    
1
  
39
UNITED
STATES
ENVIRONMENTAL
PROTECTION
AGENCY
WASHINGTON,
D.
C.
20460
OFFICE
OF
PREVENTION,
PESTICIDES
AND
TOXIC
SUBSTANCES
MEMORANDUM
Date:
April
1,
2005
Subj:
Study
Review:
Azinphos­
methyl
­
Biomonitoring
of
Applicators
Following
Airblast
Treatment
of
Orchard
Crops
using
Open
and
Closed
Cab
Equipment
(
MRID#:
463164­
06,
PC
Code(
s)
:
058001,
DP
Barcode
307562)

From:
Seyed
Tadayon,
Chemist
Reregistration
Branch
3
(
7509C)
Health
Effects
Division
Through:
Danette
Drew,
Branch
Senior
Scientist
Reregistration
Branch
3
(
7509C)
Health
Effects
Division
To:
Seyed
Tadayon,
Chemist
Reregistration
Branch
3
(
7509C)
Health
Effects
Division
Attached
is
a
review
of
the
study
entitled,
Azinphos­
methyl
­
Biomonitoring
of
Applicators
Following
Airblast
Treatment
of
Orchard
Crops
using
Open
and
Closed
Cab
Equipment
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
  
39
STUDY
TYPE
Azinphos­
methyl
­
Biomonitoring
of
Applicators
Following
Airblast
Treatment
of
Orchard
Crops
using
Open
and
Closed
Cab
Equipment
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:
M.
E.
Krolski
Title:
Azinphos­
methyl
­
Biomonitoring
of
Applicators
Following
Airblast
Treatment
of
Orchard
Crops
using
Open
and
Closed
Cab
Equipment
Report
Date:
July
7,
2004
Analytical
Laboratories:
Bayer
CropScience
Environmental
Research
Section
Bayer
Research
Park
17745
South
Metcalf
Avenue
Stilwell,
KS
66085
Identifying
Codes:
MRID:
463164­
06
Report
No.:
201054
Study
Number:
GU264704
and
GU264705
PSI
Number:
RAGUY012
and
RCGUX002
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:
(
1)
some
plot
diagrams
were
updated
and
the
initial
entries
are
not
available
in
the
electronic
raw
data,
(
2)
trials
GU
020­
03D
and
GU
024­
03D
do
not
have
chain
of
custody
or
storage
documentation
for
the
associated
field
fortification
samples,
(
3)
some
field
observations
for
trial
GU
020­
03D
were
not
made
according
to
GLP,
(
4)
sample
    
3
  
39
receipt
dates
and
weight
values
were
recorded
into
a
laboratory
information
management
system
that
was
not
validated,
and
(
5)
the
storage
container
used
in
this
study
were
not
retained
for
the
duration
of
the
study
as
required
by
160,105(
c).
The
statement
noted
that
none
of
these
exceptions
negatively
impacted
the
integrity
of
the
study.

GUIDELINE
OR
PROTOCOL
FOLLOWED:
The
Bayer
CropScience
Protocol
for
both
the
open
cab
study
(
GU264704)
and
the
closed
cab
study
(
GU264705)
were
provided
in
the
Study
Report,
including
a
list
of
deviations.
The
Study
Report
states
that
the
data
requirements
were
U.
S.
EPA
OPPTS
Harmonized
Test
Guidelines,
Series
875
Occupational
and
Residential
Exposure,
875.1500
­
Biological
Monitoring.

I.
MATERIALS
AND
METHODS
A.
MATERIALS
Formulation:
GUTHION
®
50
WP
­
water
soluble
packets
(
GUTHION
®
Solupak)
EPA
Reg.
No.
264­
733
Lot/
Batch
#
formulation:
3144145,
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
Packaging:
The
product
was
supplied
in
bags
containing
the
water
soluble
packets.

B.
STUDY
DESIGN
There
were
2
amendments
to
the
protocol
and
7
deviations
from
the
protocol
for
open
cab
trials.

The
amendments
included:(
1)
the
addition
of
two
more
control
urine
timepoints
for
trials
GU031­
03D,
GU033­
03D,
and
GU034­
03D;
and
(
2)
the
addition
of
analysis
methods
and
spiking
levels.

The
deviations
included:
(
1)
SOP=
SOO214
requires
that
QA
review
protocols
prior
to
study
initiation
and
this
was
not
done;
(
2)
protocol
definition
of
a
typical
workday
(
4­
8
hours)
was
exceed
during
trials
GU020­
03D,
GU021­
03D,
GU022­
03D,
and
GU023­
03D;
(
3)
the
reporting
frequency
of
FieldNotes
updates
as
required
by
the
protocol
was
not
met
during
trials
GU020­
03D,
GU021­
03D,
GU022­
03D,
GU023­
03D,
GU024­
03D,
GU025­
03D,
and
GU026­
03D;
(
4)
the
Master
Schedule
Form
F­
00066
was
not
sent
promptly
after
application
during
trials
GU022­
03D,
GU023­
03D,
GU024­
03D,
GU025­
03D,
and
GU026­
03D;
(
5)
the
minimum
14­
day
period
(
prior
to
testing)
in
which
a
volunteer
could
not
be
exposed
to
azinphos­
methyl
was
not
met
during
trials
GU022­
03D,
GU023­
03D,
GU024­
03D,
GU025­
03D,
and
GU026­
03D;
(
6)
the
sprayer
was
not
calibrated
prior
to
each
use
during
trial
GU022­
03D;
and
(
7)
the
protocol
requirement
of
a
7­
hour
minimum
exposure
period
for
air
samples
was
not
achieved
during
trials
GU024­
03D,
GU025­
03D
and
GU026­
03D.
    
4
  
39
There
were
2
amendments
and
10
deviations
from
the
protocol
for
the
closed
cab
trials.
The
amendments
included:

(
1)
the
addition
of
two
more
control
urine
timepoints
for
trials
GU031­
03D,
GU033­
03D,
and
GU034­
03D;
and
(
2)
the
addition
of
analysis
methods
and
spiking
levels.

The
deviations
included:
(
1)
SOP=
SOO214
requires
that
QA
review
protocols
prior
to
study
initiation
and
this
was
not
done;
(
2)
the
FieldNotes
summary
was
not
sent
to
the
Study
Director
within
30
days
of
trial
completion
for
trials
GU035­
03D
through
GU044­
03D;
(
3)
the
electronic
file
was
not
transferred
to
the
Study
Director
within
24
hours
of
critical
phase
for
trials
GU035­
03D
through
GU044­
03D;
(
4)
cultural
practices,
weather
information,
and
pesticide
history
were
not
collected
per
GLP
for
trials
GU035­
03D
through
GU044­
03D;
(
5)
records
of
sprayer
cleaning
and
maintenance
were
not
available
for
trials
GU035­
03D
through
GU044­
03D;
(
6)
the
final
electronic
file
was
to
be
sent
to
the
sponsor
within
30
days
of
the
final
event
(
last
samples
disposed
of
on
Sept.
10th)
for
trials
GU035­
03D
through
GU044­
03D;
(
7)
the
Master
Schedule
Form
F­
00066
was
not
sent
promptly
after
application
for
trial
GU045­
03D;
(
8)
the
protocol
requirement
of
a
7­
hour
minimum
exposure
period
for
air
samples
was
not
achieved
for
trial
GU045­
03D;
(
9)
the
reporting
frequency
of
FieldNotes
updates
as
required
by
the
protocol
was
not
met
for
trials
GU045­
03D
through
GU047­
03D;
(
10)
the
protocol
definition
of
a
typical
workday
(
4­
8
hours)
was
exceeded
for
trials
GU046­
03D
and
GU047­
03D.

These
deviations
from
the
protocol
were
reported
to
not
have
any
adverse
effects
on
the
study.

1.
Test
Site
Thirty
field
trials
were
conducted:
15
using
open
cab
equipment
and
15
using
closed
cab
equipment
.
The
open
cab
field
trials
were
held
in
PA
,
MD
and
WA.
The
closed
cab
field
trials
were
held
in
NY
(
1
trial),
North
Rose,
NY,
PA
and
WA.

The
plot
sizes
for
the
open
cab
field
trials
ranged
from
20
to
120
acres,
averaging
33
acres,
and
the
plot
sizes
for
the
closed
cab
field
trials
ranged
from
1.0
to
60
acres,
averaging
12
acres.
The
field
trials
were
mostly
conducted
on
apple
orchards,
although
one
of
the
open
cab
trials
(
GU026­
03D)
specified
that
applications
were
made
to
apples
and
stone
fruit.

2.
Meteorology:

Meteorological
conditions
were
recorded
during
the
application.
The
Study
Report
noted
that
none
of
the
field
sites,
except
for
an
open
cab
trial
site
(
GU021­
03D)
which
reported
0.1
inch,
reported
any
rainfall.
None
of
the
field
sites
reported
any
use
of
irrigation
from
the
first
application
through
the
last
sampling.
    
5
  
39
3.
Number
and
type
of
workers
Thirty
workers
participated
in
the
study.
Fifteen
made
applications
using
closed
cab
tractors
and
fifteen
using
open
cab
tractors.
The
weight
of
the
workers
using
open
cab
tractors
ranged
from
66
to
98
kg,
averaging
83
kg.
The
weight
of
the
workers
using
closed
cab
tractors
ranged
from
70
to
116
kg,
averaging
88
kg.
All
workers
were
reported
to
be
professional
orchardmen.
Data
from
three
of
the
worker
replicates
from
the
open
cab
study
were
excluded
from
the
data
analysis
of
dose
estimation
due
to
high
background
MSMB
residue
levels.

4.
Replicates
The
specific
activities
including
mixing/
loading
and
application
by
the
workers
were
not
described
in
the
Study
Report.
Exposure
periods
were
reported
for
each
trial
and
averaged
7
hours,
12
minutes
for
the
open
cab
trials
and
8
hours,
13
minutes
for
the
closed
cab
trials.

5.
Protective
clothing
The
Study
Report
stated
that
the
workers
wore
protective
clothing
and
respiratory
protection
as
specified
on
the
product
label.
For
open
cab
field
trials,
the
Study
Report
states
that
during
application
workers
wore:
(
1)
one­
or
two­
piece
chemical­
resistant
coveralls
made
from
TYVEK,
SARANEX,
PVC
or
similar
material
,
(
2)
long­
sleeved
shirt
and
long
pants,
(
3)
chemical­
resistant
footwear
plus
socks,
(
4)
chemical­
resistant
gloves,
(
5)
chemical­
resistant
headgear,
and
(
6)
protective
eyewear.
In
addition,
workers
wore
a
respirator
with
either
an
organic
vapor
removing
cartridge
with
a
prefilter
approved
for
pesticides,
a
canister
approved
for
pesticides,
or
a
NIOSH
approved
respirator
with
an
organic
vapor
cartridge
or
canister
with
any
N,
R,
P,
or
HE
prefilter.
During
mixing/
loading
operations,
workers
wore
a
minimum
of
long­
sleeved
shirt,
long
pants,
chemical­
resistant
gloves,
shoes
plus
socks,
protective
eyewear,
and
a
chemical­
resistant
apron.

For
closed
cab
field
trials,
the
Study
Report
states
that
workers
wore
long­
sleeved
shirts,
long
pants,
and
shoes
plus
socks.
Additional
PPE
was
provided
for
functions
requiring
it,
such
as
additional
mixing/
loading
and
equipment
adjustment.
During
mixing/
loading
operations,
the
worker
wore
a
long­
sleeved
shirt,
long
pants,
chemicalresistant
gloves,
protective
eyewear,
shoes
plus
socks
and
a
chemical­
resistant
apron.
The
Registrant
provided
a
complete
description
of
PPE
used
in
each
trail
(
not
provided
in
the
Study
Report).

6.
Application
Method
and
Rate
Application
rate(
s):
According
to
the
label
the
maximum
application
rate
recommended
for
apples
is
1.5
lb
ai/
acre.
The
application
rates
for
the
open
cab
trials
averaged
0.911
lb
ai/
acre
and
for
the
closed
cab
trials
averaged
1.407
lb
ai/
A
Application
Equipment:
Applications
were
made
with
open
and
closed
cab
tractordrawn
airblast
sprayers
    
6
  
39
Spray
Volume:
Spray
volumes
reported
for
the
open
cab
trials
ranged
from
10.2
and
109.8
gal/
acre
and
spray
volumes
reported
for
the
closed
cab
trials
ranged
from
43.5
to
102.7
gal/
acre.

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

7.
Exposure
monitoring
methodology
Urine
Samples
Total
24
hour
urine
output
was
collected
from
each
worker
performing
mixer/
loader/
applicator
activities
for
the
time
period
including
the
day
before
mixer/
loader/
applicator
activities
til
4
days
after
mixer/
loader/
applicator
activities.
Day
­
1
samples
were
those
collected
starting
after
the
first
void
of
the
bladder
in
the
morning
on
the
day
prior
to
exposure
and
ending
after
the
first
void
on
the
day
of
exposure
prior
to
initiation
of
mixer/
loader/
applicator
activities.
Day
0
samples
were
those
collected
during
the
24­
hour
period
following
the
beginning
of
exposure.
Samples
were
kept
in
refrigerators
in
individual
containers
during
the
24­
hour
collection
time.
After
collection
of
each
24­
hour
bulk
sample,
the
total
volume
of
each
sample
was
recorded.
The
samples
were
mixed
by
shaking,
and
duplicate
50­
mL
aliquots
were
transferred
to
separate
containers.
The
bulk
samples
and
aliquots
were
kept
frozen
between
collection
and
shipment.

Breathing
Zone
Air
Samples
Potential
inhalation
was
measured
using
OVS
tubes
and
a
personal
air­
sampling
pump
with
the
inlet
positioned
near
the
face
of
the
worker.
The
air
sampling
pumps
were
calibrated
prior
to
use
and
the
flow
rate
was
approximately
2
L/
min.
At
the
end
of
the
work
day,
the
OVS
tubes
were
placed
into
individually
labeled
plastic
bags
and
stored
in
a
freezer
until
shipment
.

C.
ANALYTICAL
METHODOLOGY:

1.
Sample
Extraction/
Detection:

Urine
Samples
Extraction
method:
An
MSMB­
d
3
internal
standard
was
added
to
a
10
mL
aliquot
of
urine.
The
sample
was
applied
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.
The
methylene
chloride
was
evaporated
and
the
residue
was
dissolved
in
1
mL
of
10%
aqueous
methanol.
The
resulting
solution
was
analyzed
by
LC/
MS­
MS.

Detection
methods:
See
Table
1.

Table
1.
Summary
of
Chromatographic
Conditions
for
Urine
GC
Column
Zorbax
SB
Aq,
5
µ
m,
50
mm
x
2.1
mm
    
7
  
39
Table
1.
Summary
of
Chromatographic
Conditions
for
Urine
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
Instrument
performance
and
calibration:
Calibration
curves
were
prepared
for
each
calibration
run.
The
limit
of
quantitation
for
urine
samples
was
reported
to
be
0.5
ng/
mL
and
the
limit
of
detection
was
reported
to
be
0.08
ng/
mL.
Method
validation
recoveries
were
reported
by
the
study
author
and
verified
by
HED.
Average
recoveries
ranged
from
86%
to
94%.

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.

Breathing
Zone
Air
Samples
The
top
and
bottom
sections
of
the
OVS
tubes
were
analyzed
separately.
The
top
portion
of
the
OVS
tube
(
including
the
retaining
ring,
filter,
upper
layer
of
XAD­
2
resin,
and
the
upper
foam
ring)
was
disassembled
and
placed
into
a
labeled
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
an
internal
standard
solution,
which
contained
a
mixture
of
dueterated
azinphos­
methyl
(
1.0
µ
g)
and
azinphos­
methyl
oxon
(
0.2
µ
g).
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
LC/
MS­
MS.

Detection
methods:
See
Table
2
Table
2.
Summary
of
Chromatographic
Conditions
for
OVS
Tubes
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
Instrument
performance
and
calibration:
Calibration
curves
were
prepared
for
each
calibration
run.
The
limit
of
quantitation
for
both
azinphos­
methyl
and
azinphosmethyl
oxon
was
reported
to
be
100
ng.
The
limit
of
detection
for
azinphos­
methyl
was
reported
to
be
5
ng
and
the
limit
of
detection
for
azinphos­
methyl
oxon
was
reported
to
be
9
ng.
Method
validation
recoveries
for
OVS
tubes
were
reported
by
the
study
author
and
verified
by
HED,
using
½
the
LOD
when
values
were
reported
as
less
than
the
LOD.
    
8
  
39
Average
recoveries
ranged
from
90%
to
107%
for
azinphos­
methyl
and
from
86%
to
102%
for
azinphos­
methyl
oxon.

Quantification:
The
azinphos­
methyl
or
azinphos­
methyl
oxon
residue
level
in
OVS
tubes
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.

2.
Quality
Control:

Lab
Recovery:
Concurrent
laboratory
recoveries
were
performed
for
both
urine
samples
and
for
the
OVS
tube
samples.
Urine
samples
were
fortified
at
the
0.50
ng/
mL
level
and
OVS
tubes
were
fortified
at
the
500
ng
level.
HED
verified
the
results
provided
in
the
Study
Report
and
these
are
presented
in
Tables
3
and
4.

Table
3.
Urine
Sample
Concurrent
Laboratory
Recoveries
Sample
No.
Fortification
Level
(
ng/
mL)
Measured
residue
(
ng/
mL)
Average
Blank
Sample
Residue
(
ng/
mL)
Corrected
residuea
(
ng/
mL)
Percent
Recovery
(%)
Average
Recovery
(%)
Overall
Average
Recovery
(%)

Open
cabs
(
Trials
GU020­
03D
through
GU034­
03D)

0.413
0.402
80
GU020­
03D
0.514
0.011
0.503
101
91
0.447
0.406
81
GU022­
03D
0.555
0.041
0.514
103
92
0.591
0.571
114
GU024­
03D
0.5
0.02
0.48
96
105
0.428
0.424
85
GU027­
03D
0.425
0.004
0.421
84
84
0.432
0.395
79
GU029­
03D
0.439
0.037
0.402
80
86
0.489
0.482
96
GU031­
03D
0.44
0.007
0.433
87
95
0.561
0.549
110
GU033­
03D
0.442
0.012
0.43
86
92
0.474
0.46
92
GU045­
03D
(
closed
cab
sample,
but
analyzed
with
additional
samples
in
open
cab
trial)
0.5
0.48
0.014
0.466
93
93
92
Closed
cabs
(
Trials
GU035­
03D
through
GU049­
03D)

0.451
0.437
87
GU036­
03D
0.453
0.014
0.439
88
88
0.455
0.447
89
GU037­
03D
0.46
0.008
0.452
90
90
0.457
0.454
91
GU041­
03D
0.509
0.003
0.506
101
97
0.467
0.462
92
GU042­
03D
0.53
0.005
0.525
105
96
0.474
0.46
92
GU045­
03D
0.48
0.014
0.466
93
97
0.566
0.529
106
GU046­
03D
0.5
0.037
92
93
    
9
  
39
Table
3.
Urine
Sample
Concurrent
Laboratory
Recoveries
Sample
No.
Fortification
Level
(
ng/
mL)
Measured
residue
(
ng/
mL)
Average
Blank
Sample
Residue
(
ng/
mL)
Corrected
residuea
(
ng/
mL)
Percent
Recovery
(%)
Average
Recovery
(%)
Overall
Average
Recovery
(%)

0.512
0.475
95
0.468
0.452
90
GU048­
03D
0.401
0.016
0.385
77
84
a
Corrected
residue
is
the
measured
residue
minus
the
average
blank
residue.
    
10
  
39
Table
4.
OVS
Tubes
Concurrent
Laboratory
Recoveries
Trial
Number
Fortification
Level
(
ng)
Measured
Bottom
Residue
(
ng)
Bottom
Blank
Residues
(
ng)
Corrected
Bottom
Residuea
(
ng)
Measured
Top
Residue
(
ng)
Top
Blank
Residues
(
ng)
Corrected
Top
Residuea
(
ng)
Total
Residue
(
top
+
bottom)
(
ng)
Percent
recovery
(%)
Average
Percent
Recovery
(%)

Open
cabs
(
Trials
GU020­
03D
through
GU034­
03D)

Azinphos­
methyl
(
AZM)

GU020­
03D
9.8
20.9
<
LODb
538.9
17
521.9
524.4
105
GU024­
03D
29.5
30.3
<
LOD
546.1
34.6
511.5
514
103
GU027­
03D
9.6
11.7
<
LOD
517.9
44.7
473.2
475.7
95
GU031­
03D
<
LOD
11.6
<
LOD
502.3
7.6
494.7
497.2
99
GU045­
03Dc
500
7
12.2
<
LOD
538.9
16
522.9
525.4
105
101
Azinphos­
methyl
oxon
(
AZM­
oxon)

GU020­
03D
<
LOD
<
LOD
<
LOD
479.1
<
LOD
474.6
479.1
96
GU024­
03D
<
LOD
<
LOD
<
LOD
492.2
<
LOD
487.7
492.2
98
GU027­
03D
<
LOD
<
LOD
<
LOD
478.7
<
LOD
474.2
478.7
96
GU031­
03D
<
LOD
<
LOD
<
LOD
501.6
<
LOD
497.1
501.6
100
GU045­
03Dc
500
<
LOD
<
LOD
<
LOD
480.4
<
LOD
475.9
480.4
96
97
Closed
cabs
(
Trials
GU035­
03D
through
GU049­
03D)

AZM
GU020­
03Dc
9.8
20.9
<
LOD
538.9
17
521.9
524.4
105
GU035­
03D
<
LOD
<
LOD
<
LOD
513.6
<
LOD
511.1
513.6
103
GU045­
03D
7
12.2
<
LOD
538.9
16
522.9
525.4
105
GU048­
03­
Dc
500
5.5
28.2
<
LOD
506.4
10.2
496.2
498.7
100
103
AZM­
oxon
GU020­
03Dc
<
LOD
<
LOD
<
LOD
479.1
<
LOD
474.6
479.1
96
GU035­
03D
<
LOD
<
LOD
<
LOD
467.8
<
LOD
463.3
467.8
94
GU045­
03D
<
LOD
<
LOD
<
LOD
480.4
<
LOD
475.9
480.4
96
GU048­
03­
D
500
<
LOD
<
LOD
<
LOD
468.2
<
LOD
463.7
468.2
94
95
a
Corrected
residue
is
the
measured
residue
minus
the
average
blank
residue.

b
If
values
were
<
LOD,
½
LOD
was
used
in
calculations.

c
Occasionally
a
lab
recovery
sample
collected
for
a
closed
cab
trial
was
analyzed
in
the
open
cab
sample
run
as
a
lab
recovery
sample.
Also,
occasionally
a
lab
recovery
sample
collected
in
the
open
cab
trials
was
analyzed
in
the
closed
cab
sample
run
and
used
as
a
lab
recovery
.

Field
Recovery
Urine
Samples
Four
trials
in
the
closed
cab
study
and
4
trials
in
the
open
cab
study
included
 
spiked 
fortification
urine
samples.
These
included
one
control,
three
low
fortification
(
0.50
ng/
mL)
and
three
high
fortification
(
10
ng/
mL)
samples.
These
samples
were
stored
in
a
laboratory
freezer
and
upon
collection
of
the
day­
1
samples,
the
field
fortification
samples
were
transferred
to
the
refrigerator
used
for
storing
the
urine
during
collection.
The
fortification
samples
were
returned
to
freezer
storage
after
aliquots
were
removed
from
the
final
urine
sample.
For
the
open
cab
trials,
overall
percent
recoveries
ranged
from
82%
to
91%
and
for
the
closed
cab
trials,
ranged
from
79%
to
97%.

Table
5.
Urine
Sample
Field
Fortification
Recoveries
    
11
  
39
Trial
Number
Fortification
Level
Fortified
(
ng/
mL)
Measured
residue
(
ng/
mL)
Blank
Sample
Residue
(
ng/
mL)
Corrected
residuea
(
ng/
mL)
Percent
recovery
(%)
Average
Percent
Recovery
(%)
Overall
Average
Percent
Recovery
(%)

Open
cabs
(
Trials
GU020­
03D
through
GU034­
02D)

0.409
0
0.409
82
0.406
0
0.406
81
Low
0.5
0.39
0
0.39
78
80
9.762
0
9.762
98
9.329
0
9.329
93
GU020­
03D
High
10
8.522
0
8.522
85
92
86
4.065
0.01
4.055
811
4.15
0.01
4.140
828
Lowb
0.5
3.869
0.01
3.859
772
804
(
excluded
from
the
data
set)
­­

7.602
0.01
7.592
76
8.106
0.01
8.096
81
GU024­
03D
High
10
8.009
0.01
7.999
80
79
79
0.52
0.002
0.518
104
0.464
0.002
0.462
92
Low
0.5
0.499
0.002
0.497
99
98
7.773
0.002
7.771
78
9.356
0.002
9.354
94
GU045­
03D
High
10
7.975
0.002
7.973
80
84
91
0.399
0.008
0.391
78
0.397
0.008
0.389
78
Low
0.5
0.432
0.008
0.424
85
80
8.704
0.008
8.696
87
8.735
0.008
8.727
87
GU027­
03D
High
10
7.895
0.008
7.887
79
84
82
0.500
0.023
0.477
95
0.458
0.023
0.435
87
Low
0.5
0.461
0.023
0.438
88
90
7.787
0.023
7.764
78
8.326
0.023
8.303
83
GU031­
03D
High
10
9.585
0.023
9.562
96c
85
88
Closed
cabs
(
Trials
GU035­
03D
through
GU049­
03D)

0.517
0.152
0.365
73
0.526
0.152
0.374
75
Low
0.5
0.566
0.152
0.414
83
77
8.596
0.152
8.444
84
8.024
0.152
7.872
79
GU035­
03D
High
10
7.916
0.152
7.764
78
80
79
0.664
0.132
0.532
106
0.549
0.132
0.417
83
GU040­
03D
Low
0.5
90
87
    
12
  
39
Table
5.
Urine
Sample
Field
Fortification
Recoveries
Trial
Number
Fortification
Level
Fortified
(
ng/
mL)
Measured
residue
(
ng/
mL)
Blank
Sample
Residue
(
ng/
mL)
Corrected
residuea
(
ng/
mL)
Percent
recovery
(%)
Average
Percent
Recovery
(%)
Overall
Average
Percent
Recovery
(%)

0.534
0.132
0.402
80
7.832
0.132
7.700
77
8.689
0.132
8.557
86
High
10
9.224
0.132
9.092
91
84
0.520
0.002
0.518
104
0.464
0.002
0.462
92
Low
0.5
0.499
0.002
0.497
99
98
7.773
0.002
7.771
78
9.356
0.002
9.354
94
GU045­
03D
High
10
7.975
0.002
7.973
80
84
91
0.409
0
0.409
82
0.406
0
0.406
81
Low
0.5
0.390
0
0.39
78
80
9.762
0
9.762
98
9.329
0
9.329
93
GU020­
03D
High
10
8.522
0
8.522
85
92
86
0.567
0.027
0.540
108
0.528
0.027
0.501
100
Low
0.5
0.517
0.027
0.490
98
102
9.557
0.027
9.530
95
9.363
0.027
9.336
93
GU048­
03D
High
10
8.567
0.027
8.54
85
91
97
a
Corrected
residue
is
the
measured
residue
minus
the
average
blank
residue.

b
Not
used
since
study
report
states
that
samples
were
misfortified
c
In
raw
data,
this
sample
is
listed
as
GU027­
03D;
but
it
is
assumed
that
this
is
a
typo
Breathing
Zone
Air
Samples
Four
trials
in
the
closed
cab
study
and
4
trials
in
the
open
cab
study
included
 
spiked 
fortification
samples,
two
at
the
low
fortification
(
500
ng)
level
and
two
at
the
high
fortification
(
10,000
ng)
level.
Air
was
drawn
through
the
fortified
tubes
during
a
period
equivalent
to
the
azinphos­
methyl
exposure
at
the
flow
rate
used
for
the
study.
Table
6
provides
the
field
fortification
recoveries
for
the
OVS
tubes.
For
the
open
cab
trials,
AZM
overall
average
field
fortification
recoveries
ranged
from
80%
to
93%
and
AZM­
oxon
overall
average
field
fortification
recoveries
ranged
from
88%
to
99%.
For
the
closed
cab
trials,
AZM
overall
average
field
fortification
recoveries
ranged
from
80%
to
9%
and
AZM­
oxon
overall
average
field
fortification
recoveries
ranged
from
81%
to
99%.

Table6.
OVS
Tubes
Field
Fortification
Recoveries
    
13
  
39
Trial
Number
Fortification
Level
(
ng)
Measured
Bottom
Residue
(
ng)
Bottom
Blank
Residues
(
ng)
Corrected
Bottom
Residuea
(
ng)
Measured
Top
Residue
(
ng)
Top
Blank
Residues
(
ng)
Corrected
Top
Residuea
(
ng)
Total
Residue
(
top
+
bottom)
(
ng)
Percent
recovery
(%)
Average
Percent
Recovery
(%)
Overall
Average
Recovery
(%)

Open
cabs
(
Trials
GU020­
03D
through
GU034­
02D)

AZMb
6.5
6.3
<
LODc
442.1
8.5
433.6
436.1
87
500
<
LOD
6.3
<
LOD
434.2
8.5
425.7
428.2
86
86
8.3
6.3
<
LOD
8841.7
8.5
8833.2
8835.7
88
GU020­
03D
10000
8.8
6.3
<
LOD
10104.5
8.5
10096
10098.5
101
95
91
<
LOD
2.5
<
LOD
508
18.7
489.3
491.8
98
500
<
LOD
2.5
<
LOD
503.2
18.7
484.5
487
97
98
16.3
2.5
13.8
8864.9
18.7
8846.2
8860
89
GU031­
03D
10000
17.8
2.5
15.3
8787.1
18.7
8768.4
8783.7
88
88
93
<
LOD
2.5
<
LOD
366.7
14.5
352.2
354.7
71
500
<
LOD
2.5
<
LOD
373.8
14.5
359.3
361.8
72
72
<
LOD
2.5
<
LOD
9069.6
14.5
9055.1
9057.6
91
GU045­
03D
10000
<
LOD
2.5
<
LOD
8642
14.5
8627.5
8630
86
88
80
25.4
27.3
<
LOD
368.4
14.1
354.3
356.8
71
500
23.4
27.3
<
LOD
363.9
14.1
349.8
352.3
70
71
57.5
27.3
30.2
9478.8
14.1
9464.7
9494.9
95
GU024­
03D
10000
28.1
27.3
<
LOD
9096.7
14.1
9082.6
9085.1
91
93
82
6.4
5.4
<
LOD
486.4
16.5
469.9
472.4
94
500
5.3
5.4
<
LOD
538.2
16.5
521.7
524.2
105
100
19.7
5.4
14.3
8343.5
16.5
8327
8341.3
83
GU027­
03D
10000
5.6
5.4
<
LOD
8249.9
16.5
8233.4
8235.9
82
83
91
AZM­
oxond
<
LOD
<
LOD
<
LOD
533.9
<
LOD
529.4
533.9
107
500
<
LOD
<
LOD
<
LOD
518.4
<
LOD
513.9
518.4
104
105
<
LOD
<
LOD
<
LOD
9016.8
<
LOD
9012.3
9016.8
90
GU020­
03D
10000
<
LOD
<
LOD
<
LOD
9374.6
<
LOD
9370.1
9374.6
94
92
99
<
LOD
<
LOD
<
LOD
465.3
<
LOD
460.8
465.3
93
500
<
LOD
<
LOD
<
LOD
468.8
<
LOD
464.3
468.8
94
93
13.9
9.4
9.4
9135.8
<
LOD
9131.3
9140.7
91
GU031­
03D
10000
12.5
<
LOD
<
LOD
8822.8
<
LOD
8818.3
8822.8
88
90
92
<
LOD
<
LOD
<
LOD
503.3
<
LOD
498.8
503.3
101
500
<
LOD
<
LOD
<
LOD
538.7
<
LOD
534.2
538.7
108
104
<
LOD
<
LOD
<
LOD
8479.6
<
LOD
8475.1
8479.6
85
GU045­
03D
10000
<
LOD
<
LOD
<
LOD
8160
<
LOD
8155.5
8160
82
83
94
<
LOD
<
LOD
<
LOD
411.8
<
LOD
407.3
411.8
82
GU024­
03D
500
<
LOD
<
LOD
<
LOD
402.3
<
LOD
397.8
402.3
80
81
88
    
14
  
39
Table6.
OVS
Tubes
Field
Fortification
Recoveries
Trial
Number
Fortification
Level
(
ng)
Measured
Bottom
Residue
(
ng)
Bottom
Blank
Residues
(
ng)
Corrected
Bottom
Residuea
(
ng)
Measured
Top
Residue
(
ng)
Top
Blank
Residues
(
ng)
Corrected
Top
Residuea
(
ng)
Total
Residue
(
top
+
bottom)
(
ng)
Percent
recovery
(%)
Average
Percent
Recovery
(%)
Overall
Average
Recovery
(%)

<
LOD
<
LOD
<
LOD
9440.2
<
LOD
9435.7
9440.2
94
10000
<
LOD
<
LOD
<
LOD
9348.3
<
LOD
9343.8
9348.3
93
94
<
LOD
<
LOD
<
LOD
466.8
<
LOD
462.3
466.8
93
500
<
LOD
<
LOD
<
LOD
513.8
<
LOD
509.3
513.8
103
98
12.8
<
LOD
<
LOD
8955.2
<
LOD
8950.7
8955.2
90
GU027­
03D
10000
<
LOD
<
LOD
<
LOD
8202.3
<
LOD
8197.8
8202.3
82
86
92
Closed
cabs
(
Trials
GU035­
03D
through
GU049­
03D)

AZM
6.5
6.3
<
LOD
442.1
8.5
433.6
436.1
87
500
<
LOD
6.3
<
LOD
434.2
8.5
425.7
428.2
86
86
8.3
6.3
<
LOD
8841.7
8.5
8833.2
8835.7
88
GU020­
03D
10000
8.8
6.3
<
LOD
10104.5
8.5
10096
10098.5
101
95
91
5
<
LOD
<
LOD
501.7
18.7
483
485.5
97
500
7.7
<
LOD
5.2
365.9
18.7
347.2
352.4
70
84
6
<
LOD
<
LOD
8639.4
18.7
8620.7
8623.2
86
GU048­
03D
10000
<
LOD
<
LOD
<
LOD
8637.6
18.7
8618.9
8621.4
86
86
85
<
LOD
<
LOD
<
LOD
366.7
14.5
352.2
354.7
71
500
<
LOD
<
LOD
<
LOD
373.8
14.5
359.3
361.8
72
72
<
LOD
<
LOD
<
LOD
9069.6
14.5
9055.1
9057.6
91
GU045­
03D
10000
<
LOD
<
LOD
<
LOD
8642
14.5
8627.5
8630
86
88
80
<
LOD
<
LOD
<
LOD
487.7
<
LOD
485.2
487.7
98
<
LOD
<
LOD
<
LOD
476.6
<
LOD
474.1
476.6
95
<
LOD
<
LOD
<
LOD
496.6
<
LOD
494.1
496.6
99
500
<
LOD
<
LOD
<
LOD
506.5
<
LOD
504
506.5
101
98
18.2
<
LOD
15.7
9636.9
<
LOD
9634.4
9650.1
97
17.3
<
LOD
14.8
9743.3
<
LOD
9740.8
9755.6
98
13
<
LOD
10.5
10187.2
<
LOD
10184.7
10195.2
102
GU035­
03D&
G
U040­
03D
10000
6.9
<
LOD
<
LOD
9897.1
<
LOD
9894.6
9897.1
99
99
99
AZM­
oxon
<
LOD
<
LOD
<
LOD
533.9
<
LOD
529.4
533.9
107
500
<
LOD
<
LOD
<
LOD
518.4
<
LOD
513.9
518.4
104
105
<
LOD
<
LOD
<
LOD
9016.8
<
LOD
9012.3
9016.8
90
GU020­
03D
10000
<
LOD
<
LOD
<
LOD
9374.6
<
LOD
9370.1
9374.6
94
92
99
<
LOD
<
LOD
<
LOD
437.3
<
LOD
432.8
437.3
87
500
<
LOD
<
LOD
<
LOD
326.9
<
LOD
322.4
326.9
65
76
GU048­
03D
81
    
15
  
39
Table6.
OVS
Tubes
Field
Fortification
Recoveries
Trial
Number
Fortification
Level
(
ng)
Measured
Bottom
Residue
(
ng)
Bottom
Blank
Residues
(
ng)
Corrected
Bottom
Residuea
(
ng)
Measured
Top
Residue
(
ng)
Top
Blank
Residues
(
ng)
Corrected
Top
Residuea
(
ng)
Total
Residue
(
top
+
bottom)
(
ng)
Percent
recovery
(%)
Average
Percent
Recovery
(%)
Overall
Average
Recovery
(%)

<
LOD
<
LOD
<
LOD
8599.2
<
LOD
8594.7
8599.2
86
10000
<
LOD
<
LOD
<
LOD
8674.4
<
LOD
8669.9
8674.4
87
86
<
LOD
<
LOD
<
LOD
503.3
<
LOD
498.8
503.3
101
500
<
LOD
<
LOD
<
LOD
538.7
<
LOD
534.2
538.7
108
104
<
LOD
<
LOD
<
LOD
8479.6
<
LOD
8475.1
8479.6
85
GU045­
03D
10000
<
LOD
<
LOD
<
LOD
8160
<
LOD
8155.5
8160
82
83
94
<
LOD
<
LOD
<
LOD
496.6
<
LOD
492.1
496.6
99
<
LOD
<
LOD
<
LOD
500.3
<
LOD
495.8
500.3
100
<
LOD
<
LOD
<
LOD
494.9
<
LOD
490.4
494.9
99
500
<
LOD
<
LOD
<
LOD
502.9
<
LOD
498.4
502.9
101
100
15.5
<
LOD
11
9959.1
<
LOD
9954.6
9965.6
100
16.5
<
LOD
12
9706.5
<
LOD
9702
9714
97
10.6
<
LOD
<
LOD
9671.7
<
LOD
9667.2
9671.7
97
GU035­
03D&
G
U040­
03D
10000
<
LOD
<
LOD
<
LOD
9113.8
<
LOD
9109.3
9113.8
91
96
98
a
Corrected
residue
is
the
measured
residue
minus
the
average
blank
residue.

b
AZM
=
azinphos­
methylc
For
values
less
than
the
LOD,
½
the
LOD
was
used
in
subsequent
calculations.
For
AZM
½
LOD
=
2.5
ng
and
for
AZM
oxon
½
LOD
=
4.5
ng
d
AZM­
oxon
=
azinphos­
methyl
oxon
    
16
  
39
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
30
days
prior
to
extraction
and
all
extracts
were
analyzed
within
15
days
after
extraction.
OVS
tube
samples
were
held
for
a
maximum
of
152
days
prior
to
extraction
and
all
extracts
were
analyzed
within
2
days
after
extraction.
The
Study
Report
states
that
the
acceptable
recoveries
from
the
field
fortification
samples
indicates
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
urinary
biomarker,
MSMB,
residues
measured
in
24
hour
urine
samples
collected
from
each
worker
during
a
sampling
interval
of
120
hours
following
initiation
of
exposure.
MSMB
residue
levels
are
presented
in
this
report
as
µ
g
equivalents
of
parent
azinphos
methyl.
Equivalents
were
calculated
using
a
molecular
weight
conversion
factor
of
1.328.
The
MSMB
residues
measured
in
the
urine
samples
following
entry
are
presented
both
with
a
correction
for
the
amount
of
MSMB
residue
found
in
each
worker s
urine
sample
from
the
day
before
entry
(
day
­
1,
assumed
to
be
a
background
concentration)
and
without
this
correction.
HED
also
corrected
field
fortification
samples
for
blank
sample
residues
and
corrected
all
field
samples
for
field
fortification
recoveries,
even
those
greater
than
90%
per
EPA s
request.
Corrected
residue
was
then
adjusted
for
the
volume
of
urine
collected
during
each
24
hour
sampling
interval.
The
MSMB
residue
levels
excreted
for
each
worker
over
the
entire
post­
entry
sampling
interval
(
120
hours
following
initiation
of
exposure)
were
summed
(
i.
e.,
day
0,
day
1,
day
2,
day
3,
and
day
4).
HED
adjusted
the
summed
MSMB
excreted
for
each
worker
for
the
cumulative
percent
of
the
absorbed
dose
excreted
96­
120
hours
after
exposure
(
determined
from
a
previous
study
 
83.6%)
and
the
percent
of
urine
activity
attributed
to
MSMB
(
determined
from
a
previous
study
 
9.2%).
These
results
were
then
normalized
to
body
weight
and
amount
of
active
ingredient
handled.
Table
7
provides
the
average
azinphos­
methyl
doses
for
open
and
closed
cab
field
trials
based
on
body
weight
and
pounds
of
active
ingredient
handled.
Doses
were
calculated
both
by
correcting
for
background
residues
and
not
correcting
for
background
residues
(
day
­
1
residues).
The
average
azinphos­
methyl
doses
for
open
cab
and
closed
cab
field
trials,
without
background
correction,
are
0.0035
and
0.00080
mg/
kg
body
weight,
respectively.
The
total
average
azinphos­
methyl
doses
for
open
cab
and
closed
cab
field
trials,
with
background
correction,
are
0.0027
and
0.00057
mg/
kg
body
weight,
respectively.
Azinphos­
methyl
doses
for
open
and
closed
cab
field
trials,
based
on
pounds
active
ingredient
handled,
are
0.013
and
0.0023
mg/
lb
ai
handled
(
without
background
correction)
and
0.0095
and
0.0017
mg/
lb
ai
handled
(
with
background
correction).
Tables
8
and
9
provide
individual
azinphos­
methyl
doses
for
each
field
trial,
both
corrected
for
background
residues
and
not
corrected
for
background
residues.
    
17
  
39
Breathing
Zone
Air
Samples
Potential
inhalation
exposure
was
determined
through
the
use
of
OVS
sampling
tubes
and
is
presented
in
Table
10.
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.
Average
potential
inhalation
exposures
for
open
cab
trials
were
calculated
to
be
166.8
µ
g
or
4.0
µ
g/
lb
ai
handled
and
average
exposures
for
enclosed
cab
trials
were
calculated
to
be
14.7
µ
g
or
0.2
µ
g/
lb
ai
handled.
The
inhalation
exposure
concentration
for
mixer/
loader/
applicators
using
open
cab
tractor
drawn
airblast
equipment
ranged
from
8.79
to
40.03
µ
g/
m3
and
averaged
24.5
µ
g/
m3.
For
mixer/
loader/
applicators
using
enclosed
cab
tractor
drawn
airblast
equipment
concentration
levels
ranged
from
0.37
to
5.03
µ
g/
m3
and
averaged
1.9
µ
g/
m3.

III
DISCUSSION:

A.
LIMITATIONS
OF
THE
STUDY:
This
study
met
most
of
the
Group
A
875.1300
(
inhalation
exposure)
and
875.1500
(
biological
monitoring)
Guidelines.
The
major
issues
of
concern
are:

 
The
guideline
states
that
a
sufficient
number
of
replicates
should
be
generated
to
address
the
exposure
issues
associated
with
the
population
of
interest.
The
open
cab
study
began
with
15
replicates,
however,
results
from
three
of
the
workers
were
excluded
from
the
data
analysis
due
to
unusually
high
background
(
day
­
1)
residue
levels.

·
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;
and
information
on
storage
stability
should
be
provided.
The
Study
Report
states
that
samples
were
stored
frozen
prior
to
analysis
and
that
field
fortification
samples
and
recoveries
were
used
to
demonstrate
storage
stability.
A
separate
storage
stability
study
was
not
mentioned.

·
According
to
active
AZM
label,
the
maximum
application
rate
recommended
for
apples
is
1.5
lb
ai/
acre.
The
actual
application
rates
for
the
open
cab
trials
averaged
0.911
lb
ai/
A
(
ranging
from
0.534
lb
ai/
A
to
1.098
lb
ai/
A
and
for
the
closed
cab
trials
averaged
1.407
lb
ai/
A
(
ranging
from
0.62
lb
ai/
A
to
2.052
lb
ai/
A).

·
The
guideline
states
that
data
should
be
corrected
if
any
appropriate
field
fortified,
laboratory
fortified
or
storage
stability
recovery
is
less
than
90
percent.
This
criterion
was
altered
and
the
Study
Report
states
that
corrections
were
made
for
all
field
fortification
recovery
values,
even
those
above
90%.

·
The
guideline
states
that
a
trapping
efficiency
test
for
the
monitoring
media
chosen
must
be
documented.
A
trapping
efficiency
test
was
not
reported.
However,
average
method
validation
recoveries
ranged
from
90%
to
107%
for
azinphos­
methyl
and
from
86%
to
102%
for
azinphos­
methyl
oxon.
    
18
  
39
·
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
the
extraction
efficiency
of
laboratory
fortified
controls
is
considered
acceptable
if
the
lower
limit
of
the
95%
confidence
interval
is
greater
than
75%,
unless
otherwise
specified
by
the
Agency.
At
a
minimum,
the
guideline
states
that
seven
determinations
should
be
made
at
each
fortification
level
to
calculate
the
mean
and
standard
deviation
for
recovery
and
that
the
total
recovery
from
field­
fortified
samples
must
be
greater
than
50%
for
the
study.
Laboratory
control
samples
were
fortified
and
yielded
average
recoveries
of
101%
for
azinphos­
methyl
and
97%
for
azinphos­
methyl
oxon
for
the
open
cab
field
trials
and
103%
for
azinphos­
methyl
and
95%
for
azinphos­
methyl
oxon
for
the
closed
cab
field
trials.
There
were
5
fortification
samples
at
2
levels,
with
all
recoveries
greater
than
50%.

·
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.

·
Rainfall
from
the
first
application
to
the
last
sampling
was
the
only
meteorological
condition
reported
by
the
registrant.

Additionally
other
major
issues
of
concern
were
noted
in
evaluation
of
the
study:

·
The
Registrant
presented
results
in
terms
of
the
quantity
of
azinphos­
methyl
equivalent
excreted
at
each
24
hour
sampling
interval.
This
calculation
does
not
correlate
to
the
total
dose
received
after
one
day s
exposure
to
azinphos­
methyl.
The
estimated
dose
received
after
one
day
of
exposure
is
calculated
by
adding
the
daily
amount
excreted
over
the
120
hour
collection
period
and
factoring
for
azinphos
methyl
dose
expected
to
be
excreted
in
urine
120
hours
after
exposure
and
the
percentage
of
azinphos
methyl
dose
represented
by
MSMB.

·
The
Registrant
used
an
inappropriate
adjustment
factor
to
normalize
measured
azinphos
methyl
equivalents
to
correspond
to
an
estimated
azinphos
methyl
dose.
The
authors
used
the
adjustment
factor
appropriate
for
a
collection
over
192
hours
(
not
the
120
hour
collection
used
in
the
study).
The
value
used
by
the
study
authors
was
8.2%
representing
89.3%
of
the
absorbed
dose
excreted
over
120­
192
hours.
Urine
samples
were
collected
for
120
hours
after
entry.
The
registrant
also
used
this
correction
factor
for
each
24
hour
urine
sampling
period
beginning
with
the
first
24
hours
after
entry
(
day
0).
In
order
to
estimate
the
total
absorbed
dose
of
AZM
based
on
120
hour
MSMB
residue
levels,
the
appropriate
correction
value
is
9.2%
representing
83.6%
of
the
absorbed
dose
    
19
  
39
excreted
in
urine
over
120
hours.
The
calculation
also
requires
the
addition
of
residue
values
from
all
five
sampling
intervals
(
i.
e.,
day
0,
day
1,
day
2,
day
3,
and
day
4).

·
Registrant
inhalation
exposure
estimates
are
based
on
a
breathing
rate
of
29
L/
min.
HED
inhalation
exposure
estimates
are
based
on
the
NAFTA
recommended
breathing
rate
of
16.7
L/
min
for
light
activities.

·
HED
is
concerned
about
the
methodology
used
to
 
adjust 
day
0
through
day
4
AZM
doses
by
subtracting
out
the
AZM
dose
measured
on
the
day
before
exposure
 
called
 
background
AZM 
in
the
study.
In
most
of
replicates
in
the
other
studies
and
in
the
enclosed
cab
portion
of
this
study,
the
background
AZM
is
at
or
near
the
LOD.
However,
only
three
of
the
replicates
in
the
open
cab
portion
of
this
study
had
background
levels
less
than
LOD.
In
the
rest
of
the
open­
cab
replicates,
the
 
background 
levels
are
higher
than
the
LOD
 
in
some
cases
substantially
higher
­
and
clearly
impact
the
resulting
AZM
doses.
Since
there
is
a
high
degree
of
uncertainty
about
the
pre­
study
AZM
exposures
experienced
by
the
handlers
in
this
study
 
there
are
five
study
deviations
where
handlers
did
not
have
the
minimum
14­
day
no­
exposure
period
and
three
instances
where
handler
replicates
were
thrown
out
due
to
unusually
high
 
background 
levels
of
AZM
 
the
more
protective
approach
might
be
to
not
adjust
for
 
background 
AZM
levels.

·
The
personal
protective
equipment
worn
by
handlers
in
the
open
cab
replicates
 
particularly
the
chemical­
resistant
suits
and
negative
pressure
respirators
 
presents
a
heat­
and
respiratory­
stress
concern.
The
Office
of
Pesticide
Programs 
Guide
to
Heat
Stress
in
Agriculture
indicates
that
persons
doing
light
work
in
chemical­
resistant
attire
should
work
only
30
minutes
out
of
each
hour
if
the
temperature
is
80
degrees
and
there
is
full
sun.
The
work
cycle
diminishes
to
15
minutes
at
85
degrees
and
full
sun
and
at
90
degrees
and
full
sun,
it
indicates
a
very
high
risk
of
heat­
related
illness
and
recommends
stopping
work.
Since
the
Worker
Protection
Standard
for
Agricultural
Pesticides
requires
employers
to
 
take
any
necessary
steps
to
prevent
heat
illness
while
PPE
is
being
worn, 
and
removed
all
requirements
for
chemical­
resistant
suits
from
pesticide
labels
for
routine
handling
tasks,
this
would
appear
to
make
the
use
of
chemical­
resistant
suits
for
routine
airblast
applications
in
open
cabs
impractical,
if
not
impossible,
during
the
summer
months
when
most
AZM
orchard
applications
take
place.

·
In
the
open
cab
replicates,
there
are
five
deviations
(
for
replicates
22,
23,
24,
25,
and
26)
indicating
that
the
handlers
in
those
replicates
did
not
have
the
minimum
14­
day
period
(
prior
to
testing)
in
which
the
volunteer
was
not
to
have
been
exposed
to
AZM.
Instead,
various
AZM­
free
exposure
days
are
reported
 
ranging
from
seven
exposure­
free
days
for
replicate
22
to
ten
exposure­
free
days
for
replicates
25
and
26.
After
the
data
were
analyzed,
the
study
authors
reported
that
three
of
the
open
cab
handlers
(
replicates
22,
28,
and
33)
had
 
obvious
exposure
to
AZM 
prior
to
the
study
onset
and
the
authors
did
not
include
data
from
these
three
replicates
in
when
they
analyzed/
summarized
the
open
cab
replicate
results.
No
explanation
is
given
as
to
why
replicates
28
and
33
might
have
high
background
levels
of
AZM.
Also,
by
throwing
out
the
three
replicates,
the
open
cab
portion
of
the
study
has
only
12
remaining
replicates.
    
20
  
39
·
In
the
open
cab
replicates,
handlers
wore
two
distinct
types
of
PPE.
Replicates
20
through
26
(
minus
22,
which
was
not
used)
wore
uncoated
Tyvek
coveralls
over
long­
sleeve
shirt
and
long
pants
and
some
type
of
chemical­
resistant
headgear,
whereas
replicates
27
through
34
(
minus
28
and
33,
which
were
not
used)
wore
over
their
long­
sleeve
shirt
and
long
pants
either
a
two­
piece
hooded
rubber
rainsuit
or
a
one­
piece
hooded
PVC­
coated
coverall.
Since
these
are
two
different
levels
of
personal
protective
equipment
 
double­
layer
body
protection
for
the
uncoated
Tyvek
versus
chemical­
resistant
suit
for
the
rainsuit
and
coated
Tyvek,
these
data
probably
should
be
analyzed
and
summarized
separately.

·
In
the
enclosed
cab
replicates
(
replicates
35
through
49),
all
of
the
cabs
are
listed
as
having
charcoal
filtration
systems,
except
replicates
45,
46,
47,
and
49.
However,
since
handlers
in
the
enclosed
cabs
that
did
not
list
charcoal
filtration
systems
were
apparently
not
wearing
respirators,
it
is
possible
that
all
the
enclosed
cabs
had
charcoal
filtration
systems.
Enclosed
cabs
with
charcoal
filtration
systems
are
quite
sophisticated
and
expensive
and
provide
both
dermal
and
inhalation
protection.
The
inexpensive
type
of
enclosed
cab
provides
dermal
protection
only.
HED
notes
that
the
enclosed
cabs
were
used
without
apparent
difficulty
in
apple
orchards
 
even
orchards
containing
the
smaller
hybrid
trees.

Table
7.
Azinphos­
methyl
Doses
For
Open
and
Closed
Cab
Field
Trials
by
Body
Weight
and
by
Pounds
Active
Ingredient
Handled
Open
Cab
Field
Trials
Closed
Cab
Field
Trials
Arithmetic
Mean
Geometric
Mean
Standard
Deviation
Arithmetic
Mean
Geometric
Mean
Standard
Deviation
Not
corrected
for
background
residues
mg/
kg
body
weight
0.0035
0.0029
0.0019
0.00080
0.00056
0.00070
mg/
lb
ai
handled
0.013
0.010
0.0092
0.0023
0.0016
0.0021
Corrected
for
background
residues
mg/
kg
body
weight
0.0027
0.0021
0.0016
0.00057
0.00034
0.00053
mg/
lb
ai
handled
0.0095
0.0075
0.0060
0.0017
0.0010
0.0019
    
21
  
39
Table
8.
Azinphos­
methyl
Internal
Dose
(
Not
corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

OPEN
CABS
­
1
0
2.168
1
4.727
2
3.913
3
1.624
GU020­
03D
4
1.099
13.530
83.6
9.2
176
91
0.0019
35
0.0050
­
1
0
13.031
1
9.167
2
9.820
3
5.040
GU021­
03D
4
2.695
39.754
83.6
9.2
517
95
0.0054
63
0.0082
­
1
0
6.649
1
3.699
2
8.290
3
10.477
GU022­
03D
4
3.403
Study
noted
that
sample
had
high
background;
was
not
included
in
data
analysis.

­
1
0
15.334
1
9.059
2
4.303
3
2.830
GU023­
03D
4
1.439
32.965
83.6
9.2
429
84
0.0051
33
0.013
    
22
  
39
Table
8.
Azinphos­
methyl
Internal
Dose
(
Not
corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

­
1
0
12.021
1
11.780
2
7.985
3
5.692
GU024­
03D
4
4.165
41.643
83.6
9.2
541
98
0.0055
16
0.034
­
1
0
10.589
1
8.838
2
2.135
3
0.414
GU025­
03D
4
0.801
22.777
83.6
9.2
296
66
0.0045
22
0.013
­
1
0
1.659
1
2.496
2
1.162
3
0.587
GU026­
03D
4
0.306
6.210
83.6
9.2
81
78
0.0010
8
0.010
­
1
0
4.469
1
5.049
2
3.151
3
2.723
GU027­
03D
4
1.766
17.157
83.6
9.2
223
86
0.0026
24
0.0093
­
1
GU028­
03D
Study
noted
that
sample
had
high
background;
was
not
included
in
data
analysis.
    
23
  
39
Table
8.
Azinphos­
methyl
Internal
Dose
(
Not
corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

0
46.222
1
23.713
2
36.448
3
35.335
4
23.019
­
1
0
2.750
1
2.696
2
1.770
3
0.988
GU029­
03D
4
0.433
8.637
83.6
9.2
112
70
0.0016
20
0.0056
­
1
0
5.519
1
9.346
2
2.676
3
1.550
GU030­
03D
4
1.526
20.617
83.6
9.2
268
75
0.0036
20
0.013
­
3
­
2
­
1
0
7.392
1
15.022
2
11.241
3
3.513
GU031­
03D
4
2.075
39.244
83.6
9.2
510
86
0.0059
20
0.026
    
24
  
39
Table
8.
Azinphos­
methyl
Internal
Dose
(
Not
corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

­
1
0
7.099
1
11.507
2
6.489
3
4.280
GU032­
03D
4
1.787
31.163
83.6
9.2
405
84
0.0048
20
0.020
­
3
­
2
­
1
0
33.306
1
21.906
2
15.092
3
8.272
GU033­
03D
4
5.666
Study
noted
that
sample
had
high
background;
was
not
included
in
data
analysis.

­
3
­
2
­
1
0
0.326
1
1.318
2
0.436
3
0.240
GU034­
03D
4
0.731
3.051
83.6
9.2
40
75
0.00053
20
0.0020
CLOSED
CABS
­
1
0
0.094
GU035­
03D
1.314
83.6
9.2
17
108
0.00016
24
0.00071
    
25
  
39
Table
8.
Azinphos­
methyl
Internal
Dose
(
Not
corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

1
0.427
2
0.423
3
0.269
4
0.101
­
1
0
0.925
1
2.631
2
3.303
3
2.750
GU036­
03D
4
3.354
12.964
83.6
9.2
169
91
0.0019
22
0.0075
­
1
0
0.457
1
2.495
2
2.188
3
1.416
GU037­
03D
4
0.824
7.380
83.6
9.2
96
102
0.00094
37
0.0026
­
1
0
0.422
1
0.539
2
0.273
3
0.170
GU038­
03D
4
0.135
1.540
83.6
9.2
20
91
0.00022
37
0.0005
­
1
0
0.269
1
0.571
GU039­
03D
2.272
83.6
9.2
30
71
0.00042
25
0.0012
    
26
  
39
Table
8.
Azinphos­
methyl
Internal
Dose
(
Not
corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

2
0.581
3
0.481
4
0.371
­
1
0
0.903
1
1.259
2
1.667
3
0.885
GU040­
03D
4
0.904
5.618
83.6
9.2
73
116
0.00063
30
0.0024
­
1
0
1.295
1
1.682
2
2.208
3
1.357
GU041­
03D
4
0.959
7.501
83.6
9.2
98
73
0.0013
36
0.0027
­
1
0
0.379
1
0.478
2
0.350
3
0.133
GU042­
03D
4
0.427
1.766
83.6
9.2
23
80
0.00029
45
0.00051
­
1
0
0.364
1
0.275
2
0.454
GU043­
03D
1.521
83.6
9.2
20
77
0.00026
32
0.00061
    
27
  
39
Table
8.
Azinphos­
methyl
Internal
Dose
(
Not
corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

3
0.181
4
0.247
­
1
0
0.645
1
1.003
2
1.031
3
0.960
GU044­
03D
4
0.743
4.382
83.6
9.2
57
98
0.00058
40
0.0014
­
1
0
0.090
1
0.384
2
0.246
3
0.211
GU045­
03D
4
0.094
1.025
83.6
9.2
13
73
0.00018
20
0.00067
­
1
0
2.525
1
4.034
2
2.699
3
3.192
GU046­
03D
4
1.667
14.116
83.6
9.2
184
95
0.0019
31
0.0059
­
1
0
3.456
1
2.958
2
3.092
3
2.896
GU047­
03D
15.534
83.6
9.2
202
91
0.0022
52
0.0039
    
28
  
39
Table
8.
Azinphos­
methyl
Internal
Dose
(
Not
corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

4
3.132
­
3
­
2
­
1
0
0.799
1
0.956
2
0.835
3
0.327
GU048­
03D
4
0.203
3.121
83.6
9.2
41
70
0.00058
20
0.0020
­
3
­
2
­
1
0
0.286
1
0.716
2
0.566
3
0.523
GU049­
03D
4
0.885
2.976
83.6
9.2
39
84
0.00046
20
0.0019
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
were
used
correction:

For
trials
GUO27,
GU028,
GU029,
GU030,
GU032:
80%
when
residue
<
2.2
ng/
mL
and
84%
when
residue
>
2.2
ng/
mL
For
trials
GU026:
98%
when
residue
<
2.2
ng/
mL
and
84%
when
residue
>
2.2
ng/
mL
For
trials
GU020
and
GU021:
80%
when
residue
<
2.2
ng/
mL
and
92%
when
residue
>
2.2
ng/
mL
For
trials
GU022,
GU023,
GU024,
GU025:
79%
when
residue
<
2.2
ng/
mL
and
79%
when
residue
>
2.2
ng/
mL
For
trials
GU031,
GU033,
GU034:
90%
when
residue
<
2.2
ng/
mL
and
85%
when
residue
>
2.2
ng/
mL
For
trials
GU035,
GU036,
GU)
37,
GU038,
GU039:
77%
when
residue
<
2.2
ng/
mL
and
80%
when
residue
>
2.2
ng/
mL
For
trials
GU040,
GU041,
GU042,
GU043,
GU044:
90%
when
residue
<
2.2
ng/
mL
and
84.5%
when
residue
>
2.2
ng/
mL
For
trials
GU045:
98%
when
residue
<
2.2
ng/
mL
and
84%
when
residue
>
2.2
ng/
mL
For
trials
GU046,
GU047:
80%
when
residue
<
2.2
ng/
mL
and
92%
when
residue
>
2.2
ng/
mL
For
trials
GU048,
GU049:
102%
when
residue
<
2.2
ng/
mL
and
91%
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)

d
Total
AZM
Dose
(
mg/
lb
ai
handled)
=
((
Total
AZM
Dose
(
µ
g))
/
1000)
/
lb
ai
handled
    
29
  
39
Table
9.
Azinphos­
methyl
Internal
Dose(
Corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

OPEN
CABS
­
1
0
1.322
1
3.434
2
2.309
3
0.688
GU020­
03D
4
0.000
7.752
83.6
9.2
101
91
0.0011
35
0.0029
­
1
0
10.844
1
7.653
2
6.371
3
1.591
GU021­
03D
4
0.592
27.051
83.6
9.2
352
95
0.0037
63
0.0055
­
1
0
1
2
3
GU022­
03D
4
Study
noted
that
sample
had
high
background;
was
not
included
in
data
analysis.

­
1
0
14.446
1
8.447
2
3.849
3
2.258
GU023­
03D
4
0.847
29.845
83.6
9.2
388
84
0.0046
33
0.012
    
30
  
39
Table
9.
Azinphos­
methyl
Internal
Dose(
Corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

­
1
0
6.899
1
5.839
2
1.634
3
0.000
GU024­
03D
4
0.000
14.372
83.6
9.2
187
98
0.0019
16
0.012
­
1
0
9.853
1
8.335
2
1.834
3
0.247
GU025­
03D
4
0.299
20.568
83.6
9.2
267
66
0.0041
22
0.012
­
1
0
0.910
1
1.118
2
0.177
3
0.000
GU026­
03D
4
0.000
2.205
83.6
9.2
29
78
0.00037
8
0.0034
­
1
0
4.383
1
4.988
2
3.071
3
2.591
GU027­
03D
4
1.627
16.659
83.6
9.2
217
86
0.0025
24
0.0090
­
1
GU028­
03D
Study
noted
that
sample
had
high
background;
was
not
included
in
data
analysis.
    
31
  
39
Table
9.
Azinphos­
methyl
Internal
Dose(
Corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

0
1
2
3
4
­
1
0
2.648
1
2.628
2
1.678
3
0.878
GU029­
03D
4
0.352
8.183
83.6
9.2
106
70
0.0015
20
0.0053
­
1
0
5.332
1
9.106
2
2.543
3
1.398
GU030­
03D
4
1.241
19.620
83.6
9.2
255
75
0.0034
20
0.013
­
3
­
2
­
1
0
6.533
1
14.191
2
10.038
3
2.367
GU031­
03D
4
1.273
34.402
83.6
9.2
447
86
0.0052
20
0.022
    
32
  
39
Table
9.
Azinphos­
methyl
Internal
Dose(
Corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

­
1
0
5.455
1
10.364
2
4.703
3
2.279
GU032­
03D
4
0.000
22.801
83.6
9.2
296
84
0.0035
20
0.015
­
3
­
2
­
1
0
1
2
3
GU033­
03D
4
Study
noted
that
sample
had
high
background;
was
not
included
in
data
analysis.

­
3
­
2
­
1
0
0.224
1
1.199
2
0.354
3
0.191
GU034­
03D
4
0.649
2.617
83.6
9.2
34
75
0.00045
20
0.0017
CLOSED
CABS
­
1
0.000
0
0.000
GU035­
03D
0.866
83.6
9.2
11
108
0.00010
24
0.00047
    
33
  
39
Table
9.
Azinphos­
methyl
Internal
Dose(
Corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

1
0.356
2
0.322
3
0.188
4
0.000
­
1
0
0.834
1
2.535
2
3.222
3
2.659
GU036­
03D
4
3.253
12.503
83.6
9.2
163
91
0.0018
22
0.0072
­
1
0
0.376
1
2.396
2
2.077
3
1.316
GU037­
03D
4
0.737
6.902
83.6
9.2
90
102
0.00088
37
0.0024
­
1
0
0.114
1
0.137
2
0.045
3
0.000
GU038­
03D
4
0.000
0.295
83.6
9.2
4
91
0.000042
37
0.000103
­
1
0
0.142
1
0.434
GU039­
03D
1.629
83.6
9.2
21
71
0.00030
25
0.0008
    
34
  
39
Table
9.
Azinphos­
methyl
Internal
Dose(
Corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

2
0.429
3
0.334
4
0.290
­
1
0
0.645
1
0.983
2
1.253
3
0.557
GU040­
03D
4
0.560
3.999
83.6
9.2
52
116
0.00045
30
0.0017
­
1
0
1.095
1
1.491
2
2.004
3
1.166
GU041­
03D
4
0.761
6.516
83.6
9.2
85
73
0.0012
36
0.0024
­
1
0
0.272
1
0.367
2
0.234
3
0.000
GU042­
03D
4
0.276
1.148
83.6
9.2
15
80
0.00019
45
0.00033
­
1
0
0.000
1
0.194
2
0.050
GU043­
03D
0.349
83.6
9.2
5
77
0.000059
32
0.00014
    
35
  
39
Table
9.
Azinphos­
methyl
Internal
Dose(
Corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

3
0.073
4
0.031
­
1
0
0.481
1
0.812
2
0.902
3
0.827
GU044­
03D
4
0.560
3.582
83.6
9.2
47
98
0.00048
40
0.0012
­
1
0
0.000
1
0.298
2
0.185
3
0.134
GU045­
03D
4
0.000
0.617
83.6
9.2
8
73
0.00011
20
0.00040
­
1
0
1.700
1
3.044
2
1.775
3
2.268
GU046­
03D
4
0.776
9.562
83.6
9.2
124
95
0.0013
31
0.0040
­
1
0
1.309
1
1.810
2
1.494
3
1.098
GU047­
03D
6.745
83.6
9.2
88
91
0.0010
52
0.0017
    
36
  
39
Table
9.
Azinphos­
methyl
Internal
Dose(
Corrected
for
background
residues)

Sample
Number
Sampling
Interval
MSMB
excreteda(
µ
g)
Total
MSMB
excreteda(
µ
g)
%
of
absorbed
dose
excreted
in
urine
after
120
hours
%
of
total
AZM
dose
represented
by
MSMB
Total
AZM
Doseb
(
µ
g)
Body
weight
(
kg)
Total
AZM
Dosec
(
mg/
kg
BW)
Lb
ai
Handled
Total
AZM
Dosed
(
mg/
lb
ai
handled)

4
1.034
­
3
­
2
­
1
0
0.658
1
0.794
2
0.576
3
0.111
GU048­
03D
4
0.003
2.142
83.6
9.2
28
70
0.00040
20
0.0014
­
3
­
2
­
1
0
0.060
1
0.509
2
0.369
3
0.204
GU049­
03D
4
0.566
1.708
83.6
9.2
22
84
0.00026
20
0.0011
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
were
used
correction:

For
trials
GUO27,
GU028,
GU029,
GU030,
GU032:
80%
when
residue
<
2.2
ng/
mL
and
84%
when
residue
>
2.2
ng/
mL
For
trials
GU026:
98%
when
residue
<
2.2
ng/
mL
and
84%
when
residue
>
2.2
ng/
mL
For
trials
GU020
and
GU021:
80%
when
residue
<
2.2
ng/
mL
and
92%
when
residue
>
2.2
ng/
mL
For
trials
GU022,
GU023,
GU024,
GU025:
79%
when
residue
<
2.2
ng/
mL
and
79%
when
residue
>
2.2
ng/
mL
For
trials
GU031,
GU033,
GU034:
90%
when
residue
<
2.2
ng/
mL
and
85%
when
residue
>
2.2
ng/
mL
For
trials
GU035,
GU036,
GU)
37,
GU038,
GU039:
77%
when
residue
<
2.2
ng/
mL
and
80%
when
residue
>
2.2
ng/
mL
For
trials
GU040,
GU041,
GU042,
GU043,
GU044:
90%
when
residue
<
2.2
ng/
mL
and
84.5%
when
residue
>
2.2
ng/
mL
For
trials
GU045:
98%
when
residue
<
2.2
ng/
mL
and
84%
when
residue
>
2.2
ng/
mL
For
trials
GU046,
GU047:
80%
when
residue
<
2.2
ng/
mL
and
92%
when
residue
>
2.2
ng/
mL
For
trials
GU048,
GU049:
102%
when
residue
<
2.2
ng/
mL
and
91%
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)

d
Total
AZM
Dose
(
mg/
lb
ai
handled)
=
((
Total
AZM
Dose
(
µ
g))
/
1000)
/
lb
ai
handled
    
37
  
39
Table
10.
Potential
Inhalation
Exposure
Trial
Number
Total
Inhalation
Residuea
(
ng)
Flow
Rate
(
L/
min)
NAFTA
Breathing
Rate
(
L/
min)
Potential
Inhalation
Exposure
b
(
µ
g)
Sampling
time
(
min)
Concentration
(
µ
g/
m3)
c
lb
ai
handled
Inhalation
Exposure
d
(
µ
g/
lb
ai
handled)

Open
Cab
GU020­
03D
18170
2
16.7
151.7
583
15.58
69.85
2.17
GU021­
03D
17346
2
16.7
144.8
715
12.13
126.73
1.14
GU022­
03D
14566
2
16.7
121.6
556
13.10
69.85
1.74
GU023­
03D
26846
2
16.7
224.2
649
20.68
66.86
3.35
GU024­
03D
5838
2
16.7
48.7
332
8.79
31.93
1.53
GU025­
03D
21916
2
16.7
183.0
290
37.79
43.91
4.17
GU026­
03D
18833
2
16.7
157.3
362
26.01
16.96
9.27
GU027­
03D
10496
2
16.7
87.6
427
12.29
47.94
1.83
GU028­
03D
NS
2
16.7
NS
NS
NS
31.96
NS
GU029­
03D
29118
2
16.7
243.1
374
38.93
39.95
6.09
GU030­
03D
30984
2
16.7
258.7
387
40.03
39.95
6.48
GU031­
03D
21280
2
16.7
177.7
359
29.64
39.95
4.45
GU032­
03D
30024
2
16.7
250.7
364
41.24
39.95
6.28
GU033­
03D
15152
2
16.7
126.5
370
20.48
39.95
3.17
GU034­
03D
19178
2
16.7
160.1
356
26.94
39.95
4.01
Arithmetic
Mean
166.8
24.5
4.0
Geometric
Mean
153.9
21.9
3.3
Standard
Deviation
61.8
11.5
2.0
Enclosed
Cab
GU035­
03D
689
2
16.7
5.8
468
0.74
47.94
0.12
GU036­
03D
1122
2
16.7
9.4
440
1.27
44.95
0.21
GU037­
03D
1674
2
16.7
14.0
590
1.42
74.91
0.19
GU038­
03D
786
2
16.7
6.6
498
0.79
74.91
0.09
GU039­
03D
2876
2
16.7
24.0
506
2.84
49.94
0.48
GU040­
03D
4200
2
16.7
35.1
491
4.28
59.93
0.59
GU041­
03D
1875
2
16.7
15.7
524
1.79
71.91
0.22
GU042­
03D
1055
2
16.7
8.8
509
1.04
89.89
0.10
GU043­
03D
300
2
16.7
2.5
406
0.37
64.92
0.04
GU044­
03D
1296
2
16.7
10.8
510
1.27
79.90
0.14
GU045­
03D
414
2
16.7
3.5
423
0.49
39.92
0.09
GU046­
03D
1040
2
16.7
8.7
560
0.93
61.87
0.14
GU047­
03D
7034
2
16.7
58.7
699
5.03
103.78
0.57
GU048­
03D
926
2
16.7
7.7
105
4.41
39.95
0.19
GU049­
03D
1042
2
16.7
8.7
375
1.39
39.95
0.22
Arithmetic
Mean
14.7
1.9
0.2
    
38
  
39
Table
10.
Potential
Inhalation
Exposure
Trial
Number
Total
Inhalation
Residuea
(
ng)
Flow
Rate
(
L/
min)
NAFTA
Breathing
Rate
(
L/
min)
Potential
Inhalation
Exposure
b
(
µ
g)
Sampling
time
(
min)
Concentration
(
µ
g/
m3)
c
lb
ai
handled
Inhalation
Exposure
d
(
µ
g/
lb
ai
handled)

Geometric
Mean
10.4
1.4
0.2
Standard
Deviation
14.8
1.5
0.2
a
Total
Inhalation
Residue
is
the
sum
of
the
azinphos­
methyl
and
azinphos­
methyl
oxon
residues
corrected
for
field
fortification
recovery
values.
b
Potential
Inhalation
Exposure
(
µ
g)
=(
Total
inhalation
residue
(
ng)
/
1000
ng/
µ
g)
*
(
Breathing
rate
(
16.7
L/
min)
/
Flow
rate
(
L/
min))
c
Concentration
(
µ
g/
m3)
=
Total
Inhalation
Residue
(
µ
g)
/
[(
Flow
Rate
(
L/
min)
*
Sampling
Time
(
min))
/
1000
L/
m3]
d
Potential
Inhalation
Exposure
(
µ
g/
lb
ai
handled)
=
Potential
Inhalation
Exposure
(
µ
g)
/
lb
ai
handled
    
39
  
39
