Document ID: EPA-HQ-OPP-2005-0314-0003
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2005-12-21T05:00Z

Page
1
of
14
TOLERANCE
EXEMPTION
PETITION
FOR:

COPPER
SULFATE
PENTAHYDRATE
SUBMITTED
BY:

ARCHANGEL
LLC
Page
2
of
14
SECTION
A:
CHEMICAL
IDENTITY
OF
THE
PESTICIDE
CHEMICAL
C
Chemical
Name
:

Copper
Sulfate
Pentahydrate
C
CASRN:

7758­
99­
8
C
Molecular
Formula:

Cu­
S­
O4.5H2­
O
C
Manufacturing
Process:

The
manufacturing
process
for
Copper
Sulfate
Pentahydrate
has
been
previously
provided
to
the
Agency.

C
Sample
Analysis
including
Impurities
Associated
with
Copper
Sulfate
Pentahydrate
Analytical
data
on
representative
samples
of
Copper
Sulfate
Pentahydrate
was
previously
submitted
to
the
Agency.
.

C
Physical
and
Chemical
Properties:

Physical
and
chemical
property
data
on
Copper
Sulfate
Pentahydrate
was
previously
submitted
to
the
Agency.
Please
see
chemistry
data
submitted
for
Stalosan
F
(
EPA
Application
No.
75526­
R).

*
COPPER
SULFATE
PENTAHYDRATE
is
manufactured,
using
an
integrated
formulation
system,
as
a
2.66%
granular.
The
sample
analysis
and
physical­
chemical
property
tests
were
conducted
Page
3
of
14
SECTION
B:
USE
OF
THE
PESTICIDE
CHEMICAL
Copper
sulfate
pentahydrate
is
an
antimicrobial
and/
or
fungicide
that
is
applied
by
hand
to
animal
bedding
and
stall
areas
occupied
by
food
or
feed
animals.
This
product
is
applied
at
the
rate
of
1
pound
per
100
sq.
ft.
or
0.15
oz.
per
sq.
ft.

Copper
sulfate
pentahydrate
is
applied
to
lower
the
ammonia
level
in
the
bedding,
and
also
serves
to
reduce
bacteria.
As
provided
in
additional
information,
copper
sulfate
pentahydrate
is
applied
directly
to
foods
at
levels
over
250
ppm.
The
amount
of
material
applied
to
animal
bedding
and
stall
areas
is
well
below
that
level,
and
very
little
of
the
material
will
ultimately
be
consumed
by
the
animals,
since
it
is
not
added
to
actual
food
stock.

It
is
important
to
note
that
the
Agency
has
previously
registered
Copper
Sulfate
Pentahydrate
for
use
for
all
raw
agriculatural
commodities.

The
end­
use
formulation
of
copper
sulfate
pentahydrate
is
a
granular.
The
product,
Stalosan
F
(
EPA
Appl.
No.
75526­
R)
contains
02.66%
of
the
active
ingredient,
copper
sulfate
pentahydrate..

A
copy
of
the
Stalosan
F
product
label
is
provided
on
pages
4­
5
of
this
petition
Page
4
of
14
[
bracketed
phrases
are
optional
text]

Stalosan
F
Adsorb
Plus
(
additional
brand
name)

For
use
in
livestock
housing,
to
improve
the
external
environment
and
flooring
conditions
around
animals.
Lack
of
moisture
assists
in
the
reduction
of
non­
public
health
microorganisms
Stalosan
F
adsorbs
moisture,
ammonia,
hydrogen
sulphide
and
other
gases.
[
Inhibits
the
growth
of
bacteria
and
fungi]
[
Eliminates
odor
causing
bacteria,
fungi,
mold,
and
mildew]
[
Inhibits
the
growth
of
non
public
health
bacteria]
[
Inhibits
the
growth
of
fungi]
[
Reduces
ammonia
and
moisture]
[
Eliminates
odor
causing
bacteria,
fungi,
mold,
and
mildew]
[
Eliminates
odors
associated
with
bacteria,
mold,
and
mildew]
[
Deodorizes],
[
Deodorizer]
[
Controls
and
inhibits
odor
causing
bacteria,
fungi,
mold,
and
mildew]

Caution
Keep
Out
of
Reach
of
Children
FIRST
AID
If
in
eyes:

Hold
eye
open
and
rinse
slowly
and
gently
with
water
for
15­
20
minutes.
Remove
contact
lenses,
if
present,
after
the
first
5
minutes,
then
continue
rinsing
eye.

Call
a
poison
control
center
or
doctor
for
treatment
advice.

Have
the
product
container
or
label
with
you
when
calling
a
poison
control
center
or
doctor,
or
going
for
treatment.

SEE
SIDE
PANEL
FOR
ADDITIONAL
PRECAUTIONARY
STATEMENTS
Active
Ingredients:
Copper
Sulfate
Pentahydrate*     . 
2.66%
Inert
Ingredients           
98.54%
TOTAL              .
100.00%
*
Metallic
Copper
Equivalent
Equal­­­­­
0.68%

EPA
Reg.
No.
75526­
R
ArchAngel
LLC
636
Hampshire,
Suite
208
Page
5
of
14
Quincy,
IL
62301
EPA
est.
No.
75613­
DNK­
01
phone
number
25
Kg.
Net
Wt.

PRECAUTIONARY
STATEMENTS
Hazards
to
Humans
and
Domestic
Animals
CAUTION.
Causes
moderate
eye
irritation.
Avoid
contact
with
eyes
or
clothing.
Wear
protective
eyewear.
Wash
thoroughly
with
soap
and
water
after
handling
and
before
eating,
drinking
or
using
tobacco.

ENVIRONMENTAL
HAZARDS
This
product
is
toxic
to
fish
and
aquatic
organisms.

Directions
for
Use
It
is
a
violation
of
federal
law
to
use
this
product
in
a
manner
inconsistent
with
its
labeling.
Do
not
apply
this
product
in
a
way
that
will
contact
workers
or
other
persons,
either
directly
or
through
drift.
Only
protected
handlers
may
be
in
the
area
during
application.

Add
1
pound
of
Stalosan
F
to
every
100
sq.
ft.
If
the
area
is
badly
affected,
increase
the
dosage
slightly.
Initially
apply
Stalosan
F
once
a
day
for
3
days.
Continue
treatment
once
a
week,
thereafter.
Stalosan
F
can
be
applied
while
animals
are
present.

STORAGE
AND
DISPOSAL
Do
not
contaminate
water,
food
or
feed
by
storage
or
disposal.

PESTICIDE
STORAGE:
Store
this
product
in
a
cool,
dry
area
away
from
direct
sunlight
and
heat
to
avoid
deterioration
and
in
an
area
inaccessible
to
children.

PESTICIDE
DISPOSAL:
Pesticide
wastes
are
acutely
hazardous.
Improper
disposal
of
excess
pesticide,
spray
mixture,
or
rinsate
is
a
violation
of
Federal
law.
If
these
wastes
cannot
be
disposed
of
by
use
according
to
label
instructions,
contact
your
State
Pesticide
or
Environmental
Control
Agency,
or
the
Hazardous
Waste
representative
at
the
nearest
EPA
Regional
Office
for
guidance.

CONTAINER
DISPOSAL:
Once
bag
is
empty,
dispose
of
in
a
sanitary
landfill
or
by
incineration,
or;
if
allowed
by
state
and
local
authorities,
by
burning.
If
burned,
stay
out
of
smoke.
Page
6
of
14
SECTION
C:
TOXICOLOGY
DATA
1)
Acute
Toxicology
Acute
toxicology
studies
have
been
conducted
with
Stolason
F,
which
is
a
2.66%

Formulation
of
Copper
Sulfate
Pentahydrate.
The
acute
study
results
are
summarized
below:

Data
Requirement
Study
Title
MRID
Number
Results
81­
1
Acute
Oral
Toxicity
Vol
3
LD50
=
>
5000
mg/
kg
81­
2
Acute
Dermal
Toxicity
Vol
4
LD50
=
>
5000
mg/
kg
81­
4
Primary
Eye
Irritation
Vol
6
Mildly
irritating
81­
5
Primary
Skin
Irritation
Vol.
7
Non­
Irritant
81­
6
Dermal
Sensitization
Vol.
8
Not
a
sensitizer
81­
3
Acute
Inhalation
Toxicity
Vol
5
LC50
=>
2.07
mg/
L
These
results
indicate
that
Copper
Sulfate
Pentahydrate
is
non­
toxic
by
all
routes
of
exposure.

2)
Sub­
Chronic/
Chronic
Toxicity,
Mutagenicity,
Teratology
and
Reproductive
Toxicity
Only
acute
toxicology
studies
have
been
performed
with
Copper
Sulfate
Pentahydrate.
Additional
toxicology
data
on
Copper
Sulfate
Pentahydrate
should
not
be
required
since
Copper
Sulfate
Pentahydrate,
degrades
to
common
copper.
Accordingly,
any
dietary
assessment
from
the
use
of
Copper
Sulfate
Pentahydrate
regarding
meat
animals
should
focus
on
copper.

In
1986,
a
review*
of
several
copper
compounds
by
the
Office
of
Pesticide
Programs
Toxicology
Branch
concluded
that
the
toxicity
from
dietary
exposure
to
copper
was
well­
established
in
the
published
literature
and
that
all
sub­
chronic,
chronic/
oncogenicity,
mutagenicity,
teratology
and
reproductive
data
requirements
for
the
subject
copper
compounds,
including
Copper
Sulfate
Pentahydrate,
should
be
waived.
In
support
of
its
conclusion,
the
review
made
the
following
points:

1.
Copper
is
unique
among
the
pesticides
since
it
is
also
a
nutritional
trace
element,
essential
for
growth
and
well­
being
of
both
higher
level
plants
and
animals.

2.
Humans
possess
a
natural,
efficient
homeostatic
mechanism
for
regulating
body
copper
levels
over
a
wide
range
of
dietary
intake.

5.
There
is
an
overwhelming
lack
of
evidence
of
any
chronic
effects
induced
in
normal
man
by
dietary
ingestion
of
copper
unless
the
intake
is
of
such
enormous
magnitude
that
there
is
a
disruption
of
the
natural
homeostatic
Page
7
of
14
mechanism
for
controlling
body
levels.

The
petitioner
conducted
a
comprehensive
literature
search
for
articles
on
copper
toxicity
published
subsequent
to
the
1986
Toxicology
Branch
review.
No
information
that
called
into
question
the
above
conclusions
was
found.

*
Source:
Toxicology
Chapter
for
Copper
Group
II
Registration
Standard,
D­
7828,
(
1986).

SECTION
C/
PART
2
INVESTIGATIONS
MADE
WITH
RESPECT
TO
THE
SAFETY
HUMANS
AND
DOMETIC
ANIMALS
Complete
toxicology
information
for
technical
copper
sulfate
pentahydrate
has
previously
been
submitted
to
the
Agency.
The
toxicity
data
for
Stalosan
F
were
submitted
with
the
application
for
registration,
and
indicate
a
toxicity
category
IV
level
for
all
studies,
other
than
eye
irritation,
which
may
be
listed
as
toxicity
category
III.

40
CFR,
§
180.1021
specifically
exempts
copper
sulfate
pentahydrate
from
the
requirement
of
a
tolerance
when
applied
as
a
fungicide
to
growing
crops
or
raw
agricultural
commoditites
after
harvest
(
with
no
limitation).
Copper
is
exempted
from
the
requirement
of
a
tolerance
in
meat,
poultry,
eggs,
fish,
shellfish
and
irrigated
crops
for
various
uses,
but
the
specific
use
of
adding
copper
to
animal
bedding
was
not
specifically
identified,

FDA
has
determined
that
Copper
sulfate
is
a
direct
food
substance
affirmed
as
generally
recognized
as
safe
(
GRAS)
(
Title
21,
§
184.1261).
They
have
indicated
that
this
ingredient
is
to
be
used
in
food
with
no
limitation
other
than
current
good
manufacturing
practice.
It
may
be
used
in
infant
formula
in
accordance
with
section
412(
g)
of
FFDCA.
Page
8
of
14
Regarding
the
essentiality
of
copper,
the
Food
and
Nutrition
Board
of
the
National
Academy
of
Sciences
issued
recommended
daily
allowance
(
RDA)
levels
for
copper.

These
values
are
shown
in
the
table
below:

National
Academy
of
Sciences
Recommendations
for
Copper
in
the
Diet*

Age
Estimated
Safe
and
Adequate
Daily
Dietary
Intakes
(
mg)

To
6
months
0.5­
0.7
6
months­
1
year
0.7­
1.0
1­
3
years
1.0­
1.5
4­
6
years
1.5­
2.0
7­
10
years
2.0­
2.5
11
years
and
over
2.0­
3.0
Adult
2.0­
3.0
*
Source:
Committee
on
Dietary
Allowances,
Food
and
Nutrition
Board,
National
Academy
of
Sciences­
National
Research
Council
(
1980).
Page
9
of
14
SECTION
D:
RESIDUE
DATA
AND
ANALYTICAL
METHOD
As
noted
above,
Copper
Sulfate
Pentahydrate,
upon
application,
forms
copper
hydroxide.
Accordingly,
the
nature
of
the
residue
is
copper.

The
petitioner
is
requesting
that
the
Agency
waive
all
residue
chemistry
data
requirements
for
copper
since:

C
Copper
is
an
essential
trace
element
critical
for
the
propagation
of
plants.

C
It
will
be
impossible
to
distinguish
copper
residues
resulting
from
naturally
occurring
copper
or
Copper
Sulfate
Pentahydrate.

C
Copper
is
found
in
several
fruits
and
vegetables
(
refer
to
attached
tables
on
pages
12­
14
of
this
petition).

The
amount
of
copper
applied
to
crops
from
the
use
of
Copper
Sulfate
Pentahydrate
is
equivalent
to
the
amount
of
copper
applied
from
the
use
of
compounds
such
as
copper
hydroxide
for
which
there
is
an
existing
tolerance
exemption
for
all
RAC=
s.

Regarding
the
requirement
for
a
residue
analytical
method,
the
Agency
noted
in
its
1996
residue
review
of
Group
II
Copper
Compounds
that
adequate
atomic
absorption,
emission
spectroscopic,
and
colorimetric
analytical
methods
are
available
to
determine
copper
in
formulations,
crops,
animal
tissues
and
water.
Accordingly,
there
is
no
need
to
provide
a
residue
analytical
method
for
Copper
Sulfate
Pentahydrate.
Page
10
of
14
SECTION
E:
PRACTICABLE
METHODS
FOR
REMOVING
RESIDUES
THAT
EXCEED
ANY
PROPOSED
TOLERANCE
Since
the
petitioner
is
requesting
a
tolerance
exemption
and
copper
is
a
natural
crop
constituent
and
is
part
of
the
normal
diet
of
feed
or
food
animals,
methods
for
removing
excess
residues
are
not
applicable.
Page
11
of
14
SECTION
F:
PROPOSED
TOLERANCE:

ArchAngel
LLC
is
proposing
to
amend
40
C.
F.
R.
by
revising
the
very
end
of
'
180.1021(
c),
as
follows:

'
180.1021
Copper;
exemptions
from
the
requirement
of
a
tolerance
(
a)
***

(
b)
***

(
c)
Copper
sulfate
pentahydrate
(
CAS
Reg.
No.
7758­
99­
8)
is
exempt
from
the
requirement
of
a
tolerance
when
applied
as
a
fungicide
to
growing
crops
or
to
raw
agricultural
commoditities
after
harvest,
and
in
meat,
milk,
poultry,
and
eggs
when
used
in
animal
bedding
to
inhibit
the
growth
of
bacteria
and
fungi.
Page
12
of
14
SECTION
G:
REASONABLE
GROUNDS
IN
SUPPORT
OF
THIS
PETITION
The
regulations
(
40
C.
F.
R.
'
180.1021)
permit
the
use
of
several
copper
compounds
In
meat,
milk,
poultry,
eggs,
fish,
shellfish,
growing
crops.
Since
Copper
Sulfate
Pentahydrate
is
a
substitute
for
these
copper
compounds
and,
under
use­
conditions,
releases
equivalent
amounts
of
copper,
approval
of
this
petition
will
not
result
in
any
increased
dietary
intake
or
risk.
Moreover,
copper
is
an
essential
nutrient
for
which
the
National
Academy
of
Sciences
has
established
a
recommended
daily
dietary
intake.
The
use
of
Copper
Sulfate
Pentahydrate
to
inhibit
the
growth
of
bacteria
in
animal
bedding
will,
at
most,
make
a
negligible
contribution
to
the
dietary
intake
of
naturally
occurring
copper.
As
mentioned
in
the
previous
section
Complete
toxicology
information
for
technical
copper
sulfate
pentahydrate
has
previously
been
submitted
to
the
Agency.
The
toxicity
data
for
Stalosan
F
were
submitted
with
the
application
for
registration,
and
indicate
a
toxicity
category
IV
level
for
all
studies,
other
than
eye
irritation,
which
may
be
listed
as
toxicity
category
III.

40
CFR,
§
180.1021
specifically
exempts
copper
sulfate
pentahydrate
from
the
requirement
of
a
tolerance
when
applied
as
a
fungicide
to
growing
crops
or
raw
agricultural
commoditites
after
harvest
(
with
no
limitation).
Copper
is
exempted
from
the
requirement
of
a
tolerance
in
meat,
poultry,
eggs,
fish,
shellfish
and
irrigated
crops
for
various
uses,
but
the
specific
use
of
adding
copper
to
animal
bedding
was
not
specifically
identified,

FDA
has
determined
that
Copper
sulfate
is
a
direct
food
substance
affirmed
as
generally
recognized
as
safe
(
GRAS)
(
Title
21,
§
184.1261).
They
have
indicated
that
this
ingredient
is
to
be
used
in
food
with
no
limitation
other
than
current
good
manufacturing
practice.
It
may
be
used
in
infant
formula
in
accordance
with
section
412(
g)
of
FFDCA.
Page
13
of
14
SECTION
H:
SUPPLEMENTAL
INFORMATION­
AGGREGATE
EXPOSURE
Aggregate
human
exposure,
excluding
occupational,
to
copper
was
examined
in
a
1987
U.
S.
EPA
report
*.
The
estimates
provided
in
the
report
of
copper
exposure
from
drinking
water,
food
and
air
are
summarized
below:

Drinking
Water
The
report
noted
that
naturally
occurring
levels
of
copper
in
drinking
water
are
less
than
50
ppb
and
exposure
was
largely
due
to
corrosion
of
plumbing
materials.
A
survey
cited
in
the
report
indicated
that
~
10%
of
the
taps
sampled
had
copper
levels
of
500
ppb
and
~
2%
had
levels
above
1.3
ppm
(
the
MCL
for
copper
is
1
ppm).
Another
report
*
issued
by
U.
S.
EPA
stated
that
the
average
copper
concentration
in
drinking
water
is
~
130
ppb
and
a
little
over
1%
of
the
drinking
water
in
the
U.
S.
exceeds
the
MCL.

Food
Daily
intakes
of
copper
from
twelve
FDA
total
diet
studies
conducted
from
mid
1982­
1984
are
provided
on
the
attached
table.
The
dietary
levels
range
from
0.77
to
1.24
mg/
day.

Air
Data
on
air
concentrations
of
copper
were
collected
by
U.
S.
EPA=
s
Environmental
Monitoring
Systems
Laboratory.
The
data
were
from
a
nationwide
study
on
copper
concentrations
in
ambient
air
for
the
years
1977­
1983.
Concentrations
in
the
23,
814
air
samples
analyzed
ranged
from
0.003­
7.32
ug/
m
3
.

*
U.
S.
EPA.
1987.
Drinking
Water
Criteria
Document
for
Copper,
Prepared
by
U.
S.
EPA
Office
of
Health
and
Environmental
Assessment.
Page
14
of
14
**
U.
S.
EPA.
1987.
Health
Issue
Assessment:
Copper.

Based
on
the
above
data,
the
petitioner
estimates
the
aggregate
exposure
to
copper
from
food,
drinking
water
and
air
ranges
from
1.2­
3.0
mg/
day.

Occupational
copper
exposure
may
occur
to
workers
involved
in
the
following
jobs:
copper
manufacture,
asphalt
and
battery
production,
electroplating,
wood
preservation,
paint
formulation,
water
treatment,
rayon
production,
copper
fungicide
application,
gem
coloring,

lithography,
pigment
manufacture
and
soldering.
The
OSHA
standard
for
copper
is
0.1
mg/
m
3
(
copper
fume)
and
1
mg/
m
3
(
copper
dust).