Document ID: EPA-HQ-OPP-2004-0001-0004
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2004-02-17T05:00Z

MEMORANDUM
SUBJECT:
Review
of
Data/
Information
Submitted
by
Certis
USA
to
Support
a
Tolerance
Exemption
(
Petition
No.
2F6477)
for
Residues
of
Ammonium
Bicarbonate
in
Olives
(
D288947;
Case
295326;
S631096)

TO:
Andrew
Bryceland,
RAL
Biochemical
Pesticides
Branch
(
BPB)
Biopesticides
and
Pollution
Prevention
Division
(
BPPD)

FROM:
Roy
D.
Sjoblad
BPB,
BPPD
Background:
The
petition
by
Certis
on
June
17,
2002
for
a
tolerance
exemption
for
ammonium
bicarbonate
in
olives
failed
to
pass
an
initial
BPB
screen
(
deficiencies
stated
in
10/
28/
02
letter
from
S.
Reilly
to
Certis
USA).
On
2/
13/
03,
Certis
responded
to
the
deficiencies
of
the
10/
28/
02
letter.
This
Memorandum
comprises
review
of
the
data/
information
submitted
to
support
the
tolerance
petition.

BPB
Conclusion:
The
data/
information
submitted,
and
the
request
for
waivers
of
all
further
additional
studies,
are
acceptable
and
support
the
request
for
an
exemption
from
the
requirement
of
a
tolerance
for
ammonium
bicarbonate
when
used
as
a
pesticide
active
ingredient
as
proposed.

Data/
information
submitted:

Volume
4:
Physical
and
Chemical
Properties:

Study
Title:
"
Ammonium
Bicarbonate
Feeding
Attractant
Physical
and
Chemical
Properties
Data
Summary
and
Request
for
Data
Waivers"
(
J.
M.
Wagner,
11/
11/
02;
Wagner
Regulatory
Associates,
Inc.
Delaware).
The
information
presented
in
volume
4,
has
been
culled
from
MRID
457120­
01
submitted
with
the
original
petition.

Ammonium
bicarbonate
is
produced
from
ammonia
in
water
upon
passing
through
of
excess
carbon
dioxide.
The
process
involves
cooling
and
crystallization,
and
subsequent
thickening
and
drying
of
the
crystal
suspension.
There
are
no
other
reactants
and
thus
no
impurities.
The
registrant
purchases
food
grade
ammonium
bicarbonate
from
a
supplier
which
is
certified
as
at
least
99.2
%
pure
(
preliminary
analysis,
930.1700).
An
enforcement
analytical
method
(
830.1800)
was
provided,
which
involves
titration
with
1N
HCl
in
a
weighed
sample
of
ammonium
bicarbonate
to
which
has
been
added
methyl
red
TS.
HCl
is
added
until
the
solution
­
2­

becomes
pink;
the
solution
is
boiled
and
then
cooled.
The
titration
continues
until
the
pink
color
does
not
fade
after
boiling.
The
ammonium
bicarbonate
is
then
bound
in
a
polymer,
which
is
attached
to
a
cellulose
card.
During
use,
the
card
is
suspended
from
olive
tree
limbs.
The
amount
of
ammonium
bicarbonate
applied
per
orchard
acre
is
168
grams
(
0.3
lbs).
Exposure
of
the
ammonium
bicarbonate
to
ambient
sunlight
and
heat
results
in
the
slow
release
of
small
amounts
of
ammonia,
which
as
a
signal
of
decomposing
protein,
attracts
insects.

Following
are
the
physical
and
chemical
properties:

Color/
odor
(
830.6302/
830.6304)
­
Clear/
white,
with
faint
ammonia
smell
Physical
state
(
830.6303)
­
Solid
crystals
Stability
(
830.6313)
­
Decomposes
to
ammonia
(
21.5%),
carbon
dioxide
(
55.7%)
and
water
(
22.8%)
at
60C
Oxidation/
reduction
(
830.6314)
­
Reacts
strongly
to
strong
acids
and
strong
bases.
Incompatible
also
with
alkali
metals,
copper,
nickel.
Flammability
(
830.6315)
­
Non­
combustible
Storage
stability
(
830.6317)
­
Stable
at
normal
temperatures
and
pressure
Corrosion
characteristics
(
830.6320)
­
None
noted,
stable
at
normal
temperatures
and
pressure.
Miscibility
(
830.6319)
­
Not
applicable;
EP
is
not
an
emulsifiable
concentrate
and
is
not
to
be
diluted
with
petroleum
products
pH
(
830.7000)
­
7.8
(
0.1N)
Viscosity
(
830.7100)
­
Not
applicable;
product
is
not
a
liquid.
Melting
point
(
830.7200)
­
107.5C
Boiling
point
(
830.7220)
­
Not
applicable;
Technical
is
not
a
liquid.
Density/
specific
gravity
(
830.7300)
­
1.573­
1.586
Dissociation
constant
(
830.7370)
­
1.45
Partition
coefficient
(
830.7550)
­
Not
applicable;
technical
is
not
organic.
Solubility
(
830.7840)
­
Soluble
water,
glycerol.
Not
soluble
in
acetone,
alcohol.
Vapor
pressure
(
830.7950)
­
60
mm
Hg
@
20C.

BPB
Discussion:
There
are
no
deficiencies
in
requirements
to
address
product
identity,
manufacturing
process,
and
physical
and
chemical
properties.
The
data
are
Acceptable.

Volume
5:

Study
title:
"
Ammonium
Bicarbonate
Insect
Feeding
Attractant
Summary
of
Toxicity
Data
and
Request
for
Data
Waivers"
(
J.
M.
Wagner,
11/
11/
02;
Wagner
Regulatory
Associates,
Inc.,
Delaware).
The
information
presented
in
Volume
5
has
been
culled
from
MRID
457120­
01
and
MRID
457120­
02
submitted
with
the
original
petition.

Acute
oral
LD50
toxicity
study
in
the
rat.
No
study
was
submitted,
however,
the
literature
and
submitted
MSD
sheets,
report
an
acute
oral
LD50
value
of
1576
mg/
kg
in
the
rat.
This
information
is
Acceptable
to
allow
placement
of
ammonium
bicarbonate
in
Toxicity
category
­
3­

III
for
the
oral
route.

Genotoxicity.
Ammonium
bicarbonate
(
with
or
without
S9
mix
activation)
was
not
mutagenic
in
the
Ames
assay
when
S.
typhimurium
strains
TA97
and
TA102
were
exposed
to
0.1
to
10
mg/
assay
plate.

Other:
The
mouse
intravenous
LD
50
value
was
reported
as
245
mg/
kg.
Ammonium
bicarbonate
can
be
irritating
to
the
eyes
of
rabbits,
but
the
information
was
not
adequate
to
establish
a
Toxicity
category.
An
LC50
value
(
at
96
hours)
of
17300
ug/
L
has
been
reported
for
the
rainbow
trout.

The
registrant
has
requested
a
waiver
for
any/
and
all
mammalian
toxicity
studies
typically
required
to
support
a
tolerance
exemption
for
ammonium
bicarbonate.
These
studies
include
acute
oral,
dermal,
and
inhalation
toxicity
studies,
eye
and
skin
irritation,
and
mutagenicity
studies,
a
90­
day
feeding,
a
developmental
toxicity
and
an
immunotoxicity
study.

The
reasons
set
forth
for
supporting
the
waiver
requests
were
as
follows:

1.
The
ammonium
bicarbonate
in
the
end­
use
product
is
contained
within
a
polymeric
substance,
and
the
end­
use
product
is
attached
to
olive
tree
branches.
Thus
oral,
dermal,
and
inhalation
exposure
are
unlikely
2.
The
maximum
seasonal
use
rate
of
ammonium
bicarbonate
is
168
g/
acre.
.

3.
In
the
product,
the
ammonium
bicarbonate
will
slowly
decompose
to
ammonia,
carbon
dioxide,
and
water.
The
total
yield
of
ammonia
would
be
34.5
grams
per
season.
If
36
g
of
ammonia
is
distributed
in
a
single
point
in
time
over
an
acre
of
olive
orchard
to
a
height
of
15
feet,
the
calculated
concentration
of
ammonia
would
be
3
ppb.
Assuming
a
release
of
ammonia
from
the
product
occurs
over
a
4­
5
month
period,
a
theoretical
daily
concentration
can
be
estimated
at
about
0.03
ppb/
day
during
this
time.

4.
This
0.03
ppb
value
is
about
100
times
less
than
the
worldwide
ambient
atmospheric
estimates
of
1­
3
ppb,
and
about
10,000
fold
lower
than
ammonia
concentrations
(
i.
e.,
300
ppb)
reported
over
an
agricultural
field
after
fertilizer
application.

5.
Acute
inhalation
LC50
values
after
15
minutes
of
exposure
to
ammonia
are
reported
as
17,401
ppm
in
the
rat,
and
after
30
minutes
of
exposure,
21,430
ppm
in
the
mouse.

6.
Ammonium
bicarbonate
is
exempt
from
the
requirement
of
a
tolerance
when
used
as
a
surfactant,
or
a
suspending
or
dispensing
agent
in
formulations
applied
to
growing
crops
or
to
food
commodities
after
harvest.
[
40
CFR
180.1001(
c)].

7.
The
US
FDA
considers
ammonium
bicarbonate
as
GRAS
(
21
CFR
582.1135),
and
allows
its
­
4­

use
as
a
Direct
Food
Additive
(
21
CFR
184.1135)
with
an
upper
limit
of
3.2%
(
3200
ppm),
when
used,
for
example,
as
a
leavening
agent
in
baked
bread.

The
following
useful
information
from
human
exposure
to
ammonia,
presented
in
MRID
457120­
02,
was
not
culled
out
by
the
registrant
and
was
not
included
in
the
resubmission:

1.
"
Ammonia
is
produced
in
the
human
body
from
metabolism
of
protein,
amino
acids
and
other
nitrogen­
containing
chemicals...
A
large
amount
of
ammonia
(>
50
mg/
kg)
is
produced
in
the
body
each
day
[
from]
breakdown
of
dietary
protein
and
amino
acids."

2.
Acute
and
chronic
inhalation
minimal
risk
levels
(
MRLs)
of
0.5
ppm
and
0.3
ppm,
respectively,
have
been
derived
from
studies
with
humans.

3.
The
Occupational
Safety
and
Health
Administration
(
OSHA)
has
set
a
short­
term
(
15
minute)
exposure
level
of
35
ppm
for
ammonia.
The
National
Institute
for
Occupational
Safety
and
Health
(
NIOSH)
recommends
that
ammonia
levels
in
the
workplace
be
limited
to
50
ppm
for
5
minutes
of
exposure.

4.
Ammonia
is
slightly
irritating
to
the
eyes
of
humans
at
100
ppm,
and
is
immediately
irritating
to
the
eyes
and
throat
at
698
ppm.

BPB
Discussion:
The
above
reasons
serve
as
an
acceptable
rationale
for
waiver
of
acute
and
subchronic
oral
studies,
a
dermal
toxicity
study,
an
acute
inhalation
study,
mutagenicity
studies,
an
immunotoxicity
study,
and
a
developmental
toxicity
study.
Exposure
to
either
ammonium
bicarbonate,
or
to
the
ammonia
component
of
ammonium
bicarbonate,
from
the
pesticidal
use
is
not
likely
to
add
significantly
to
ambient
exposures
already
documented
and
without
reported
adverse
effects.
The
amounts
of
ammonia
released
from
the
product
over
time
result
in
calculated
concentrations
of
0.03
ppb/
day,
well
below
the
chronic
human
inhalation
MRL
of
0.3
ppm.
Since
the
rationales
support
waivers
for
all
oral
exposure
study
requirements
the
tolerance
exemption
can
be
supported.

The
rationales
do
not
support
waivers,
however,
for
the
primary
dermal
and
eye
irritation
studies
for
ammonium
bicarbonate,
and
for
reporting
of
hypersensitivity
incidents.
However,
the
precautionary
label
statement
of
"
Warning"
and
the
requisite
hazard
and
first
aid
statements
(
e.
g.,
wear
protective
eyewear,
rinse
skin
with
water
for
15­
20
minutes,
repeated
skin
contact
may
cause
allergic
skin
reactions)
­
presumably
triggered
by
adverse
reactions
that
might
occur
from
exposure
to
a
different
active
ingredient
in
the
product
­
are
sufficient
to
protect
from
any
adverse
reactions
that
may
occur
from
exposure
to
ammonium
bicarbonate.
In
addition,
the
First
Aid
label
statements
for
treatment
of
eye
and
dermal
exposures
are
at
least
as
restrictive
as
the
First
Aid
measures
accompanying
the
MSD
sheets
submitted
by
the
registrant
for
99­
100%
ammonium
bicarbonate.
Any
adverse
reactions
from
handling
or
use
of
the
product
must
be
reported.