    
1
  
19
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
Harvesting
of
Blueberries
MRID#:
463164­
04
DP
Barcode:
D307560
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
Harvesting
of
Blueberries.
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
  
19
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
Harvesting
of
Blueberries
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
04
Report
No.:
201043
Study
Number:
GU264702
PSI
Number:
RCGUX003
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)
and
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.
    
3
  
19
GUIDELINE
OR
PROTOCOL
FOLLOWED:
The
Bayer
CropScience
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
Harmonized
Test
Guidelines,
Series
875
Occupational
and
Residential
Exposure.

I.
MATERIALS
AND
METHODS
A.
MATERIALS
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
15
deviations
from
the
protocol.
These
deviations
included:

(
1)
Control
urine
and
blood
samples
were
collected
from
2
additional
workers
up
to
the
beginning
of
harvest.
Since
these
workers
were
not
needed
at
the
time
of
harvest,
they
were
released
from
the
study.
(
2)
For
some
worker
participants,
2
control
blood
samples
were
collected
1
day
before
harvest
and
on
the
day
of
harvest
before
exposure,
since
a
new
worker
was
brought
on
to
replace
a
worker
who
had
chosen
to
leave
the
study.
(
3)
Blood
samples
collected
from
workers
on
the
day
of
harvest
were
transported
to
Bayer
Research
Park
by
the
Study
Director
on
the
day
after
collection.
(
4)
Workers
wore
clothing
typical
of
what
they
wore
when
harvesting
blueberries
and
may
not
have
been
exactly
what
was
stated
in
protocol
or
the
AHETF
Worker
Clothing
Acceptability
Criteria
document.
(
5)
Activities
of
workers
were
only
recorded
during
the
actual
harvest.
(
6)
Workers
continued
to
harvest
during
a
brief
(
3­
5
min)
rain
shower.
(
7)
The
minimum/
maximum
thermometers
were
not
reset
when
placed
in
the
refrigerators
used
to
store
the
­
1
day
samples;
therefore,
the
maximum
temperature
did
not
reflect
the
actual
maximum
storage
temperatures.
(
8)
Occasionally,
urine
sample
storage
temperatures
were
above
or
below
what
is
considered
a
normal
refrigerator
temperature
range.
(
9)
At
times,
urine
samples
were
maintained
cold
in
a
freezer.
(
10)
Worker
#
15
transferred
a
portion
of
his
­
1
day
urine
sample
to
a
1­
quart
plastic
orange
juice
container
from
the
designated
collection
container.
The
sample
was
out
of
cold
storage
for
about
2.5
hours.
Prior
to
subsampling,
the
sample
was
returned
to
the
designated
collection
container.
(
11)
Transfer
of
the
control
and
fortified
urine
samples
from
the
freezers
to
the
refrigerator
was
done
on
the
day
prior
to
starting
the
collection
of
the
­
1
day
interval
urine
samples.
The
date
and
    
4
  
19
time
was
recorded
on
paper,
but
not
in
FieldNotes.

(
12)
Maximum
freezer
temperatures
were
not
recorded
for
2
days
during
freezer
storage
of
urine
and
OVS
tube
field
control
and
fortified
samples.
(
13)
FieldNotes
update
transfers
were
sent
more
than
7
days
after
sampling
and
sample
shipment.
The
final
notebook
transfer
was
sent
more
than
30
days
after
final
sample
shipment.
(
14)
Only
PFI
and
Field
Tech
were
listed
in
the
FieldNotes
project
personnel
list.
All
other
field
project
personnel
were
listed
in
a
paper
notebook.
(
15)
Documentation
of
not
having
been
exposed
to
organophosphate
and
carbamate
chemicals
for
at
least
10
days
prior
to
reentry
activity
was
not
available
for
all
workers.

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

1.
Test
Site:
The
test
site
was
a
single
blueberry
bush
plot
located
in
EPA
Region
5
(
Michigan).
1.13
acres
of
the
blueberry
site
were
used
for
the
reentry
monitoring
study.
No
maintenance
chemicals
containing
organophosphates
were
used
during
the
current
growing
season
and
no
maintenance
chemicals
containing
carbamate
were
used
for
at
least
31
days
prior
to
the
reentry
activity
of
blueberry
harvest.
Typical
cultural
and
irrigation
practices
were
employed
at
the
site.

The
variety
of
blueberries
used
was
Jersey
(
highbush).
The
distance
between
rows
was
reported
to
be
10
feet
and
the
distance
between
bushes
in
a
row
was
4
feet.
The
Study
Report
stated
that
the
density
was
1,089
bushes
per
acre.

2.
Meteorology:
Meteorological
conditions
were
recorded
during
the
two
applications.
This
information
is
provided
in
Table
1.
The
Study
Report
also
noted
that
rainfall
between
the
first
application
and
the
reentry
activity
was
0.95
inches.
Irrigation
between
the
first
application
and
reentry
activity
was
reported
to
be
0.3
inches.

Table
1.
Meteorological
Conditions
During
Two
Applications
Conditions
Application
1
Application
2
Air
Temperature
(
F)
74
81
Wind
Speed
(
mph)
1
to
2
2
to
3
Wind
Direction
SW
SW
Percent
Cloud
Cover
95
10
Rainfall
Within
24
Hours
of
Application
(
inches)
0.4
0.35
3.
Number
and
type
of
workers:
Fifteen
workers
were
monitored
for
this
study;
10
male
workers
and
5
female
workers.
The
Study
Report
stated
that
all
participants
were
experienced
agricultural
workers
who
had
recently
been
picking
blueberries.
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,
documentation
of
not
having
been
exposed
was
not
available
for
all
workers
(
see
protocol
deviations
under
section
B
of
this
study
review).
The
workers
ranged
in
age
from
    
5
  
19
19
years
to
58
years.
The
weight
of
the
workers
ranged
from
48.1
kg
to
134.2
kg.
For
5
of
the
workers
the
number
of
years
experience
were
unknown.
For
the
remaining
10
workers
experience
ranged
from
0.5
years
to
9
years.

One
worker
was
added
to
the
study
on
the
day
before
reentry
to
replace
a
worker
who
withdrew
from
the
study.
Two
spare
workers
were
also
added
to
the
study
on
the
day
before
reentry
to
increase
the
probability
of
15
workers
being
available
on
the
day
of
reentry.
These
workers
were
ultimately
not
used,
as
15
workers
were
available
on
the
day
of
reentry.

4.
Replicates:
Harvesting
activities
took
place
7
days
after
the
second
of
2
azinophos­
methyl
applications.
Each
worker
picked
blueberries
from
designated
bushes
for
a
total
of
8
hours
(
including
breaks).
The
workers
entered
the
field
at
the
same
time,
took
the
same
40
minute
lunch
break
and
20
minute
mid­
morning
break,
and
ended
the
work
day
at
the
same
time.

The
workers
placed
the
picked
blueberries
into
individual
4­
quart
pails,
which
were
positioned
on
the
front
side
of
the
worker.
The
contents
of
the
pail,
once
full,
were
transferred
to
a
plastic
bin.
Table
6
of
the
Study
Report
provides
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
was
listed
in
Table
6
of
the
Study
Report,
and
typically
included
long
sleeve
shirts
or
sweatshirts
and
jeans,
sweatpants,
or
long
work
pants.
Each
worker
wore
a
painter
hat,
supplied
by
the
Principle
Field
Investigator.

6.
Application
Method
and
Rate:

Application
rate(
s):
The
target
application
rate
was
0.75
lb
ai/
acre/
application.
According
to
the
label
obtained
by
Versar,
the
maximum
application
rate
recommended
for
blueberries
is
0.75
lb
ai/
acre.
The
actual
application
rates
were
reported
to
be
0.749
lb
ai/
A
for
each
application.
Two
foliar
applications
were
made.
The
first
application
was
made
on
July
21,
2003,
when
70%
of
the
fruit
had
reached
final
size.
The
second
application
was
made
on
July
31,
2003,
when
the
fruit
had
begun
to
ripen
and
show
coloration.

Application
Equipment:
Application
was
made
with
a
tractor­
drawn
FMC
airblast
sprayer,
Model
DP
100.
Four
nozzles
on
one
side
of
the
sprayer
were
used
during
both
applications.
The
sprayer
had
a
100­
gallon
tank.

Spray
Volume:
The
target
spray
volume
was
37
gal/
acre.
The
actual
spray
volume
was
reported
to
be
36.9
and
36.7
gal/
acre
for
application
1
and
application
2,
respectively.

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

7.
Exposure
monitoring
methodology:
Urine
Samples
Total
urine
output
was
collected
from
each
worker
during
each
24­
hour
period
starting
1
day
    
6
  
19
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
refrigerators
during
the
24­
hour
collection
time,
except
for
the
day
0
samples
which
were
kept
cool
using
a
freezer
powered
by
a
portable
generator.
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
(
day
­
3)
(
except
for
the
replacement
worker
and
the
spare
workers),
(
2)
1
day
prior
to
reentry
(
day
­
1),
(
3)
on
the
day
of
reentry
before
start
of
work
(
only
for
the
replacement
worker
and
spare
workers
to
be
used
as
control
samples),
(
4)
on
the
day
of
reentry
after
a
full
work
day
(
day
0),
and
(
5)
4
days
following
reentry
(
day
4).
Blood
was
collected
from
the
replacement
worker
and
spare
workers
on
the
day
of
reentry
before
the
start
of
work
in
order
to
have
two
control
blood
samples
for
these
workers.
The
control
samples
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
to
Bayer
Research
Park
on
the
day
of
collection,
except
for
Day
0
samples,
which
were
transported
the
following
day.

Breathing
Zone
Air
Samples
Breathing
zone
air
samples
were
taken
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).
The
air
sampling
pumps
were
calibrated
at
a
rate
of
approximately
2
L/
min
using
a
BIOS
Dry
Val
DC­
Lite
Primary
flow
meter
within
1
day
of
monitoring.
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
    
7
  
19
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
35oC
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
(
lc­
ms/
ms).

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
Samples
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:
Auto
sampler
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
limit
of
quantitation
for
urine
samples
was
reported
to
be
0.10
ng/
mL
and
the
limit
of
detection
was
reported
to
be
0.08
ng/
mL.
Average
recoveries
ranged
from
86%
to
93%,
with
an
overall
average
of
91%.

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
    
8
  
19
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
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
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
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
Instrument
performance
and
calibration:
Calibration
curves
were
prepared
for
each
calibration
run.
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
was
reported
to
be
5
ng
and
the
limit
of
detection
for
azinphos­
methyl
oxon
was
reported
to
be
9
ng.
Average
recoveries
for
azinphos­
methyl
ranged
from
90%
to
107%
and
for
azinphos­
methyl
oxon,
ranged
from
86%
to
102%.

Quantification:
The
azinphos­
methyl
or
azinphos­
methyl
oxon
residue
level
in
urine
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
of
MSMB
per
mL
of
urine
level
and
OVS
    
9
  
19
tubes
were
fortified
at
the
500
ng
level.
Results
provided
in
the
Study
Report
were
verified
and
are
presented
in
Tables
4
and
5.
    
10
  
19
Table
4.
Urine
Sample
Concurrent
Laboratory
Recoveries
Sample
No.
Fortification
Level
(
ng/
mL)
Measured
residue
a
(
ng/
mL)
Average
Blank
Sample
Residue
a
(
ng/
mL)
Corrected
residue
a,
b
(
ng/
mL)
Percent
Recovery
(%)
Average
Percent
Recovery
(%)

0.5
0.53
0.002
0.528
106
GUO18­
03D­
1H
0.5
0.462
0.002
0.46
92
99
0.5
0.53
0.008
0.522
104
GUO18­
03D+
0H
0.5
0.533
0.008
0.525
105
105
0.5
0.551
0.019
0.532
106
GUO18­
03D+
1H
(
repeat)
c
0.5
0.592
0.019
0.573
115
111
0.5
0.464
0.008
0.456
91
GUO18­
03D+
2H
0.5
0.469
0.008
0.461
92
92
0.5
0.412
0.023
0.389
78
GUO18­
03D+
3H
0.5
0.511
0.023
0.488
98
88
0.5
0.61
0.024
0.586
117
GUO18­
03D+
4H
(
repeat)
d
0.5
0.523
0.024
0.499
100
109
a
Sample
concentrations
are
reported
as
ng/
mL
equivalents
of
parent
azinphos­
methyl.
b
Corrected
residue
is
the
measured
residue
minus
the
average
blank
residue.
c
The
Study
Report
states
that
these
samples
are
from
an
analytical
set
in
which
the
1
day
interval
field
urine
samples
were
re­
analyzed
due
to
misidentification
of
the
samples
during
the
initial
analysis.
d
The
Study
Report
states
that
these
samples
are
from
an
analytical
set
in
which
the
4
day
interval
field
urine
samples
were
re­
analyzed
due
to
unacceptable
concurrent
recoveries
from
the
laboratory
control
fortification
samples
during
initial
analysis.

Table
5.
OVS
Tubes
Concurrent
Laboratory
Recoveries
Sample
No.
Fortification
Level
(
ng)
Measured
Bottom
Residue
(
ng)
Bottom
Blank
Residues
(
ng)
Corrected
Bottom
Residue
a
(
ng)
Measured
Top
Residue
(
ng)
Top
Blank
Residues
(
ng)
Corrected
Top
Residue
a
(
ng)
Total
Residue
(
top
+
bottom)
(
ng)
Percent
recovery
(%)

AZM
b
6.1
11.6
<
LOD
c
542.8
9.7
533.1
535.6
107
AZM­
oxon
c
500
<
LOD
<
LOD
<
LOD
d
501.2
<
LOD
e
496.7
501.2
100
a
Corrected
residue
is
the
measured
residue
minus
the
blank
residue.
b
AZM
=
azinphos­
methyl
c
AZM­
oxon
=
azinphos­
methyl
oxon
d
Since
the
correct
bottom
residue
was
less
than
the
LOD,
½
the
LOD
was
used
in
subsequent
calculations.
e
½
LOD
used
in
calculations
where
residue
level
is
<
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.
0.100
mL
of
a
    
11
  
19
1.00
µ
g/
mL
fortification
solution
containing
MSMB
was
added
to
one
aliquot,
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.
Recovery
data
are
presented
for
two
sampling
intervals.
Day
1
and
day
4
samples
were
reanalyzed
due
to
misidentification
of
samples
and
unacceptable
concurrent
recoveries,
respectively.
The
average
low
level
field
fortification
recoveries
were
109%
for
sampling
intervals
­
1
day,
0
day,
2
day,
and
3
day
and
96%
for
sampling
intervals
1
day
and
4
day.
The
average
high
level
field
fortification
recoveries
were
71%
for
sampling
intervals
­
1
day,
0
day,
2
day,
and
3
day
and
81%
for
sampling
intervals
1
day
and
4
day.

Table
6.
Urine
Sample
Field
Fortification
Recoveries
Fortification
Level
(
ng/
mL)
Sampling
Interval
Measured
residue
a
(
ng/
mL)
Blank
Sample
Residue
a
(
ng/
mL)
Corrected
residue
b
(
ng/
mL)
Percent
recovery
(%)
Average
Percent
recovery
(%)

0.671
0
0.671
134
0.464
0
0.464
93
­
1
day,
0
day,
2
day,
and
3
day
0.504
0
0.504
101
109
0.458
0.01
0.448
90
0.499
0.01
0.489
98
Low
fortification
level
0.5
1
day
and
4
day
0.511
0.01
0.501
100
96
6.45
0
6.45
65
8.741
0
8.741
87
­
1
day,
0
day,
2
day,
and
3
day
6.245
0
6.245
62
71
7.349
0.01
7.339
73
9.423
0.01
9.413
94
High
fortification
level
10
1
day
and
4
day
7.496
0.01
7.486
75
81
NOTE:
Recovery
data
are
presented
for
two
sampling
intervals.
Day
1
and
day
4
samples
were
reanalyzed
due
to
misidentification
of
samples
and
unacceptable
concurrent
recoveries,
respectively..
a
Sample
concentrations
are
reported
as
ng/
mL
equivalents
of
parent
azinphos­
methyl.
b
Corrected
residue
is
the
measured
residue
minus
the
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.
For
azinphos­
methyl,
the
average
low
level
field
fortification
recovery
was
94%
and
the
high
level
was
86%.
For
azinphos­
methyl
oxon,
the
average
low
level
field
fortification
recovery
was
98%
and
the
high
level
was
88%.
    
12
  
19
Table
7.
OVS
Tubes
Field
Fortification
Recoveries
Sample
No.
Fortificati
on
Level
(
ng)
Measured
Bottom
Residue
(
ng)
Bottom
Blank
Residues
(
ng)
Corrected
Bottom
Residue
a
(
ng)
Measured
Top
Residue
(
ng)
Top
Blank
Residues
(
ng)
Corrected
Top
Residue
a
(
ng)
Total
Residue
(
top
+
bottom)
(
ng)
Percent
Recovery
(%)
Average
Percent
Recovery
(%)

500
<
LOD
c
<
LOD
<
LOD
440.4
<
LOD
437.9
440.4
88
500
<
LOD
<
LOD
<
LOD
462.7
<
LOD
460.2
462.7
93
500
<
LOD
<
LOD
<
LOD
504.3
<
LOD
501.8
504.3
101
94
10000
10.4
<
LOD
7.9
8390.2
<
LOD
8387.7
8395.6
84
10000
5.1
<
LOD
2.6
8543.6
<
LOD
8541.1
8543.7
85
AZMa
10000
<
LOD
<
LOD
<
LOD
8775.8
<
LOD
8773.3
8775.8
88
86
500
<
LOD
<
LOD
<
LOD
485.5
<
LOD
481
485.5
97
500
<
LOD
<
LOD
<
LOD
468.4
<
LOD
463.9
468.4
94
500
<
LOD
<
LOD
<
LOD
495.7
<
LOD
491.2
495.7
99
97
10000
<
LOD
<
LOD
<
LOD
8891.8
<
LOD
8887.3
8891.8
89
10000
<
LOD
<
LOD
<
LOD
8522.1
<
LOD
8517.6
8522.1
85
AZMoxon
b
10000
<
LOD
<
LOD
<
LOD
9081.7
<
LOD
9077.2
9081.7
91
88
a
Corrected
residue
is
the
measured
residue
minus
the
blank
residue.
b
AZM
=
azinphos­
methyl
c
AZM­
oxon
=
azinphos­
methyl
oxon
d
Since
the
correct
bottom
residue
was
less
than
the
LOD,
½
the
LOD
was
used
in
subsequent
calculations.

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:
    
13
  
19
Internal
Dose
The
internal
azinphos­
methyl
dose
was
determined
from
the
residues
measured
in
urine
samples
collected
from
each
worker.
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
reentry
were
corrected
for
the
amount
of
MSMB
residue
found
in
each
worker's
urine
sample
from
the
day
before
reentry
(
day
­
1,
assumed
to
be
a
background
concentration).
The
residue
level
in
ng/
mL
was
multiplied
by
the
corresponding
24
hour
urine
volume
in
order
to
present
results
in
ng.
The
field
fortification
samples
were
corrected
for
blank
residues
and
then
corrected
field
samples
for
all
field
fortification
recoveries,
even
those
greater
than
90%.
The
MSMB
excreted
was
adjusted
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%)

The
MSMB
excreted
for
each
worker
was
summed
over
the
120
hour
sampling
period.
The
total
MSMB
excreted
for
each
worker
over
120
hours
was
adjusted
for
the
cumulative
percent
of
the
absorbed
dose
expected
to
be
excreted
96­
120
hours
after
exposure
and
the
percent
of
the
total
azinphos
methyl
dose
represented
by
MSMB.
The
azinphos­
methyl
doses
were
then
averaged
for
males,
females,
and
all
workers
combined.
Table
8
provides
the
total
azinphos­
methyl
dose
for
males,
females,
and
all
workers
based
on
body
weight.
Doses
were
calculated
by
correcting
for
background
residues
(
day
­
1
residues).
The
total
average
azinphos­
methyl
doses
for
males,
females,
and
all
workers
combined
are
0.043,
0.0064,
and
0.0050
mg/
kg
body
weight,
respectively.
Table
9
provides
individual
azinphos­
methyl
doses
for
each
worker.

Breathing
Zone
Air
Samples
Air
samples
were
collected
in
the
breathing
zones
of
workers
using
OVS
tubes
connected
to
personal
air
sampling
pump.
The
air
samples
were
collected
over
the
entire
work
day
at
a
flow
rate
of
approximately
2
L/
min.
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
measure
of
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.
The
air
concentration
for
males
averaged
6.2
µ
g/
m3,
8.5
µ
g/
m3
for
females,
and
6.9
µ
g/
m3
for
all
workers
combined.

Cholinesterase
Activity
Cholinesterase
activity
(
both
plasma
and
red
blood
cells)
was
monitored
through
blood
sampling
prior
to
reentry
(
specified
as
background
and
collected
on
days
­
3
and
­
1)
and
on
day
0
(
following
completion
of
the
full
work
day)
and
day
4.
The
depression
of
cholinesterase
activity
was
then
determined
by
comparing
the
background
activity
to
the
activity
measured
on
days
0
and
4.
These
results
are
provided
in
Table
12.
The
percent
decrease
in
plasma
cholinesterase
on
day
0
ranged
from
­
7%
(
male
worker)
to
11%
(
male
worker).
The
percent
decrease
in
plasma
cholinesterase
on
day
4
ranged
from
­
10%
(
male
worker)
to
6%
(
both
a
male
and
a
female
worker).
The
percent
decrease
in
red
blood
cell
cholinesterase
on
day
0
ranged
from
­
3%
(
male
worker)
to
20%
(
female
worker).
The
percent
decrease
in
red
blood
cell
cholinesterase
on
day
4
    
14
  
19
ranged
from
­
1%
(
both
a
male
and
a
female
worker)
to
18%
(
female
worker).

Workers
entered
blueberry
field
that
had
been
treated
with
azinphos
methyl
7
days
earlier.
The
average
percent
change
in
plasma
cholinesterase
(
ChE)
immediately
following
the
day
of
entry
was
negative
four
percent
with
a
range
of
±
5
percent.
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
negative
six
percent
with
a
range
of
±
6
percent.
That
remained
about
constant
on
day
4.
The
blueberry
harvester
study
included
five
female
workers
and
ten
male
workers.
The
average
percent
change
in
plasma
cholinesterase
activity
was
very
similar
for
males
and
females
on
day
zero
following
exposure
and
on
day
four
following
exposure.
However,
the
average
percent
change
in
RBC
ChE
activity
was
dissimilar
for
males
versus
females,
particularly
on
day
zero
following
exposure
with
males
having
a
negative
three
percent
change
with
a
range
of
±
4
percent
and
females
having
a
negative
eleven
percent
change
with
a
range
of
±
6
percent.

III
DISCUSSION:

A.
LIMITATIONS
OF
THE
STUDY:

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

 
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.

 
The
guideline
states
that
data
should
be
corrected
if
any
appropriate
field
fortified,
laboratory
fortified
or
storage
stability
recovery
is
less
than
90
percent.
The
Study
Report
states
that
corrections
were
made
even
if
field
fortification
recoveries
were
above
90%.
Per
EPA's
request,
Versar
also
corrected
field
samples
for
all
field
fortification
recoveries.

 
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
azinphosmethyl
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
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
    
15
  
19
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.
The
Study
Report
states
that
two
laboratory
control
samples
were
fortified
and
yielded
recoveries
of
107%
for
azinphos­
methyl
and
99%
for
azinphos­
methyl
oxon.
There
were
3
fortification
samples
at
each
of
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.

 
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
include:

 
The
baseline
cholinesterase
levels
for
workers
was
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.

 
For
several
workers
and
on
several
occasions
(
e.
g.,
for
as
many
as
9
of
the
15
replicates),
the
quantity
of
urine
collected
daily
during
the
study
falls
well
below
the
range
(
800­
2,000
mL/
24
hours)
that
is
considered
a
normal
daily
void.
This
may
indicate
that
workers
may
have
failed
to
collect
all
the
urine
for
a
given
day.
If
that
occurred,
it
would
result
in
lower
recovery
of
AZM
equivalents
and
underestimate
worker
exposure
to
AZM.
    
16
  
19
Table
8.
Total
Azinphos­
methyl
Dose
For
Males,
Females,
and
All
Workers
(
mg/
kg
BW)

Male
Female
All
Workers
Arithmetic
Mean
Geometric
Mean
Standard
Deviation
Arithmetic
Mean
Geometric
Mean
Standard
Deviation
Arithmetic
Mean
Geometric
Mean
Standard
Deviation
0.0043
0.0032
0.0039
0.0064
0.0049
0.0055
0.0050
0.0037
0.0044
Table
9.
Azinphos­
methyl
Internal
Dose
in
Workers
(
mg/
kg
BW)

Worker
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)

1
(
male)
0
day
3.755
16.37
83.6
9.2
213
106.1
0.002
1
day
5.285
2
day
3.988
3
day
3.152
4
day
0.193
2
(
female)
0
day
11.835
43.45
83.6
9.2
565
75.3
0.0075
1
day
13.414
2
day
11.722
3
day
3.786
4
day
2.696
3
(
male)
0
day
2.457
11.11
83.6
9.2
144
88.4
0.0016
1
day
5.366
2
day
1.635
3
day
0.967
4
day
0.688
4
(
female)
0
day
7.092
21.36
83.6
9.2
278
66.7
0.0042
1
day
8.016
2
day
3.33
3
day
2.553
4
day
0.371
5
(
female)
0
day
1.756
14.85
83.6
9.2
193
85.7
0.0023
1
day
5.755
2
day
4.671
3
day
2.075
4
day
0.593
6
(
female)
0
day
31.356
109.8
83.6
9.2
1428
91.6
0.016
1
day
38.359
2
day
25.013
3
day
10.446
4
day
4.626
7
(
male)
0
day
13.14
41.51
83.6
9.2
540
64.4
0.0084
1
day
4.42
2
day
12.955
3
day
9.067
4
day
1.928
8
(
male)
0
day
20.574
97.07
83.6
9.2
1262
98.9
0.013
1
day
40.216
2
day
23.486
3
day
10.557
4
day
2.241
9
(
male)
0
day
0.01
13.65
83.6
9.2
177
70.7
0.0025
    
17
  
19
Table
9.
Azinphos­
methyl
Internal
Dose
in
Workers
(
mg/
kg
BW)

Worker
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)

1
day
2.868
2
day
8.172
3
day
2.074
4
day
0.522
10
(
male)
0
day
0
6.58
83.6
9.2
86
69.4
0.0012
1
day
3.061
2
day
2.306
3
day
0.899
4
day
0.312
11
(
male)
0
day
7.354
55.62
83.6
9.2
723
97.5
0.0074
1
day
11.5
2
day
16.439
3
day
16.429
4
day
3.893
12
(
male)
0
day
0.021
12.63
83.6
9.2
164
48.1
0.0034
1
day
5.24
2
day
5.908
3
day
0.762
4
day
0.704
13
(
female)
0
day
1.829
16.72
83.6
9.2
217
87.5
0.0025
1
day
5.776
2
day
5.596
3
day
3.034
4
day
0.486
15
(
male)
0
day
0.614
8.78
83.6
9.2
114
75.7
0.0015
1
day
2.834
2
day
3.729
3
day
1.337
4
day
0.27
17
(
male)
0
day
6.982
16.76
83.6
9.2
218
88.4
0.0025
1
day
2.572
2
day
3.325
3
day
2.843
4
day
1.042
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:
For
days
­
1,0,2,3
when
residue
<
2.2
ng/
mL
used
109%
For
days
1,4
when
residue
<
2.2
ng/
mL
used
96%
For
days
­
1,0,2,3
when
residue
>
2.2
ng/
mL
used
71%
For
days
1,4
when
residue>
2.2
ng/
mL
used
81%
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)
    
18
  
19
Table
11.
Potential
Breathing
Zone
Air
Samples
Exposure
Worker
No.
Total
Residue
a
(
ng)
Sampling
Time
(
min)
Flow
Rate
(
L/
min)
Air
Concentration
b
(
µ
g/
m3)

1
(
male)
4170
480
2.075
4.19
2
(
female)
8343
480
2.005
8.67
3
(
male)
4197
480
1.942
4.5
4
(
female)
3889
480
1.809
4.48
5
(
female)
1884
480
2.077
1.89
6
(
female)
18912
480
1.998
19.72
7
(
male)
7128
480
2.092
7.1
8
(
male)
4096
480
2.026
4.21
9
(
male)
4738
480
1.833
5.39
10
(
male)
855
480
2.054
0.87
11
(
male)
13074
480
1.816
15
12
(
male)
8609
480
1.961
9.15
13
(
female)
7506
480
2.051
7.62
15
(
male)
6382
480
2.02
6.58
17
(
male)
4014
480
2.074
4.03
Arithmetic
Mean
49.7
Geometric
Mean
40.6
Males
Standard
Deviation
30.9
Arithmetic
Mean
67.9
Geometric
Mean
51.6
Females
Standard
Deviation
54.7
Arithmetic
Mean
55.3
Geometric
Mean
43.5
All
Workers
Standard
Deviation
39.3
a
Total
Residue
is
the
sum
of
the
azinphos­
methyl
and
azinphos­
methyl
oxon
residues
corrected
for
field
fortification
recovery
values
of:
AZM
samples:
94%
when
sample
residue
<
2,250
ng
AZM
samples:
86%
when
sample
residue
.>
2,250
ng
AZM
oxon
samples:
97%
when
sample
residue
<
2,250
ng
AZM
oxon
samples:
88%
when
sample
residue
>
2,250
ng
b
Concentration
(
µ
g/
m3)
=
Total
Residue
(
µ
g)
/
[(
Flow
Rate
(
L/
min)
*
Sampling
Time
(
min))
/
1000
L/
m3]
    
19
  
19
Table
12
Percent
Depression
of
Cholinesterase
Activity
Worker
Average
Cholinesterase
Activity
Determined
on
Days
­
1
and
­
3
Cholinesterase
Activity
on
Sampling
Days
0
and
4
and
Percent
Depression
Plasma
Red
Blood
Cells
Sampling
Date
Plasma
%
Depression
Red
Blood
Cells
%
Depression
1
(
male)
4.47
16.46
0
4.15
7
15.18
8
2
(
female)
3.14
16.12
0
3.08
2
12.94
20
3
(
male)
3.75
13.99
0
3.83
­
2
12.83
8
4
(
female)
3.18
14.39
0
3.08
3
13.13
9
5
(
female)
3.89
14.43
0
3.52
9
13.94
3
6
(
female)
3.53
14.97
0
3.57
­
1
13.12
12
7
(
male)
3.55
13.6
0
3.37
5
12.88
5
8
(
male)
4.37
13.68
0
4.24
3
13.63
0
9
(
male)
3.12
14.77
0
2.98
4
15.11
­
2
10
(
male)
3.54
17.44
0
3.38
4
16.79
4
11
(
male)
3.14
15.98
0
3.369
­
7
15.29
4
12
(
male)
2.33
15.24
0
2.19
6
14.46
5
13
(
female)
3.09
16
0
2.9
6
14.58
9
15
(
male)
3.27
16.34
0
2.9
11
15.5
5
17
(
male)
4.26
12.98
0
3.97
7
13.38
­
3
1
(
male)
4.47
16.46
4
4.3
4
15.32
7
2
(
female)
3.14
16.12
4
3.38
­
8
13.29
18
3
(
male)
3.75
13.99
4
3.76
0
13.09
6
4
(
female)
3.18
14.39
4
3.1
2
13.63
5
5
(
female)
3.89
14.43
4
3.67
6
14.6
­
1
6
(
female)
3.53
14.97
4
3.53
0
14.16
5
7
(
male)
3.55
13.6
4
3.75
­
6
13.18
3
8
(
male)
4.37
13.68
4
4.45
­
2
12.89
6
9
(
male)
3.12
14.77
4
3.44
­
10
13.99
5
10
(
male)
3.54
17.44
4
3.7
­
5
16.38
6
11
(
male)
3.14
15.98
4
3.11
1
15.13
5
12
(
male)
2.33
15.24
4
2.19
6
14.93
2
13
(
female)
3.09
16
4
3.15
­
2
15.01
6
15
(
male)
3.27
16.34
4
3.1
5
15.09
8
17
(
male)
4.26
12.98
4
4.19
2
13.11
­
1
