Document ID: EPA-HQ-OPP-2005-0061-0138
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2006-06-09T04:00Z

1
  
31
UNITED
STATES
ENVIRONMENTAL
PROTECTION
AGENCY
WASHINGTON,
D.
C.
20460
OFFICE
OF
PREVENTION,
PESTICIDES
AND
TOXIC
SUBSTANCES
MEMORANDUM
Date:
May
9,
2005
Subj:
Study
Review:
GUTHION
®
50
WP
­
Biological
Monitoring
of
Post­
Application
Workers
During
Manual
Thinning
and
Harvesting
of
Apples
MRID#:
463164­
03
DP
Barcode:
D307558
PC
Code(
s)
:
058001
From:
Steven
Weiss,
Industrial
Hygienist
Health
Effects
Division/
Reregistration
Branch
3
(
7509C)

Through:
Seyed
Tadayon,
Chemist
Health
Effects
Division/
Reregistration
Branch
3
(
7509C)

To:
Catherine
Eiden,
Chief
Health
Effects
Division/
Reregistration
Branch
3
(
7509C)

Attached
is
a
review
of
the
study
entitled,
GUTHION
®
50
WP
­
Biological
Monitoring
of
Post­
Application
Workers
During
Manual
Thinning
and
Harvesting
of
Apples.
A
primary
review
of
the
study
was
performed
by
Versar,
Inc.
under
the
supervision
of
HED.
It
has
undergone
secondary
review
in
HED
and
has
been
revised
to
reflect
Agency
policies.
    
2
  
31
STUDY
TYPE:
Biological
and
breathing
zone
air
monitoring
during
postapplication
activities.

TEST
MATERIAL:
Azinphos­
methyl
SYNONYMS:
GUTHION
®
;
S­(
3,4­
dihydro­
4­
oxobenzo[
d]­[
1,2,3]­
trizin­
3­
ylmethyl)
O,
O­
dimethyl
phosphorodithioate;
O,
O­
dimethyl
S­[(
4­
oxo­
1,2,3­
benzotriazin­
3(
4H)­
yl)
methyl]
phosphorodithioate
CITATION:
Study
Author:
D.
R.
Fischer
Title:
GUTHION
®
50
WP
­
Biological
Monitoring
of
Post­
Application
Workers
During
Manual
Thinning
and
Harvesting
of
Apples
Report
Date:
July
8,
2004
Analytical
Laboratories:
Bayer
CropScience
Environmental
Research
Bayer
Research
Park
17745
South
Metcalf
Avenue
Stilwell,
KS
66085­
9104
Identifying
Codes:
MRID:
463164­
03
Report
No.:
201042
Study
Number:
GU264701
PSI
Number:
RCGUX001
SPONSOR:
Bayer
CropScience
Product
Safety
Management
2
T.
W.
Alexander
Drive
Research
Triangle
Park,
NC
27709
COMPLIANCE:
Signed
and
dated
GLP,
Data
Confidentiality
statements,
and
Quality
Assurance
statements
were
provided
in
the
Study
Report.
The
Study
Report
states
that
it
meets
FIFRA
Good
Laboratory
Practices
40
CFR
part
160
with
the
following
exceptions:
weather
data,
maintenance
chemical
applications,
pesticide
history
data,
irrigation
records,
and
cultural
practices
were
not
collected
under
GLP.
Other
exceptions
included:
(
1)
not
all
data
entries
were
made
promptly,
(
2)
sample
receipt
dates
and
weight
values
were
recorded
into
a
LIMS
system
which
was
not
validated,
(
3)
the
plot
map
within
FieldNotes
was
changed
but
the
original
plot
map
was
not
retained,
and
(
4)
the
bathroom
scale
used
to
weigh
the
workers
was
not
maintained/
calibrated
in
accordance
with
GLP.
The
GLP
statement
also
noted
that
the
storage
containers
of
test
material
were
not
retained
for
the
duration
of
the
study
as
required
due
to
the
nature
of
the
GUTHION
®
50
WP
Solupack
packaging
system.
The
statement
noted
that
none
of
these
exceptions
negatively
impacted
the
integrity
of
the
study.

GUIDELINE
OR
PROTOCOL
FOLLOWED:
The
Bayer
Crop
Science
Protocol
was
provided
in
the
Study
Report,
including
a
list
of
deviations
from
the
protocol.
The
Study
Report
states
that
the
data
requirements
were
U.
S.
EPA
OPPTS
    
3
  
31
Harmonized
Test
Guidelines,
Series
875
Occupational
and
Residential
Exposure.

I.
MATERIALS
AND
METHODS
A.
MATERIALS
Test
Material:

Formulation:
GUTHION
®
50
WP
­
water
soluble
packets
(
GUTHION
®
Solupak)

Lot/
Batch
#
formulation:
3144032
Purity:
The
purity
of
the
batch
was
verified
at
49.91%
azinphos
methyl
with
an
expiration
date
of
April
23,
2005.

CAS
#(
s):
CAS
86­
50­
0
Other
Relevant
Information:
EPA
Reg.
No.
264­
733
Packaging:
The
product
was
supplied
in
bags
containing
the
water
soluble
packets.

B.
STUDY
DESIGN
There
were
3
amendments
to
the
protocol
and
17
deviations
from
the
protocol.

The
amendments
included:
(
1)
Applications
4,
5,
and
6
for
Trial
GU015­
03D
were
incorrectly
referred
to
as
applications
3,
4,
and
5
within
the
Application
Information
Table.
(
2)
The
volume
of
the
urine
subsamples
was
changed
from
25
mL
to
a
minimum
of
50
mL.
(
3)
An
amendment
was
added
to
allow
shipment
of
the
­
3,
­
1,
and
4
day
time
point
duplicate
blood
samples
via
two
different
overnight
express
carriers
to
increase
the
probability
of
safe
receipt
at
the
laboratory
for
cholinesterase
testing
within
the
required
time
from
sample
collection.
Samples
collected
at
the
0
day
time
point
will
be
hand
carried
from
the
sampling
location
to
the
laboratory
by
Bayer
CropScience
personnel,
therefore,
only
one
vial
of
blood
will
be
collected
at
that
event.

The
deviations
included:
(
1)
The
blood
samples
collected
from
the
workers
on
the
day
of
thinning
for
trial
GU016­
03D
were
transported
to
BRP
by
the
Study
Director
on
the
day
after
collection.
(
2)
Other
than
during
actual
thinning
or
actual
harvest,
the
activities
of
the
workers
were
not
recorded
during
the
sample
collection
period
as
required
by
the
protocol.
However,
the
workers
were
sequestered
during
the
sample
collection
period
and
the
activities
were
monitored
so
that
they
did
not
receive
any
exposure
to
other
pesticides.
(
3)
Control
urine
and
blood
samples
were
collected
from
an
extra
worker
for
trial
GU015­
03D
to
    
4
  
31
increase
the
probability
of
having
15
worker
participants
available
for
the
day
of
harvest.
(
4)
FedEx
delivered
the
­
3
day
and
­
1
day
blood
samples
from
trial
GU015­
03D
to
BRP
to
the
laboratory
one
day
late.
The
cold
packs
and
packaging
container
were
sufficient
to
maintain
the
samples
in
a
cool
condition
during
the
time
of
shipment.
(
5)
The
blood
samples
collected
from
the
workers
on
the
day
of
harvest
for
GU015­
03D
were
transported
to
BRP
by
the
Study
Director.
The
blood
samples
collected
from
the
workers
4
days
after
harvest
were
transported
to
BRP
by
the
Grayson
Project
Manager
in
charge
of
the
study.
(
6)
Each
worker
individually
chose
and
wore
clothing
typical
of
what
they
normally
wore
when
working.
Therefore,
this
clothing
may
not
have
necessarily
been
`
single
layer'
as
stated
in
the
protocol
or
`
long
sleeves'
or
`
sleeves
not
rolled
up'
as
stated
in
the
AHETF
Worker
Clothing
Acceptability
Criteria
Document.
(
7)
For
trial
GU015­
03D,
the
first
application
was
made
when
the
majority
of
the
petals
had
fallen
and
not
at
petal
fall.
The
application
timing
was
correct
based
on
what
was
typical
for
the
trial
location.
The
second
application
was
made
at
9
days
(
not
10
days)
after
the
first
application.
(
8)
For
trial
GU015­
03D
and
GU016­
03D,
the
urine
samples
were
maintained
cold
(
but
not
frozen)
using
either
a
cooler
with
frozen
gel
packs,
a
refrigerator
or
a
freezer
during
collection
and
while
subsampling.
The
protocol
specifies
that
a
refrigerator
be
used
for
storage
of
these
urine
samples
during
collection.
(
9)
For
trials
GU015­
03D
and
GU016­
03D,
FieldNotes
did
not
list
all
field
project
personnel.
(
10)
For
trials
GU015­
03D
and
GU016­
03D,
the
date
and
time
that
some
urine
samples
were
transferred
to
the
refrigerators/
freezers/
coolers
used
for
storing
the
workers'
urine
samples
during
collection
was
not
recorded
within
FieldNotes.
For
the
thinning
activity,
the
control
and
fortified
urine
samples
were
not
transferred
to
coolers
right
at
the
beginning
of
urine
collection.
(
11)
For
trial
GU016­
03D,
temperature
records
were
not
maintained
for
the
coolers
used
to
store
the
control
urine
samples.
Occasionally,
the
urine
and
OVS
tube
sample
storage
temperatures
were
not
within
what
would
be
considered
normal
refrigerator
or
freezer
temperature
ranges.
(
12)
For
trial
GU016­
03D,
some
FieldNote
update
transfers
were
sent
more
than
7
days
after
critical
events
and
the
final
notebook
was
sent
more
than
30
days
after
final
sample
shipment.
(
13)
For
trial
GU016­
03D,
the
spray
volume
for
the
first
application
was
higher
than
the
spray
volume
calculated
using
estimated
tree
dimensions
and
a
factor
to
convert
the
tree
volume
to
a
recommended
spray
volume.
However,
this
spray
volume
did
not
initiate
drip.
(
14)
For
trial
GU016­
03D,
during
thinning,
subjects
worked
from
6:
30
AM
to
2:
30
PM
and
the
pumps
for
the
field
control
and
fortified
OVS
tubes
were
run
from
7:
14
AM
to
4:
15
pm
or
later.
During
the
harvest
event,
the
subjects
worked
from
6:
45
AM
to
3PM,
while
the
pumps
for
the
field
control
and
fortified
OVS
tubes
were
run
from
7:
35
AM
to
3
PM.
(
15)
For
trial
GU016­
03D,
the
second
set
of
duplicate
blood
samples
was
discarded
after
successful
receipt
and
analysis
of
the
first
set
of
duplicate
blood
samples.
(
16)
For
trial
GU016­
03D,
documentation
of
the
workers
not
having
been
exposed
to
organophosphate
and
carbamate
chemicals
for
at
least
10
days
prior
to
the
reentry
activity
was
not
available
for
every
worker.
(
17)
For
trial
GU015­
03D,
the
refrigerator
used
during
the
collection
of
the
24­
hour
composite
urine
samples
for
two
of
the
workers
(
Reps
6
and
7)
did
not
operate
properly.
Therefore,
the
urine
samples
collected
from
these
individuals
were
not
maintained
in
a
cool
condition
over
the
24
hour
collection
period
as
required
in
the
protocol.
The
effect
on
the
study
is
not
known.
Except
for
deviation
#
17,
these
deviations
from
the
protocol
were
reported
to
not
have
any
adverse
effects
on
the
study.
The
effect
of
deviation
#
17
on
the
study
is
not
known.
    
5
  
31
1.
Test
Site:

The
test
sites
were
located
in
North
Rose,
New
York
(
EPA
Region
1)
and
in
Tygh
Valley,
Oregon
(
EPA
Region
11).

New
York:
At
the
New
York
site,
6.5
acres
of
apple
trees
(
Ida
Red
variety)
were
dedicated
to
the
reentry
monitoring
activity
of
harvesting.
The
distance
between
rows
within
the
test
plot
was
20
feet
and
the
distance
between
trees
within
a
row
was
25
feet.
No
organophosphate
or
carbamate
pesticides
were
used
as
maintenance
chemicals
during
the
current
growing
season.
Typical
cultural
and
irrigation
practices
were
employed
at
the
site.

Oregon:
At
the
Oregon
site,
10.1
acres
of
apple
trees
(
Granny
Smith
variety)
were
dedicated
to
the
reentry
monitoring
activities
of
thinning
and
harvesting.
The
distance
between
rows
within
the
test
plot
was
16
feet
and
the
distance
between
trees
within
a
row
was
8
feet.
No
organophosphate
or
carbamate
pesticides
were
used
as
maintenance
chemicals
for
at
least
45
days
prior
to
reentry
activities
of
apple
thinning
and
harvest.
Typical
cultural
and
irrigation
practices
were
employed
at
the
site.

2.
Meteorology:
Meteorological
conditions,
including
air
temperature,
wind
speed,
wind
direction,
percent
cloud
cover,
and
rainfall
within
24
hours
of
application
were
recorded
for
each
application
event.
Additionally,
the
Study
Report
provided
the
rainfall
amount
between
the
first
application
and
the
reentry
activities.
The
meteorological
information
is
provided
in
Table
1.

Table
1.
Meteorological
Conditions
During
Application
Application
No.
Air
Temperatu
re
(
°
°
F)
Wind
Speed
(
mph)
Wind
Direction
Percent
Cloud
Cover
Rainfall
Within
24
Hours
of
Application
(
inches)
Total
Rainfall
from
1st
application
to
reentry
activity
(
inches)
Total
Irrigation
from
1st
application
to
reentry
activity
(
inches)

New
York
Site
1
62
0
NA
90
None
2
56
2
to
4
SW
30
None
3
66
2
to
4
NW
30
None
4
73
0
NA
30
None
5
60
0
NA
0
None
6
61
0
NA
0
None
11.44
None
Oregon
Site
1
63
0
to
10
SW
100
None
2
85
0
to
3
SW
0
None
3
64
0
to
5
N
50
None
0.02
(
thinning)
0.78
(
harvest)
2
(
thinning)
11
(
harvest)

3.
Number
and
type
of
workers:

New
York:
15
male
workers
were
monitored
for
harvesting
apples.
The
Study
Report
stated
that
all
    
6
  
31
participants
were
experienced
agricultural
workers
who
had
recently
been
working
in
vineyards.
The
Study
Report
also
stated
that
the
workers
were
not
exposed
to
azinphos­
methyl
or
any
other
organophosphate
or
carbamate
chemicals
for
at
least
10
days
prior
to
harvest.
The
workers
ranged
in
age
from
19
years
to
69
years.
The
weight
of
the
workers
ranged
from
55.8
kg
to
102
kg.
The
workers'
years
of
experience
performing
agricultural
work
ranged
from
1
to
24.

To
increase
the
probability
of
15
workers
being
available
for
participation
in
the
reentry
activity,
the
trial
was
initiated
with
16
workers.
The
spare
worker
(#
3)
was
not
needed
and
released
from
the
study
just
prior
to
the
start
of
harvest.

Oregon:
15
male
workers
were
monitored
for
apple
thinning
and
a
second
set
group
of
15
male
workers
were
monitored
for
apple
harvesting.
The
Study
Report
stated
that
all
participants
were
experienced
agricultural
workers
who
had
recently
been
picking
strawberries
(
apple
thinning
workers)
or
hops
(
apple
harvesting
workers).
The
Study
Report
also
stated
that
the
workers
were
not
exposed
to
azinphos­
methyl
or
any
other
organophosphate
or
carbamate
chemicals
for
at
least
10
days
prior
to
harvest.
However,
a
protocol
deviation
also
states
that
documentation
of
the
workers
not
having
been
exposed
to
organophosphate
and
carbamate
chemicals
for
at
least
10
days
prior
to
the
reentry
activity
was
not
available
for
every
worker.
For
the
apple
thinning
workers,
their
ages
ranged
from
24
years
to
37
years,
their
weights
ranged
from
60.3
kg
to
88.9
kg,
and
their
years
of
experience
performing
agricultural
work
ranged
from
9
to
30.
For
the
apple
harvesting
workers,
their
ages
ranged
from
26
years
to
39
years,
their
weights
ranged
from
59.9
kg
to
83.0
kg,
and
their
years
of
experience
performing
agricultural
work
ranged
from
1
to
10.

4.
Replicates:

Thinning:
Worker
exposure
during
thinning
activities
was
monitored
at
the
Oregon
site.
The
monitoring
took
place
14
days
after
the
first
application
of
the
test
substance.
The
workers
thinned
apples
by
hand
from
the
designated
trees
in
the
treated
plot
for
approximately
8
hours
(
including
breaks).
The
workers
entered
the
plot
at
6:
30
AM,
took
a
40
minute
lunch
break
and
a
20
minute
morning
break,
and
ended
the
work
day
at
2:
30
PM.

During
the
thinning
activity,
each
worker
picked
and
discarded
the
unwanted
and
excess
fruit
onto
the
ground.

Table
11
of
the
Study
Report
provides
observations
of
the
workers
recorded
during
the
study.

Harvesting.:
Worker
exposure
during
hand
harvesting
activities
was
monitored
at
the
New
York
and
Oregon
sites.
The
monitoring
took
place
14
days
after
the
last
application
of
the
test
substance.
The
workers
harvested
apples
from
the
designated
trees
in
the
treated
plot
for
8
hours
(
including
breaks).
At
the
New
York
site
,
the
workers
entered
the
plot
at
7:
10
AM,
took
a
40
minute
lunch
break
and
a
20
minute
morning
break,
and
ended
the
work
day
at
3:
10
PM.
At
the
Oregon
site,
the
workers
entered
the
plot
at
6:
54
AM,
took
a
30
to
40
min
lunch
break
and
20
min
morning
break,
and
ended
the
work
day
at
3:
00
PM.

During
the
manual
harvesting
activity,
each
worker
placed
the
harvested
fruit
directly
into
    
7
  
31
individual
commercial
harvesting
bags
supplied
by
the
grower.
The
harvesting
bag
was
positioned
on
the
front
side
of
the
worker
with
straps
fitted
over
the
worker's
shoulders
to
hold
the
bag
in
place.
When
the
bag
was
full,
the
contents
were
transferred
to
a
wooden
bin
by
releasing
the
ties
that
secured
the
bottom
of
the
bag
shut
and
gently
allowing
the
fruit
to
pass
through
the
bottom
of
the
bag.

Tables
10
and
12
of
the
Study
Report
provide
observations
of
the
workers
recorded
during
the
study.

5.
Protective
clothing:
The
Study
Report
stated
that
the
workers
wore
clothing
typical
of
what
they
would
normally
wear
when
performing
agricultural
work.
The
workers
clothing
is
listed
in
Tables
10,
11
and
12
of
the
Study
Report,
and
typically
included
long
sleeve
shirts
and
long
pants.
Three
workers
wore
short
sleeve
or
sleeveless
shirts
and
a
seven
workers
wore
a
t­
shirt
underneath
their
long
sleeve
shirt.
Each
worker
wore
a
painters
hat
provided
by
the
Principle
Field
Investigator.
No
personal
protective
equipment,
including
gloves,
was
worn
by
the
workers
during
any
of
the
reentry
activities.

6.
Application
Method
and
Rate:

Application
rate(
s):
The
application
rate
listed
on
the
current
product
label
for
apples
is
1
to
1.5
lb
ai/
A/
application;
however,
applications
made
at
rates
above
1
lb
ai/
A
can
only
be
made
in
conjunction
with
an
Integrated
Pest
Management
(
IPM)
program.
Additionally,
the
label
states
that
up
to
4
lb
ai/
A/
season
can
be
applied,
with
a
minimum
of
7
days
between
applications.
According
to
the
Study
Report,
application
rates
for
this
study
were
chosen
to
reflect
agricultural
practices
within
key
apple
growing
regions
within
the
U.
S.

At
both
sites,
the
chosen
target
application
rates
were
adjusted
based
on
the
actual
tree
size
at
the
trial
site
using
the
tree
row
volume
concept.
The
following
equation
was
used
to
calculate
the
amount
of
test
substance
needed
for
each
application
for
a
given
tree
size:

Calculated
application
rate
(
lb
ai/
A)
=
Tree
volume
(
GPA)
x
target
application
rate
(
lb
ai/
A)
Reference
application
volume
(
400
GPA)

Where
tree
volume
(
GPA)
=
volume
of
water
required
to
produce
full
coverage
and
initiate
drip.
This
number
can
be
calculated
as
shown
in
Example
3
Appendix
1
of
the
Study
Report;
or
an
"
infield
determination
can
be
made.

New
York:
Actual
application
rates
ranged
from
0.274
to
0.277
lb
ai/
A.
Six
foliar
airblast
spray
applications
were
made
to
apple
trees
at
a
target
rate
of
0.5
lb
ai/
A/
application
based
on
a
standard
of
400
gallons
of
dilute
spray
per
acre
for
large
trees.
The
calculated
target
application
rate
was
0.275
lb
ai/
A/
application,
based
on
tree
row
volume
concept
described
above
and
actual
application
rates
ranged
from
0.274
to
0.277
lb
ai/
A.

Oregon:
Actual
application
rates
ranged
from
0.471
to
0.479
lb
ai/
A.
Three
foliar
airblast
spray
applications
were
made
to
apple
trees
at
a
target
rate
of
1.0
lb
ai/
A/
application
based
on
a
standard
of
400
gallons
of
dilute
spray
per
acre
for
large
trees.
The
calculated
target
application
    
8
  
31
rate
was
0.47
lb
ai/
A/
application,
based
on
tree
row
volume
concept
described
above
and
actual
application
rates
ranged
from
0.471
to
0.479
lb
ai/
A.

Application
Regime:
According
to
the
current
label,
the
minimum
application
interval
is
7
days.
Application
intervals
used
in
this
study
are
presented
below.

New
York:
Six
applications
were
made
to
the
site
with
10
day
application
intervals
between
the
first
three
and
last
three
applications,
and
a
53
day
application
interval
between
the
third
and
fourth
applications.
The
first
application
occurred
on
May
28,
2003;
the
second
application
occurred
on
June
06,
2003;
the
third
application
occurred
on
June
16,
2003;
the
fourth
application
occurred
on
August
8,
2003;
the
fifth
application
occurred
on
August
18,
2003;
and
the
last
application
occurred
on
August
28,
2003.

Oregon:
Three
applications
were
made
to
the
site
with
a
15
day
application
interval
between
the
first
and
second
applications
and
a
76
day
application
interval
between
the
second
and
third
applications.
The
first
application
occurred
on
June
19,
2003;
the
second
application
occurred
on
July
4,
2003;
and
the
last
application
occurred
on
September
18,
2003.

Application
Equipment:

New
York:
The
test
product
was
applied
to
the
apple
trees
using
a
Durand­
Wayland
airblast
sprayer.

Oregon:
The
test
product
was
applied
to
the
apple
trees
using
a
Pul­
Blast
airblast
sprayer.

Spray
Volume:
New
York:
The
actual
spray
volumes
ranged
from
55
to
62
GPA.

Oregon:
The
actual
spray
volumes
ranged
from
90
to
225
GPA.

Equipment
Calibration:
The
authors
reported
that
the
sprayers
were
calibrated
prior
to
the
application.

7.
Exposure
monitoring
methodology:

Urine
Samples
Total
urine
output
was
collected
from
each
worker
during
each
24­
hour
period
starting
1
day
prior
to
reentry
through
4
days
after
reentry.
Day
­
1
samples
were
those
collected
starting
after
the
first
void
of
the
bladder
in
the
morning
on
the
day
prior
to
reentry
and
ending
after
the
first
void
on
the
day
of
reentry.
Day
0
samples
were
those
collected
during
the
24­
hour
period
starting
when
the
workers
began
the
reentry
activities.
Samples
were
collected
in
individually
labeled
4­
L
Urisafe
®
bulk
containers.
Samples
were
kept
in
coolers,
freezers,
or
refrigerators
during
the
24­
    
9
  
31
hour
collection.
After
collection
of
each
24­
hour
bulk
sample,
the
total
volume
of
each
sample
was
recorded.
The
samples
were
mixed
by
shaking,
and
duplicate
25­
mL
aliquots
were
transferred
to
90­
mL
urine
specimen
containers.
The
bulk
samples
and
aliquots
were
kept
frozen
and
the
aliquots
were
shipped
frozen
to
Bayer
Research
Park.
The
bulk
samples
were
kept
frozen
until
notification
by
Bayer,
at
which
time
they
were
discarded.

Blood
Samples
Blood
samples
were
collected
from
each
worker
at
the
following
time
intervals:
(
1)
3
days
prior
to
reentry,
(
2)
1
day
prior
to
reentry;
and
(
3)
on
the
day
of
reentry
after
a
full
work
day,
and
(
4)
4
days
following
reentry.
The
control
samples
collected
3
days
and
1
day
prior
to
the
reentry
activity
for
each
worker
were
used
to
establish
baseline
cholinesterase
activity.
The
samples
were
collected
into
individually
labeled
collection
tubes
containing
EDTA
K3
as
an
additive.
Prior
to
sample
collection,
the
skin
was
thoroughly
cleaned
to
eliminate
possible
contamination
of
pesticide
residue
that
may
have
been
on
the
skin.
Blood
samples
were
packaged
in
compliance
with
International
Air
Transport
Association
Packaging
Instructions
650
and
were
maintained
cool
during
transport
in
a
styrofoam
cooler
containing
frozen
gel
packs.
Samples
were
shipped
or
hand
delivered
to
Bayer
Research
Park
on
either
the
day
of
collection
or
the
following
day.

Breathing
Zone
Air
Samples
Breathing
zone
air
samples
were
collected
using
OVS
tubes
containing
XAD­
2
sorbent
and
a
personal
air­
sampling
pump
attached
to
the
worker's
belt.
The
OVS
tubes
consisted
of
a
glass
fiber
filter,
secured
with
a
Teflon
®
holding
ring,
covering
a
270
mg
layer
of
XAD­
2
sorbent
in
the
top,
primary
bed
and
a
140
mg
layer
of
XAD­
2
sorbent
in
the
bottom,
backup
bed.
The
OVS
tube
was
connected
to
the
pump
using
Tygon
®
tubing
and
clipped
onto
the
worker's
outer
clothing,
with
the
inlet
positioned
in
the
breathing
zone
of
the
worker.
The
air
samples
were
collected
by
operating
the
pumps
over
the
entire
workday
(
including
breaks).
Just
prior
to
monitoring
the
reentry
activity,
the
air
sampling
pumps
were
calibrated
at
a
rate
of
approximately
2
L/
min.
The
pump
flow
rates
were
collected
before
and
after
the
monitoring
period
and
the
pumps
were
checked
throughout
the
monitoring
period
to
ensure
continual
operation.
At
the
end
of
the
work
day,
the
OVS
tube
was
disconnected
and
caps
were
fitted
onto
the
ends.
A
label
was
placed
on
the
tube,
which
was
placed
into
a
pre­
labeled
plastic
bag.
The
samples
were
stored
and
then
shipped
frozen
to
Bayer
Research
Park.

C.
ANALYTICAL
METHODOLOGY:

1.
Sample
Extraction/
Detection:

Urine
Samples
Extraction
method:
0.100
mL
of
[
2H3]
MSMB
internal
standard
solution
(
0.300
µ
g/
mL)
was
added
to
a
10
mL
aliquot
of
urine.
The
sample
was
added
to
a
10
mL
Chem
Elut
cartridge
and
the
cartridge
was
eluted
with
three
20
mL
portions
of
methylene
chloride
into
a
60
mL
vial.
A
TurboVap
was
used
to
evaporate
the
methylene
chloride
at
35C
for
45
minutes.
The
residue
was
dissolved
in
0.10
mL
of
methanol,
a
0.9
mL
aliquot
of
0.1%
formic
acid
was
added
and
the
sample
was
mixed.
An
aliquot
of
the
sample
was
then
analyzed
using
high
pressure
liquid
chromatography­
triple
stage
quadrupole
mass
spectrometry.
    
10
  
31
The
method
for
urine
creatinine
analysis
was
reported
to
be
based
on
the
Jaffe/
Alkaline
Picrate/
Kinetic
method.

Detection
methods:
See
Table
2
Table
2.
Summary
of
HPLC
and
MS
Conditions
for
Urine
HPLC
Conditions
GC
Column:
Zorbax
SB
Aq,
5
µ
m,
50
mm
x
2.1
mm
Solvents:
0.1%
aqueous
formic
acid
(
solvent
A)
and
methanol
(
solvent
B)
Solvent
Program:
Time
(
min)
Solvent
A(%)
Solvent
B(%)
Flow
(
mL/
min)
Initial
68
32
0.200
2.5
68
32
0.200
2.85
15
85
0.200
2.90
68
32
0.300
5.00
68
32
0.300
5.05
68
32
0.200
Injection
Volume:
Autosampler
with
a
20
µ
L
loop
MS
Conditions
Collision
cell
pressure:
1.5
mTorr
Spray
Voltage:
1900
kV
Capillary
temperature:
390C
Sheath:
90
psi
Auxilary
gas:
20
Ionization
mode:
Positive
ion
Divert
valve:
On
from
0.60
minutes
to
2.60
minutes
(
HPLC
effluent
enters
the
LC/
MS)

Instrument
performance
and
calibration:
Calibration
curves
were
prepared
for
each
calibration
run.
The
relative
response
of
the
detector
in
the
lc/
ms­
ms
chromatographic
system
to
MSMB
in
solvent
was
linear
over
the
range
of
0.05
ng/
mL
to
10
ng/
mL.
The
correlation
of
coefficients
were
all
>
99%.
The
limit
of
quantitation
for
urine
samples
was
reported
to
be
0.10
ng/
mL
of
MSMB.
The
limit
of
detection
for
the
urine
samples
was
reported
to
be
0.08
ng/
mL.

Quantification:
The
MSMB
residue
level
in
urine
was
determined
by
comparing
the
LC/
MS
measurement
of
MSMB
to
the
measurement
of
the
MSMB
internal
standard.

Blood
Samples
Extraction/
Detection
method:
Blood
samples
were
analyzed
for
plasma
and
red
blood
cell
cholinesterase
activity.
The
method
was
reported
to
be
a
modification
of
the
method
described
by
Ellman
(
Ellman,
M.
L.,
K.
D.
Cortney,
V.
Andres,
and
R.
M.
Featherston.
1961.
A
New
and
Rapid
Colorimetric
Determination
of
Acetylcholinesterase
Activity.
Biochemical
Pharmocology
7:
88­
95).

Breathing
Zone
Air
Samples
    
11
  
31
Extraction
method:
The
top
and
bottom
sections
of
the
OVS
tubes
were
analyzed
separately.
The
top
portion
of
the
OVS
tube
(
including
the
Teflon
®
ring,
filter,
upper
layer
of
XAD­
2
resin,
and
the
upper
foam
ring)
was
disassembled
and
placed
into
a
labelled
40
mL
vial.
The
bottom
portion
of
the
OVS
tube
(
lower
layer
of
XAD­
2
resin
and
lower
foam
plug)
was
disassembled
and
placed
into
a
separate,
labeled
40
mL
vial.
Each
sample
received
10
mL
of
acetonitrile
and
0.100
mL
of
an
internal
standard
solution,
which
contained
a
mixture
of
[
2H6]
azinphos­
methyl
(
10.0
µ
g/
mL)
and
[
2H6]
azinphos­
methyl
oxon
(
2.0
µ
g/
mL).
Each
sample
was
then
sonicated
for
2
minutes
and
a
0.25
mL
aliquot
was
removed
and
diluted
with
0.75
mL
of
water.
The
diluted
samples
were
analyzed
by
high
pressure
liquid
chromatography­
triple
stage
quadrupole
mass
spectrometry.

Detection
methods:
See
Table
3
Table
3.
Summary
of
HPLC
and
MS
Conditions
for
Breathing
Zone
Air
Samples
HPLC
Conditions
GC
Column
Xterra
MS
C18,
3.5
µ
m,
50
mm
x
4.6
mm
Solvents
0.1%
aqueous
formic
acid
(
solvent
A)
and
methanol
(
solvent
B)
Solvent
Program
Isocratic
at
38%
Solvent
A
and
62%
Solvent
B
Flow
Rate
1.00
mL/
min
Injection
Volume
Autosampler
with
a
20
µ
L
loop
MS
Conditions
Instrument
Setup
LC­
MS/
MS
with
electrospray
interface
and
1:
4
split
Collision
cell
pressure
1.5
m
Torr
Spray
voltage
5.900
kV
Capillary
temperature
235C
Sheath
gas
100
psi
Auxiliary
gas
30
Ionization
mode
Positive
ion
Divert
valve
On
from
0.5
min
to
2.50
min
(
HPLC
effluent
enters
LC/
MS)

Instrument
performance
and
calibration:
Calibration
curves
were
prepared
for
each
calibration
run.
The
relative
response
of
the
detector
in
the
lc/
ms­
ms
chromatographic
system
to
MSMB
in
solvent
was
linear
over
the
range
of
30
ng
to
30,000
ng.
The
correlation
of
coefficients
were
all
>
99%.
The
limit
of
quantitation
for
both
azinphos­
methyl
and
azinphos­
methyl
oxon
was
reported
to
be
100
ng.
The
limit
of
detection
for
azinphos­
methyl
and
azinphos­
methyl
oxon
were
reported
as
5
ng
and
9
ng,
respectively.

Quantification:
The
azinphos­
methyl
or
azinphos­
methyl
oxon
residue
level
in
air
samples
was
determined
by
comparing
the
LC/
MS
measurement
of
azinphos­
methyl
or
azinphos­
methyl
oxon
to
the
measurement
of
the
azinphos­
methyl
or
azinphos­
methyl
oxon
internal
standard.
    
12
  
31
2.
Quality
Control:

Lab
Recovery:
Concurrent
laboratory
recoveries
were
performed
for
both
urine
and
breathing
zone
air
samples.
Urine
samples
were
fortified
at
the
0.50
ng/
mL
level
and
OVS
tubes
were
fortified
at
the
500
ng
level.
The
results
provided
in
the
Study
Report
were
verified
and
these
are
presented
in
Tables
4
and
5.

Table
4.
Urine
Sample
Concurrent
Laboratory
Recoveries
a
Sample
No.
Fortificati
on
Level
(
ng/
mL)
Measure
d
residue
(
ng/
mL)
Average
Blank
Sample
Residue
(
ng/
mL)
Corrected
residueb
(
ng/
mL)
Recovery
(%)
Average
Percent
Recovery
(%)

TRIAL
GU015­
03D
(
NEW
YORK)­
HARVESTING
0.5
0.591
0.5355
107
GUO15­
03D­
1H
0.5
0.514
0.0555
0.4585
92
99
0.5
0.495
0.426
85
GUO15­
03D+
0H
0.5
0.515
0.069
0.446
89
87
0.5
0.506
0.08
0.426
85
GUO15­
03D+
1H
0.5
0.515
0.435
87
86
0.5
0.533
0.054
0.479
96
GUO15­
03D+
2H
0.5
0.513
0.459
92
94
0.5
0.53
0.09
0.441
88
GUO15­
03D+
3H
0.5
0.511
0.422
84
86
0.5
0.526
0.079
0.448
90
GUO15­
03D+
4H
0.5
0.511
0.433
87
88
TRIAL
GU016­
03D
(
OREGON)
­
HARVESTING
0.5
0.511
0.061
0.451
90
GUO16­
03D­
1H
0.5
0.518
0.458
92
91
0.5
0.462
0.014
0.448
90
GUO16­
03D+
0H
0.5
0.481
0.467
93
92
0.5
0.501
0.015
0.486
97
GUO16­
03D+
1H
0.5
0.469
0.454
91
94
0.5
0.455
0.027
0.429
86
GUO16­
03D+
2H
0.5
0.455
0.429
86
86
0.5
0.503
0.026
0.477
95
GUO16­
03D+
3H
0.5
0.48
0.454
91
93
0.5
0.485
0.023
0.463
93
GUO16­
03D+
4H
0.5
0.465
0.443
89
91
TRIAL
GU016­
03D
(
OREGON)
­
THINNING
0.5
0.442
0.012
0.431
86
GUO16­
03D­
1T
0.5
0.437
0.426
85
86
0.5
0.463
0.023
0.44
88
GUO16­
03D+
0T
0.5
0.509
0.486
97
93
0.5
0.506
0.48
96
GUO16­
03D+
1T
0.5
0.484
0.026
0.458
92
94
    
13
  
31
0.5
0.472
0.468
94
GUO16­
03D+
2T
0.5
0.493
0.005
0.489
98
96
0.5
0.569
0.547
109
GUO16­
03D+
3T
0.5
0.496
0.022
0.474
95
102
0.5
0.445
0.433
87
GUO16­
03D+
4T
0.5
0.475
0.013
0.463
93
90
a
Recoveries
were
calculated
using
raw
data
provided
in
Appendix
3
of
the
Study
Report.
b
Corrected
residue
is
the
measured
residue
minus
the
average
blank
residue.

Table
5.
OVS
Tubes
Concurrent
Laboratory
Recoveries
a
Analyte
Fortificati
on
Level
(
ng)
Measure
d
Bottom
Residue
(
ng)
Bottom
Blank
Residue
s
(
ng)
Correcte
d
Bottom
Residue
b
(
ng)
Measured
Top
Residue
(
ng)
Top
Blank
Residues
(
ng)
Corrected
Top
Residue
(
ng)
Total
Residue
(
top
+
bottom)
(
ng)
Percent
recovery
(%)

TRIAL
GU015­
03D
(
NEW
YORK)
­
HARVESTING
AZMc
500
12.1
38.6
­
26.5e
384.3
6.2
378.1
380.6
76
AZM­
oxond
500
4.5f
29.3
­
24.8e
485.1
4.5e
480.6
485.1
97
TRIAL
GU016­
03D
(
OREGON)
­
HARVESTING
AZMc
500
12.1
17.5
­
5.4e
417.8
17.5
400.3
402.8
81
AZM­
oxond
500
4.5f
4.5f
0e
510.2
4.5e
505.7
510.2
102
TRIAL
GU016­
03D
(
OREGON)
­
THINNING
AZMc
500
11.2
20.7
­
9.5e
380.1
2.5e
377.6
380.1
76
AZM­
oxond
500
4.5f
4.5f
0e
512.6
4.5e
508.1
512.6
103
a
Recoveries
calculated
using
raw
data
provided
in
Appendix
3
of
the
Study
Report.
b
Corrected
residue
is
the
measured
residue
minus
the
average
blank
residue.
c
AZM
=
azinphos­
methyl
d
AZM­
oxon
=
azinphos­
methyl
oxon
e
Since
the
corrected
bottom
residue
was
less
than
the
LOD,
½
the
LOD
was
used
in
subsequent
calculations.
F
Residues
<
LOD
are
shown
as
1/
2
LOD.

Field
recovery:

Urine
Samples
Field
fortification
samples
were
prepared
at
0.50
ng/
mL
and
10.0
ng/
mL
for
urine
samples.
The
fortification
samples
were
prepared
from
two
200
mL
aliquots
of
control
urine.
One
aliquot
received
0.100
mL
of
a
1.00
µ
g/
mL
fortification
solution
containing
MSMB,
while
the
other
received
two
mL
of
the
fortification
solution.
The
solutions
were
then
mixed
well
and
three
50
mL
aliquots
were
removed
and
placed
in
separate
containers.
The
results
provided
in
the
Study
Report
were
verified
are
presented
in
Table
6.
The
average
low
and
high
level
fortification
recoveries,
respectively,
were
99%
and
93%
for
the
New
York
harvesting
trial,
96%
and
90%
for
the
Oregon
harvesting
trial,
and
70%
and
77%
for
the
Oregon
thinning
trial.
    
14
  
31
Table
6.
Urine
Sample
Field
Fortification
Recoveries
a
Fortification
Level
(
ng/
mL)
Measured
residue
(
ng/
mL)
Blank
Samples
(
ng/
mL)
Corrected
residue
b
(
ng/
mL)
Recovery
(%)
Average
Recovery
(%)

TRIAL
GU015­
03D
(
NEW
YORK)
­
HARVESTING
0.501
0.472
94
0.538
0.509
102
Low
fortification
level
0.5
0.538
0.509
102
99
9.186
9.157
92
9.256
9.227
92
High
fortification
level
10
9.406
0.029
9.377
94
93
TRIAL
GU016­
03D
(
OREGON)
­
HARVESTING
0.508
0.481
96
0.469
0.442
88
Low
fortification
level
0.5
0.54
0.513
103
96
9.339
9.312
93
7.881
7.854
79
High
fortification
level
10
9.752
0.027
9.725
97
90
TRIAL
GU016­
03D
(
OREGON)
­
THINNING
0.277
0.267
53
0.331
0.321
64
Low
fortification
level
0.5
0.471
0.461
92
70
7.59
7.58
76
9.129
9.119
91
High
fortification
level
10
6.4
0.01
6.39
64
77
a
Recoveries
calculated
using
raw
data
provided
in
Appendix
3
of
the
Study
Report.
b
Corrected
residue
is
the
measured
residue
minus
the
average
blank
residue.

Breathing
Zone
Air
Samples
Field
fortification
samples
were
prepared
at
500
ng
and
10,000
ng
for
OVS
tubes.
0.050
mL
of
a
fortification
solution
containing
10
µ
g/
mL
azinphos­
methyl
and
10
µ
g/
mL
azinphos­
methyl
oxon
were
added
to
blank
laboratory
control
OVS
tubes
for
the
low
field
fortification
samples.
0.050
mL
of
a
fortification
solution
containing
200
µ
g/
mL
azinphos­
methyl
and
200
µ
g/
mL
azinphosmethyl
oxon
were
added
to
blank
laboratory
control
OVS
tubes
for
the
high
field
fortification
samples.
Air
was
then
drawn
through
the
tubes
for
10
minutes
at
a
rate
of
3
mL/
min
to
evaporate
the
solvent.
The
tubes
were
then
capped
and
labeled.
The
results
provided
in
the
Study
Report
were
verified
and
are
presented
in
Table
7.
For
azinphos­
methyl,
the
average
low
and
high
level
fortification
recoveries,
respectively,
were
88%
and
94%
for
the
New
York
harvesting
trial,
94%
and
105%
for
the
Oregon
harvesting
trial,
and
83%
and
96%
for
the
Oregon
thinning
trial.
For
azinphos­
methyl
oxon,
the
average
low
and
high
level
fortification
recoveries,
respectively,
were
105%
and
102%
for
the
New
York
harvesting
trial,
115%
and
110%
for
the
Oregon
harvesting
trial,
and
106%
and
95%
for
the
Oregon
thinning
trial.
    
15
  
31
Table
7.
OVS
Tubes
Field
Fortification
Recoveries
a
Analyte
Fortification
Level
(
ng)
Measure
d
Bottom
Residue
(
ng)
Bottom
Blank
Residues
(
ng.)
Correcte
d
Bottom
Residue
(
ng)
Measured
Top
Residue
(
ng)
Top
Blank
Residues
(
ng)
Corrected
Top
Residue
b
(
ng)
Total
Residue
(
top
+
bottom)
(
ng)
Recovery
(%)
Overall
Average
Recovery
(%)

TRIAL
GU015­
03D
(
NEW
YORK)
­
HARVESTING
500
5.3
­
3.4e
419
416
419
84
500
2.5f
­
6.2e
426
423
426
85
500
2.5f
­
6.2e
469
467
469
94
88
10,000
2.5f
­
6.2e
9,267
9,264
9,267
93
10,000
5.4
­
3.3e
9,089
9,087
9,089
91
AZMc
10,000
22.2
8.7
13.5
9,693
2.5
f
9,691
9,704
97
94
500
4.5f
0e
528
523
528
106
500
4.5f
0e
545
540
545
110
500
4.5f
0e
496
492
496
100
105
10,000
4.5f
0e
10,725
10,720
10,725
107
10,000
4.5f
0e
9,950
9,945
9,950
99
AZMoxond
10,000
17.9
4.5f
13.4
10,055
4.5f
10,050
10,064
101
102
TRIAL
GU016­
03D
(
OREGON)
­
HARVESTING
500
7.6
­
3.2e
418
412
414
83
500
2.5f
­
8.3e
438
431
434
87
500
2.5f
­
8.3e
570
563
566
113
94
10,000
11.5
0.7e
10,207
10,201
10,203
102
10,000
2.5f
­
8.3e
10,455
10,448
10,451
105
AZMc
10,000
2.5f
10.8
­
8.3e
10,980
6.4
10,973
10,976
110
105
500
4.5f
0e
585
575
579
116
500
4.5f
0e
543
533
537
107
500
4.5f
0e
618
607
612
122
115
10,000
4.5f
0e
10,833
10,823
10,827
108
10,000
4.5f
0e
11,049
11,039
11,043
110
AZMoxond
10,000
4.5f
4.5f
0e
11,058
10.3
11,048
11,053
111
110
TRIAL
GU016­
03D
(
OREGON)
­
THINNING
500
2.5f
0e
392
389
392
78
500
2.5f
0e
406
403
406
81
500
2.5f
0e
444
441
444
89
83
10,000
2.5f
0e
9,283
9,281
9,283
93
10,000
2.5f
0e
9,590
9,588
9,590
96
AZMc
10,000
6.4
2.5f
3.9
9,951
2.5f
9,948
9,951
100
96
500
4.5f
0e
538
534
538
108
500
4.5f
0e
539
535
539
108
500
4.5f
0e
497
493
497
99
106
10,000
4.5f
0e
9,415
9,410
9,415
94
10,000
4.5f
0e
9,425
9,420
9,425
94
AZMoxond
10,000
4.5f
4.5f
0e
9,559
4.5f
9,555
9,559
96
95
a
Recoveries
calculated
using
raw
data
provided
in
Appendix
3
of
the
Study
Report.
b
Corrected
residue
is
the
measured
residue
minus
the
average
blank
residue.
c
AZM
=
azinphos­
methyl
d
AZM­
oxon
=
azinphos­
methyl
oxon
e
Since
the
corrected
bottom
residue
was
less
than
the
LOD,
½
the
LOD
was
used
in
subsequent
calculations.
F
Residues
<
LOD
are
shown
as
1/
2
LOD
LOD
levels
for
AZM
on
OVS
tubes
were
5
ng
and
9
ng
    
16
  
31
for
AZM
oxon.

Tank
mix:
No
information
on
tank
mix
analysis
was
provided
in
the
Study
Report.

Travel
Recovery:
Travel
recovery
was
not
assessed
in
the
Study
Report.

Storage
Stability:
All
samples
were
stored
frozen
prior
to
analysis.
Urine
samples
were
held
for
a
maximum
of
4.2
months
(
126
days)
prior
to
extraction
and
all
extracts
were
analyzed
within
10
days
after
extraction.
OVS
tube
samples
were
held
for
a
maximum
of
3.9
months
(
117
days)
prior
to
extraction
and
all
extracts
were
analyzed
within
4
days
after
extraction.
The
Study
Report
states
that
the
acceptable
recoveries
from
the
field
fortification
samples
indicate
that
the
field
samples
would
be
stable
over
the
period
of
collection,
storage,
and
shipping
through
sample
analysis.
A
separate
storage
stability
study
was
not
performed.

II.
RESULTS
AND
CALCULATIONS:

A.
EXPOSURE
CALCULATIONS:

Internal
Dose
The
internal
azinphos­
methyl
dose
was
determined
from
the
MSMB
residues
measured
in
24
hour
urine
samples
collected
from
each
worker.
The
Registrant
corrected
measured
residues
for
all
field
fortification
recoveries,
even
those
greater
than
90%.
Additionally,
the
Registrant
corrected
the
MSMB
residues
measured
in
the
urine
samples
following
reentry
for
the
amount
of
MSMB
residue
found
in
each
worker's
urine
sample
on
the
day
before
reentry
(
day
­
1).
For
the
harvesting
trial
in
New
York,
the
background
residues
were
<
LOD
in
nine
of
the
workers
and
ranged
from
0.056
µ
g
to
0.173
µ
g
in
the
remaining
six
workers
(
Nos.
2,
4,
5,
9,
10,
and
14).
For
the
harvesting
trial
in
Oregon,
the
background
residues
were
<
LOD
in
eight
of
the
workers
and
ranged
from
0.085
µ
g
to
0.406
µ
g
in
the
remaining
seven
workers
(
Nos.
1,
2,
4,
6,
7,
8,
10).
For
the
thinning
trial
in
Oregon,
the
background
residues
were
<
LOD
in
all
the
workers.
All
sample
concentrations
were
reported
as
ng/
mL
equivalents
of
parent
azinphos­
methyl.
Equivalents
were
calculated
using
a
molecular
weight
conversion
factor
of
1.328.
The
background
corrected
residue
levels
in
ng/
mL
were
multiplied
by
the
appropriate
24
hour
urine
volume
and
normalized
to
the
worker's
body
weight.

By
adding
the
daily
amount
excreted
over
the
4
day
collection
period
and
factoring
for
expected
dose
excreted
over
120
hours
and
the
percentage
of
AZM
dose
represented
by
MSMB,
the
estimated
dose
received
after
one
day
of
exposure
was
estimated.
Using
the
raw
data
provided
in
the
Study
Report,
azinphos­
methyl
internal
dose
estimates
in
mg/
kg
body
weight
were
estimated
for
each
worker
and
each
trial
over
the
4
sampling
days
(
120
hrs).
Results
were
presented
with
correction
for
the
background
(
day
­
1)
levels
of
azinphos­
methyl
demonstrated
in
pre­
reentry
samples.
Measured
residues
were
corrected
to
100%
recovery
based
on
recoveries
of
the
associated
field
fortification
samples.
Residues
<
LOD
were
set
to
½
LOD
for
all
calculations.
After
the
measured
residues,
corrected
for
background
residues
and/
or
field
fortification
recoveries
were
adjusted
for
the
volume
of
urine
collected,
the
internal
dose
was
calculated
by
adjusting
the
MSMB
excreted
during
all
the
sampling
intervals
for
the
cumulative
percent
of
the
absorbed
dose
    
17
  
31
excreted
120
hours
after
exposure
(
as
determined
from
a
previous
study
­­
83.6%)
and
the
percent
of
the
total
azinphos­
methyl
dose
represented
by
MSMB
(
determined
from
a
previous
study
­­
9.2%).

Table
8
provides
the
total
internal
azinphos­
methyl
dose
(
over
120
hrs)
for
each
trial
based
on
body
weight.
The
total
average
azinphos­
methyl
doses
based
on
body
weight
for
the
harvesting
trial
in
New
York,
the
harvesting
trial
in
Oregon,
and
the
thinning
trial
in
Oregon,
are
0.00416,
0.00688,
and
0.00199
mg/
kg
body
weight,
respectively.

Breathing
Zone
Air
Samples
Air
samples
were
collected
in
the
breathing
zone
of
workers
using
OVS
sampling
tubes.
Residues
of
both
azinphos­
methyl
and
azinphos­
methyl
oxon
were
measured
on
the
top
and
bottom
portions
of
the
sampling
tubes
and
combined
for
a
total
azinphos­
methyl
residue.
All
field
samples
were
adjusted
for
field
fortification
recoveries.
Residues
that
were
reported
as
<
LOD
were
included
in
calculations
as
½
LOD.

Breathing
zone
air
concentrations
for
harvesters
at
the
New
York
test
site
averaged
5.16
µ
g/
m3.
For
harvesters
in
Oregon
the
breathing
zone
air
concentration
averaged
17.64
µ
g/
m3
and
following
thinning
activities
in
Oregon
the
breathing
zone
air
concentration
averaged
3.35
µ
g/
m3.

Cholinesterase
Activity
Cholinesterase
activity
(
both
plasma
and
red
blood
cells)
was
monitored
through
blood
sampling
prior
to
reentry
(
on
days
­
3
and
­
1)
and
on
day
0
(
following
completion
of
the
full
work
day)
and
day
4
following
the
postapplication
activity.
The
depression
of
cholinesterase
activity
was
then
determined
by
comparing
the
pre­
reentry
cholinesterase
levels
to
those
measured
on
days
0
and
4.
These
results
are
provided
in
Tables
15
to
17.
For
the
harvesting
activities
at
the
New
York
site
and
the
Oregon
site,
the
percent
decrease
in
plasma
cholinesterase
on
day
0
ranged
from
1%
to
16%
and
from
0%
to
13%,
respectively,
and
the
percent
decrease
in
red
blood
cell
cholinesterase
on
day
0
ranged
from
­
8%
to
4%
and
from
­
4%
to
4%,
respectively.
On
day
4,
the
percent
decrease
in
plasma
cholinesterase
ranged
from
­
11%
to
28%
and
from
­
11%
to
­
1%,
respectively,
and
the
percent
decrease
in
red
blood
cell
cholinesterase
ranged
from
­
7%
to
5%
and
from
­
3%
to
7%,
respectively.
For
the
thinning
activities
at
the
Oregon
site,
the
percent
decrease
in
plasma
cholinesterase
on
day
0
ranged
from
2%
to
13%
and
the
percent
decrease
in
red
blood
cell
cholinesterase
on
day
0
ranged
from
­
10%
to
7%.
On
day
4,
the
percent
decrease
in
plasma
cholinesterase
ranged
from
­
11%
to
4%
and
the
percent
decrease
in
red
blood
cell
cholinesterase
ranged
from
­
9%
to
9%.

The
average
percent
change
in
plasma
cholinesterase
(
ChE)
immediately
following
the
day
of
entry
was
negative
eight
percent
with
a
range
of
±
4
percent
for
apple
harvesters
in
New
York,
negative
six
percent
with
a
range
of
±
4
percent
for
apple
harvesters
in
Oregon,
and
negative
eight
percent
with
a
range
of
±
3
percent
for
apple
thinners
in
Oregon.
The
data
indicate
that
by
day
4
following
exposure,
the
average
plasma
ChE
levels
returned
to
baseline
levels.
The
average
percent
change
in
red
blood
cell
(
RBC)
cholinesterase
levels
immediately
following
the
day
entry
was
positive
one
percent
with
a
range
of
±
3
percent
for
harvesters
in
New
York,
zero
percent
with
a
range
of
±
3
percent
for
harvesters
in
Oregon,
and
negative
two
percent
with
a
range
of
±
4
percent
for
thinners
in
Oregon.
That
remained
about
constant
on
day
4
following
exposure.
III
DISCUSSION:
    
18
  
31
A.
LIMITATIONS
OF
THE
STUDY:

This
study
met
most
of
the
Group
B
875.2500
(
inhalation
exposure)
and
875.2600
(
biological
monitoring)
Guidelines.
The
major
issues
of
concern
are:

 
The
guideline
states
that
for
urine
monitoring,
there
should
also
be
a
sufficient
time
period
between
exposures
to
the
test
substance
or
structurally
related
compounds
and
participation
in
the
study
to
ensure
adequate
urinary
clearance
of
the
compound
and
its
metabolites,
based
on
pharmacokinetic
data.
The
Study
Report
stated
that
workers
were
not
exposed
to
azinphos­
methyl
or
any
other
organophosphate
and
carbamate
chemicals
for
at
least
10
days
prior
to
harvest.
However,
it
should
be
noted
that
MSMB
residues
were
detected
above
the
LOQ
in
the
background
urine
samples
from
some
workers
participating
in
the
harvesting
activities
at
the
New
York
and
Oregon
sites.

 
The
guideline
states
that
samples
should
be
stored
in
a
manner
that
will
minimize
deterioration
and
loss
of
analytes
between
collection
and
analysis.
Biological
monitoring
samples
(
e.
g.,
serum,
plasma
and
urine)
should
be
refrigerated
or
stored
frozen
prior
to
analysis.
Whole
blood
should
not
be
frozen.
Information
on
storage
stability
should
be
provided.
These
criteria
were
mostly
met.
Urine
and
OVS
tube
samples
were
stored
frozen
prior
to
analysis
and
blood
samples
were
stored
cool
prior
to
analysis.
According
to
the
protocol
deviations
reported,
the
refrigerator
used
during
the
collection
of
the
24­
hour
composite
urine
samples
for
two
of
the
workers
(
Reps
6
and
7)
in
the
New
York
trial
did
not
operate
properly.
Therefore,
the
urine
samples
collected
from
these
individuals
were
not
maintained
in
a
cool
condition
over
the
24
hour
collection
period
as
required
in
the
protocol.
The
effect
on
the
study
is
not
known.
Field
fortification
samples
and
recoveries
were
used
to
demonstrate
storage
stability.
A
separate
storage
stability
study
was
not
mentioned.

 
The
guideline
states
that
a
trapping
efficiency
test
for
the
monitoring
media
chosen
must
be
documented.
A
trapping
efficiency
test
was
not
reported.
However,
method
validation
data
exhibited
recoveries
of
103­
107%
for
azinphos­
methyl
and
94­
101%
for
azinphos­
methyl
oxon.

 
The
guideline
states
that
air
samples
should
also
be
tested
for
breakthrough
to
ensure
that
collected
material
is
not
lost
from
the
medium
during
sampling
and
it
is
recommended
that
at
least
one
test
be
carried
out
where
the
initial
trap
contains
10X
the
highest
amount
of
residue
expected
in
the
field.
A
breakthrough
test
was
not
mentioned
in
the
Study
Report.

 
The
guideline
states
that
if
trapping
media
or
extracts
from
field
samples
are
to
be
stored
after
exposure,
a
stability
test
of
the
compound
of
interest
must
be
documented
and
the
media
must
be
stored
under
the
same
conditions
as
field
samples.
Storage
stability
samples
should
be
extracted
and
analyzed
immediately
before
and
at
appropriate
periods
during
storage
and
the
time
periods
for
storage
should
be
chosen
so
that
the
longest
corresponds
to
the
longest
projected
storage
period
for
field
samples.
There
was
no
information
in
storage
stability
included
in
the
study
report;
however,
field
fortification
samples
were
collected,
stored
and
analyzed
with
the
field
samples.
    
19
  
31
 
The
guideline
calls
for
creatinine
determination
as
a
qualitative
measure
of
monitoring
completeness
of
urine
collection
samples.
These
levels
were
determined
and
are
presented
in
the
Study
Report,
but
the
findings
are
never
addressed
in
the
text
Other
major
issues
of
concern
in
evaluation
of
the
study
include:

 
The
baseline
cholinesterase
(
ChE)
levels
for
workers
were
established
by
taking
a
sample
3
days
prior
and
another
sample
one
day
prior
to
the
day
where
the
workers
were
exposed
to
AZM
residues
while
performing
postapplication
tasks.
Most
guidelines
recommend
that
baseline
blood
samples
be
taken
at
a
time
when
the
worker
has
not
been
exposed
to
organophosphates
or
n­
methyl
carbamates
for
at
least
30
days.
Workers
in
the
study
stated
that
they
had
not
been
exposed
to
organophosphates
or
n­
methyl
carbamates
for
at
least
10
days
prior
to
the
study,
but
that
could
not
be
independently
verified.
Guidelines
generally
also
recommend
that
establishing
a
stable
baseline
requires
a
minimum
of
two
pre­
exposure
tests
taken
at
least
3
days,
but
not
more
than
14
days,
apart.
Considering
these
factors,
the
baseline
ChE
levels
in
the
study
may
not
reflect
actual
baseline
levels
in
unexposed
workers.
The
baseline
ChE
levels
measured
in
the
study
fall
within
the
normal
range
of
ChE
levels
in
the
blood.

 
Since
the
blood
cholinesterase
data
reflect
a
single
day
of
exposure,
it
would
be
expected
that
successive
days
of
exposure
would
result
in
additional
depression
of
ChE
that
could
be
cumulative.
The
data
do
not
permit
estimating
the
slope
of
recovery
for
ChE
plasma
and
RBC
levels
back
to
normal
levels,
therefore
it
is
difficult
to
predict
the
cumulative
effect
of
successive
days
of
exposure.

Table
8.
Total
Azinphos­
methyl
Dose
By
Trial
(
mg/
kg
bw)

Trial
GU015­
03D
(
New
York)
­
Harvesting
Trial
GU016­
03D
(
Oregon)
­

Harvesting
Trial
GU016­
03D
(
Oregon)
­
Thinning
Arithmetic
Mean
Geometric
Mean
Standard
Deviation
Arithmetic
Mean
Geometric
Mean
Standard
Deviation
Arithmetic
Mean
Geometric
Mean
Standard
Deviation
0.00416
0.00374
0.0021
0.00688
0.00613
0.00359
0.00199
0.00175
0.001021
    
20
  
31
Table
9.
Calculated
Azinphos­
methyl
Internal
Doses
in
Workers
During
Harvesting
Trial
GU015­
03D
(
New
York)

Worker
Number
Sampling
Interval
MSMB
excreted
(
µ
g)
Total
MSMB
excreteda
(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
AZM
dose
present
as
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)

1
0
day
6.26
35.05
83.6
9.2
456
101.61
0.00448
1
day
12.79
2
day
10.25
3
day
4.45
4
day
1.29
2
0
day
7.03
33.02
83.6
9.2
429
99.79
0.0043
1
day
13.26
2
day
7.39
3
day
3.63
4
day
1.72
4
0
day
7.77
22.85
83.6
9.2
297
74.39
0.004
1
day
7.18
2
day
4.93
3
day
2
4
day
0.97
5
0
day
0.14
7.17
83.6
9.2
93
65.32
0.0014
1
day
1.08
2
day
3.51
3
day
2.11
4
day
0.33
6
0
day
10.74
41.59
83.6
9.2
541
86.64
0.0062
1
day
14.87
2
day
8.83
3
day
5.44
4
day
1.7
7
0
day
6.08
29.64
83.6
9.2
385
72.58
0.0053
1
day
10.73
2
day
7.02
3
day
3.76
4
day
2.07
8
0
day
5.62
17.34
83.6
9.2
225
76.66
0.0029
1
day
6.03
2
day
3.44
3
day
1.58
4
day
0.67
9
0
day
0.98
23.07
83.6
9.2
300
76.66
0.0039
1
day
11.09
2
day
5.71
3
day
4.03
4
day
1.26
10
0
day
2.12
25.59
83.6
9.2
333
78.93
0.0042
1
day
10.19
2
day
6.19
3
day
5.41
4
day
1.69
11
0
day
15.51
94.25
83.6
9.2
1225
119.75
0.0102
    
21
  
31
Table
9.
Calculated
Azinphos­
methyl
Internal
Doses
in
Workers
During
Harvesting
Trial
GU015­
03D
(
New
York)

Worker
Number
Sampling
Interval
MSMB
excreted
(
µ
g)
Total
MSMB
excreteda
(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
AZM
dose
present
as
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)

1
day
31.93
2
day
25.69
3
day
14.9
4
day
6.23
12
0
day
6.63
20.19
83.6
9.2
263
73.94
0.0036
1
day
6.71
2
day
4.69
3
day
1.73
4
day
0.42
13
0
day
2.76
20.03
83.6
9.2
260
97.07
0.0027
1
day
7.75
2
day
5.71
3
day
2.63
4
day
1.18
13
0
day
2.41
14.49
83.6
9.2
188
69.85
0.0027
1
day
6.63
2
day
3.2
3
day
1.53
4
day
0.73
15
0
day
1.13
7.99
83.6
9.2
104
55.79
0.0019
1
day
3.23
2
day
2.34
3
day
0.79
4
day
0.5
16
0
day
3.73
20.97
83.6
9.2
273
60.78
0.0045
1
day
9.52
2
day
3.91
3
day
3.08
4
day
0.74
a
Total
MSMB
excreted
(
ug)
=[(
measured
MSMB
(
AZM
equivalents)
ng/
mL
/
field
fortification
recovery
correction
factor)
x
24
hour
urine
volume
(
mL)]
1
ug/
1000
ng.
This
amount
was
calculated
for
each
day
(
0­
4)
and
then
summed
to
give
a
120
hour
total
residue
estimate.
Field
fortification
recovery
values
used
for
correction:
99%
when
residue
<
2.2
ng/
mL
93%
when
residue
>
2.2
ng/
mL
b
Total
AZM
Dose
(
µ
g)
=
Total
MSMB
excreted
(
µ
g)
*
%
of
absorbed
dose
excreted
in
urine
after
120
hours/
100
*
%
of
total
AZM
dose
represented
by
MSMB/
100
c
Total
AZM
Dose
(
mg/
kg
BW)
=
((
Total
AZM
Dose
(
µ
g))/
1000)
/
Body
Weight
(
kg)
    
22
  
31
Table
10.
Calculated
Azinphos­
methyl
Internal
Doses
in
Workers
During
Harvesting
Trial
GU016­
03D
(
Oregon)

Worker
Number
Samplin
g
Interval
MSMB
excreted
(
µ
g)
Total
MSMB
excreteda
(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
AZM
dose
present
as
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)

1
0
day
5.35
20.06
83.6
9.2
261
67.59
0.00386
1
day
7.79
2
day
3.91
3
day
2.33
4
day
0.69
2
0
day
5.94
30.13
83.6
9.2
392
76.66
0.0051
1
day
11.41
2
day
6.16
3
day
4.67
4
day
1.96
3
0
day
5.75
30.48
83.6
9.2
396
63.96
0.0062
1
day
14.27
2
day
5.6
3
day
3.25
4
day
1.61
4
0
day
13.89
89.77
83.6
9.2
1167
82.55
0.0141
1
day
32.77
2
day
23.47
3
day
11.62
4
day
8.03
5
0
day
14.11
74.74
83.6
9.2
972
72.12
0.0135
1
day
28.89
2
day
15.44
3
day
10.92
4
day
5.39
6
0
day
5.15
27.78
83.6
9.2
361
75.75
0.0048
1
day
10.57
2
day
5.82
3
day
4.85
4
day
1.4
7
0
day
6.89
18.07
83.6
9.2
235
59.87
0.0039
1
day
6.81
2
day
3.37
3
day
0.86
4
day
0.13
8
0
day
19.3
49.69
83.6
9.2
646
64.86
0.01
1
day
19.51
2
day
6.58
3
day
3.3
4
day
1.01
9
0
day
5.06
19.49
83.6
9.2
253
63.5
0.004
1
day
6.78
2
day
5.49
    
23
  
31
Table
10.
Calculated
Azinphos­
methyl
Internal
Doses
in
Workers
During
Harvesting
Trial
GU016­
03D
(
Oregon)

Worker
Number
Samplin
g
Interval
MSMB
excreted
(
µ
g)
Total
MSMB
excreteda
(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
AZM
dose
present
as
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)

3
day
2
4
day
0.16
10
0
day
11.92
42.4
83.6
9.2
551
68.04
0.0081
1
day
17.51
2
day
7.03
3
day
4.26
4
day
1.67
11
0
day
0.1
31.94
83.6
9.2
415
74.84
0.0055
1
day
16.89
2
day
8.14
3
day
4.78
4
day
2.03
12
0
day
9.73
38.8
83.6
9.2
505
79.83
0.0063
1
day
15.36
2
day
7.52
3
day
4.33
4
day
1.86
13
0
day
15.38
63.36
83.6
9.2
824
77.11
0.0107
1
day
29.6
2
day
12.53
3
day
4.47
4
day
1.38
14
0
day
4.8
22.1
83.6
9.2
287
73.03
0.0039
1
day
8.43
2
day
4.18
3
day
3.02
4
day
1.68
15
0
day
7.81
20.02
83.6
9.2
260
83.01
0.0031
1
day
6.28
2
day
3.18
3
day
2.08
4
day
0.67
a
Total
MSMB
excreted
(
ug)
=[(
measured
MSMB
(
AZM
equivalents)
ng/
mL
/
field
fortification
recovery
correction
factor)
x
24
hour
urine
volume
(
mL)]
1
ug/
1000
ng.
This
amount
was
calculated
for
each
day
(
0­
4)
and
then
summed
to
give
a
120
hour
total
residue
estimate.
Field
fortification
recovery
values
used
for
correction:
96%
when
residue
<
2.2
ng/
mL
90%
when
residue
>
2.2
ng/
mL
b
Total
AZM
Dose
(
µ
g)
=
Total
MSMB
excreted
(
µ
g)
*
%
of
absorbed
dose
excreted
in
urine
after
120
hours/
100
*
%
of
total
AZM
dose
represented
by
MSMB/
100
c
Total
AZM
Dose
(
mg/
kg
BW)
=
((
Total
AZM
Dose
(
µ
g))/
1000)
/
Body
Weight
(
kg)
    
24
  
31
Table
11.
Calculated
Azinphos­
methyl
Internal
Doses
in
Workers
During
Thinning
Trial
GU016­
03D
(
Oregon)

Worker
Number
Sampling
Interval
MSMB
excreted
(
µ
g)
Total
MSMB
excreteda
(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
AZM
dose
present
as
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)

1
0
day
0.63
6.61
83.6
9.2
86
77.57
0.01074
1
day
3.57
2
day
1.19
3
day
1.06
4
day
0.16
2
0
day
2.94
12.36
83.6
9.2
161
64.18
0.020
1
day
5.35
2
day
2.85
3
day
0.94
4
day
0.28
3
0
day
2.57
16.73
83.6
9.2
218
64.86
0.027
1
day
8.38
2
day
3.61
3
day
1.14
4
day
1.03
4
0
day
0.9
9.33
83.6
9.2
121
69.17
0.015
1
day
5.34
2
day
1.7
3
day
1.06
4
day
0.33
5
0
day
1.64
9.4
83.6
9.2
122
88.91
0.015
1
day
4.96
2
day
1.3
3
day
1.13
4
day
0.37
6
0
day
2.57
10.16
83.6
9.2
132
60.33
0.017
1
day
4.34
2
day
1.83
3
day
1.2
4
day
0.22
7
0
day
2.71
9.95
83.6
9.2
129
61.01
0.016
1
day
3.77
2
day
2.08
3
day
1.13
4
day
0.27
8
0
day
0.39
10.72
83.6
9.2
139
81.65
0.017
1
day
5.4
2
day
3
3
day
1.21
4
day
0.73
9
0
day
0
3.17
83.6
9.2
41
78.7
0.005
1
day
0.2
2
day
1.79
3
day
0.96
4
day
0.22
10
0
day
3.2
15.24
83.6
9.2
198
68.27
0.025
1
day
7.04
    
25
  
31
Table
11.
Calculated
Azinphos­
methyl
Internal
Doses
in
Workers
During
Thinning
Trial
GU016­
03D
(
Oregon)

Worker
Number
Sampling
Interval
MSMB
excreted
(
µ
g)
Total
MSMB
excreteda
(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
AZM
dose
present
as
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)

2
day
3.22
3
day
1.44
4
day
0.35
11
0
day
0.01
6.03
83.6
9.2
78
66.23
0.010
1
day
2.71
2
day
1.29
3
day
1.29
4
day
0.73
12
0
day
1.53
9.65
83.6
9.2
125
73.94
0.016
1
day
4.38
2
day
1.72
3
day
1.58
4
day
0.42
13
0
day
3.11
23.57
83.6
9.2
306
68.95
0.038
1
day
8.26
2
day
7.14
3
day
3.34
4
day
1.73
14
0
day
1.1
4.44
83.6
9.2
58
69.85
0.007
1
day
2.05
2
day
0.77
3
day
0.41
4
day
0.1
15
0
day
0.69
10.41
83.6
9.2
135
62.82
0.017
1
day
5.16
2
day
2.55
3
day
1.83
4
day
0.19
a
Total
MSMB
excreted
(
ug)
=[(
measured
MSMB
(
AZM
equivalents)
ng/
mL
/
field
fortification
recovery
correction
factor)
x
24
hour
urine
volume
(
mL)]
1
ug/
1000
ng.
This
amount
was
calculated
for
each
day
(
0­
4)
and
then
summed
to
give
a
120
hour
total
residue
estimate.
Field
fortification
recovery
values
used
for
correction:
70%
when
residue
<
2.2
ng/
mL
77%
when
residue
>
2.2
ng/
mL
b
Total
AZM
Dose
(
µ
g)
=
Total
MSMB
excreted
(
µ
g)
*
%
of
absorbed
dose
excreted
in
urine
after
120
hours/
100
*
%
of
total
AZM
dose
represented
by
MSMB/
100
c
Total
AZM
Dose
(
mg/
kg
BW)
=
((
Total
AZM
Dose
(
µ
g))/
1000)
/
Body
Weight
(
kg)
    
26
  
31
Table
12.
Potential
Inhalation
Exposure
During
Harvesting
in
Trial
GU015­
03D
(
New
York)

Worker
No.
Total
Residue
a
(
ng)
Flow
Rate
(
L/
min)
Sampling
Time
(
min)
Air
Concentration
b
(
µ
g/
m3)

1
4,530
2.06
490
4.5
2
6,574
2.06
490
6.52
4
3,609
2.1
490
3.51
5
4,602
2.13
490
4.41
6
6,747
2.11
490
6.51
7
5,317
1.99
490
5.46
8
8,032
2.1
490
7.81
9
4,376
2.14
490
4.18
10
3,290
2.13
490
3.15
11
5,174
2.08
490
5.08
12
6,310
2.08
490
6.19
13
4,768
2.03
490
4.8
14
6,048
2.13
490
5.8
15
3,186
2.14
490
3.03
16
6,693
2.11
490
6.46
Average
5.16
Geometric
Mean
4.98
Standard
Deviation
1.4
a
Total
Residue
is
the
sum
of
the
azinphos­
methyl
and
azinphos­
methyl
oxon
residues
in
both
top
and
bottom
tube
sections.
1/
2
LOD
was
used
in
calculations
for
residues
<
LOD.
Data
were
corrected
for
AZM
and
AZM
oxon
field
fortification
recovery
values
of
94%
and
115%
,
respectively
were
used
when
residues
were
<
2,250
ng.
When
residue
values
were
>
2,250
ng
recovery
values
of
105%
and
110%
were
used
for
AZM
and
AZM
oxon,
respectively.

b
Air
Concentration
(
µ
g/
m3)
=
Total
Residue
(
µ
g)
[(
Flow
Rate
(
L/
min)
*
Sampling
Time
(
min))
/
1000
L/
m3]
    
27
  
31
Table
13.
Potential
Inhalation
Exposure
During
Harvesting
in
Trial
GU016­
03D
(
Oregon)

Worker
No.
Total
Inhalation
Residueb
(
ng)
Flow
Rate
(
L/
min)
Sampling
Time
(
min)
Air
Concentration
b
(
µ
g/
m3)

1
13,206
2.2
486
12.36
2
22,480
2.17
486
21.29
3
23,465
2.1
486
23.03
4
22,222
2.17
486
21.09
5
15,909
2.19
486
14.97
6
13,854
1.93
486
14.75
7
16,709
2.21
486
15.58
8
19,579
2.22
486
18.12
9
11,696
2.16
486
11.12
10
28,618
2.19
486
26.85
11
13,600
2.17
486
12.88
12
46,290
2.16
486
44.03
13
13,714
2.14
486
13.21
14
5,197
2.07
486
5.18
15
10,146
2.07
486
10.08
Average
17.64
Geometric
Mean
15.77
Standard
Deviation
9.18
a
Total
Inhalation
Residue
is
the
sum
of
the
azinphos­
methyl
and
azinphos­
methyl
oxon
residues
in
both
top
and
bottom
tube
sections.
1/
2
LOD
was
used
in
calculations
for
residues
<
LOD.
Data
were
corrected
for
AZM
and
AZM
oxon
field
fortification
recovery
values
of
94%
and
115%
,
respectively
were
used
when
residues
were
<
2,250
ng.
When
residue
values
were
>
2,250
ng
recovery
values
of
105%
and
110%
were
used
for
AZM
and
AZM
oxon,
respectively.

b
Air
Concentration
(
µ
g/
m3)
=
Total
Residue
(
µ
g)
[(
Flow
Rate
(
L/
min)
*
Sampling
Time
(
min))
/
1000
L/
m3]
    
28
  
31
Table
14.
Potential
Inhalation
Dose
for
Exposure
During
Thinning
in
Trial
GU016­
03D
(
Oregon)

Worker
No.
Total
Inhalation
Residue
a
(
ng)
Flow
Rate
(
L/
min)
Sampling
Time
(
min)
Concentration
b
(
µ
g/
m3)

1
6,190
2.12
478
6.11
2
1,411
2.15
478
1.37
3
4,674
2.17
478
4.5
4
2,767
1.89
478
3.06
5
1,916
2.09
478
1.92
6
5,747
2.08
478
5.59
7
2,973
2.14
478
2.91
8
2,681
2.13
478
2.64
9
4,818
2.1
478
4.79
10
5,301
2.12
478
5.23
11
1,082
2.1
478
1.08
12
2,567
2.14
478
2.51
13
2,622
1.99
478
2.76
14
1,801
2.03
478
1.86
15
3,517
1.99
478
3.69
Average
3.35
Geometric
Mean
2.97
Standard
Deviation
1.6
a
Total
Inhalation
Residue
is
the
sum
of
the
azinphos­
methyl
and
azinphos­
methyl
oxon
residues
in
both
top
and
bottom
tube
sections.
1/
2
LOD
was
used
in
calculations
for
residues
<
LOD.
Data
were
corrected
for
AZM
and
AZM
oxon
field
fortification
recovery
values
of
94%
and
115%
,
respectively
were
used
when
residues
were
<
2,250
ng.
When
residue
values
were
>
2,250
ng
recovery
values
of
105%
and
110%
were
used
for
AZM
and
AZM
oxon,
respectively.

b
Air
Concentration
(
µ
g/
m3)
=
Total
Residue
(
µ
g)
[(
Flow
Rate
(
L/
min)
*
Sampling
Time
(
min))
/
1000
L/
m3]
    
29
  
31
Table
15.
Percent
Depression
of
Cholinesterase
Activity
for
Trial
GU015­
03D
(
New
York)
­
Harvesting
Average
Cholinesterase
Activity
Determined
on
Days
­
1
and
­
3
Cholinesterase
Activity
and
%
Depression
on
Sampling
Day
0
Cholinesterase
Activity
and
%
Depression
on
Sampling
Day
4
Worker
Number
Plasma
Red
Blood
Cells
Plasma
%
Depression
Red
Blood
Cells
%
Depression
Plasma
%
Depression
Red
Blood
Cells
%
Depression
1
3.47
13.66
3.25
6
13.91
­
2
3.64
­
5
14.14
­
4
2
3.78
13.33
3.69
2
13.5
­
1
3.99
­
6
13.76
­
3
4
3.15
13.62
2.79
11
14.03
­
3
3.47
­
10
14.02
­
3
5
3.64
13.67
3.11
15
13.79
­
1
4.05
­
11
14.1
­
3
6
4.44
13.6
4.32
3
13.03
4
4.44
0
12.98
5
7
3.6
13.66
3.27
9
13.42
2
3.79
­
5
14.05
­
3
8
4.37
13.76
4.22
3
13.57
1
3.15
28
13.75
0
9
3.97
14.12
3.65
8
14.25
­
1
3.96
0
14.3
­
1
10
3.42
13.28
3.38
1
13.99
­
5
3.76
­
10
13.47
­
1
11
3.67
13.6
3.42
7
13.52
1
3.65
0
13.81
­
2
12
3.81
13.9
3.19
16
14.17
­
2
3.57
6
14.16
­
2
13
4.56
15.8
4.08
10
15.59
1
4.53
1
15.47
2
14
3.8
14.13
3.45
9
13.91
2
3.77
1
14.62
­
4
15
3.41
11.12
3.09
9
11.2
­
1
3.43
­
1
11.33
­
2
16
3.79
13.14
3.38
11
14.16
­
8
4.15
­
9
14.06
­
7
Average
3.79
13.62
3.49
8.08
13.74
­
0.88
3.82
­
1.46
13.87
­
1.85
    
30
  
31
Table
16.
Percent
Depression
of
Cholinesterase
Activity
for
Trial
GU016­
03D
(
Oregon)
­
Harvesting
Average
Cholinesterase
Activity
Determined
on
Days
­
1
and
­
3
Cholinesterase
Activity
and
%
Depression
on
Sampling
Day
0
Cholinesterase
Activity
and
%
Depression
on
Sampling
Day
4
Worker
Number
Plasma
Red
Blood
Cells
Plasma
%
Depression
Red
Blood
Cells
%
Depression
Plasma
%
Depression
Red
Blood
Cells
%
Depression
1
3.14
13.65
2.95
6
13.72
­
1
3.29
­
5
13.36
2
2
4.47
13.73
4.1
8
13.77
0
4.78
­
7
13.55
1
3
3.98
13.8
3.75
6
13.7
1
4.4
­
11
13.71
1
4
4.06
13.01
3.95
3
12.63
3
4.3
­
6
12.59
3
5
3.27
14.81
2.99
9
15.16
­
2
3.4
­
4
14.42
3
6
3.08
12.61
3.07
0
12.8
­
2
3.24
­
5
12.96
­
3
7
2.35
13.14
2.21
6
13.5
­
3
2.4
­
2
12.99
1
8
3.11
12.85
2.83
9
13.39
­
4
3.14
­
1
13.28
­
3
9
3.33
13.44
3.09
7
12.9
4
3.35
­
1
13.06
3
10
3.48
14.19
3.02
13
13.8
3
3.55
­
2
13.56
4
11
3.83
12.58
3.6
6
12.85
­
2
4.1
­
7
12.47
1
12
2.87
11.42
2.87
0
11.52
­
1
3.15
­
10
11.58
­
1
13
3.8
13.46
3.41
10
13.39
1
4.1
­
8
13.59
­
1
14
4.1
13.76
4.11
0
13.74
0
4.45
­
9
13.73
0
15
4.39
13.98
3.96
10
13.42
4
4.51
­
3
13.08
6
Average
3.55
13.36
3.33
6.13
13.35
0.07
3.74
­
5.34
13.2
1.14
    
31
  
31
Table
17.
Percent
Depression
of
Cholinesterase
Activity
for
Trial
GU016­
03D
(
Oregon)
­
Thinning
Average
Cholinesterase
Activity
Determined
on
Days
­
1
and
­
3
Cholinesterase
Activity
and
%
Depression
on
Sampling
Day
0
Cholinesterase
Activity
and
%
Depression
on
Sampling
Day
4
Worker
Number
Plasma
Red
Blood
Cells
Plasma
%
Depression
Red
Blood
Cells
%
Depression
Plasma
%
Depression
Red
Blood
Cells
%
Depression
1
2.86
11.42
2.55
11
11.6
­
2
2.83
1
12.41
­
9
2
3.9
12.66
3.72
4
12.48
1
3.98
­
2
13.27
­
5
3
3.43
15.32
3.18
7
14.17
7
3.32
3
15.18
1
4
3.27
13.58
2.97
9
13.23
3
3.23
1
13.62
0
5
3.44
13.68
3.2
7
13.7
0
3.82
­
11
12.67
7
6
4.18
14.32
3.62
13
13.25
7
4.34
­
4
13.87
3
7
2.28
12.54
2.1
8
12.16
3
2.43
­
7
12.14
3
8
4.99
14.8
4.55
9
14.46
2
4.83
3
13.48
9
9
4.87
13.77
4.4
10
13.46
2
4.74
3
13.92
­
1
10
3.43
13.69
3.19
7
13.46
2
3.38
1
13.33
3
11
3.29
13.59
3.16
4
13.33
2
3.19
3
13.7
­
1
12
4.17
13.79
3.66
12
13.15
5
3.98
4
13.8
0
13
3.31
14.05
3.01
9
13.8
2
3.21
3
13.67
3
14
3.37
12.54
3.12
7
11.82
6
3.54
­
5
12.23
2
15
3.67
13.82
3.59
2
15.26
­
10
3.76
­
3
13.59
2
Average
3.63
13.57
3.33
7.93
13.29
2.06
3.64
­
0.61
13.39
1.3