
identify
bus
stop
(
or
cab
stand)
satisfies
above
conditions
and
confirm
high
concentrations
using
sniffer.
With
cart
inlet
in
breathing
zone,
stand/
sit
at
this
location
(
within
three
feet
of
curb)
for
the
entire
60­
minute
test.

11.
Toll
booth
 
Rush
hour/
maximal
usage
sampling
 
Lack
of
mechanical
ventilation,
if
available
 
Enclosed
queues
(
e.
g.,
from
parking
garages,
tunnels,
testing
facilities)
 
Central
booth
&
location
most
shielded
from
air
dispersion
by
topography
 
Downwind
direction
from
centroid
of
traffic
mass
Protocol:
Prior
to
test,
identify
tollbooth
that
satisfies
above
conditions
and
confirm
high
concentrations
using
sniffer.
With
cart
inlet
in
the
breathing
zone,
sample
in
the
booth
and
externally
within
three
feet
of
booth
door
or
window
(
conditions
permitting)
alternatively
for
30­
minute
intervals
during
the
60­
minute
test.

12.
Auditorium/
stadium
external
parking
lots
 
Rush
hour/
maximal
usage
sampling
 
High
capacity
&
usage
location
 
Near
internal
entrance/
exit
lanes
 
Downwind
direction
from
centroid
of
traffic
mass
 
Location
most
shielded
from
air
dispersion
by
topography
Protocol:
Prior
to
test,
identify
stadium
parking
lot
that
satisfies
above
conditions
and
use
sniffer
to
locate
parking
area
within
lot
associated
with
highest
concentrations.
Sample
during
60­
minute
test
with
front
windows
down
and
vents
open.
Sample
20
minutes
in
cabin
during
entry
and
parking
of
vehicle
beginning
at
the
time
that
the
parking
lot
is
approximately
half­
filled
to
capacity
(
usually
about
one
hour
before
the
start
of
the
sports/
exhibition
event
­
e.
g.,
professional
baseball,
football,
basketball
home
game,
ice­
skating
event).
With
cart
inlet
in
breathing
zone,
sample
next
20­
minute
period
outside
near
rear
of
parked
vehicle
with
open
hatch/
trunk
to
simulate
`
tailgate'
picnic.
Close
vehicle
windows/
doors.
With
cart
inlet
in
breathing
zone,
sample
next
20­
minute
period
making
way
through
parking
lot
to
stadium
entrance.
Reverse
this
process
in
a
second
ME
test
to
sample
exposures
during
exiting
of
the
parking
lot
beginning
near
the
end
of
the
sports
event.
With
cart
inlet
in
breathing
zone,
sample
during
initial
20­
minute
sampling
period
making
way
through
parking
lot
to
parking
location.
Stand
near
the
rear
of
the
parked
vehicle
during
the
next
20­
minute
period
to
simulate
packing
up
the
vehicle
after
the
game.
Open
vehicle
windows
&
vents.
Sample
during
the
final
20­
minute
period
in
the
vehicle
cabin
making
way
from
the
parking
location
to
the
parking
lot
exit.

Appendices
A,
B
and
C
contain
the
draft
protocols
for
sampling
in
Houston,
Atlanta,
and
Chicago,
respectively.
3­
20
3.3
Meteorology
(
Task
5)

For
portions
of
the
sampling
periods
involving
stationary
activities,
a
portable
weather
station
will
be
set
up
at
an
adjacent
location.
During
both
these
and
mobile
sampling
periods,
additional
information
representing
regional
conditions
will
be
obtained
from
nearby
NOAA/
FAA
sites,
or
other
agencies
if
available.
Stability
information
requires
upper
air
data.
The
closest
locations
to
the
selected
cities
of
San
Antonio,
Houston,
Atlanta,
and
Chicago,
that
take
routine
radiosonde
measurements,
are
at
Corpus
Christi
TX,
Lake
Charles
LA,
Peachtree
City
GA,
and
Davenport
IA
or
Lincoln
IL.
Sections
of
two
of
the
cities,
Houston
and
Chicago,
can
also
be
affected
by
land/
ocean
breezes.
Although
in
situ
surface­
based
observations
are
preferable,
diagnostic
output
from
operational
numerical
models
can
also
be
analyzed.

The
local
on­
site
measurements
using
a
portable
meteorological
station
will
be
made
by
field
participants
in
the
experiment.
Remaining
phases
will
be
undertaken
by
Dr.
Kelly
Redmond,
Regional
Climatologist,
of
the
Western
Regional
Climate
Center
(
WRCC).
A
principal
role
of
this
NOAA­
funded
facility,
housed
within
DRI's
Division
of
Atmospheric
Sciences,
is
to
acquire,
store,
summarize,
distribute,
and
interpret
atmospheric
data.
The
Climate
Center
has
excellent
access
to
past
data
nationwide
through
its
own
considerable
in­
house
capabilities,
as
well
as
strong
programmatic
ties
to
the
other
five
Regional
Climate
Centers
and
to
the
National
Climate
Data
Center.
(
The
entire
national
program
is
funded
through
DRI.)
Each
day
WRCC
processes
approximately
100­
200
MB
of
weather
and
climate
data
from
the
national
distribution
circuits,
and
saves
indefinitely
the
entire
feed
containing
observations
from
all
NOAA/
FAA
sites
in
North
America.
The
Climate
Center
has
a
wide
variety
of
software
for
producing
climatological
summaries
of
differing
degrees
of
sophistication,
depending
on
the
need.

3.4
Data
Analysis
(
Task
6)

Task
6a:
Compile
summary
statistics
of
the
data,
perform
consistency
checks,
and
identify
outliers.

The
data
validation
process
consists
of
procedures
that
identify
deviations
from
measurement
assumptions
and
procedures.
We
will
apply
the
following
tests
to
evaluate
the
internal,
spatial,
temporal,
and
physical
consistency
of
each
data
set
and
identify
invalid
data
and
outliers.
DRI
will
compile
and
validate
the
data
from
Tasks
2
through
4
and
prepare
statistical
summaries
of
the
data
and
perform
the
following
validation
checks.

 
Compare
averages
derived
from
continuous
and
semi­
continuous
measurements
with
data
from
time­
integrated
samples.
Determine
systematic
biases.

 
Derive
summary
statistics
(
mean,
maximum,
standard
deviation)
for
all
species,
sort
the
concentrations
and
note
any
unusually
high
or
low
concentrations.

 
Compare
sum
of
designated
species
to
TVOC.
3­
21
 
Determine
variations
in
fractions
of
benzene,
toluene,
ethylbenzene,
xylenes,
MTBE,
and
ethanol,
formaldehyde,
acetaldehyde
to
TVOC
and
significant
differences
in
the
ratios
among
microenvironments.

 
Prepare
scatterplots
of
CO
with
TVOC,
BTEX,
1,3­
butadiene,
MTBE,
ethanol,
formaldehyde
and
acetaldehyde.

 
Determine
ratios
of
the
sum
of
formaldehyde
and
acetaldehyde
to
CO,
and
relate
variations
in
the
ratios
with
MEs
and
time
of
day
with
expectations
in
the
relative
contributions
of
direct
emissions
versus
photochemical
formation.

Task
6b:
Evaluate
the
suitability
of
candidate
measurement
methods
for
use
in
the
main
exposure
study.

 
Summarize
results
of
laboratory
evaluations
of
continuous
and
semi­
continuous
methods.

 
Compare
time­
averaged
continuous
data
from
the
pilot
study
with
corresponding
semicontinuous
and
time­
integrated
measurements
over
the
same
time
intervals.
Determine
significant
biases
among
methods
and
determine
whether
continuous
measurements
will
be
suitable
for
determining
time­
integrated
exposure
or
for
documenting
peak
exposures
only.

Task
6c:
Determine
quantitative
relationships
between
tailpipe
emission
rates
and
variations
in
fuel
formulations
with
exposures
in
the
cabin
of
a
trailing
vehicle.

 
Quantify
the
variations
in
the
background
values
for
BTEX,
MTBE,
1,3­
butadiene,
HCHO,
CH3CHO,
EtOH,
TVOC
and
CO
during
the
initial
and
final
loops
without
the
test
vehicle.

 
Subtract
the
average
time­
integrated
background
values
from
the
corresponding
time
integrated
exposure
levels
for
the
default
driving
condition
for
each
of
the
24
test
combinations
(
i.
e.,
two
test
vehicles,
two
emission
conditions,
three
fuels,
and
two
season)
and
four
replicates.

 
Quantify
separately
for
each
of
the
two
vehicles,
the
specific
differences
due
to
emission
condition,
fuel
and
season.
Quantify
absolute
differences
for
each
designated
species
and
differences
normalized
to
concurrent
CO
data.

 
Variations
in
MTBE/
benzene
and
EtOH/
benzene
ratios
(
or
other
HC
species)
will
be
related
to
extent
of
the
potential
contribution
of
tailpipe
and
evaporative
emissions.

 
Determine
the
effect
on
cabin
exposure
of
varying
speed,
spacing
between
test
and
trailing
vehicle,
and
degree
of
ventilation.

 
Determine
variations
of
the
in­
cabin
exposures
within
the
test
and
trailing
vehicle
due
to
variation
in
normal/
malfunction
test
vehicle
emission
rates
under
idle.
3­
22
Task
6d:
Determine
quantitative
relationships
between
evaporative
emission
rates
and
variations
in
fuel
formulations
with
exposures
in
a
residence
with
an
attached
garage.

 
Subtract
the
time­
integrated
background
values
of
BTEX,
MTBE,
and
TVOC
from
the
corresponding
time
integrated
exposure
levels
in
the
garage
and
in
the
adjacent
room
and
determine
the
increased
exposure
due
to
hot­
soak
evaporative
emissions
for
the
vehicle
and
fuel
combinations
that
were
tested.

 
Determine
the
time­
evolution
in
the
levels
of
the
BTEX,
MTBE,
and
TVOC
above
background
levels
and
determine
the
penetration
of
evaporative
emissions
from
the
garage
to
the
adjacent
room
for
the
vehicle
and
fuel
combinations
that
were
tested.

Task
6e:
Quantify
personal
exposures
to
conventional
and
oxygenated
evaporative
and
exhaust
emission
in
microenvironments.

 
Process
GPS
data
and
develop
a
log
of
exposure
measurements
with
respect
time,
location,
and
speed.

 
Compare
time­
integrated
exposure
levels
measured
in
the
microenvironments
that
were
investigated
in
Task
3
among
the
three
cities
and
season.
Quantify
absolute
differences
for
each
designated
species
and
differences
normalized
to
concurrent
CO
data.

 
Characterize
the
extremes
in
exposure
levels
during
the
test
periods.

 
Determine
the
effect
of
varying
cabin
ventilation
conditions
on
exposure
levels
using
the
ratios
of
in
cabin
CO
concentrations
to
ambient
CO
(
measured
in
the
mobile
laboratory).

Task
6f:
Quantify
personal
exposures
scripted
activity.

 
Process
GPS
data
and
develop
a
log
of
the
measurements
of
scripted
worker
exposures
with
respect
time
and
location.

 
Compare
time­
integrated
exposure
levels
measured
in
the
microenvironments
that
were
investigated
in
Task
4
among
the
three
cities
and
season.
Quantify
absolute
differences
for
each
designated
species.

 
Compare
CO/
BTEX/
HCHO/
NMHC
levels
that
were
measured
during
the
exposure
study
with
nearby
values
from
the
local
ambient
air
monitoring
station.

 
Estimate
the
relative
importance
of
tailpipe
and
evaporative
emissions
on
exposure
using
the
ratio
of
MTBE
to
benzene
as
described
in
the
RFP.
Relative
contributions
will
be
determined
by
the
Chemical
Mass
Balance
(
CMB)
receptor
modeling
if
the
optional
speciation
profiles
for
exhaust
and
evaporative
are
obtained.
The
default
approach
is
only
applicable
to
cities
with
oxygenated
fuels,
while
the
CMB
approach
can
also
be
applied
to
the
city
with
conventional
gasoline.
3­
23
 
Determine
the
levels
of
the
designated
species
in
the
urine
and
breath
of
technicians
carrying
out
the
scripted
behaviors
and
determine
significant
differences
due
to
varying
fuel
formulation.

3.5
Reporting
This
task
will
require
completion
of
the
following:

 
Interim
report
after
completion
of
the
pilot
study
 
Detailed
preliminary
protocol
(
peer­
reviewed
by
API
and
submitted
for
EPA
approval
prior
to
initiating
the
main
exposure
measurements)
 
Final
protocol
(
after
incorporating
protocol
changes)
 
Comprehensive
draft
report
(
including
the
hypotheses,
descriptions
of
statistical
analyses,
and
interpretations
of
the
findings)
 
Final
report
incorporating
reviewers'
comments
(
submitted
to
EPA
for
review
and
approval
together
with
the
reviewers'
comments
and
a
statement
of
the
disposition
of
the
reviewers'
comments)
4­
1
4.
PROJECT
SCHEDULE
AND
DELIVERABLES
The
following
is
list
of
major
milestones
and
deliverables.

1.
Pilot
Study
2/
25/
02
to
3/
1/
02
2.
Pilot
study
report
4/
12/
02
3.
Draft
Exposure
Protocol
and
Study
Plan
4/
19/
02
4.
Final
Exposure
Protocol
and
Study
Plan
5/
30/
02
5.
Controlled
Exposure
Tests
in
San
Antonio
(
summer
fuels)
6/
17/
02
to
7/
03/
02
6.
Urban
Exposure
Measurements
in
three
cities
(
summer)
7/
08/
02
to
8/
30/
02
7.
Controlled
Exposure
Tests
in
San
Antonio
(
winter
fuels)
1/
06/
03
to
1/
24/
02
8.
Urban
Exposure
Measurements
in
three
cities
(
winter)
1/
27/
03
to
3/
21/
03
9.
Draft
Final
Report
6/
30/
03
10.
Final
Report
ten
days
after
receipt
of
comments
5­
1
5.
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96/
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Fung,
K.,
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Grosjean
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Determination
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53,
168­
171.

Fustinoni,
S.,
R.
Giampiccolo,
S.
Pulvirenti,
M.
Buratti,
and
A.
Colombi
(
1999).
Headspace
solid­
phase
microextraction
for
the
determination
of
benzene,
toluene,
ethylbenzene
and
xylenes
in
urine.
J.
Chromatogr.
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723:
105­
115.

Goliff,
W.
S.
and
B.
Zielinska
(
2001).
Long­
Term
Stability
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Oxygenated
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in
Electropolished
Canisters,
Paper
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403,
presented
at
the
94th
N+
Annual
A&
WMA
Conference
and
Exhibition,
June
24­
28,
2001,
in
Orlando,
Florida.

Kelly,
T.
J.
and
C.
R.
Fortune
(
1994).
Continuous
Monitoring
of
Gaseous
Formaldehyde
Using
an
Improved
Fluorescence
Approach.
Intern.
J.
Environ.
Anal.
Chem.,
54:
249­
263
Kleipas,
N.
E.
(
1999).
An
Introduction
to
the
Indirect
Exposure
Assessment
Approach:
Modeling
Human
Exposure
Using
Microenvironmental
Measurements
and
the
recent
National
Human
Activity
Pattern
Survey,
Environmental
Health
Perspectives,
107,
365­
374.

Lee,
C.
W.
and
C.
P.
Weisel
(
2001).
Toxicokinetics
of
Human
Exposure
to
Methyl
tertiary­
butyl
ether
(
MTBE)
Following
Short­
Term
Controlled
Exposures.
J.
Exposure
Anal.
And
Environ.
Epi.,
11,
67­
78
Lindstrom,
A.
B.,
and
J.
D.
Pleil
(
1996).
Alveolar
Breath
Sampling
and
Analysis
to
Assess
Exposures
to
Methyl
Tertiary
Butyl
Ether
(
MTBE)
During
Motor
Vehicle
Refueling.,
J.
Air
and
Waste
Management,
V.
46,
p.
676­
682
5­
2
Martos,
P.
and
J.
Pawliszyn
(
1998).
Sampling
and
Determination
of
Formaldehyde
Using
Solid­
Phases
Microextraction
with
On­
Fiber
Derivation,
Analytical
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70,
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Pleil,
J.
and
A.
Lindstrom
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2002).
A
review
of
the
USEPA's
single
breath
canister
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SBC)
method
for
exhaled
volatile
organic
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208
Rasmussen,
R.
A.
(
1992).
"
The
ABCs
of
stainless
steel
canister
clean­
up
and
certification."
Presented
at
the
1992
U.
S.
EPA/
A&
WMA
International
Symposium
on
Measurement
of
Toxic
and
Related
Air
Pollutants,
Durham,
NC,
May
1992.

Shire,
J.;
Harshfield,
G.;
Zielinska,
B.;
Pasek,
R.
"
A
Comparison
of
Analytical
Methods
for
Oxygenated
Volatile
Organic
Compounds
in
Ambient
Air,"
In:
Proceeding
of
the
U.
S.
EPA/
A&
WMA
International
Symposium
on
Measurements
of
Toxic
and
Related
Air
Pollutants:
Durham,
NC
May
1996.

Tsai,
P.
and
C.
P.
Weisel
(
2000).
Penetration
of
Evaporative
Emissions
into
a
Home
from
an
M85­
Fueled
Vehicle
Parked
in
an
Attached
Garage,
Journal
of
the
Air
&
Waste
Management
Association,
50:
371­
377.

Vayghani,
S.
A.,
C.
Weisel,
(
1999)
The
MTBE
air
concentrations
in
the
cabin
of
automobiles
while
fueling,
Journal
of
Exposure
Analysis
and
Environmental
Epidemiology,
9,
261­
267.
A­
1
APPENDIX
A
Exposure
Protocol
and
Study
Plan
for
the
Section
211(
B)
Tier
2
High
End
Exposure
Screening
Study
of
Baseline
and
Oxygenated
Gasoline
­
Summer
2002
Sampling
Plan
for
Houston
DRAFT
Prepared
for
AMERICAN
PETROLEUM
INSTITUTE
1220
L
Street
Washington,
DC
20005­
4070
Prepared
by
DESERT
RESEARCH
INSTITUTE
2215
Raggio
Parkway
Reno,
NV
89512
July
1,
2002
A­
2
INTRODUCTION
This
sampling
plan
specifies
the
details
for
the
field
measurement
program
that
will
be
carried
out
in
Houston,
Texas
during
the
summer
of
2002
as
part
of
a
screening
study
of
the
high­
end
exposures
to
baseline
and
oxygenated
gasoline.
It
specifies
the
dates,
times
and
measurement
locations
for
the
twelve
categories
of
microenvironments
and
explains
the
selections
with
respect
to
the
objective
of
capturing
the
upper­
end
of
the
distribution
of
exposures
for
each
microenvironment.
This
document
is
an
addendum
to
the
June
13,
2002
Exposure
Protocol
and
Study
Plan,
which
describes
the
proposed
measurement
methods
and
rationale
for
their
selection.

Exposure
levels
are
directly
related
to
the
activity
and
emission
rates
of
sources
in
the
microenvironment
and
inversely
related
to
the
distances
between
sources
of
emissions
and
the
measurement
location
and
the
extent
of
dilution
of
emissions,
which
is
a
function
of
meteorological
conditions
and
the
presence
of
physical
obstruction
that
inhibit
dispersion.
The
API
and
EPA
have
prescribed
a
goal
to
capture
the
99th
percentile
exposure
levels
within
each
type
of
microenvironment.
Due
to
the
scope
of
this
study,
it
will
not
be
possible
to
fully
characterize
(
by
measurements)
the
range
of
exposures
that
include
the
99th
percentile.
However,
we
considered
available
surrogate
parameters
for
emission
levels
and
dispersion
to
select
sampling
times
and
locations
with
the
greatest
potential
for
higher
exposures.
These
emission
surrogates
include
traffic
counts,
and
diurnal
variations
in
average
highway
speeds,
length
of
queues
at
toll
plazas,
number
of
cars
refueling
or
entering
and
exiting
parking
garages.
Surrogates
for
dispersion
include
wind
roses
and
diurnal
variations
in
temperature.
Measurements
in
microenvironments
with
unrestricted
dispersion
will
be
made
in
the
early
morning
or
evening
during
calm
conditions
and
minimal
vertical
mixing.
In
moderate
wind
conditions,
we
will
drive
parallel
to
the
prevailing
wind
to
reduce
the
impact
of
cross
winds.
Our
sampling
strategy
also
recognizes
that
vehicle
exhaust
emission
levels
are
significantly
higher
for
high
emitters
and
are
higher
for
all
vehicles
during
cold
starts
and
accelerations.
All
of
these
factors
are
important
in
understanding
the
large
temporal
and
spatial
variations
that
are
likely
to
exist
within
each
of
the
microenvironments.
We
plan
to
examine
available
hourly
CO
data
and
PAMS
BTEX
and
1,3­
butadiene
data
for
June
through
September
2002
to
place
the
field
measurement
data
in
context
with
seasonal
variations.

Desert
Research
Institute
personnel,
accompanied
by
the
API
project
officer,
surveyed
potential
microenvironments
in
Houston
on
June
20­
22,
2002
(
Thursday
to
Saturday).
The
objectives
of
the
survey
were
to
ascertain
the
suitability
of
sampling
locations
with
respect
to
access
and
potential
for
higher­
end
exposures,
and
to
determine
the
variations
in
air
pollutant
levels
in
several
of
the
microenvironments
with
a
portable
gas
analyzer.
We
visited
the
following
locations:
I­
10
during
the
morning
commute
period,
urban
canyons
in
downtown
Houston,
Washburn
Tunnel,
various
toll
plazas
on
the
Sam
Houston
Tollway
and
Hardy
Toll
Road,
toll
plaza
at
the
Ship
Channel
Bridge,
covered
terminals
at
the
Bush
International
and
Hobby
Airports,
parking
garages
in
downtown
Houston
and
the
Texas
Medical
Center,
underground
parking
garages
at
the
City
Hall
Annex
and
Greenway
Plaza
(
Compaq
Center),
and
parking
lots
at
Minute
Maid
Park
after
a
Houston
Astros
baseball
game.
A
RAE
Systems
Model
PGM­
7240
(
ppbRAE)
portable
PID
monitor
was
used
to
continuously
monitor
ambient
VOC
levels
in
several
of
the
microenvironments.
The
monitor
is
equipped
with
a
10.6
eV
photoionization
(
PID)
detector
and
responds
to
certain
organic
and
inorganic
gases
that
have
an
ionization
potential
of
A­
3
less
than
10.6
eV,
which
includes
most
compounds
of
interest
in
this
study.
It
does
not
respond
to
light
hydrocarbons
such
as
methane,
ethane,
and
propane
or
to
acetylene,
formaldehyde
or
methanol.
Comparisons
of
the
ppbRAE
data
with
integrated
canister
and
DNPH
samples
are
currently
underway.
For
the
purposes
of
the
survey
of
microenvironments
in
Houston,
the
PID
detector
was
used
to
measure
variations
rather
than
absolute
VOC
levels.

SURVEY
RESULTS
Figures
1
through
5
show
the
time­
series
plots
of
the
PID
response
in
several
microenvironments.
Data
are
plotted
for
the
10­
second
average
and
maximum
PID
response
during
each
10­
second
interval.
Because
we
inspected
many
sampling
locations
within
a
short
time,
much
of
the
PID
measurements
do
not
coincide
with
periods
of
highest
emissions.
Coupled
with
expected
variations
in
emission
activity
levels,
these
measurements
may
be
used
to
assess
the
potential
for
high
exposures.
Figure
6
shows
the
historic
mean
wind
speed
and
direction
in
Houston
for
July.

Figure
1
shows
the
PID
response
for
a
one­
hour
trip
during
the
morning
commute
period
on
eastbound
I­
10
from
Barker­
Cypress
Rd.
to
downtown
Houston
via
southbound
I­
45.
The
trip
ended
south
of
the
downtown
area
at
the
Fannin
St.
exit
off
westbound
SR­
59.
The
trip
was
made
on
Thursday,
June
20,
2002
from
7:
27
to
8:
27
a.
m.
The
first
40
minutes
of
the
trip
was
in
congested
traffic
(
average
speed
of
20­
25
mph).
For
most
of
this
period,
the
maximum
PID
response
hovered
around
100
ppb
with
occasional
excursions
to
up
to
200
ppb.
The
maximum
PID
response
increased
to
between
400
and
600
ppb
during
a
three­
minute
period
in
the
first
ten
minutes
of
the
trip.
These
high
values
were
associated
with
a
suspected
high
emitter.
The
vehicle
was
a
landscape
service
truck,
which
was
towing
a
trailer
containing
lawn
and
garden
equipment.
Three
spikes
in
the
PID
response
coincided
with
slow
downs
in
traffic
followed
by
accelerations.
Without
concurrent
CO
data,
we
cannot
rule
out
evaporative
emissions
from
the
lawn
and
garden
equipment.
However,
we
followed
one
other
landscape
service
truck
with
no
increase
in
the
PID
response.
From
the
I­
610
loop
to
I­
45,
the
traffic
moved
near
the
speed
limit
and
the
PID
response
was
consistently
at
or
below
100
ppb.
VOC
concentrations
were
higher
during
the
last
ten
minutes
of
the
trip
when
we
encountered
congested
traffic
in
downtown
Houston
and
substantial
backup
at
the
junction
of
southbound
I­
45
and
westbound
SR­
59.
This
trip
demonstrates
what
we
have
observed
with
similar
measurements.
A
great
majority
of
the
on­
road
vehicle
fleet
are
relatively
low
emitters
that
have
little
impact
on
in­
cabin
exposure
levels
at
highway
speed.
Congested
stop­
and­
go
conditions
result
in
some
increase
in
exposure
levels
due
to
shorter
gap
between
vehicles
and
due
to
intermittent
accelerations.
Higher
exposures
are
anticipated
when
following
high
emitters.

Figure
2
shows
the
time­
series
of
the
PID
response
during
a
1.3­
hour
tour
through
downtown
Houston.
The
first
half
of
the
tour
covered
the
westside
of
downtown
with
potential
urban
canyons.
The
PID
response
varied
with
traffic
in
the
area,
which
was
relatively
light
during
this
period.
We
sampled
in
an
aboveground
parking
garage
at
about
9:
00
a.
m.
for
about
five
minutes.
The
VOC
levels
measured
in
the
garage
were
not
significantly
above
the
surrounding
urban
background.
The
second
half
of
the
tour
covered
the
eastside
of
downtown
A­
4
near
Minute
Maid
Park
(
Houston
Astros
baseball
stadium).
The
large
parking
lot
east
of
the
stadium
is
a
potential
sampling
site
during
ballgames
(
see
Figure
4).

Congested
Freeway
0
100
200
300
400
500
600
700
0727
0732
0737
0742
0747
0752
0757
0802
0807
0812
0817
0822
Time,
CDT
PID
Response
(
ppb)
Average
Maximum
Figure
1.
Eastbound
I­
10
from
Barker­
Cypress
Rd.
through
downtown
Houston
via
southbound
I­
45
and
westbound
SR­
59
and
ending
at
Fannin
exit.

Downtown
Houston
0
100
200
300
400
500
600
0830
0835
0840
0845
0850
0855
0900
0905
0910
0915
0920
0925
0930
0935
0940
0945
0950
Time,
CDT
PID
Response
(
ppb)
Average
Maximum
A­
5
Figure
2.
Tour
of
downtown
Houston.

Bush
Int.
Airport,
Highways
8,
59,
and
10,
and
Washburn
Tunnel
0
100
200
300
400
500
1240
1245
1250
1255
1300
1305
1310
1315
1320
1325
1330
1335
1340
1345
Time,
CDT
PID
Response
(
ppb)
Average
Maximum
Figure
3.
George
Bush
International
Airport
and
drive
to
Washburn
Tunnel.

Minute
Maid
Stadium
Parking
Lot
After
Houston
Astros
Baseball
Game
0
100
200
300
400
500
600
700
2145
2150
2155
2200
2205
2210
2215
Time,
CDT
PID
Response
(
ppb)
Average
Maximum
Figure
4.
Minute
Maid
Park
at
the
end
of
a
ballgame
on
evening
of
June
21,
2002.
A­
6
Wahburn
Tunnel
and
Ship
Channel
Bridge
Toll
Plaza
0
100
200
300
400
500
1345
1350
1355
1400
1405
1410
1415
1420
Time,
CDT
PID
Response
(
ppb)
Average
Maximum
Figure
5.
Tour
of
Washburn
Tunnel
and
the
Ship
Channel
Toll
Plaza
on
the
Sam
Houston
Tollway.

The
first
20
minutes
in
Figure
3
show
the
variations
in
PID
response
at
the
George
Bush
International
Airport.
The
road
through
the
airport
is
split
into
two
levels
at
each
of
the
four
terminals
with
passenger
pick­
up
being
the
lower,
covered
level.
Terminal
C
appeared
to
have
the
greatest
length
of
covered
roadway
in
front
of
the
terminal.
Traffic
was
light
during
this
time
and
we
observed
about
a
50
to
100
percent
increase
in
PID
response
while
driving
past
Terminal
C.
We
expect
significantly
higher
VOC
levels
during
peak
periods.
We
also
visited
the
Hobby
Airport
(
data
not
shown),
which
also
has
a
two­
level
road
at
the
terminal.
The
length
of
covered
roadway
is
greater
at
Hobby
and
adjacent
parking
garage
is
larger.
We
propose
to
sample
incabin
exposure
at
the
Hobby
Airport
terminal
during
peak
periods.

Figure
3
also
shows
the
variations
in
PID
response
during
three
trips
through
the
Washburn
Tunnel.
The
first
three
spikes
in
Figure
5
correspond
to
trips
through
the
tunnel
on
another
day.
Travel
time
through
the
tunnel
is
52
seconds
at
35
mph
from
portal
to
portal.
The
tunnel
is
book
ended
on
each
side
by
a
rotary.
Passage
through
the
tunnel
is
controlled
during
peak
periods
to
avoid
congestion
within
the
tunnel.
A
queue
of
vehicles
develops
during
these
controlled
periods.
We
propose
to
sample
during
peak
periods
in
order
to
measure
exposure
while
in
the
queue
as
well
as
in
the
tunnel.

Figure
4
shows
the
time­
series
of
the
PID
response
at
Minute
Maid
Park
at
the
end
of
a
ballgame
on
the
evening
of
June
21,
2002.
We
were
parked
in
the
middle
of
Lot
C
and
made
A­
7
Figure
6.
Frequencies
of
wind
speed
and
direction
in
Houston
during
July.

measurements
at
this
location
for
about
ten
minutes
while
vehicles
began
to
leave
the
lot.
The
PID
response
was
nearly
constant
during
this
period.
We
then
walked
to
the
parking
lot
exit
and
made
measurements
there.
The
spikes
in
the
PID
coincide
with
the
passage
of
vehicles
accelerating
out
the
parking
lot,
while
presumably
still
in
cold­
start
mode.
We
then
walked
along
the
sidewalk
towards
the
park.
These
measurements
were
lower
than
at
the
parking
lot
exit
but
higher
and
more
variable
than
at
the
center
of
the
parking
lot.
Based
upon
these
results,
we
propose
to
sample
with
a
sampling
cart
for
a
one­
hour
period
at
the
end
of
the
game
with
15­
minute
sampling
times
alternating
between
a
fixed
location
at
the
exit
of
the
parking
lot
and
a
walk
along
the
sidewalk.

The
second
half
of
the
time­
series
in
Figure
5
shows
the
variations
in
the
PID
response
at
the
toll
plaza
at
the
Sam
Houston
Tollway
Ship
Channel
Bridge.
The
speed
limit
on
the
Tollway
is
70
mph.
As
the
vehicles
leave
the
toll
plaza,
they
accelerate
rapidly
leaving
a
puff
of
higher
emissions
at
the
tollbooth.
The
emissions
of
vehicles
are
typically
much
higher
under
hard
accelerations.
The
spikes
in
PID
response
in
Figure
5
coincide
with
vehicles
accelerating
rapidly
from
the
tollbooth.
Based
on
these
results,
we
propose
to
sample
with
a
sampling
cart
as
close
to
A­
8
a
tollbooth
as
allowed
by
the
Harris
County
Tollway
Authority.
Prior
to
setup,
we
will
make
one
pass
through
the
toll
plaza
to
measure
in­
cabin
exposure
with
continuous
instruments
only.

DESCRIPTIONS
OF
MICROENVIRONMENTS
(
ME)
AND
SAMPLING
PROTOCOL
1.
In
vehicle:
commuter
rush
hour
in
stop­
and­
go
traffic
(
ME1)

Make
two
roundtrips
on
a
segment
of
freeway
during
peak
weekday
morning
commuter
traffic
(
Option
A
or
B
depending
upon
wind
speed
and
direction)
from
7:
00
to
8:
00
a.
m.
Each
roundtrip
will
take
25
to
30
minutes
with
the
inbound
and
outbound
directions
of
the
freeway
segment
taking
16
to
20
minutes
and
8
to
10
minutes,
respectively.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
the
first
roundtrip
and
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
during
winter)
during
the
second
roundtrip.
Maintain
a
safe
following
distance,
about
one
car
length
(
15
feet)
per
10
mph
speed,
closing
to
within
3
feet
during
stopped
conditions.
Use
the
middle
lane
and
do
not
follow
the
same
vehicle
for
more
than
two
minutes.
Attempt
to
get
behind
at
least
one
high­
emitter
during
each
of
the
two
inbound
trips.

Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
one
for
each
of
the
two
inbound
trips
(
approximately
15
minutes)
and
one
during
the
first
outbound
trip
(
approximately
8
minutes).
Begin
each
SPME
sample
when
the
sampling
van
has
entered
the
freeway
and
is
in
the
middle
lane
and
stop
the
sample
just
before
exiting
the
freeway
at
the
end
of
the
trip.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
The
effect
of
high
and
low
ventilation
conditions
will
be
normalized
to
the
PID
data.
The
portable
PID
monitor
replaces
the
second
CO
analyzer
(
in
the
trailing
mobile
laboratory)
that
is
specified
in
the
Exposure
Protocol
and
Study
Plan
of
June
13,
2002.
Monitor
and
record
the
van's
position
(
GPS),
and
in­
cabin
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.
Other
relevant
data
collected
by
the
City
of
Houston
include
CO
and
meteorological
data
at
the
Lang
(
C408)
monitoring
station
in
west
Houston
at
4401
½
Lang.
Check
wind
data
at
the
mobile
laboratory
and
traffic
conditions
(
radio
reports
of
any
accidents
on
sampling
routes)
prior
to
sampling
run
and
select
the
appropriate
sampling
route
from
the
following
options.

a.
Option
A
(
use
for
calm
wind
conditions
or
winds
from
west
or
east).
A
six­
mile
segment
of
I­
10
between
Dairy
Ashford
Rd.
(
2
mile
west
of
the
Sam
Houston
Tollway)
and
Voss
Rd.
(
4
miles
east
of
the
SH
Tollway).
Start
with
the
inbound
(
east)
direction
at
Dairy
Ashford
Rd.
Average
speeds
in
the
inbound
and
outbound
directions
are
20­
25
mph
and
50­
60
mph,
respectively.

b.
Option
B
(
use
for
moderate
winds
from
south­
southeast
or
north­
northwest).
An
eightmile
segment
of
US­
290
between
N.
Eldridge
Parkway
(
3
miles
northwest
of
SH
A­
9
Tollway)
to
Bingle
Rd
(
5
miles
southeast
of
SH
Tollway).
Start
with
inbound
(
southeast)
direction
from
N.
Eldridge
Parkway.
Average
speeds
in
the
inbound
and
outbound
directions
are
about
30
mph
and
65­
70
mph,
respectively.

2.
In
vehicle:
urban
street
canyons
(
ME2)

The
greatest
volume
of
traffic
in
the
downtown
Houston
occurs
during
the
morning
and
afternoon
commute
periods
and
to
a
lesser
extent
during
the
noon
hour.
We
propose
the
weekday
afternoon
commute
period
from
4:
00
to
5:
00
p.
m.
because
the
vehicles
exiting
the
parking
garages
may
still
be
in
cold­
start
mode
and
because
ME1
precludes
ME2
during
the
morning
commute
period.

Make
multiple
trips
during
a
one­
hour
period
along
a
four
by
one
block
surface
street
loop
in
downtown
Houston.
The
loop
consists
of
four
one­
way
streets
and
four
left
turns.
Starting
from
the
intersection
of
Louisiana
and
Clay,
go
northeast
on
Louisiana
for
four
blocks,
turn
left
on
Walker,
left
on
Smith,
left
on
Clay,
and
left
on
Louisiana
to
complete
the
loop.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
first
30
minutes
and
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
during
winter)
during
second
30
minutes.
Drive
at
or
near
the
end
of
a
pack
of
vehicles
as
much
as
possible.

Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
samples
during
the
high
ventilation
condition
and
one
sample
during
the
first
15
minutes
of
the
low
ventilation
condition.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
van's
position
(
GPS),
and
in­
cabin
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.
Other
relevant
data
collected
by
the
City
of
Houston
include
CO
and
meteorological
data
at
the
Houston
Texas
Avenue
(
C411)
monitoring
station
in
downtown
Houston
at
2311
Texas
Avenue.

3.
In
vehicle:
refueling
(
ME3)

Select
appropriate
refueling
location(
s)
and
sampling
times
based
on
the
following
guidance.
The
fuel
pump
islands
should
be
located
on
the
lee
side
of
the
service
station
building
or
other
large
obstruction
such
as
the
raised
section
of
highway.
Given
the
prevailing
southerly
to
southeasterly
winds,
the
turnarounds
at
the
north
sides
of
I­
10,
South
I­
610
loop,
or
SR
59
are
potential
areas
for
the
search.
Conduct
sampling
during
the
peak
or
near­
peak
refueling
periods
for
the
station
as
indicated
by
service
station
personnel.

Park
sampling
van
at
refueling
location
and
sample
alternate
30­
minute
periods
under
high
and
low
ventilation.
Park
the
van
downwind
from
the
centroid
of
the
pump
locations.
Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
A­
10
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
samples
during
the
high
ventilation
sampling
period
and
one
15­
minute
sample
at
the
midpoint
of
the
low
ventilation
sampling
period.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
in­
cabin
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.

4.
In
vehicle:
parking
garage
(
ME4)

Drive
within
a
parking
garage
for
one
hour.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
first
30
minutes
and
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
during
winter)
during
second
30
minutes.
Potential
garages
include
the
Houston
City
Hall
Annex,
Greenway
Plaza,
and
Hobby
Airport
(
covered
road
in
front
of
terminal
and
adjacent
parking
structure).

Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
samples
during
the
high
ventilation
condition
and
one
sample
during
the
first
15
minutes
of
the
low
ventilation
condition.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
incabin
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.

5.
In
vehicle:
toll
plaza
(
ME5)

Measurements
for
this
microenvironment
are
combined
with
the
tunnel
and
tollbooth
microenvironments.
See
ME6
and
ME12.

6.
In
vehicle:
tunnel
(
ME6)

Make
several
trips
though
the
Washburn
Tunnel
for
one
hour
during
peak
periods
when
traffic
through
the
tunnel
is
controlled.
Obtain
information
regarding
peak
traffic
periods
and
average
queue
times
from
the
gate
operator.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
first
30
minutes
and
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
during
winter)
during
second
30
minutes.

Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
one
15­
minute
samples
each
during
midpoint
of
the
high
ventilation
and
the
midpoint
of
the
low
ventilation
sampling
period,
and
one
sample
during
time
spent
in
the
queue.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
van's
position
(
GPS),
and
in­
cabin
temperature
and
relative
A­
11
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
be
located
on­
site
just
south
of
the
south
entrance
to
the
Tunnel.
There
should
be
space
just
south
of
the
rotary.
Park
the
RV
with
the
generator
exhaust
downwind
relative
to
the
inlet
for
the
CO
monitor.

7.
Outdoor:
refueling
vehicle
(
ME7)

Select
appropriate
refueling
location(
s)
and
sampling
times
based
on
the
following
guidance.
The
fuel
pump
islands
should
be
located
on
the
lee
side
of
the
service
station
building
or
other
large
obstruction
such
as
the
raised
section
of
highway.
Given
the
prevailing
southerly
to
southeasterly
winds,
the
turnarounds
at
the
north
sides
of
I­
10,
South
I­
610
loop,
or
SR
59
are
potential
areas
for
the
search.
Conduct
sampling
during
the
peak
or
near­
peak
refueling
periods
for
the
station
as
indicated
by
service
station
personnel.
Conduct
samplng
in
the
morning
to
accommodate
the
collection
of
biomarker
samples.

Park
the
van
downwind
from
the
centroid
of
the
pump
locations.
With
sampling
inlet
in
the
breathing
zone,
refuel
the
vehicle
over
a
1
to
2
minute
active
refueling
period.
During
refueling,
maintain
manual
control
of
the
nozzle
and
stand
downwind
of
the
vehicle
fuel
tank
inlet.
Ask
to
refuel
other
vehicles
on
the
other
side
of
the
pump
island
as
the
opportunity
arises
or
stand
as
close
as
possible
to
the
person
refueling
the
vehicle.
Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples
during
three
separate
active
refueling
periods.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.

8.
Outdoor:
sidewalk
near
high­
density
traffic
(
ME8)

Conduct
sidewalk
sampling
in
downtown
Houston
along
the
city
block
bordered
by
Polk,
Louisiana,
Clay
and
Smith.
A
portion
of
Polk
St.
is
covered
and
several
eating
establishment
are
located
there
with
outdoor
seating.
Start
at
this
location
and
walk
around
the
block.
After
the
first
trip
around
the
block,
remain
in
the
covered
section
of
Polk
Street
for
at
least
15
minutes,
then
continue
the
walk
around
the
block.
Sampling
should
be
conducted
during
the
morning
and
afternoon
commute
periods
and
during
the
noon
hour.

Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
samples
during
the
walk
around
the
block
and
one
sample
at
the
covered
section
of
Polk
Street.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.

9.
Outdoor:
bus
stop
(
ME9)
A­
12
Sample
the
ambient
air
at
a
bus
stop
in
downtown
Houston
during
the
morning
and
afternoon
commute
periods.

10.
Outdoor:
stadium
parking
lot
(
ME10)

Sample
for
1
hour
at
the
end
of
Houston
Astros
baseball
game
Games
are
scheduled
on
July
11
(
Thu)
at
7:
05
PM,
July
12
(
Fri)
at
7:
05
PM,
July
13
(
Sat)
at
12:
15
PM,
July
14
(
Sun)
at
1:
35
PM,
July
15
(
Mon)
at
7:
05
PM,
and
July
16
(
Tue)
at
3:
05
PM.
Because
the
atmosphere
is
more
stable
in
the
evening,
night
games
are
preferable
to
day
games.
Sample
ambient
air
with
a
sampling
cart
for
a
one­
hour
period
at
the
end
of
the
game
with
15­
minute
sampling
times
alternating
between
a
fixed
location
at
the
south
exit
of
parking
lot
C
and
a
walk
along
the
sidewalk
toward
the
Park
and
back
Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
samples
at
the
exit
of
Lot
C
and
one
sample
during
the
walk.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.

11.
In­
doors:
underground
parking
garage
(
ME11)

Sample
the
ambient
air
in
an
underground
parking
garage
with
a
sampling
cart
for
a
one
hour.
Potential
garages
include
the
Houston
City
Hall
Annex
and
the
Greenway
Plaza.
The
Greenway
Plaza
is
preferable
for
several
reasons.
The
Greenway
Plaza
is
a
business
complex
of
ten
office
towers,
the
Renaissance
Hotel
and
the
Compaq
center,
home
to
the
NBA
Houston
Rockets
and
the
WNBA
Comets.
The
complex
includes
13,000
parking
spaces.
A
large
fraction
of
the
parking
is
underground.
During
our
study
period
in
Houston,
the
Comets
are
scheduled
to
play
only
once
on
Tuesday
July
9
at
7:
30
p.
m.
We
propose
three
separate
one­
hour
sampling
periods
on
that
day.
The
first
will
be
from
4:
00
to
5:
00
p.
m.
when
the
office
workers
leave
the
complex
(
cold
start
emissions).
The
second
is
from
7:
00
to
8:
00
p.
m.
when
the
basketball
fans
arrive
for
the
game
(
hot
stabilized
exhaust
and
hot
soak
emissions)
and
the
final
sampling
period
will
be
from
after
the
game
(
cold
start
emissions).

Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
four
SPME
samples
with
each
sampling
period
lasting
15
minutes.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.

12.
Outdoors:
toll
booth
(
ME12)

Sample
the
ambient
air
at
the
Ship
Channel
Bridge
toll
plaza
for
one
hour
from
7:
00
to
8:
00
a.
m.
Locate
the
sampling
cart
behind
the
concrete
barrier
on
the
west
end
of
the
plaza
as
close
to
the
tollbooth
as
possible.
Notify
Patricia
Watson
of
the
Harris
County
Tollway
A­
13
Authority
(
281/
875­
1400)
of
the
Harris
County
Tollway
Authority
at
least
24
hours
prior
to
sampling.

Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
four
SPME
samples
with
each
sampling
period
lasting
15
minutes.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
be
located
on­
site
near
the
toll
plaza
office
building.
Park
the
RV
with
the
generator
exhaust
downwind
relative
to
the
inlet
for
the
CO
monitor.
.

If
time
permits
before
or
after
the
sampling
period
and
sufficient
traffic
exist,
conduct
measurement
of
in­
cabin
exposure
during
one
pass
through
the
toll
plaza.
Collect
one
SPME
sample
during
this
sampling
period.

DAILY
SAMPLING
SCHEDULE
The
daily
schedule
for
the
Houston
summer
sampling
program
is
summarized
in
Table
1.
In
order
to
stay
on
project
schedule
as
much
as
possible,
sampling
will
be
conducted
on
weekends
in
case
we
encounter
unsuitable
meteorological
conditions
on
scheduled
sampling
days.
Possible
alternative
microenvironments
on
weekends
include
outdoor
cafes
in
the
theater
district
in
downtown
Houston,
parking
garages
at
malls,
sporting
events
or
other
special
event.
A­
14
Table
1
Daily
Sampling
Schedule
for
Houston
No.
ME
Date
Start
Time
ME
ME
Description
1
11
7/
9/
02
1600
In­
door,
underground
garage
Grrenway
Plaza
garage
2
11
7/
9/
02
1900
In­
door
underground
garage
Greenway
Plaza
garage
near
Compac
Center
before
game,
hot
exhaust
and
evaporative
3
11
7/
9/
02
2100
In­
door
underground
garage
Greenway
Plaza
garage
near
Compac
Center
after
game,
cold
start
4
1
7/
10/
02
700
In­
cabin,
conjested
freeway
I­
10
or
SR290
5
3
7/
10/
02
900
In­
cabin,
refueling
TBD
6
2
7/
10/
02
1600
In­
cabin,
urban
Canyon
Loop
bordered
by
Walker,
Smith,
Clay,
and
Louisianna
7
1
7/
11/
02
700
In­
cabin,
conjested
freeway
I­
10
or
SR290
8
2
7/
11/
02
1600
In­
cabin,
urban
Canyon
Loop
bordered
by
Walker,
Smith,
Clay,
and
Louisianna
9
10
7/
11/
02
2100
Outdoor,
surface
parking
Minute
Maid
Park
after
game,
cold
start
10
1
7/
12/
02
700
In­
cabin,
conjested
freeway
I­
10
or
SR290
11
2
7/
12/
02
1600
In­
cabin,
urban
Canyon
Loop
bordered
by
Walker,
Smith,
Clay,
and
Louisianna
12
10
7/
12/
02
2100
Outdoor,
surface
parking
Minute
Maid
Park
after
game,
cold
start
13
7
7/
15/
02
700
Outdoor,
refueling
TBD
14
3
7/
15/
02
900
In­
cabin,
refueling
TBD
15
6
7/
15/
02
1600
In­
cabin,
roadway
tunnel
Washburn
Tunnel
16
10
7/
15/
02
2100
Outdoor,
surface
parking
Minute
Maid
Park
after
game,
cold
start
17
9
7/
16/
02
700
Outdoor­
bus
stop
On
Louisiana
or
Smith
18
8
7/
16/
02
800
Outdoor,
sidewalk
near
traffic
City
block
bordered
by
Polk,
Louisiana,
Clay
and
Smith
19
8
7/
16/
02
1200
Outdoor,
sidewalk
near
traffic
City
block
bordered
by
Polk,
Louisiana,
Clay
and
Smith
20
9
7/
16/
02
1600
Outdoor­
bus
stop
On
Louisiana
or
Smith
21
8
7/
16/
02
1700
Outdoor,
sidewalk
near
traffic
City
block
bordered
by
Polk,
Louisiana,
Clay
and
Smith
22
7
7/
17/
02
700
Outdoor,
refueling
TBD
23
3
7/
17/
02
900
In­
cabin,
refueling
TBD
24
4
7/
17/
02
1600
In­
cabin,
parking
garage
Greenway
Plaza
garage
25
5
7/
18/
02
600
In­
vehicle
toll
plaza
Sam
Houston
Tollway
Ship
Channel
Bridge
26
12
7/
18/
02
700
Outdoor,
toll
plaza
Sam
Houston
Tollway
Ship
Channel
Bridge
27
6
7/
18/
02
1600
In­
cabin,
roadway
tunnel
Washburn
Tunnel
28
5
7/
19/
02
600
In­
vehicle
toll
plaza
Sam
Houston
Tollway
Ship
Channel
Bridge
29
12
7/
19/
02
700
Outdoor,
toll
plaza
Sam
Houston
Tollway
Ship
Channel
Bridge
30
6
7/
19/
02
1600
In­
cabin,
roadway
tunnel
Washburn
Tunnel
31
4
7/
19/
02
1800
In­
cabin,
airport
terminal
Hobby
Airport
baggage
&
passenger
pickup
32
5
7/
19/
02
1900
In­
cabin,
airport
terminal
Hobby
Airport
baggage
&
passenger
pickup
33
7
7/
22/
02
700
Outdoor,
refueling
TBD
34
4
7/
22/
02
1600
In­
cabin,
parking
garage
City
Hall
Annex
35
5
7/
23/
02
600
In­
vehicle
toll
plaza
Sam
Houston
Tollway
Ship
Channel
Bridge
36
12
7/
23/
02
700
Outdoor,
toll
plaza
Sam
Houston
Tollway
Ship
Channel
Bridge
B­
1
APPENDIX
B
Exposure
Protocol
and
Study
Plan
for
the
Section
211(
B)
Tier
2
High
End
Exposure
Screening
Study
of
Baseline
and
Oxygenated
Gasoline
Addendum
B
­
Summer
2002
Sampling
Plan
for
Atlanta
DRAFT
Prepared
for
AMERICAN
PETROLEUM
INSTITUTE
1220
L
Street
Washington,
DC
20005­
4070
Prepared
by
DESERT
RESEARCH
INSTITUTE
2215
Raggio
Parkway
Reno,
NV
89512
July
26,
2002
B­
2
INTRODUCTION
This
sampling
plan
specifies
the
details
for
the
field
measurement
program
that
will
be
carried
out
in
Atlanta,
GA
during
the
summer
of
2002
as
part
of
a
screening
study
of
the
highend
exposures
to
baseline
and
oxygenated
gasoline.
It
specifies
the
dates,
times
and
measurement
locations
for
the
twelve
categories
of
microenvironments
and
explains
the
selections
with
respect
to
the
objective
of
capturing
the
upper­
end
of
the
distribution
of
exposures
for
each
microenvironment.
This
document
is
an
addendum
to
the
June
13,
2002
Exposure
Protocol
and
Study
Plan,
which
describes
the
proposed
measurement
methods
and
rationale
for
their
selection.

Desert
Research
Institute
personnel,
accompanied
by
the
API
project
officer,
surveyed
potential
microenvironments
in
Atlanta
on
July
24­
26,
2002.
The
objectives
of
the
survey
were
to
ascertain
the
suitability
of
sampling
locations
with
respect
to
access
and
potential
for
higherend
exposures,
and
to
determine
the
variations
in
air
pollutant
levels
in
several
of
the
microenvironments
with
a
portable
gas
analyzer.
We
visited
the
following
locations:
I­
20
W
and
I­
75
NW
during
the
morning
commute
period,
urban
canyons
in
downtown
Atlanta,
Justus
C.
Martin
Jr.
Tunnel,
GA400
toll
road
plaza,
parking
garages
in
downtown
and
midtown
Atlanta
and
in
Buckhead,
service
stations,
parking
garage
at
the
Georgia
Dome
and
parking
lots
at
Turner
Field.
A
RAE
Systems
Model
PGM­
7240
(
ppbRAE)
portable
PID
monitor
was
used
to
continuously
monitor
ambient
VOC
levels
in
several
of
the
microenvironments.
The
monitor
is
equipped
with
a
10.6
eV
photoionization
(
PID)
detector
and
responds
to
certain
organic
and
inorganic
gases
that
have
an
ionization
potential
of
less
than
10.6
eV,
which
includes
most
compounds
of
interest
in
this
study.
It
does
not
respond
to
light
hydrocarbons
such
as
methane,
ethane,
and
propane
or
to
acetylene,
formaldehyde
or
methanol.
Comparisons
of
the
ppbRAE
data
with
integrated
canister
and
DNPH
samples
are
currently
underway.
For
the
purposes
of
the
survey
of
microenvironments
in
Houston,
the
PID
detector
was
used
to
measure
relative
variations
rather
than
absolute
VOC
levels.

Information
for
the
survey
were
obtained
from
the
following
Atlanta
web
sites:

Air
Quality
Agencies
http://
www.
dnr.
state.
ga.
us/
environ/
Georgia
Environmental
Protection
Division
http://
www.
air.
dnr.
state.
ga.
us/
amp/
index.
html
Current
air
quality
http://
www.
cleanairforce.
com/
Vehicle
inspection
program
http://
www.
atlreg.
com/
Atlanta
Regional
Commission
http://
www.
atlanta­
airport.
com/
Atlanta
Airport
http://
www.
dot.
state.
ga.
us/
Georgia
Dept.
of
Transportation
http://
www.
accessatlanta.
com/
autos/
special/
roadwords.
html
Road
works
http://
www.
georgia­
navigator.
com/
traffic/
Real­
time
traffic
map
http://
www2.
georgianavigator.
com/
links.
html
Atlanta
Visitor
Links
http://
www.
itsmarta.
com/
Metro
Atlanta
Rapid
Transit
Authority
http://
www.
metrogirl.
com/
dna/
links.
htm
Downtown
Atlanta
Links
http://
www.
atlantadowntown.
com/
downtownlivedirectory.
htm
Downtown
Events
B­
3
http://
www.
gadome.
com/
Georgia
Dome/
World
Congress
Center,
Falcons
http://
braves.
mlb.
com/
NASApp/
mlb/
atl/
ballpark/
atl_
ballpark_
history.
jsp
Turner
Field,
Braves
http://
www.
atlantaarena.
com/
st0300/
main/
main.
shtml
Phillips
Arena,
Hawks
http://
www.
aaaparking.
com/
property2.
htm
parking
garages
http://
www.
accessatlanta.
com/
shopping/
guides/
mallguide.
html
Mall
Guide
DESCRIPTIONS
OF
MICROENVIRONMENTS
(
ME)
AND
SAMPLING
PROTOCOL
13.
In
vehicle:
commuter
rush
hour
in
stop­
and­
go
traffic
(
ME1)

Drive
in
congested
freeway
traffic
during
weekday
morning
rush
hour
from
0700
to
0800,
local
time
or
evening
rush
hour
from
1700
to
1800.
During
the
morning,
drive
southbound
on
I­
75
beginning
at
S.
Marietta
Parkway
to
downtown
Atlanta.
Drive
the
opposite
direction
during
the
evening
rush
hour.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
the
first
30
minutes
and
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
during
winter)
during
the
second
30
minutes.
Maintain
a
safe
following
distance,
about
one
car
length
(
15
feet)
per
10
mph
speed,
closing
to
within
3
feet
during
stopped
conditions.
Use
the
middle
lane
and
do
not
follow
the
same
vehicle
for
more
than
two
minutes.
Attempt
to
get
behind
at
least
one
high­
emitter
during
each
of
the
two
ventilation
conditions.

Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
period
during
the
high
ventilation
condition
and
one
15­
minute
period
during
the
midpoint
of
the
low
ventilation
condition.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
The
effect
of
high
and
low
ventilation
conditions
will
be
normalized
to
the
PID
data.
Monitor
and
record
the
van's
position
(
GPS),
and
in­
cabin
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.
Other
relevant
data
collected
by
the
City
of
Atlanta
include
CO
and
meteorological
data
at
the
Roswell
monitoring
station
at
4434
Roswell
Rd.
and
the
PM
Supersite
at
829
Jefferson
St.
NW.

14.
In
vehicle:
urban
street
canyons
(
ME2)

Make
multiple
trips
during
a
one­
hour
period
along
a
surface­
street
loop
in
downtown
Atlanta
bordered
by
Peachtree
Street
NW,
Forsyth/
Carnegie,
Spring
Steet
NW,
and
Harris
Street
(
four
right
turns).
Make
the
measurements
during
either
the
morning
commute
period
from
0700
to
0800
or
evening
commute
period
from
1700
to
1800.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
first
30
minutes
and
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
during
winter)
during
second
30
minutes.
Drive
at
or
near
the
end
of
a
pack
of
vehicles
at
stop
lights
as
much
as
possible
and
attempt
to
get
behind
at
least
one
high­
emitter
during
each
of
the
two
ventilation
conditions.
B­
4
Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
samples
during
the
high
ventilation
condition
and
one
15­
minute
sample
during
the
midpoint
of
the
low
ventilation
condition.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
van's
position
(
GPS),
and
in­
cabin
temperature
and
relative
humidity.

15.
In
vehicle:
refueling
(
ME3)

Sample
for
one
hour
at
the
Racetrak
or
Quicktrip
(
QT)
service
station
located
north
of
the
Thornton
Rd
exit
off
I­
20.
Conduct
sampling
during
the
peak
or
near­
peak
refueling
periods
for
the
station
as
indicated
by
service
station
personnel.

Park
the
sampling
van
at
the
center
downwind
pump
of
the
center
pump
station
island
and
sample
alternate
30­
minute
periods
under
high
and
low
ventilation.
Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
samples
during
the
high
ventilation
sampling
period
and
one
15­
minute
sample
at
the
midpoint
of
the
low
ventilation
sampling
period.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
in­
cabin
temperature,
relative
humidity,
and
wind
speed.
Note
the
number
of
gallons
dispensed.

16.
In
vehicle:
parking
garage
(
ME4)

Drive
within
a
parking
garage
for
one
hour.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
first
30
minutes
and
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
during
winter)
during
second
30
minutes.
Potential
garages
include
Colony
Square
parking
garage
at
Peachtree
Street
and
14th
Street
in
Midtown
Atlanta
during
the
morning
and
evening
commute
period
and
prior
to
and
after
the
Atlanta
Falcons'
pre­
season
football
game
at
the
Georgia
Dome
parking
garage
on
the
evening
of
August
9.

Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
samples
during
the
high
ventilation
condition
and
one
sample
during
the
first
15
minutes
of
the
low
ventilation
condition.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
incabin
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.

17.
In
vehicle:
toll
plaza
(
ME5)

Sample
during
the
morning
commute
period
between
0700
and
0800
at
the
toll
plaza
between
exit
2
and
3
on
the
GA
400
toll
road.
Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
B­
5
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
one
15­
minute
samples
each
during
midpoint
of
the
high
ventilation
and
the
midpoint
of
the
low
ventilation
sampling
period,
and
one
sample
during
time
spent
in
the
queue.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
van's
position
(
GPS),
and
in­
cabin
temperature
and
relative
humidity.

18.
In
vehicle:
tunnel
(
ME6)

The
Justus
C.
Martin
Jr.
Tunnel
is
the
only
roadway
tunnel
in
Atlanta.
It
is
located
less
than
two
miles
south
of
the
toll
plaza
on
GA
400.
The
tunnel
consists
of
separate
bores
for
the
northbound
and
southbound
direction
consisting
of
four
lanes
each.
The
tunnel
is
very
short
and
is
unlikely
to
restrict
dilution
of
emissions
to
any
significant
degree.
Traffic
in
both
directions
remains
uncongested
during
the
evening
commute
period.
No
sampling
is
planned
for
this
microenvironment
in
Atlanta.

19.
Outdoor:
refueling
vehicle
(
ME7)

Sample
for
one
hour
at
the
Racetrak
or
Quicktrip
(
QT)
service
station
located
north
of
the
Thornton
Rd
exit
off
I­
20.
Conduct
sampling
during
the
peak
or
near­
peak
refueling
periods
for
the
station
as
indicated
by
service
station
personnel.

Park
the
van
downwind
from
the
centroid
of
the
pump
locations.
With
sampling
inlet
in
the
breathing
zone,
refuel
the
vehicle
over
a
1
to
2
minute
active
refueling
period.
During
refueling,
maintain
manual
control
of
the
nozzle
and
stand
downwind
of
the
vehicle
fuel
tank
inlet.
Ask
to
refuel
other
vehicles
on
the
other
side
of
the
pump
island
as
the
opportunity
arises
or
stand
as
close
as
possible
to
the
person
refueling
the
vehicle.
Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples
during
three
separate
active
refueling
periods.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature,
relative
humidity,
and
wind
speed.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.
Note
the
number
of
gallons
of
fuel
dispensed.
Urine
samples
are
also
collected
for
this
microenvironment
in
accordance
with
the
study
protocol.

20.
Outdoor:
sidewalk
near
high­
density
traffic
(
ME8)

Conduct
sidewalk
sampling
in
downtown
Atlanta
along
the
city
block
bordered
by
Peachtree
Street
NE,
Andrew
Young
International,
Spring
Street
NW,
and
Harris
Street
NW.
Sampling
should
be
conducted
during
the
morning
and
afternoon
commute
periods
and
during
the
noon
hour.

Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
samples
during
the
walk
around
the
block
and
one
sample
at
the
covered
section
of
Polk
Street.
Record
the
ambient
B­
6
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature,
relative
humidity,
wind
speed
and
direction.
.

21.
Outdoor:
bus
stop
(
ME9)

Combined
with
ME8.

22.
Outdoor:
stadium
parking
lot
(
ME10)

Sample
for
1
hour
at
the
end
of
Atlanta
Braves
baseball
game
Games
are
scheduled
on
July
27
(
Sat)
at
1:
15
PM,
July
28
(
Sun)
at
1:
05
PM,
July
30
(
Tue)
at
7:
35
PM,
July
31
(
Wed)
at
7:
05
PM,
Aug
1
(
Thu)
at
7305
PM,
Aug
2
(
Fri)
at
7:
35
PM,
Aug
3
(
Sat)
at
1:
15
PM,
Aug
4
and
(
Sun)
at
8:
05
PM.
Because
the
atmosphere
is
more
stable
in
the
evening,
night
games
are
preferable
to
day
games.
Sample
ambient
air
with
a
sampling
cart
for
a
one­
hour
period
at
the
end
of
the
game
with
15­
minute
sampling
times
alternating
between
a
downwind
fixed
location
at
the
south
exit
of
the
green
parking
and
a
walk
along
the
sidewalk
toward
the
Park
and
back
Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
samples
at
the
exit
of
Lot
C
and
one
sample
during
the
walk.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature,
relative
humidity,
wind
speed
and
direction
at
the
site.

23.
Underground
parking
garage
(
ME11)

Sample
the
ambient
air
in
the
Colony
Square
underground
parking
garage
(
Peachtree
and
14th
Streets)
for
a
one
hour
from
5:
00
to
6:
00
p.
m.
when
office
workers
leave
the
complex
(
cold
start
emissions).
Sample
at
exit
queue
and
ramps.
Measure
temperature,
humidity
and
ventilation
velocities.

Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
four
SPME
samples
with
each
sampling
period
lasting
15
minutes.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.

24.
Outdoors:
toll
booth
(
ME12)

Make
the
measurement
on
the
northbound
side
of
the
toll
plaza.
Access
to
the
toll
plaza
is
from
the
northbound
direction.
This
is
an
employee
parking
lot
on
the
eastside
of
the
plaza.
The
southbound
lanes
are
accessed
by
an
underground
tunnel.
There
is
an
elevator
down
to
the
tunnel.
Contact
the
John
Leonard,
deputy
director
at
the
Georgia
Department
of
Transportation,
24
hours
prior
to
sampling
(
404/
463­
8766).
On­
site
supervisor
at
the
toll
plaza
is
Robert
Smith.
Clarice
Boone
is
another
on­
site
contact
(
404/
760­
5893).
B­
7
Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
four
SPME
samples
with
each
sampling
period
lasting
15
minutes.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
be
located
on­
site
near
the
toll
plaza
office
building.
Park
the
RV
with
the
generator
exhaust
downwind
relative
to
the
inlet
for
the
CO
monitor.
.

If
time
permits
before
or
after
the
sampling
period
and
sufficient
traffic
exist,
conduct
measurement
of
in­
cabin
exposure
during
one
pass
through
the
toll
plaza.
Collect
one
SPME
sample
during
this
sampling
period.

25.
Trailing
high
emitters
(
ME12)

Attempt
to
trail
high
emitters
in
Atlanta
locations
with
higher
fractions
of
high
emitters.

DAILY
SAMPLING
SCHEDULE
The
daily
schedule
for
the
Atlanta
summer
sampling
program
is
summarized
in
Table
1.
In
order
to
stay
on
project
schedule
as
much
as
possible,
sampling
will
be
conducted
on
weekends
in
case
we
encounter
unsuitable
meteorological
conditions
on
scheduled
sampling
days.
B­
8
Table
1
Daily
Sampling
Schedule
for
Atlanta
No.
ME
Date
DOW
Start
Time
ME
ME
Description
1
10
7/
28/
2002
Sun
1500
outdoor
parking
Turner
Field
after
game,
cold
start
2
7
7/
29/
2002
Mon
700
outdoor
refueling
Racetrak
3
3
7/
29/
2002
Mon
1000
in­
cabin
refueling
QT
4
8
7/
29/
2002
Mon
noon
outdoor,
sidewalk
near
traffic
5
8/
9
7/
29/
2002
Mon
1700
outdoor,
sidewalk/
bus
stop
6
1
7/
30/
2002
Tue
700
congested
freeway
50
minute
sample
0700­
0750
7
5
7/
30/
2002
Tue
810
in­
cabin
toll
plaza
50
minute
sample
0810­
0900
8
13
7/
30/
2002
Tue
noon
surface
Street
highemitter
9
2
7/
30/
2002
Tue
1700
in­
cabin
urban
canyon
10
1
7/
31/
2002
Wed
700
congested
freeway
50
minute
sample
0700­
0750
11
5
7/
31/
2002
Wed
810
in­
cabin
toll
plaza
50
minute
sample
0810­
0900
12
13
7/
31/
2002
Wed
noon
surface
Street
highemitter
13
1
7/
31/
2002
Wed
1700
congested
freeway
14
12
8/
1/
2002
Thu
800
outdoor
toll
plaza
15
11
8/
1/
2002
Thu
1700
outside,
underground
garage
Colony
Square
parking
garage
16
12
8/
2/
2002
Fri
800
outdoor
toll
plaza
17
8
8/
2/
2002
Fri
noon
outdoor,
sidewalk
near
traffic
18
8/
9
8/
2/
2002
Fri
1700
outdoor
sidewalk/
bus
stop
19
10
8/
2/
2002
Fri
2200
Outdoor,
surface
parking
Turner
Field
after
game,
cold
start
20
4
8/
3/
2002
Sat
1000
in­
cabin
parking
garage
Phipps
or
Lennox
mall
21
4
8/
3/
2002
Sat
noon
in­
cabin
parking
garage
Phipps
or
Lennox
mall
22
10
8/
3/
2002
Sat
1500
Outdoor,
surface
parking
Turner
Field
after
game,
cold
start
23
13
8/
3/
2002
Sat
1700
surface
street
highemitter
8/
4/
2002
Sun
24
7
8/
5/
2002
Mon
800
outdoor
refueling
25
8
8/
5/
2002
Mon
noon
outdoor,
sidewalk
near
traffic
26
8/
9
8/
5/
2002
Mon
900
outdoor
sidewalk/
bus
stop
27
2
8/
6/
2002
Tue
700
in­
cabin
urban
canyon
50
minute
sample
0700­
0750
28
5
8/
6/
2002
Tue
810
in­
cabin
toll
plaza
50
minute
sample
0810­
0900
29
3
8/
6/
2002
Tue
1400
in­
cabin
refueling
30
2
8/
6/
2002
Tue
1700
in­
cabin
urgban
canyon
31
12
8/
7/
2002
Wed
800
outdoor,
toll
plaza
northbound
GA400
32
11
8/
7/
2002
Wed
1700
underground
garage
Colony
Square
parking
garage
33
7
8/
8/
2002
Thu
800
outdoor,
refueling
34
3
8/
8/
2002
Thu
noon
in­
cabin
refueling
35
11
8/
8/
2002
Thu
1700
underground
garage
Colony
Square
parking
garage
36
4
8/
9/
2002
Fri
2200
In­
cabin,
parking
garage
Georgia
Dome
parking
garage
after
game
C­
1
APPENDIX
C
Exposure
Protocol
and
Study
Plan
for
the
Section
211(
B)
Tier
2
High
End
Exposure
Screening
Study
of
Baseline
and
Oxygenated
Gasoline
Addendum
C
­
Sampling
Plan
for
Chicago
DRAFT
Prepared
for
AMERICAN
PETROLEUM
INSTITUTE
1220
L
Street
Washington,
DC
20005­
4070
Prepared
by
DESERT
RESEARCH
INSTITUTE
2215
Raggio
Parkway
Reno,
NV
89512
August
21,
2002
C­
2
INTRODUCTION
This
sampling
plan
specifies
the
details
for
the
field
measurement
program
that
will
be
carried
out
in
Chicago,
Il
during
the
summer
of
2002
or
2003
and
winter
2002/
3
as
part
of
a
screening
study
of
the
high­
end
exposures
to
baseline
and
oxygenated
gasoline.
It
specifies
the
measurement
locations
for
the
twelve
categories
of
microenvironments
and
explains
the
selections
with
respect
to
the
objective
of
capturing
the
upper­
end
of
the
distribution
of
exposures
for
each
microenvironment.
This
document
is
an
addendum
to
the
June
13,
2002
Exposure
Protocol
and
Study
Plan,
which
describes
the
proposed
measurement
methods
and
rationale
for
their
selection.

Desert
Research
Institute
personnel
surveyed
potential
microenvironments
in
Chicago
on
August
14­
16,
2002.
The
objectives
of
the
survey
were
to
ascertain
the
suitability
of
sampling
locations
with
respect
to
access
and
potential
for
higher­
end
exposures,
and
to
determine
the
variations
in
air
pollutant
levels
in
several
of
the
microenvironments
with
a
portable
gas
analyzer.
We
visited
the
following
locations:
I­
57
and
I­
94
during
the
morning
commute
period,
urban
canyons
in
downtown
Chicago
(
particularly
under
the
elevated
trains),
Tri­
State
Tollway
((
I­
294)
toll
plazas,
parking
garages
in
downtown
Chicago
(
Millennium,
Monroe
St
and
Grant
Park
underground
garages),
service
stations
(
Gas
City
in
Tinley
Park),
parking
lots
at
United
Center
(
Chicago
Bulls
and
Blackhawks)
and
Comiskey
Park
(
White
Sox),
and
three
centralized
vehicle
inspection
stations
(#
14,
27
and
28).
A
RAE
Systems
Model
PGM­
7240
(
ppbRAE)
portable
PID
monitor
and
Langan
Products
Inc.
T15d
were
used
to
continuously
monitor
ambient
VOC
and
CO
levels,
respectively,
in
several
of
the
microenvironments.
For
the
purposes
of
the
survey
of
microenvironments
in
Chicago,
the
PID
detector
was
used
to
measure
relative
variations
rather
than
absolute
VOC
levels.

The
location
of
the
mobile
laboratory
is
a
significant
logistical
consideration
in
the
selection
of
some
of
the
microenvironments.
Accordingly,
selecting
a
base
of
operations
for
the
mobile
laboratory
was
the
initial
task
during
the
survey
trip.
A
suitable
RV
park
is
located
in
Tinley
Park
(
Windy
City
Campground
at
18701
South
80th
Avenue),
which
is
about
20
miles
southeast
of
Downtown
Chicago.
Our
search
for
some
microenvironments
such
as
service
stations,
vehicle
inspection
stations,
and
congested
freeway
was
focused
in
this
general
area.

DESCRIPTIONS
OF
MICROENVIRONMENTS
(
ME)
AND
PROPOSED
SAMPLING
PROTOCOL
26.
In
vehicle:
commuter
rush
hour
in
stop­
and­
go
traffic
(
ME1)

Begin
the
run
at
0700
in
South
Chicago
near
the
I­
57
and
I­
94
interchange
and
drive
north
on
I­
94
towards
Downtown
Chicago.
The
ten
miles
to
the
I­
290
(
Eisenhower
Expressway)
and
I­
94
interchange
will
take
roughly
30
minutes.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
the
first
30
minutes
of
the
run.
Continue
north
on
I­
94
and
turn
around
about
5
miles
north
of
the
I­
290
and
I­
94
interchange.
Reenter
the
I­
94
going
south
and
exit
the
freeway
after
the
second
30
minutes.
This
stretch
of
freeway
includes
a
series
of
overpasses,
with
the
longest
about
a
quarter
of
a
mile.
Use
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
C­
3
during
winter)
during
the
second
30
minutes
Maintain
a
safe
following
distance,
about
one
car
length
(
15
feet)
per
10
mph
speed,
closing
to
within
3
feet
during
stopped
conditions.
Use
the
middle
lane
and
do
not
follow
the
same
vehicle
for
more
than
two
minutes.
Attempt
to
get
behind
at
least
one
high­
emitter
during
each
of
the
two
ventilation
conditions
Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
API
CO
analyzer,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
period
during
the
high
ventilation
condition
and
one
15­
minute
period
during
the
midpoint
of
the
low
ventilation
condition.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
The
effect
of
high
and
low
ventilation
conditions
will
be
normalized
to
the
PID
data.
Monitor
and
record
the
van's
position
(
GPS),
and
in­
cabin
temperature
and
relative
humidity.
Relevant
data
collected
by
the
Illinois
EPA
include
CO
and
meteorological
data
at
the
CTA
Building
monitoring
station
at
320
S.
Franklin.

27.
In
vehicle:
urban
street
canyons
(
ME2)

Make
multiple
trips
during
a
one­
hour
period
along
a
surface­
street
loop
in
downtown
Chicago
bordered
by
Lake
Street,
Wabash
Avenue,
Van
Buren
Street,
and
State
Street
(
four
right
turns).
The
elevated
train
covers
three
sides
of
this
loop.
Make
the
measurements
during
either
the
morning
commute
period
from
0700
to
0800
or
evening
commute
period
from
1700
to
1800.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
first
30
minutes
and
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
during
winter)
during
second
30
minutes.
Drive
at
or
near
the
end
of
a
pack
of
vehicles
at
stoplights
as
much
as
possible
and
attempt
to
get
behind
at
least
one
high­
emitter
during
each
of
the
two
ventilation
conditions.

Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
API
CO
analyzer,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
samples
during
the
high
ventilation
condition
and
one
15­
minute
sample
during
the
midpoint
of
the
low
ventilation
condition.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
van's
position
(
GPS),
and
in­
cabin
temperature
and
relative
humidity.

28.
In
vehicle:
refueling
(
ME3)

Sample
for
one
hour
at
the
Gas
City
(
80th
Avenue
just
north
of
I­
80)
or
Speedway
(
Harlem
Avenue
just
north
of
I­
80)
service
stations
in
Tinley
Park.
Conduct
sampling
during
the
peak
or
near­
peak
refueling
periods
for
the
station
as
indicated
by
service
station
personnel.

Park
the
sampling
van
at
the
center
downwind
pump
of
the
center
pump
station
island
and
sample
alternate
30­
minute
periods
under
high
and
low
ventilation.
Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
API
CO
analyzer
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
samples
during
C­
4
the
high
ventilation
sampling
period
and
one
15­
minute
sample
at
the
midpoint
of
the
low
ventilation
sampling
period.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
in­
cabin
temperature,
relative
humidity,
and
wind
speed.
Note
the
number
of
gallons
dispensed.

29.
In
vehicle:
parking
garage
(
ME4)

Drive
within
a
parking
garage
for
one
hour.
Use
high
ventilation
conditions
(
window
and
vent
open,
AC
on
during
summer
and
heater
on
during
winter)
during
first
30
minutes
and
low
ventilation
(
windows
and
vent
closed,
AC
on
during
summer
and
heater
on
during
winter)
during
second
30
minutes.
Potential
garages
include
Millennium,
Monroe
Street,
or
Grant
Park
underground
parking
garages
in
Downtown
Chicago.
Millennium
and
Monroe
Street
garages
use
the
same
access.
Millennium
is
to
the
left
after
entering
the
underground
garage
complex,
and
the
Monroe
Street
garage
is
to
the
right.
Millennium
is
closer
to
the
downtown
office
building
and
has
many
more
parked
cars
than
the
Monroe
St
garage,
which
is
located
closer
to
the
Michigan
Lake
shoreline.
Monroe
St.
garage
was
mostly
empty
during
the
weekday,
but
may
see
for
use
during
the
weekends.
Grant
Park
garage
was
nearly
full
and
appears
to
have
high
fraction
of
commuters.
Park
adjacent
to
the
northbound
pay
station.
We
observed
150
to
500
ppbC
on
PID
and
8
to
26
ppm
CO
at
this
location
during
the
1700
to
1800
period.

Sample
in­
cabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
15­
minute
samples
during
the
high
ventilation
condition
and
one
sample
during
the
first
15
minutes
of
the
low
ventilation
condition.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
incabin
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.

30.
In
vehicle:
toll
plaza
(
ME5)

Sample
during
the
morning
commute
period
between
0700
and
0800
on
tollways
with
high
traffic
volume
and
higher
fraction
of
time
spent
at
toll
plazas
(
e.
g.,
exit
with
ramps
in
both
directions
within
short
distances
before
and
after
the
toll
plaza).
Potential
plazas
include
82nd
Street
(
southbound)/
83rd
Street
(
northbound)
and
Cermak
Road
(
all
traffic)
on
the
Tri­
State
Tollway
(
I­
294)
and
the
York
Road
(
all
traffic)
on
the
East­
West
Tollway
(
I­
88).
Sample
incabin
air
at
driver's
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
API
CO
analyzer,
and
Alpha
Omega
HCHO
analyzer
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
one
15­
minute
samples
each
during
midpoint
of
the
high
ventilation
and
the
midpoint
of
the
low
ventilation
sampling
period,
and
one
sample
during
time
spent
in
the
queue.
Sample
the
outside
air
with
a
portable
PID
monitor
during
the
entire
hour
without
compromising
the
ventilation
condition
in
the
cabin.
Monitor
and
record
the
van's
position
(
GPS),
and
in­
cabin
temperature
and
relative
humidity.
C­
5
31.
In
vehicle:
tunnel
(
ME6)

There
are
no
tunnels
in
Chicago.
There
are
freeway
overpasses
(
see
#
1).

32.
Outdoor:
refueling
vehicle
(
ME7)

Sample
for
one
hour
at
the
Gas
City
(
80th
Avenue
just
north
of
I­
80)
or
Speedway
(
Harlem
Avenue
just
north
of
I­
80)
service
stations
in
Tinley
Park.
Conduct
sampling
during
the
peak
or
near­
peak
refueling
periods
for
the
station
as
indicated
by
service
station
personnel.

Park
the
van
downwind
from
the
centroid
of
the
pump
locations.
With
sampling
inlet
in
the
breathing
zone,
refuel
the
vehicle
over
a
1
to
2
minute
active
refueling
period.
During
refueling,
maintain
manual
control
of
the
nozzle
and
stand
downwind
of
the
vehicle
fuel
tank
inlet.
Ask
to
refuel
other
vehicles
on
the
other
side
of
the
pump
island
as
the
opportunity
arises
or
stand
as
close
as
possible
to
the
person
refueling
the
vehicle.
Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples
during
three
separate
active
refueling
periods.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature,
relative
humidity,
and
wind
speed.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.
Note
the
number
of
gallons
of
fuel
dispensed.
Urine
samples
are
also
collected
for
this
microenvironment
in
accordance
with
the
study
protocol.

33.
Outdoor:
sidewalk
near
high­
density
traffic
(
ME8)

Conduct
sidewalk
sampling
in
downtown
Chicago
along
the
city
block
bordered
by
Monroe
Street,
Wabash
Avenue,
Adams
Street,
and
State
Street.
Sampling
should
be
conducted
during
the
morning
periods
and
during
the
noon
hour.

Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
samples
during
the
walk
around
the
block
and
one
sample
at
the
covered
section
of
Polk
Street.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature,
relative
humidity,
wind
speed
and
direction.
.

34.
Outdoor:
bus
stop
(
ME9)

Combined
with
ME8.

35.
Outdoor:
stadium
parking
lot
(
ME10)

Sample
for
1
hour
at
the
end
of
a
Chicago
White
Sox
baseball
game
at
Comiskey
Park
during
the
summer
and
after
a
Chicago
Bulls
or
Blackhawks
game
at
the
United
Center.
Because
the
atmosphere
is
more
stable
in
the
evening,
night
games
are
preferable
to
day
games.
Sample
ambient
air
with
a
sampling
cart
for
a
one­
hour
period
at
the
end
of
the
game
with
15­
minute
C­
6
sampling
times
alternating
between
a
downwind
fixed
location
at
the
south
exit
of
the
green
parking
and
a
walk
along
the
sidewalk
toward
the
Park
and
back
Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
three
SPME
samples,
two
samples
at
the
exit
of
Lot
C
and
one
sample
during
the
walk.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature,
relative
humidity,
wind
speed
and
direction
at
the
site.

36.
Underground
parking
garage
(
ME11)

Sample
in
an
underground
parking
garage
for
a
one
hour
from
5:
00
to
6:
00
p.
m.
when
office
workers
leave
the
complex
(
cold
start
emissions).
Sample
at
exit
queue
and
ramps.
Measure
temperature,
humidity
and
ventilation
velocities.
Potential
garages
include
Millennium,
Monroe
Street,
or
Grant
Park
underground
parking
garages
in
Downtown
Chicago.

Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
four
SPME
samples
with
each
sampling
period
lasting
15
minutes.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
remain
at
the
RV
Park
during
these
measurements.

37.
Outdoors:
toll
booth
(
ME12)

Two
possible
locations
for
this
microenvironment
are
toll
booths
on
tollways
or
one
of
the
centralize
vehicle
inspection
stations.
The
vehicle
inspection
station
at
3824
159th
Place
is
reasonably
close
to
the
RV
Park
and
has
good
access.
Sampling
at
the
toll
plaza
would
be
conducted
behind
the
toll
booth
similar
to
arrangement
in
Atlanta.
For
the
vehicle
inspection
station,
we
would
sample
near
the
dynamometers.
We
will
need
to
obtain
permission
from
the
Illinois
EPA
to
conduct
sampling
at
the
inspection
station.

Sample
the
breathing
zone
continuously
with
a
KORE
MS
200,
Langan
T15,
Alpha
Omega
HCHO
analyzer,
and
portable
PID
monitor
and
collect
one
set
of
canister
and
DNPH
samples
integrated
over
the
entire
hour.
Collect
four
SPME
samples
with
each
sampling
period
lasting
15
minutes.
Record
the
ambient
temperature
and
relative
humidity.
Ancillary
data
from
the
mobile
laboratory
include
ambient
CO,
wind
speed
and
direction,
temperature
and
relative
humidity.
The
mobile
laboratory
will
be
located
on­
site
near
the
toll
plaza
office
building.
Park
the
RV
with
the
generator
exhaust
downwind
relative
to
the
inlet
for
the
CO
monitor.
.

If
time
permits
before
or
after
the
sampling
period
and
sufficient
traffic
exist,
conduct
measurement
of
in­
cabin
exposure
during
one
pass
through
the
toll
plaza.
Collect
one
SPME
sample
during
this
sampling
period.

38.
Trailing
high
emitters
(
ME12)

Attempt
to
trail
high
emitters
in
Chicago
locations
with
higher
fractions
of
high
emitters.
C­
7
DAILY
SAMPLING
SCHEDULE
The
daily
schedule
for
the
Chicago
sampling
program
will
be
determined
after
a
decision
has
been
made
to
proceed
with
sampling
in
Chicago.
In
order
to
stay
on
project
schedule
as
much
as
possible,
sampling
will
be
conducted
on
weekends
in
case
we
encounter
unsuitable
meteorological
conditions
on
scheduled
sampling
days.
D­
1
APPENDIX
D
Example
of
a
Diary
Page
D­
2
START
TIME*

AM
PM
STOP
TIME*

AM
PM
A.
ACTIVITY
(
please
specify)

_____________________________________

_____________________________________

_____________________________________

B.
SPECIAL
CONDITIONS
Me
Others
Cooking
with
gas
........................................
01
02
Cooking
with
other
fuel
..............................
03
04
Eating
hot
food
...........................................
05
06
Drinking
alcoholic
beverage.......................
07
08
Cleaning
with
detergents
...........................
09
10
Using
personal
care
products
....................
11
12
Newly­
cut
vegetation/
wood........................
13
14
Solvent
use.................................................
15
16
Gasoline
handling
......................................
17
18
Gasoline­
powered
tool
...............................
19
20
Clothes
recently
dry­
cleaned
.....................
21
22
Other
(
open
flame,
smoke,
odor,
etc.)
...................
23
Specify
condition,
potential
emission
source,

and
proximity
_________________________

_____________________________________

C.
LOCATION
In
transit,
car............................................................
24
In
transit,
other
vehicle............................................
25
Specify
___________________________

Indoors,
residence...................................................
26
Indoors,
garage
.......................................................
27
Indoors,
service
station
...........................................
28
Indoors,
other
..........................................................
29
Specify
___________________________

Outdoors,
within
10
yards
of
road
or
street
........................................................
30
Traffic
count:
________
vehicles/
minute
I
am
__
upwind
__
downwind
of
road.

Outdoors,
other
.......................................................
31
Specify
___________________________

Uncertain
.................................................................
32
D.
SMOKING
I
am
smoking............................................................
33
Others
are
smoking
.................................................
34
No
one
is
smoking
...................................................
35
E.
ONLY
IF
INDOORS
OR
IN
VEHICLE
(
1)
Windows
open?

Yes...........................................................
36
No
............................................................
37
Uncertain
.................................................
38
(
2)
Air
conditioning
on?

Yes...........................................................
39
No
............................................................
40
Uncertain
.................................................
41
F.
ONLY
IF
INDOORS
OR
OUTDOORS
Give
address
or
nearest
intersection:

_____________________________________

_____________________________________

G.
NEAREST
ROAD
(
ALL
LOCATIONS)

Give
route
number
or
street
name
of
nearest
road
and
circle
type:

_____________________________________

_____________________________________

Highway
..................................................................
42
Arterial
road
............................................................
43
Residential
area
......................................................
44
Downtown
street
.....................................................
45
Urban
street
canyon
...............................................
46
Other
........................................................................
47
Specify
___________________________

H.
TOWN
Reno.........................................................................
48
Other
........................................................................
49
Specify
__________________________
