Document ID: EPA-HQ-OPP-2005-0177-0003
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2005-12-28T05:00Z

UNITED
STATES
ENVIRONMENTAL
PROTECTION
AGENCY
WASHINGTON,
D.
C.
20460
OFFICE
OF
PREVENTION,
PESTICIDES
AND
TOXIC
SUBSTANCES
PC
Code
No.:
014601
DP
Barcode:
D305901
Date:
June
21,
2005
MEMORANDUM
SUBJECT:
Environmental
Fate
and
Ecological
Risk
Assessment
for
Metiram,
Section
4
Reregistration
for
Control
of
Fungal
Diseases
on
Apples,
Potatoes,
Potato
seed,
Certain
Ornamental
Plants
and
Tobacco
Seedling
Plants
(
Phase
3
Response).

TO:
Michael
Goodis,
Branch
Chief
Tawanda
Spears,
Chemical
Review
Manager
Special
Review
and
Reregistration
Division
(
7508C)

FROM:
ERB
V
Team
for
EBDCs:
Gabe
Patrick,
Biologist,
Ecological
Effects
Reviewer
M.
A.
Ruhman,
Ph.
D.,
Agronomist,
Environmental
Fate
Reviewer
Ronald
Parker,
Ph.
D.,
Environmental
Engineer,
Environmental
Fate
Reviewer
Environmental
Fate
and
Effects
Division
(
7507C)

THROUGH:
Mah
T.
Shamim,
Ph.
D.,
Chief
Environmental
Risk
Branch
V
Environmental
Fate
and
Effects
Division
(
7507C)

The
EFED
screening
level
Environmental
Risk
Assessment
is
attached.
This
RED
document
should
be
considered
with
the
accompanied
ETU
chapter,
the
degradate
of
concern
for
metiram.

The
following
is
an
overview
of
our
findings:

Risk
to
Terrestrial
and
Aquatic
Organisms
EFED
expects
chronic
risk
to
birds
and
mammals
to
be
a
potential
major
concern
in
this
assessment.
Chronic
Levels
Of
Concern
(
LOCs)
were
exceeded
for
almost
all
uses.
The
chronic
Risk
Quotients
(
RQs)
for
birds
range
from
91
on
tobacco
to
a
low
of
1
on
ornamentals
using
a
default
half­
life
value
of
35
days.
Using
a
3­
day
half­
life
reduced
the
chronic
risk
to
birds
(
RQs
ranged
from
51
for
tobacco
to
0.4
for
ornamentals).
However
most
avian
chronic
RQs
still
exceeded
the
LOC
of
1.0.
For
mammals,
chronic
RQs
ranged
from
113
on
tobacco
to
a
low
of
1
on
ornamentals
using
a
default
halflife
value
of
35
days.
Modeling
using
a
3­
day
half­
life
reduced
the
chronic
risk
to
mammals
(
RQs
ranged
from
63.4
for
tobacco
to
0.6
for
ornamentals).
However
most
chronic
mammalian
RQs
still
exceeded
the
LOC
of
1.0
even
when
EFED
used
a
low­
end
value
to
estimate
the
total
foliar
1
In
this
document
three
important
abbreviations
are
used:
Parent
metiram,
Metiram
complex
and
Bound
species.
Parent
metiram
is
the
polymeric
parent
metiram
present
in
the
active
ingredient.
Metiram
complex
is
a
suite
of
multi
species
residue
resulting
from
degradation
of
the
polymeric
parent
metiram.
The
suite
includes
the
following:
(
a)
species
reported
to
be
present
but
not
specifically
identified:
variable/
low
molecular
weight
polymeric
chains
(
i.
e
polymer
fragments),
monomeric
species,
and
EBDC
ligand
in
association
with
other
metal
ions
that
might
be
present
in
the
environment;
(
b)
species
identified
and
quantified:
Transient
species,
ETU
and
ETU
degradates;
and
(
c)
unidentified
species
that
bound
to
soil
and
sediment
particles
(
referred
to
as
Bound
species).

2
dissipation
half­
life
(
3
days).
Metiram's
acute
bird
dietary
RQs
exceed
acute,
acute
restricted
use
and
acute
endangered
species
LOCs
for
tobacco,
apple,
and
potato
uses.
The
avian
RQs
range
from
0.56
to
1.22.
Acute
risk
to
mammals
was
assumed
to
be
low
since
the
compound
was
practically
nontoxic
(
LD50
>
5000
mg/
Kg
).
Similarly,
since
metiram
is
practically
nontoxic
to
honeybees,
(
acute
contact
LD
50
=
437
µ
g/
bee)
low
risk
is
assumed.
Also,
there
are
no
incident
data
reporting
adverse
effects
to
honeybees
from
the
use
of
metiram.
In
addition,
data
were
inadequate
to
evaluate
the
risk
of
metiram
to
terrestrial
non­
target
plants.

Based
on
limited
data,
RQs
for
the
metiram
complex1
(
suite
of
transient
species
and
degradation
products
from
metiram)
exceeded
acute
restricted
use
and
acute
endangered
species
LOCs
for
freshwater
fish
for
the
uses
modeled
(
the
RQs
range
from
0.24
on
potatoes
to
0.43
on
apples).
Based
on
metiram's
use
on
apples,
acute
LOCs
are
exceeded
for
nonvascular
aquatic
plants
(
RQ
=
1.28).
There
are
inadequate
data
to
evaluate
acute
risks
to
freshwater
invertebrates,
estuarine
or
marine
animals,
and
aquatic
plants
from
exposure
to
the
metiram
complex.
There
are
no
data
to
evaluate
chronic
risks
to
freshwater
and
estuarine/
marine
organisms
from
exposure
to
the
metiram
complex.

Risks
to
Endangered
Species
Based
on
available
screening
level
information
there
is
a
potential
concern
for
acute
effects
on
listed
birds
and
freshwater
fish
species
and
chronic
effects
on
listed
birds
and
mammals
should
exposure
actually
occur.
Even
though
metiram
is
only
slightly
toxic
to
birds,
metiram's
uses
exceed
the
endangered
species
LOC
(
RQs
range
from
0.11
to
1.22)
at
maximum
Estimated
Environmental
Concentrations
(
EEC)
levels.
EFED
does
not
expect
metiram
exposure
to
pose
acute
risk
to
nontarget
insects
because
metiram
is
practically
nontoxic
to
honeybees,
(
acute
contact
LD
50
=
437
µ
g/
bee)
and
there
are
no
incident
data
reporting
adverse
effects
to
honeybees.
The
Agency
does
not
currently
have
enough
data
to
perform
a
screening
level
assessment
for
metiram's
effects
on
listed
non­
target
terrestrial
plants,
freshwater
invertebrates,
estuarine/
marine
fish,
or
vascular
aquatic
plants.
There
are
no
nonvascular
aquatic
plants
or
estuarine/
marine
invertebrate
species
on
the
endangered
species
list.

Risk
to
the
Water
Resources
Metiram
is
non­
persistent
as
it
is
expected
to
decompose
rapidly
(
to
<
10%
of
the
applied
within
6
days)
by
hydrolytic
reactions
in
the
main
compartments
of
the
natural
environment.
The
degradate
of
concern
in
the
process
of
metiram
decomposition
is
ETU,
a
B2
carcinogen
(
US
EPA,
2002).
Therefore,
risk
assessment
for
the
water
resource,
from
the
common
EBDCs
degradate
ETU,
was
performed
for
the
application
of
all
EBDCs
including
metiram.
The
reader
is
referred
to
the
accompanied
ETU
document
for
this
assessment.

Uncertainties
3
(
1)
Environmental
Fate
EECs
for
parent
metiram
were
estimated
for
water
bodies/
soils
using
aqueous
hydrolysis
half­
lives.
The
same
hydrolysis
half­
lives
were
used
for
soils
assuming
sufficient
moisture
is
available
in
soil
pores
for
hydrolysis
to
occur
at
the
same
rate.
Uncertainties
exist
on
whether
half­
lives
used
are
applicable
because
soil
moisture
level
is
expected
to
impact
resultant
EECs.
Lower
EECs
are
expected
in
irrigated
and/
or
rain­
fed
soils
with
high
water
holding
capacity
(
WHC)
and
higher
EECs
are
expected
in
low
WHC
soils
under
dry
conditions.
EFED
believes
that
this
is
a
reasonable
assumption
giving
the
fact
that
metiram
is
applied
to
growing
crops
where
moisture
is
expected
to
be
available
as
the
case
in
irrigated
and/
or
rain­
fed
crops
grown
in
soils
with
high
water
holding
capacity
(
WHC).
Therefore,
EEC
values
can
be
higher
than
that
estimated
in
low
WHC
soils
under
dry
conditions.
Other
factors
that
are
known
to
affect
hydrolytic
stability
of
metiram
include:
particle
size;
molecular
weight
distribution;
aqueous
media
pH
and
O
2
concentration;
and
concentration
of
metal
ions.

EECs
for
metiram
complex,
as
a
whole,
were
estimated
using
the
physicochemical
properties
and
hydrolysis
half­
lives
of
parent
metiram
in
addition
to
aerobic
soil
metabolism
half­
lives
and
sorption
coefficients
which
were
assigned
to
this
metiram
complex
rather
than
the
parent.
Uncertainty
exists
in
these
residue
half­
lives
as
they
are
conservative
and
affected
by
the
validity
of
the
assumption
that
the
only
bio­
degradation
of
the
complex
was
represented
by
evolved
CO
2
.
Degradates,
including
ETU,
were
considered
as
part
of
the
complex
and
were
not
considered
separately
because
determined
concentrations
were
affected
by
impurities
in
the
test
materials,
hydrolytic
reactions
and
possible
artificial
degradation
during
extraction.

Several
problems
were
identified
in
submitted
fate
studies
for
the
EBDCs
including
metiram.
These
problems
are
presented
in
detail
in
Appendix
I.
Stated
problems
adds
a
degree
of
uncertainty
for
estimated
fate
parameters
for
parent
metiram
and
metiram
complex
and
consequently
resultant
EECs
estimated
from
modeling.

In
the
degradation
process
for
metiram,
Zn
ions/
salts
are
expected
to
dissipate
into
the
environment.
EFED
recognizes
that
Zn
is
a
micronutrient
but
no
data
were
presented
to
evaluate
the
risk
that
might
be
associated
with
this
release
in
certain
sensitive
environmental
settings
and
therefore,
uncertainty
exists
in
this
aspect
of
risk
assessment.

(
2)
Ecological
Effects
EFED
is
uncertain
about
metiram's
acute
risk
to
estuarine/
marine
fish,
aquatic
invertebrates,
and
terrestrial
plants
because
EFED
lacks
toxicity
data
for
surrogate
species
representing
these
groups.
Because
EFED
lacks
chronic
metiram
toxicity
data,
EFED
is
uncertain
about
the
chronic
risks
to
freshwater
and
estuarine/
marine
organisms.

Endocrine
Disruption
Observed
reproductive
effects
on
mammals
and
avian
studies
would
support
the
concern
that
metiram
may
be
a
potential
endocrine
disruptor.
The
avian
reproductive
studies,
reviewed
by
EFED,
revealed
metiram
reproductive
effects
such
as
reduced
egg
production,
mean
egg
weight,
fertility
rate,
number
of
hatched
ducklings,
number
of
14­
day
old
survivors,
and
an
increased
rate
of
early
embryonic
deaths.
Metiram
mammalian
effects,
from
a
reproductive
study,
included
parental
toxicity
resulting
in
decreased
body
weight
during
gestation
and
lactation
for
females.
Also,
the
reproductive
toxicity
4
resulted
in
decreased
mating
performance
(
increased
precoital
time)
in
the
F2
generation
(
two
generations
removed
from
the
original
parent
generation).
In
a
3
month
feeding
study
submitted
to
The
Agency
(
MRID
42590­
01),
there
was
a
significant
decrease
in
total
serum
thyroxine
(
T4)
concentrations
in
both
sexes
of
mice.
These
effects,
noted
in
both
birds
and
mammals,
may
be
a
result
of
possible
hormonal
disruptions.
EFED
recommends
subjecting
metiram
to
more
definitive
testing
to
better
characterize
effects
related
to
its
endocrine
disruption
when
EPA
develops
suitable
screening
and
testing
protocols.

Data
Gaps
Environmental
Fate
Complete
characterization
of
the
fate
of
metiram
complex
requires
more
information
on
the
various
species
that
constitute
this
residue
including
the
soil/
sediment
bound
species.
Information
needed
are
for
each
of
these
constituents
and
includes:
their
physicochemical
properties
and
the
nature
of
their
association
with
soil/
sediment
particles.
Additionally,
full
characterization
of
the
processes
involved
in
parent
metiram
dissipation
requires
additional
information
on
the
release
of
Zn
ions
from
metiram
in
order
to
evaluate
possible
environmental
risk
that
might
be
associated
with
such
release
in
specific
environmental
settings.

Several
problems
were
identified
in
submitted
fate
studies
for
the
EBDCs
including
metiram.
These
problems
are
presented
in
details
in
Appendix
I.
The
registrant
is
requested
to
address
these
problems.
The
following
Table
lists
the
status
of
the
fate
data
requirements
for
metiram.
In
the
Table,
hydrolysis,
adsorption/
desorption
and
leaching
studies
are
listed
as
supplemental
however,
no
new
studies
are
required
because
problems
found
in
these
studies
are
mostly
associated
with
the
unique
characteristics
of
this
chemical
in
aqueous
media.
Not
all
the
requirements
of
these
guideline
studies
can
be
met
due
to
the
high
susceptibility
of
this
chemical
to
hydrolysis.
In
contrast,
some
of
the
aerobic
soil
studies
are
classified
as
supplemental
mainly
because
of
incomplete
characterization
of
the
significant
bound
species.
Without
a
complete
characterization
of
these
bound
species,
EFED
was
only
able
to
estimate
conservative
half­
lives
based
on
complete
mineralization
of
the
residue
into
CO
2
.
The
issues
of
the
bound
species
and
use
of
CS
2
data
are
presented
in
detail
elsewhere
in
this
document
(
section
IV.
b.
iv);
the
registrant
is
requested
to
address
these
issues.

A
high
tier
targeted
monitoring
study
was
submitted
for
ETU,
the
degradate
of
concern
for
all
EBDCs
including
metiram,
therefore,
no
new
terrestrial
field
dissipation
study
is
required
at
this
time.

Status
of
environmental
data
requirements
for
Metiram.
5
Guideline
Number
Data
Requirement
Is
Data
Needed?
MRID
Number
Study
Classification
161­
1
835.2
Hydrolysis
1
No
001467­
64
[
001551­
89
&
001619­
37]
Supplemental
161­
2
835.2
Photo
Degradation
in
Water
2
No
[
001551­
90
&
001619­
38]
Acceptable
161­
3
835.2
Photo
Degradation
on
Soil
No
001570­
31
Acceptable
162­
1
835.4
Aerobic
Soil
Metabolism
No
459069­
01
Acceptable
451452­
03
Supplemental
001552­
88
3
162­
2
835.4
Anaerobic
Soil
Reserved
001552­
88
3
Not
Acceptable
162­
3
835.4
Anaerobic
Aquatic
Metabolism
Reserved
No
Studies
submitted
162­
4
835.4
Aerobic
Aquatic
Metabolism
No
4593344­
01
Acceptable
163­
1
835.1230
Adsorption/
Desorption
No
Studies
submitted
835.1240
Leaching
No
001552­
88
3
Supplemental
405763­
01
Supplemental
164­
1
835.6
Terrestrial
Field
Dissipation
No
001619­
35
Supplemental
No
414408­
01
Not
Acceptable
414408­
02
165­
4
850.2
Accumulation
in
Fish
Waived
because
metiram
Kow
is
below
100
1
MRID
001467­
64
is
only
a
report
on
a
study
(
Study
itself
was
not
found);
MRID
001619­
37
is
an
addendum
to
MRID
001551­
89
2
MRID
001619­
38
is
an
addendum
to
MRID
001551­
90
3
MRID
001552­
88
included
aerobic/
anaerobic
soil
and
leaching
experiments;
The
anaerobic
portion
of
the
study
was
not
acceptable.

Ecotoxicity
EFED
is
uncertain
about
metiram's
acute
risk
to
estuarine/
marine
fish,
aquatic
invertebrates,
and
terrestrial
plants
because
EFED
lacks
toxicity
data
for
surrogate
species
representing
these
groups.
Because
EFED
lacks
chronic
metiram
toxicity
data,
EFED
is
uncertain
about
the
chronic
risks
to
freshwater
and
estuarine/
marine
organisms.
EFED
needs
studies
submitted
to
evaluate
these
uncertainties.
EFED
needs
whole
sediment
acute
toxicity
testing
on
freshwater
invertebrates
and
estuarine/
marine
invertebrates
because
a
significant
part
of
the
metiram
complex
binds
to
sediment
and
EFED
needs
to
know
how
toxic
these
bound
species
are
to
benthic
organisms.
In
some
risk
6
evaluations
EFED
has
used
supplemental
studies
to
make
a
risk
determination.
EFED
needs
core
studies
to
confirm
these
findings.

EFED
has
not
received
Tier
I
seedling
emergence
[
guideline
122­
1(
a)]
and
vegetative
vigor
[
guideline
122­
1(
b)]
studies
for
metiram.
EFED
needs
submission
of
these
studies
for
review.
The
submission
of
Tier
II
seedling
emergence
[
guideline
123­
1(
a)]
and
vegetative
vigor
[
guideline
123­
1(
b)]
testing
for
the
metiram
is
being
held
in
reserve
pending
the
results
of
Tier
I
testing.

EFED
needs
Core
Tier
I
or
Tier
II
aquatic
plant
growth
testing
for
duckweed
(
Lemna
gibba),
marine
diatom
(
Skeletonema
costatum),
blue­
green
algae
(
Anabaena
flos­
aquae),
freshwater
green
alga
(
Selenastrum
capricornutum)
and
a
freshwater
diatom.

The
following
Table
lists
the
status
of
the
ecological
data
requirements
for
metiram.

Status
of
ecological
data
requirements
for
Metiram.

Date:
May
31,
2005
Case
No:
0643
Chemical
No:
014601
METIRAM
ECOLOGICAL
DATA
REQUIREMENTS
FOR
THE
ENVIRONMENTAL
FATE
AND
EFFECTS
DIVISION
Data
Requirement
Composition1
Use
Pattern1
Does
EPA
Have
Data
To
Satisfy
This
Need?
Bibliographic
Citation
Study
Classification
Additional
Data
Needed
Under
FIFRA
3(
c)(
2)(
B)?

§
158.490
WILDLIFE
AND
AQUATIC
ORGANISMS
71­
1(
a)
Acute
Avian
Oral,
Quail/
Duck
TGAI
1,
2,
3
Yes
40656901
Core
No
71­
1(
b)
Acute
Avian
Oral,
Quail/
Duck
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
No
71­
2(
a)
Acute
Avian
Diet,
Quail
TGAI
1,
2,
3
Yes2
00108004
Core
No
71­
2(
b)
Acute
Avian
Diet,
Duck
TGAI
1,
2,
3
Yes2
00108005
Core
No
71­
3
Wild
Mammal
Toxicity
1,
2,
3
No
Not
applicable
Not
applicable
No
71­
4(
a)
Avian
Reproduction
Quail
TGAI
1,
2,
3
No
41082001
Supplemental3
No
71­
4(
b)
Avian
Reproduction
Duck
TGAI
1,
2,
3
Yes
42539102
Core
No
71­
5(
a)
Simulated
Terrestrial
Field
Study
1,
2,
3
No
Not
applicable
Not
applicable
No
71­
5(
b)
Actual
Terrestrial
Field
Stud
1,
2,
3
No
Not
applicable
Not
applicable
No
72­
1(
a)
Acute
Fish
Toxicity
Bluegill
TGAI
1,
2,
3
No
Not
applicable
Not
applicable
Yes
72­
1(
b)
Acute
Fish
Toxicity
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
No
72­
1(
c)
Acute
Fish
Toxicity
Rainbow
Trout
TGAI
1,
2,
3
Yes
43525001
45933402
Core
Supplemental
No
72­
1(
d)
Acute
Fish
Toxicity
Rainbow
Trout
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
No
Date:
May
31,
2005
Case
No:
0643
Chemical
No:
014601
METIRAM
ECOLOGICAL
DATA
REQUIREMENTS
FOR
THE
ENVIRONMENTAL
FATE
AND
EFFECTS
DIVISION
Data
Requirement
Composition1
Use
Pattern1
Does
EPA
Have
Data
To
Satisfy
This
Need?
Bibliographic
Citation
Study
Classification
Additional
Data
Needed
Under
FIFRA
3(
c)(
2)(
B)?

7
72­
2(
a)
Acute
Aquatic
Invertebrate
TGAI
1,
2,
3
No
44301101
Supplemental
Yes4
72­
2(
b)
Acute
Aquatic
Invertebrate
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
No
850.1735
Whole
Sediment
Acute
Toxicity
Invertebrates,
Freshwater
TGAI
1,
2,
3
No
Not
applicable
Not
applicable
Yes
72­
3(
a)
Acute
Est/
Mar
Toxicity
Fish
TGAI
1,
2,
3
No
Not
applicable
Not
applicable
Yes
72­
3(
b)
Acute
Est/
Mar
Toxicity
Mollusk
TGAI
1,
2,
3
No
Not
applicable
Not
applicable
Yes
72­
3(
c)
Acute
Est/
Mar
Toxicity
Shrimp
TGAI
1,
2,
3
No
Not
applicable
Not
applicable
Yes
72­
3(
d)
Acute
Est/
Mar
Toxicity
Fish
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
No
72­
3(
e)
Acute
Est/
Mar
Toxicity
Mollusk
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
No
72­
3(
f)
Acute
Est/
Mar
Toxicity
Shrimp
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
No
850.1740
Whole
Sediment
Acute
Toxicity
Invertebrates,
Est/
Mar
TGAI
1,
2,
3
No
Not
applicable
Not
applicable
Yes
72­
4(
a)
Early
Life
Stage
Fish
(
Freshwater
&
Estuarine/
Marine)
TGAI
1,
2,
3
No
Not
applicable
Not
applicable
Yes
(
Freshwater)
Reserved
(
Estuarine/
Marine)

72­
4(
b)
Life
Cycle
Aquatic
Invertebrate
(
Freshwater
&
Estuarine/
Marine)
TGAI
1,
2,
3
No
Not
applicable
Not
applicable
Yes
(
Freshwater)
Reserved
(
Estuarine/
Marine)

72­
5
Life
Cycle
Fish
(
Freshwater
&
Estuarine/
Marine)
TGAI
1,
2,
3
No
Not
applicable
Not
applicable
Reserved
72­
6
Aquatic
Organism
Accumulation
TGAI
1,
2,
3
72­
7(
1)
Simulated
Aquatic
Field
Study
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
No
72­
7(
b)
Actual
Aquatic
Field
Study
1,
2,
3
No
Not
applicable
Not
applicable
No
§
158.540
PLANT
PROTECTION
1,
2,
3
122­
1(
a)
Seed
Germ.,
Seedling
Emergence
­
Tier
I
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
Yes
122­
1(
b)
Vegetative
Vigor­
Tier
I
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
Yes
Date:
May
31,
2005
Case
No:
0643
Chemical
No:
014601
METIRAM
ECOLOGICAL
DATA
REQUIREMENTS
FOR
THE
ENVIRONMENTAL
FATE
AND
EFFECTS
DIVISION
Data
Requirement
Composition1
Use
Pattern1
Does
EPA
Have
Data
To
Satisfy
This
Need?
Bibliographic
Citation
Study
Classification
Additional
Data
Needed
Under
FIFRA
3(
c)(
2)(
B)?

8
122­
2
Aquatic
Plant
Growth
­
Tier
I
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
Yes
123­
1(
a)
Seed
Germ./
Seedling
Emerg..­
Tier
II
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
Reserved
123­
1(
b)
Vegetative
Vigor.­
Tier
II
(
TEP)
1,
2,
3
No
Not
applicable
Not
applicable
Reserved
123­
2
Aquatic
Plant
Growth.­
Tier
II
(
TEP)
1,
2,
3
No
43199601
Supplemental
Yes
5
124­
1
Terrestrial
Field
Study
1,
2,
3
No
Not
applicable
Not
applicable
No
124­
2
Aquatic
Field
Study
1,
2,
3
No
Not
applicable
Not
applicable
No
§
158.490
Non­
target
INSECT
TESTING
1,
2,
3
141­
1
Honey
Bee
Acute
Contact
TGAI
1,
2,
3
Yes2
00066220
Core
No
141­
2
Honey
Bee
Residue
on
Foliage
1,
2,
3
No
Not
applicable
Not
applicable
No
141­
5
Fueld
Test
for
Pollinators
1,
2,
3
No
Not
applicable
Not
applicable
No
FOOTNOTES:

1..
Composition:
TGAI=
Technical
grade
of
the
active
ingredient;
PAIRA=
Pure
active
ingredient,
radiolabeled;
TEP=
Typical
end­
use
product
1=
Terrestrial
Food;
2=
Terrestrial
Feed;
3=
Terrestrial
Non­
Food;
4=
Aquatic
Food;
5=
Aquatic
Non­
Food(
Outdoor);
6=
Aquatic
Non­
Food
(
Industrial);
7=
Aquatic
Non­
Food
(
Residential);
8=
Greenhouse
Food;
9=
Greenhouse
Non­
Food;
10=
Forestry;
11=
Residential
Outdoor;
12=
Indoor
Food;
13=
Indoor
Non­
Fod;
14=
Indoor
Medicinal;
15=
Indoor
Residential.

2
Although
these
studies
are
required
to
be
conducted
on
the
TGAI,
the
percentage
of
active
ingredient
in
the
formulation
tested,
Polyam
80%,
is
high.
Testing
is
considered
satisfied.

3
Although
classified
supplemental,
the
study
does
not
have
to
be
repeated;
results
of
the
mallard
study
show
it
to
be
much
more
senitive
than
the
bobwhite;
the
mallard
will
be
used
for
risk
assessment
purposes.

4
Study
is
classified
supplemental
because
(
1)
an
EC
50
was
not
established;
(
2)
there
was
a
high
variability
in
analytical
results;
and
(
3)
analytical
measurements
were
not
made
on
new
solutions
in
this
static
renewal
test.
Based
on
the
median
analytical
recover
rate
of
all
tested
concentrations
(
51.1%),
the
reported
48­
hour
EC
50
was
>
358
ppb,
which
classifies
metiram
as
highly
toxic
to
Daphnia
magna.
The
study
must
be
repeated.

5
Green
algae
study
is
classified
supplemental.
In
addition
to
reasons
listed
in
the
DER,
reasons
for
requiring
repeat
of
the
study
include
an
inappropriate
lighting
regime
(
2x
recommended)
and
inappropriate
cell
inoculum
levels
(
4x
recommended);
Core
Tier
I
or
Tier
II
aquatic
plant
growth
testing
need
to
be
submitted
for
duckweed
(
Lemna
gibba),
marine
diatom
(
Skeletonema
costatum),
blue­
green
algae
(
Anabaena
flos­
aquae),
freshwater
green
alga
(
Selenastrum
capricornutum),
and
a
freshwater
diatom.

Environmental
Hazards
Labeling
Statements
for
Metiram
Manufacturing
Use
Do
not
discharge
effluent
containing
this
product
into
lakes,
streams,
ponds,
estuaries
oceans
or
other
waters
unless
in
accordance
with
the
requirements
of
a
National
Pollutant
Discharge
Elimination
System
(
NPDES)
permit
and
the
permitting
authority
has
been
notified
in
writing
prior
to
discharge.
Do
not
discharge
effluent
containing
this
product
to
sewer
systems
without
previously
notifying
the
9
local
sewage
treatment
plant
authority.
For
guidance
contact
your
State
Water
Board
or
Regional
Office
of
the
EPA.

End
Use
Products
This
product
is
toxic
to
aquatic
organisms.
Do
not
apply
directly
to
water
or
to
areas
where
surface
water
is
present
or
to
intertidal
areas
below
the
mean
high­
water
mark.
Do
not
contaminate
water
when
disposing
of
equipment
wash
water
or
rinsate.
Apply
this
product
only
as
specified
on
the
label.

Label
statements
for
spray
drift
management
AVOIDING
SPRAY
DRIFT
AT
THE
APPLICATION
SITE
IS
THE
RESPONSIBILITY
OF
THE
APPLICATOR.
The
interaction
of
many
equipment­
and­
weather­
related
factors
determine
the
potential
for
spray
drift.
The
applicator
is
responsible
for
considering
all
these
factors
when
making
decisions.
Where
states
have
more
stringent
regulations,
they
should
be
observed.
UNITED
STATES
ENVIRONMENTAL
PROTECTION
AGENCY
WASHINGTON,
D.
C.
20460
OFFICE
OF
PREVENTION,
PESTICIDES,
AND
TOXIC
SUBSTANCES
Environmental
Fate
and
Ecological
Risk
Assessment
for
the
Reregistration
of
Metiram
Tris
[
ammine
­
[
ethylen
bis
(
dithiocarbamate)]
zinc(
II)]
[
tetrahydro
­
1,2,4,7
­
dithiadiazocine
­
3,8
­
dithione]
polymer
Prepared
by:
Mohammed
A.
Ruhman,
Ph.
D.
Ronald
Parker,
Ph.
D.
Gabe
Patrick
United
States
Environmental
Protection
Agency
Office
of
Pesticide
Programs
Environmental
Fate
and
Effects
Division
Environmental
Risk
Branch
V
401
M
Street,
SW
Mail
Code
7507C
Washington,
D.
C.
20460
Reviewed
by:
Mah
Shamim,
Ph.
D.
Acknowledgments
to:
Joanne
Edwards,
Entomologist,
for
the
substantial
contributions
to
earlier
drafts
and
organization
of
this
assessment.
ii
TABLE
OF
CONTENTS
I.
Executive
Summary
.
.
.
.
.
.
.
.
.
.
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.
.
1
II.
Introduction
.
.
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.
.
.
.
4
a.
Use
Characterization
.
.
.
.
.
.
.
.
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.
.
4
b.
Problem
Formulation
.
.
.
.
.
.
.
.
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.
.
.
5
i.
Assessment
Endpoints
.
.
.
.
.
.
.
.
.
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.
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.
.
.
5
ii.
Conceptual
Model
.
.
.
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.
.
.
.
.
5
iii.
Analysis
Plan
.
.
.
.
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.
6
III.
Integrated
Environmental
Risk
Characterization
.
.
.
.
.
.
.
.
.
.
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.
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.
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.
.
.
.
11
a.
Overview
of
Environmental
Risk
.
.
.
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.
.
11
b.
Key
Issues
and
Uncertainty
.
.
.
.
.
.
.
.
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.
.
12
i.
Environmental
Fate
.
.
.
.
.
.
.
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.
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.
.
.
.
12
ii.
Ecological
Effects
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
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.
.
.
.
13
c.
Endangered
Species
Conclusions
.
.
.
.
.
.
.
.
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.
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.
.
.
.
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.
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.
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.
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.
.
.
.
.
.
17
d.
Endocrine
Disruption
Concerns
.
.
.
.
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.
.
.
.
.
17
IV.
Environmental
Fate
and
Transport
Assessment
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
19
a.
Chemical
Identity
and
Physicochemical
Properties
.
.
.
.
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.
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19
b.
Fate
Processes
.
.
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.
20
i.
Aqueous
Solutions
.
.
.
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21
ii.
Soil
.
.
.
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.
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.
22
iii.
Sediment/
Water
Systems
.
.
.
.
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.
.
.
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.
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.
23
iv.
Bound
Species,
CS2­
data
and
Half­
life
Determination
for
EBDCs
.
.
.
.
.
.
.
.
.
.
.
.
.
24
c.
Mobility
.
.
.
.
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.
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.
.
25
d.
Field
Dissipation
.
.
.
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.
26
e.
Bio­
accumulation
.
.
.
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.
26
f.
Transformation
Products
.
.
.
.
.
.
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.
.
.
26
V.
Water
Resource
Assessment
.
.
.
.
.
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.
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.
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.
.
.
.
.
.
29
a.
Surface
Water
Monitoring
and
Modeling
.
.
.
.
.
.
.
.
.
.
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.
.
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.
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.
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.
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.
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.
.
.
29
b.
Ground
Water
Monitoring
and
Modeling
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
30
c.
Drinking
Water
Assessment
.
.
.
.
.
.
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.
.
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.
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.
.
30
VI.
Aquatic
Exposure
and
Risk
Assessment
.
.
.
.
.
.
.
.
.
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.
.
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.
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.
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.
.
.
31
a.
Hazards
Summary
.
.
.
.
.
.
.
.
.
.
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.
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.
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.
.
.
.
.
31
b.
Exposure
and
Risk
Quotients
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
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.
.
.
.
.
.
.
.
33
c.
Aquatic
Risk
Assessment
.
.
.
.
.
.
.
.
.
.
.
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.
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.
.
.
.
.
.
.
.
.
35
i.
Incidents
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
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.
.
.
.
.
35
ii.
Endocrine
Disruptors
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
36
iii.
Endangered
Species
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
36
VII.
Terrestrial
Exposure
and
Risk
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
37
a.
Hazards
Summary
(
Acute/
Chronic)
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
37
b.
Exposure
Summary
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
38
c.
Risk
Quotients
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
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.
.
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.
.
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.
.
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.
.
.
.
.
.
.
.
38
iii
d.
Terrestrial
Risk
Assessment
.
.
.
.
.
.
.
.
.
.
.
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.
.
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.
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.
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.
.
.
.
.
.
.
42
i.
Incidents
.
.
.
.
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.
.
.
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.
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.
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.
.
.
.
.
.
48
ii.
Endocrine
Disruption
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
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.
.
.
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.
.
.
.
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.
.
.
.
.
.
.
.
.
.
.
.
48
iii.
Endangered
Species
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
49
APPENDIX
I:
Metiram
Registered
Uses
&
Notes
on
Fate
Studies
and
Modeling
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
50
a.
Metiram
Registered
Uses
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
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.
.
.
.
.
.
.
.
.
.
.
.
50
b.
Notes
on
Fate
Studies
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
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.
.
.
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.
.
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.
.
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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
51
i.
Aqueous
medium
studies
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
51
ii.
Soil/
sediment
studies
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
.
.
.
.
.
51
c.
Notes
on
Modeling
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
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.
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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
54
i.
EECs
for
Parent
metiram
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
54
ii.
Background
Information
on
the
PRZM
and
EXAMS
models
&
the
Index
Reservoir
Scenario
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
54
iii.
Background
Information
on
SCIGROW
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
55
APPENDIX
II:
Terrestrial
Modeling
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
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.
.
.
.
.
.
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.
.
.
.
.
.
.
56
a.
Hoerger­
Kenaga
Estimates
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
56
b.
Fate
v.
5.0
Model
Terrestrial
Exposure
Values
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
57
c.
Fate
v.
5.0
Model
Sample
Output
for
Metiram
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
58
APPENDIX
III:
Ecological
Hazards
Assessment
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
60
a.
Scope
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
60
b.
Toxicity
to
Terrestrial
Animals
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
60
i.
Birds,
Acute,
Subacute
and
Chronic
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
60
ii.
Mammals,
Acute
and
Chronic
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
63
1.
Acute
Dermal
and
Inhalation
Toxicity
Testing
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
64
2.
Mammalian
Sub­
chronic
Toxicity
Testing
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
64
3.
Mammalian
Reproductive
and
Developmental
Toxicity
Testing
.
.
.
.
.
.
.
.
.
65
iii.
Insect
Acute
Contact
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
66
iv.
Insect
Residual
Contact
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
67
v.
Terrestrial
Field
Testing
.
.
.
.
.
.
.
.
.
.
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.
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.
.
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.
.
.
67
c.
Aquatic
Organism
Toxicity
.
.
.
.
.
.
.
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.
.
.
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.
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.
.
.
67
i.
Toxicity
to
Freshwater
Animals
.
.
.
.
.
.
.
.
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.
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.
.
.
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.
.
.
.
.
67
1.
Freshwater
Fish,
Acute
.
.
.
.
.
.
.
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.
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.
.
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.
.
67
2.
Freshwater
Fish,
Chronic
.
.
.
.
.
.
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.
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.
68
3.
Freshwater
Invertebrates,
Acute
.
.
.
.
.
.
.
.
.
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.
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.
68
4.
Freshwater
Invertebrate,
Chronic
.
.
.
.
.
.
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.
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.
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.
.
.
.
.
69
5.
Freshwater
Whole
Sediment
Toxicity
Invertebrates,
Acute
.
.
.
.
.
.
.
.
.
.
.
.
.
69
6.
Freshwater
Field
Studies
.
.
.
.
.
.
.
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.
.
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.
.
.
.
.
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.
.
70
ii.
Toxicity
to
Estuarine
and
Marine
Animals
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
70
1.
Estuarine
and
Marine
Fish,
Acute
.
.
.
.
.
.
.
.
.
.
.
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.
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.
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.
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.
.
.
.
.
70
2.
Estuarine
and
Marine
Fish,
Chronic
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
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.
.
.
.
.
70
3.
Estuarine
and
Marine
Invertebrates,
Acute
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
70
4.
Estuarine
and
Marine
Invertebrate,
Chronic
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
70
5.
Estuarine
and
Marine
Whole
Sediment
Toxicity
Invertebrates,
Acute
.
.
.
.
.
71
6.
Estuarine
and
Marine
Field
Studies
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
.
.
71
iii.
Toxicity
to
Plants
.
.
.
.
.
.
.
.
.
.
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.
.
.
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.
.
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.
.
.
.
.
.
.
.
71
1.
Terrestrial
Plants
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
71
2.
Aquatic
Plants
.
.
.
.
.
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.
.
.
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.
.
71
iv
3.
Aquatic
Plant
Field
Studies
.
.
.
.
.
.
.
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.
.
.
.
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.
.
72
APPENDIX
IV:
Environmental
Exposure
Assessment
.
.
.
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.
.
73
a.
Review
of
Risk
Quotients
(
RQs)
.
.
.
.
.
.
.
.
.
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.
73
b.
Exposure
and
Risk
to
Terrestrial
Animals
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
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.
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.
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.
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.
.
.
.
75
i.
Birds
.
.
.
.
.
.
.
.
.
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.
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.
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.
.
75
ii.
Mammals
.
.
.
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.
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.
79
iii.
Insects
.
.
.
.
.
.
.
.
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.
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.
.
.
81
c.
Exposure
and
Risk
to
Aquatic
Organisms
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
82
i.
Overview
.
.
.
.
.
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.
.
82
ii.
Freshwater
Fish
.
.
.
.
.
.
.
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.
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.
.
.
.
83
iii.
Freshwater
Invertebrates
.
.
.
.
.
.
.
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.
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.
.
.
.
.
.
.
84
d.
Exposure
and
Risk
to
Non­
target
Plants:
Aquatic
Plants
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
85
e.
Endangered
Species
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
.
.
86
f.
Ecological
Incidents
.
.
.
.
.
.
.
.
.
.
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.
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.
.
.
86
APPENDIX
V:
Relevant
Eco­
toxicity
Data
Correspondence
.
.
.
.
.
.
.
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.
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.
.
.
.
.
87
APPENDIX
VI:
US
EPA
Ecological
Incident
Information
System
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
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.
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.
.
91
APPENDIX
VII:
EBDC
Aquatic
Studies
.
.
.
.
.
.
.
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.
93
REFERENCES
.
.
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.
96
a.
Environmental
Fate
.
.
.
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.
.
96
b.
Ecological
Effects
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
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.
.
97
2
Two
generations
removed
from
the
original
parent
generation.

1
I.
Executive
Summary
There
are
potential
acute
risks
to
birds
and
chronic
risks
to
birds
and
mammals.
There
are
potential
acute
risks
to
freshwater
fish,
and
acute
risks
to
aquatic
nonvascular
plants.
These
potential
risks
occur
for
all
or
some
of
metiram's
uses.
Because
EFED
lacks
data,
EFED
is
uncertain
about
mancozeb's
potential
acute
risks
to
terrestrial
plants
and
acute
risks
to
aquatic
vascular
plants.
EFED
is
also
uncertain
about
the
chronic
risks
to
freshwater
fish,
acute
and
chronic
risks
to
freshwater
invertebrates
and
estuarine/
marine
animals
because
EFED
needs
guideline
data.

EFED
expects
metiram's
potential
chronic
risk
to
birds
and
mammals
to
be
a
major
concern.
Avian
and
mammalian
RQs
exceed
the
chronic
LOCs
for
all
metiram
modeled
exposures.
The
chronic
RQs
for
birds
range
from
91
on
tobacco
to
a
low
of
1
on
ornamentals
using
a
default
half­
life
value
of
35
days.
RQs
were
lessened
when
a
3­
day
half­
life
was
used
(
RQs
ranged
from
51
for
tobacco
to
0.4
for
ornamentals),
however
most
avian
chronic
RQs
still
exceeded
the
LOC
of
1.0.
EFED
based
these
potential
chronic
effects
on
an
avian
reproduction
study
using
the
mallard
duck.
Avian
chronic
effects
noted
included
reduced
egg
production;
reduced
mean
egg
weight;
reduced
fertility
rate;
reduced
number
of
hatched
ducklings;
reduced
number
of
14­
day
old
survivors;
and
an
increased
rate
of
early
embryonic
deaths.
Even
though
metiram,
acutely,
is
only
slightly
toxic
to
birds,
RQs
for
all
uses
exceed
endangered
species
LOCs
at
maximum
EEC
levels
(
RQ
range
from
0.11
to
1.22
using
a
35­
day
metiram
half­
life
value
estimate).
These
RQs
for
birds
largely
result
from
metiram's
high
exposure
levels.

For
mammals,
chronic
RQs
ranged
from
a
high
of
113
on
tobacco
to
a
low
of
1
on
ornamentals
using
a
35
day
default
half­
life.
Chronic
RQs
were
lessened
when
a
3­
day
half­
life
was
used
(
RQs
ranged
from
63.4
for
tobacco
to
0.6
for
ornamentals).
However,
most
mammalian
chronic
RQs
still
exceeded
the
LOC
of
1.0.
These
RQs
were
based
on
chronic
effects
in
mammals
from
a
3­
generation
reproduction
study
in
rats.
This
study
showed
parental
and
reproductive
toxicity.
The
parental
toxicity
resulted
in
decreased
body
weight
during
gestation
and
lactation
for
females.
The
reproductive
toxicity
resulted
in
decreased
mating
performance
(
increased
precoital
time
in
the
F2
generation2).
EFED
expects
the
acute
risk
to
mammals
from
metiram's
uses
to
be
low
since
metiram
is,
acutely,
practically
nontoxic
to
mammals.

There
are
no
metiram
incident
data
reported
in
the
Ecological
Incident
Information
System
(
EIIS).
Given
the
long
historical
use
of
metiram
[
first
US
registration
date
was
October
7,
1983.
(
OPPIN.
2003.)],
EFED
does
not
expect
metiram's
potential
acute
risks
to
be
a
major
risk
concern
to
birds
or
mammals.
EFED
expects
the
potential
chronic
risks
to
birds
and
mammals
to
be
a
more
critical
issue
than
the
potential
acute
risks
with
chronic
LOCs
exceeded
for
almost
all
uses.
EFED
expects
chronic
problems
that
affect
wildlife
from
the
use
of
metiram
would
go
unnoticed
in
the
field
and
thus
EFED
would
not
expect
incident
reports,
from
adverse
chronic
exposure.
EFED
does
not
expect
metiram
exposure
to
pose
acute
risk
to
nontarget
insects
because
metiram
is
practically
nontoxic
to
honeybees,
(
acute
contact
LD
50
=
437
µ
g/
bee)
and
there
are
no
incident
data
reporting
adverse
effects
to
honeybees.
There
are
no
data
to
evaluate
metiram's
risk
to
terrestrial
nontarget
plants.
3
In
this
document
three
important
abbreviations
are
used:
Parent
metiram,
Metiram
complex
and
Bound
species.
Parent
metiram
is
the
polymeric
parent
metiram
present
in
the
active
ingredient.
Metiram
complex
is
a
suite
of
multi
species
residue
resulting
from
degradation
of
the
polymeric
parent
metiram.
The
suite
includes
the
following:
(
a)
species
reported
to
be
present
but
not
specifically
identified:
variable/
low
molecular
weight
polymeric
chains
(
i.
e
polymer
fragments),
monomeric
species,
and
EBDC
ligand
in
association
with
other
metal
ions
that
might
be
present
in
the
environment;
(
b)
species
identified
and
quantified:
Transient
species,
ETU
and
ETU
degradates;
and
(
c)
un­
identified
species
that
bound
to
soil
and
sediment
particles
(
referred
to
as
Bound
species).

2
There
are
potential
acute
risks
to
freshwater
fish
and
nonvascular
aquatic
plants.
Based
on
limited
data,
RQs
for
metiram
complex3
exceeded
acute
restricted
use
and
acute
endangered
species
LOCs
for
freshwater
fish
for
all
uses
modeled
(
the
RQs
range
from
0.24
on
potatoes
to
0.43
on
apples).
Based
on
metiram's
use
on
apples,
acute
LOCs
are
exceeded
for
nonvascular
aquatic
plants
(
RQ
=
1.28).
EFED
is
uncertain
about
the
risks
to
freshwater
invertebrates,
estuarine/
marine
animals,
and
aquatic
vascular
plants.
There
is
inadequate
data
to
evaluate
metiram
complex's
acute
risks
to
freshwater
invertebrates,
estuarine/
marine
animals,
and
aquatic
vascular
plants.
There
is
no
data
to
evaluate
metiram
complexes'
chronic
risks
to
freshwater
and
estuarine/
marine
organisms.

Metiram
is
a
nonsystemic
fungicide
applied
to
foliage
for
control
of
fungal
diseases
on
apples,
potatoes,
potato
seed,
certain
ornamental
plants
and
tobacco
seedling
plants.
The
proposed
maximum
application
rates
for
the
major
crops
are
19.2
lbs
a.
i./
acre/
year
for
apples
and
11.2
lbs
a.
i./
acre/
year
for
potatoes.
Metiram
labeling
allows
ground,
aerial,
and
chemigtion
applications
to
apples
and
potatoes.

Metiram
is
a
polymer
in
which
the
ethylenebisdithiocarbamate
(
EBDC)
ligand
present
in
coordination
with
the
Zn+
2
metal
ions.
Foliar
application
of
metiram
cause
it
to
reach
plant/
soil
surfaces
directly
and
air/
water
bodies
by
drift.
In
the
air,
metiram
will
eventually
be
deposited
onto
soil/
plant/
water
bodies
with
minimal
change.
On
plant
surfaces,
it
is
affected
by
physical
wash­
off
and
abiotic
hydrolytic
decomposition
given
time
and
water
availability.
Fate
of
metiram
reaching
the
soil
and
water/
sediment
systems
is
controlled
by
hydrolytic
decomposition
and
soil/
sediment
adsorption.

Parent
metiram
(
complete
polymeric
chains)
is
non­
persistent
in
most
of
the
natural
environments
as
it
is
expected
to
decompose
rapidly
(
reach
<
10%
of
the
applied
within
6
days)
by
hydrolytic
reactions.
Initial
hydrolytic
decomposition
of
metiram
appears
to
be
a
complex
process
and
may
involve
its
breakdown
into
variable/
low
molecular
weight
polymeric
chains
(
i.
e
polymer
fragments),
monomeric
species
and
EBDC
ligand
in
association
with
metal
ions.
The
rate
of
parent
metiram
hydrolytic
decomposition
appears
to
increase
with
particle
size
reduction
of
the
applied
parent
and
availability
of
moisture,
oxygen,
and
high
acidic
and
alkaline
conditions.
The
final
product
of
hydrolytic
decomposition
of
parent
metiram
in
water/
soil
pore
water
is
a
multi
species
residue
hereinafter
the
"
metiram
complex".
It
is
noted
that
parent
metiram
is
not
expected
to
partition
into
the
air
from
soil
and
water
surfaces
due
to
low
vapor
pressure
and
low
Henry's
Law
constant.
Low
K
ow
values
are
reported
for
most
natural
aquatic
environments
(
pH
.
5­
8.5),
therefore
the
chemical
will
not
be
significantly
bio­
concentrated
by
aquatic
organisms
such
as
fish.

In
contrast,
metiram
complex,
consists
of
transient
species
and
degradates
including
the
degradate
of
concern,
ETU
(
US
EPA,
2002)
and
its
degradates.
In
aqueous
media,
transient
species
are
shortlived
while
ETU
is
persistent;
unless
it
is
subjected
to
rapid
degradation
by
microbial
activity
and/
or
indirect
photolysis.
In
soils/
sediments,
a
significant
portion
of
the
complex
partitions
into
the
4
Available
dislodgeable
foliar
residue
(
DFR)
half­
life
data
from
the
Health
Effects
Division
(
HED)
showed
metiram's
half­
life
was
31.4
days
(
see
Table
II­
2).
This
single
metiram
half­
life
value,
from
one
DFR
study,
with
no
total
foliar
residue
(
TFR)
data
for
metiram
available
was
a
limitation.
Because
of
this
limited
data
EFED
felt
the
use
of
a
3­
day
half­
life
value
for
modeling
would
provide
an
EEC
range
for
comparing
metiram's
risks
to
birds
and
mammals.
EFED
selected
the
3­
day
half­
life
value
for
metiram
as
a
possible
low­
end
TFR
value.
From
DFR
and
TFR
values
for
maneb
and
mancozeb
(
two
EBDCs
chemically
related
to
metiram),
there
is
a
sign
3
days
may
be
an
approximate
lowend
foliar
dissipation
half­
life
estimate
for
the
EBDCs
in
general.
EFED
provides
a
brief
discussion
of
the
foliar
half­
life
values
ranges
for
maneb
and
mancozeb
in
Section
II­
Introduction,
Subsection
iii­
Analysis
Plan.

3
soil/
sediment
particles
(
reached
70
to
78%
of
the
applied
parent
within
one
week).
In
these
systems,
species
identified
in
the
liquid/
extractable
phase
were
similar
in
identity
(
differ
in
concentration)
to
those
identified
in
aqueous
media.
Soil/
sediment
bound
species
were
poorly
characterized
and
claimed,
by
the
registrant,
to
be
dominated
by
ethylenediamine
(
EDA).
In
the
absence
of
experimental
proof
of
EDA
or
complete
characterization
of
these
bound
species,
EFED
is
concerned
about
the
residue
as
it
is
persistent
and
could
contain
precursors
for
ETU.
This
conclusion
was
supported
by
sulfur
material
balance
whereas
quantified
parent
metiram
and
degradates
did
not
account
for
the
amount
of
sulfur
present
in
the
test
material
at
time
zero.

The
Metiram
complex,
in
association
with
soil/
sediment,
appears
to
bio­
degrade
at
a
very
slow
rate
possibly
producing
metiram
degradates
that
may
include
ETU;
at
low
concentration
and
very
slow
rate.
Residue
species
left
in
the
liquid
phase
may
continue
to
be
affected
by
hydrolytic
decomposition
along
with
microbial
activity
(
when
present)
producing
degradates
including
ETU.
Submitted
fate
and
effects
data
are
adequate
to
characterize
the
environmental
fate
and
transport,
toxicity,
and
risk
of
the
"
multi
species
residue"
of
metiram
as
a
whole.
Based
on
submitted
fate
data,
most
of
the
constituents
of
this
complex
are
immobile
and
highly
persistent
in
the
environment,
with
aerobic
soil
metabolism
being
the
major
route
of
its
slow
dissipation.
As
metiram
and
its
complex
dissipate
in
aquatic
and
soil
systems,
degradation
products
are
produced
including
ETU
and
its
degradates.

EFED
relied
on
a
default
total
foliar
dissipation
half­
life
of
35
days
to
evaluate
exposure
to
terrestrial
organisms
with
additional
evaluation
using
a
half­
life
of
3
days.
The
35­
day
value
is
a
standard
EFED
default
value
when
the
total
foliar
dissipation
half­
life
is
unknown
for
a
pesticide.
EFED
used
the
3­
day
half­
life
value
for
comparative
purposes.
4
The
stressor
in
this
case
is
the
parent
metiram
although
hydrolytic
reactions
on
foliage
may
result
in
the
presence
of
the
metiram
complex
as
well.
Terrestrial
exposure
was
quantified
as
Estimated
Environmental
Concentrations
(
EECs)
by
modeling
for
the
maximum
application
rates.
For
the
aquatic
environment,
the
main
stressor
is
the
metiram
complex
and
its
EECs
were
estimated
using
tier
2
PRZM/
EXAM
modeling
for
the
various
crop
scenarios.
Drinking
water
assessment
was
performed
only
for
ETU
(
refer
to
the
accompanied
ETU
document);
the
degradate
of
concern
present
in
the
complex.
In
both
terrestrial
and
aquatic
assessments,
equal
toxicity
was
assumed
for
parent
metiram
and
metiram
complex.
4
II.
Introduction
Metiram
is
a
nonsystemic,
broad
spectrum,
polymeric,
dithiocarbamate
fungicide.
Metiram
is
applied
to
foliage
for
control
of
fungal
diseases
on
apples,
potatoes,
potato
seed,
certain
ornamental
plants
and
tobacco
seedling
plants.
Metiram
acts
by
inhibiting
certain
fungal
enzyme
systems.
Metiram
formulation
types
include
dust,
dry
flowable
and
wettable
powder.
Metiram
is,
or
is
planned
to
be,
marketed
by
several
companies
under
various
trade
names
and
formulations
(
Appendix
I).

a.
Use
Characterization
Table
II­
1
lists
a
summary
of
metiram's
major
uses.
Appendix
I
details
of
all
metiram's
registered
uses.
To
profile
metiram's
use
pattern,
EFED
used
OPP's
Label
Use
Information
System
(
LUIS)
for
labels
accepted
by
11/
1/
2001.
On
receipt
and
acceptance
of
changed
labeling
from
BASF
(
see
table
footnote
in
Appendix
I),
the
listing
will
be
in
accord
with
Special
Review
and
Reregistration
Division's
12/
99
Use
Closure
memo.
BEAD's
Quantitative
Usage
Analysis
for
Metiram,
dated
November
1,
2002
covers
the
period
1992
through
2001.
This
report
shows
11%
of
apples
and
11%
of
potatoes
grown
in
the
US
are
treated
with
metiram.
EFED
expects
the
environmental
exposure
from
applications
on
tobacco
are
less
than
applications
to
apples
and
potatoes
because
the
pesticide
is
applied
to
less
acreage.
Metiram's
labeling
directions
specify
tobacco
applications
on
a
square
foot,
rather
than
acre
basis.
This
smaller
application
area
implies
ground
applications
on
a
small­
scale.
Figure
II­
1
shows
the
general
use
areas
for
metiram
across
the
US.
The
estimated
total
active
ingredient
"
a.
i."
applied
was
614,448
lbs/
year
for
apples
and
307,596
lbs/
year
for
potatoes.
These
estimates
are
based
on
pesticide
use
rates
for
individual
crops
at
the
state­
level.
The
state­
level
estimates
were
compiled
by
the
National
Center
for
Food
and
Agricultural
Policy
(
NCFAP)
for
1991­
1993
and
1995.
County­
based
crop
acreage
data
was
obtained
from
the
1992
Census
of
Agriculture.

Table
II­
1.
Metiram
use
patterns.

Crop
Maximum
Application
Rate
(
lbs
a.
i./
acre)
Maximum
Application
Rate
(
lbs
a.
i./
acre/
year)
Number
of
Applications
Minimum
Application
Interval
(
days)

Apples
4.8
19.2
4
7
Potatoes
1.6
11.2
7
5
Tobacco
6.8
not
specified
not
specified
4
Ornamentals
(
nonflowering
plants)
1.6
not
specified
not
specified
7
Ornamentals
(
woody
shrubs
&
vines)
1.2
not
specified
not
specified
7
5
Figure
II­
1.
Estimated
annual
use
of
metiram
in
the
US
(
http://
ca.
water.
usgs.
gov/
pnsp/
use92/
metiram.
html)

b.
Problem
Formulation
Problem
formulation
produces
three
products:
assessment
endpoints;
a
conceptual
model;
and
an
analysis
plan
(
US
EPA,
April,
1998).
Assessment
endpoints
identify
nontarget
organisms
at
risk
from
the
stressors
(
parent
metiram
and
metiram
complex).
The
conceptual
model
provides
a
set
of
risk
theories
and
a
graphic
depiction
of
the
connection
between
the
assessment
endpoints
and
the
stressors.
The
analysis
plan
decides
how
EFED
will
assess
these
risks.

i.
Assessment
Endpoints
EFED
performs
a
screening
level
assessment
to
decide
what
nontarget
organisms
are
at
risk
from
exposure
to
parent
metiram
and
metiram
complex.
For
this
purpose,
EFED
uses
a
surrogate
species
testing
scheme
to
assess
the
risk
from
identified
chemicals
to
broad
categories
of
nontarget
organisms.
In
a
screening
level
assessment,
the
assessment
endpoints
include
toxicity
to
birds,
mammals,
fish,
invertebrates
and
plants.
Proposed
application
of
metiram
to
various
crops
can
cause
it
and
its
residue
to
reach
important
terrestrial
and
aquatic
compartments
of
the
natural
environment
presenting
risks
to
many
nontarget
organisms.

ii.
Conceptual
Model
As
a
screening
level
assessment,
EFED
hypothesizes
metiram
and/
or
its
complex
are
a
potential
risk
to
all
nontarget
organisms
(
terrestrial
and
aquatic)
and
to
the
drinking
water
resources.
These
nontarget
organisms
at
presumed
risk
are
birds,
mammals,
fish,
aquatic
invertebrates,
terrestrial
invertebrates,
plants
and
threatened
and
endangered
species.
An
analysis
plan
for
metiram
risk
assessment
is
drawn
using
available
data/
information
to
test
this
hypothesis.
6
iii.
Analysis
Plan
The
risk
assessment
plan
for
metiram
and/
or
its
complex
(
i.
e
stressors)
is
executed
in
two
tasks
namely,
the
ecological
and
the
drinking
water
resource
risk
assessments.
Each
of
these
tasks
contains
four
common
steps
and
differ
in
the
last
fifth
step.

The
first
common
step
in
the
plan
involves
examination
of
the
application
procedure
in
order
to
identify
major
source(
s)
of
chemical
contamination
to
important
compartments
of
the
environment.
It
also
involves
determination
of
expected
chemical
distribution
in
these
compartments.

The
second
common
step
involves
examination
of
the
fate
and
transport
data
to
identify
various
chemicals
and
processes
involved
in
transformation
and
transport
of
metiram
and
its
complex.

The
third
common
step
requires
identification
of
important
stressor(
s)
that
are
involved
in
ecological
and
water
resource
exposure.
For
example,
execution
of
the
first
three
steps
in
the
analysis
plan
for
metiram
indicates
that
the
major
ecological
stressor
is
parent
metiram
for
terrestrial
life­
forms
and
metiram
complex
for
aquatic
life­
forms.
Data
and
information
used
to
arrive
at
these
conclusions
are
covered
in
various
sections
of
this
document:
Introduction
for
the
first
step,
Environmental
Fate
and
Transport
characterization
for
the
second/
third
steps.

The
fourth
common
step
is
to
quantify
the
environmental
exposure
for
identified
stressors
by
calculating
EECs.
For
the
terrestrial
exposure,
EECs
for
parent
metiram
from
the
FATE
version
5.0
model
that
calculates
the
decay
of
a
chemical
applied
to
foliar
surfaces
for
single
or
multiple
applications.
The
model
assumes
initial
concentrations
on
plant
surfaces
based
on
Kenaga
predicted
maximum
and
mean
residues
as
adjusted
by
Fletcher
and
others
(
1994)
and
assumes
1st
order
dissipation.
Kenaga
estimates
and
an
explanation
of
the
model
with
a
sample
are
in
Appendix
II.
Without
foliar
dissipation
half­
life
data
for
metiram,
EFED
used
a
35­
day
half­
life.
EFED
selected
this
half­
life
based
on
the
upper
limit
of
pesticide,
foliar
dissipation
half­
lives
provided
in
the
half­
life
listing
of
Willis
and
McDowell,
1987.
EFED
uses
this
value
as
a
default
value
when
the
foliar
dissipation
for
a
particular
pesticide
is
unknown.
For
tobacco,
ornamental
nonflowering
plants
and
ornamental
woody
shrubs
and
vines,
EFED
assumed
3
applications
each
crop
cycle.
EFED
assumed
this
since
labeling
directions
did
not
provide
the
maximum
allowable
number
of
applications
but
labeling
directions
did
show
the
minimum
intervals
between
applications
for
these
sites.

EFED
needs
total
foliar
dissipation
residue
or
total
foliar
residue
(
TFR)
half­
life
information
as
a
modeling
input
value
to
estimate
terrestrial
wildlife
exposure.
TFR
is
the
total
pesticide
residue
contained
both
on
the
surface
and
absorbed
into
treated
leaves.
EFED
has
no
requirements
for
submitting
such
data
now
and
relies
on
available
data
chiefly
from
Willis
and
McDowell
(
1987).
Since
metiram
TFR
half­
life
information
was
not
available
from
Willis
and
McDowell
(
1987)
EFED
sought
surrogate
information
from
HED.
HED
receives
dislodgeable
foliar
residue
(
DFR)
dissipation
half­
life
data
(
guideline
875.2100)
to
estimate
exposures
to
individuals
working
in
an
environment
that
has
been
treated
with
a
pesticide
(
also
referred
to
as
reentry
exposure).
DFR
is
the
amount
of
pesticide
residue
on
treated
leaves'
surface.
For
metiram
HED
(
Dole
and
Dawson,
2003)
provided
the
data
summarized
in
Table
II­
2.
7
Table
II­
2.
Summary
of
Metiram
DFR
Data
MRID
(
Year)
CROP
(
Location)
Application
Method
Lb
ai/
acre
DFR
Half
Life
TFR
Half
Life
413399­
01(
88)
CA
Apples
(
Tulane)
Airblast
4.8
*
3
(
42
days)
1
31.4
days
Not
available
Mancozeb
Study
With
Both
DFR
and
TFR
Data
411339­
01(
86)
411339­
01(
86)
CA
Grapes
(
Madera)
CA
Grapes
(
Fresno)
Airblast
Airblast
3.2
*
3
3.2
*
3
15.2
days
9.6
days
14.9
days
9.3
days
Note
1:
This
means
that
4.8
lb
ai/
acre
was
applied
3
times
with
an
application
interval
of
42
days
between
each
application.

This
single
metiram
DFR
study
was
the
only
study
available
from
HED.
There
were
eight
mancozeb
and
six
maneb
DFR
studies
submitted.
Based
on
a
review
of
all
the
EBDC
DFR
studies
submitted
EFED
would
expect
a
variation
in
DFR
half­
life
values.
This
variation
would
be
because
of
differences
in
application
methods
such
as
application
rates,
differences
crops
such
as
morphology,
and
regional
differences
such
as
weather.
HED's
review
showed
the
effects
of
climate
was
a
greater
effect
than
the
effects
of
crop
morphology
or
application
method.
"
The
EBDC
and
ETU
half
lives
were
typically
twice
as
long
in
the
west
as
in
the
east..."(
Dole
and
Dawson,
2003).

Most
DFR
studies
used
the
standard
dislodging
technique.
The
1986
mancozeb
study
on
grapes
at
Madera
and
Fresno,
California
(
MRID
411339­
01)
also
used
the
total
extraction
method
(
T.
Dole,
per.
com.,
9/
13/
01).
Based
on
this
mancozeb
study
EFED
expects
the
EBDC's
DFR
half­
life
would
be
comparable
to
the
EBDC's
TFR
half­
life
since
the
1986
mancozeb
study
on
grapes
at
Madera
and
Fresno,
California
showed
similar
DFR
and
TFR
half­
lives.
EFED
might
not
expect
such
a
similarity
if
the
pesticide
showed
systemic
activity
but
none
of
the
EBDCs
are
systemic.

The
single
study
on
apples
in
Tulare
County,
California
shows
a
31.4
day
DFR
half­
life
at
the
maximum
allowable
single
application
rate.
Metiram
is
used
on
five
crop
grouping
(
see
Table
II­
1)
and
this
DFR
study
provides
half­
life
information
on
one
crop,
apples.
Given
this
limited
information
EFED
feels
it
is
a
reasonable
to
use
a
35­
day
TFR
half­
life
for
metiram
as
a
conservative
upper­
bound
estimate
in
this
screening
level
assessment.
EFED
understands
the
35­
day
TFR
half­
life
used
in
calculating
avian
and
mammalian
RQs
represents
an
uncertainty
because
metiram's
TFR
half­
life
range
is
unknown.
For
comparative
purposes,
EFED
also
provided
an
estimate
of
metiram's
risk
to
birds
and
mammals
based
on
lessened,
3­
day
TFR
half­
life
value.
From
DFR
and
TFR
values
for
maneb
and
mancozeb
(
two
EBDCs
chemically
related
to
metiram),
there
is
a
sign
3
days
may
be
an
approximate
low­
end
foliar
dissipation
half­
life
estimate
for
the
EBDCs.
Limited
data
for
maneb
showed
DFR
half­
life
values
ranged
from
7.2
days
on
apples
to
32.8
days
on
grapes
(
US
EPA.
2005).
Maneb
TFR
half­
life
values
ranged
from
2.8
for
snap
beans
to
7.3
days
for
homogenized
samples
of
the
tomato
fruit
or
raw
agricultural
commodity
(
RAC)
samples
(
US
EPA.
2005).
Limited
data
for
mancozeb
showed
DFR
half­
life
values
ranged
from
2.3
days
for
turf
to
35.4
days
for
grapes
(
US
EPA.
2005a).
Mancozeb
TFR
half­
life
values
ranged
from
1.6
days
for
homogenized
samples
of
the
tomato
fruit
or
RAC
samples
to
14.9
days
for
grapes
(
US
EPA.
2005a).
The
RQs
calculated
using
a
3­
day
TFR
half­
life
value
for
metiram
are
in
Appendix
IV.

For
the
aquatic
environments,
Parent
metiram
is
short­
lived
in
the
environment
as
indicated
from
half­
lives
calculated
from
registrant­
submitted
hydrolysis
studies.
With
the
exception
of
low
water
field
capacity
soils
in
very
dry
environments,
expected
environmental
concentrations
(
EECs)
for
the
parent
is
low.
These
EECs
were
calculated
using
a
spread
sheet
based
on
the
hydrolysis
first
order
8
rate
constant.
Parameters
determined
from
environmental
fate
studies
and
information
on
physicochemical
properties
were
used
in
estimating
EECs
of
the
resultant
metiram
complex.
This
complex
rather
than
parent
was
considered
to
be
the
stressor.
Metiram
complex
was
determined
to
consist
of
a
suite
of
chemical
species:
transient
species
(
EBIS,
carbimid
and
TDIT),
ETU,
ETU
degradates
(
EU,
hydantoine
and
others)
and
the
significant
unknown
bound
species
in
the
soil
system
(
suspected
of
containing
persistent
precursors
for
ETU).

EECs
were
estimated
using
tier
II
modeling,
the
linked
PRZM
and
EXAMS
models
(
PRZM/
EXAMS).
In
modeling,
metiram
uses
on
apples
and
potatoes
were
chosen.
Apples
and
potatoes
were
chosen
because
they
are
the
major
uses
for
metiram
(
BEAD's
Quantitative
Usage
Analysis
for
Metiram
dated
November
1,
2002)
and
PRZM­
EXAMS
modeling
scenarios
exist
for
these
uses.
Although
the
tobacco
use
has
a
much
higher
use
rate
(
6.8
lb
ai/
A
see
Table
II­
1),
the
overall
exposure
is
considered
to
be
less
than
that
for
apples
and
potatoes
because
the
use
pattern
is
for
seedling
beds.
Tobacco
applications
are
by
ground
using
dusting
machines
and
the
label
directions
specify
application
of
the
product
on
a
square
foot
basis;
i.
e.,
12
x
75
ft
plots,
equivalent
to
900
square
feet.
Therefore,
tobacco
exposure
is
considered
to
be
less
than
the
other
sites
because
the
pesticide
is
applied
to
less
acreage
(
label
directions
specify
to
apply
on
a
square
foot,
rather
than
acre
basis).
The
ornamental
uses
of
metiram
are
also
expected
to
be
much
less
than
the
apple
and
potato
uses
plus
Tier
II
modeling
scenarios
for
the
ornamental
uses
have
not
yet
been
developed.
Risk
assessments
were
not
performed
on
the
treated
potato
seed
use.
Because
of
the
cultural
practices
(
e.
g.,
incorporate
to
a
depth
of
4
inches),
minimal
risk
to
terrestrial
animals
is
expected
from
this
use.
A
low
potential
for
movement
into
surface
water,
is
also
expected.
Modeling
was
performed
using
expected
quantities
of
parent
from
application
(
i.
e.
the
application
rate)
or
the
degradate
of
concern,
ETU,
that
would
be
produced
from
application
of
the
parent
based
on
molar
conversion.
Applied
quantities
of
parent
or
equivalent
degradates
at
time
zero
were
modeled
to
arrive
at
related
EECs
using
available
physicochemical
and
fate
properties
determined
for
each
chemical.

The
fifth
step
for
drinking
water
assessment,
is
to
communicate
the
Estimated
Drinking
Water
Concentrations
(
EDWCs)
results
[
for
ETU,
the
stressor
identified
by
the
MARC
meeting
as
the
degradate
of
concern
(
US
EPA,
2002)]
for
HED.
Details
are
presented
in
the
accompanied
ETU
document
(
the
drinking
water
assessment
memorandum
covering
metiram
and
the
other
two
EBDCs:
mancozeb
and
maneb).

The
fifth
step
for
ecological
risk
assessment,
is
to
use
terrestrial
and
aquatic
EECs
along
with
related
ecological
effects
data
(
i.
e.,
available
terrestrial
and
aquatic
toxicity
data),
to
evaluate
and
characterize
ecological
risk
of
identified/
quantified
stressors
to
the
environment
by
calculating
risk
quotients
(
RQs).
RQs
are
the
ratio
of
estimated
environmental
concentrations
(
EECs)
to
ecotoxicity
values
(
see
Appendix
IV).

The
final
step
of
the
analysis
plan
will
decide
what
nontarget
organisms
are
at
potential
risk,
what
nontarget
organisms
are
at
a
low
risk,
and
where
areas
of
uncertainty
exists.
EFED
compares
the
calculated
RQs
to
the
level
of
concern
(
LOC;
Appendix
IV)
to
ascertain
potential
risk.
EFED
uses
this
practice
to
detect
potential
risk
to
nontarget
organisms
and
the
resulting
need
for
possible
regulatory
action.
Figures
II­
2
and
II­
3
present
the
complete
analysis
plan
.
Figure
II­
2
shows
the
first
five
steps
in
one
page
and
Figure
II­
3
shows
the
last
step
on
the
following
page.
In
the
diagram
for
the
last
step,
Figure
II­
3
shows
multiple
stressors
in
blue,
and
the
assessment
endpoints
in
yellow.
The
assessment
endpoints
include
the
potential
short­
term
(
that
is,
acute)
and
long­
lasting
(
that
is,
9
chronic)
effects
to
categories
of
organisms
that
may
result
because
of
exposure
to
parent
metiram
and/
or
its
complex.

Figure
II­
2.
Summary
of
the
risk
assessment
procedure
for
metiram,
the
first
to
fifth
step:
results
and
conclusions.
10
Figure
II­
3.
Risk
assessment
analysis
plan
and
conclusions
for
metiram,
the
last
step:
results
and
conclusions.
11
III.
Integrated
Environmental
Risk
Characterization
a.
Overview
of
Environmental
Risk
There
are
potential
acute
risks
to
birds,
chronic
risks
to
birds
and
mammals,
acute
risks
to
freshwater
fish,
and
acute
risks
to
aquatic
nonvascular
plants.
These
potential
risks
occur
for
all
or
some
of
metiram's
uses.
Because
EFED
lacks
data,
EFED
is
uncertain
about
mancozeb's
potential
acute
risks
to
terrestrial
plants,
chronic
risks
to
freshwater
fish,
acute
and
chronic
risks
to
freshwater
invertebrates
and
estuarine/
marine
animals,
and
acute
risks
to
aquatic
vascular
plants.

EFED
expects
potential
chronic
risk
to
birds
and
mammals
from
metiram's
uses.
Avian
and
mammalian
RQs
exceed
the
chronic
LOCs
for
all
metiram
modeled
exposures.
The
chronic
RQs
for
birds
range
from
91
on
tobacco
to
a
low
of
1
on
ornamentals
using
a
default
half­
life
value
of
35
days.
RQs
were
lessened
when
a
3­
day
half­
life
was
used
(
RQs
ranged
from
51
for
tobacco
to
0.4
for
ornamentals),
however
most
chronic
RQs
still
exceeded
the
LOC
of
1.0.
For
mammals,
chronic
RQs
ranged
from
a
high
of
113
on
tobacco
to
a
low
of
1
on
ornamentals
using
a
35­
day
default
half­
life.
RQs
were
lessened
when
a
3­
day
half­
life
was
used
(
RQs
ranged
from
63.4
for
tobacco
to
0.6
for
ornamentals),
however
most
chronic
RQs
still
exceeded
the
LOC
of
1.0.
Even
though
metiram
is
only
slightly
toxic
to
birds
(
bobwhite
quail
dietary
LC
50
=
3,712
ppm),
all
metiram's
uses
exceed
the
endangered
species
LOC
with
some
acute
LOC
exceedances
for
some
uses.
Metiram's
RQs,
exceeding
LOCs,
range
from
0.11
on
ornamental
(
woody
shrubs
and
vines)
to
1.22
on
tobacco
using
a
35­
day
foliar
dissipation
half­
life
at
maximum
EEC
levels.
As
identified
in
Appendix
III,
acutely,
metiram
is
practically
nontoxic
(
rat
LD
50
>
5,000
mg/
kg)
to
mammals.
Because
metiram
is
practically
nontoxic
to
mammals,
metiram's
acute
rat
LD
50
is
an
indefinite
endpoint,
and
there
are
no
incident
data
in
EIIS
showing
metiram
adversely
mammals,
EFED
didn't
calculate
RQs
for
acute
mammalian
exposure.
EFED
expects
metiram
to
be
a
low
acute
risk
to
mammals.

EFED
does
not
expect
metiram
exposure
to
pose
acute
risk
to
nontarget
insects
because
metiram
is
practically
nontoxic
to
honeybees,
(
acute
contact
LD
50
=
437
µ
g/
bee)
and
there
are
no
incident
data
reporting
adverse
effects
to
honeybees.
EFED
does
not
assess
risk
to
bees
using
RQs
because
a
screening
level
RQ
assessment
method
for
estimating
the
risk
to
bees
is
not
available.
EFED
has
not
developed
an
exposure
design
for
bees
to
estimate
the
risk
using
a
risk
quotient
method.

Data
were
inadequate
to
evaluate
the
risk
of
metiram
to
terrestrial
nontarget
plants.
There
are
potential
acute
endangered
species
risks
to
freshwater
fish
and
acute
risk
to
nonvascular
aquatic
plants.
Based
on
limited
data,
RQs
for
the
metiram
complex
exceeded
acute
restricted
use
and
acute
endangered
species
LOCs
for
freshwater
fish
(
the
RQs
range
from
0.24
on
potatoes
to
0.43
on
apples).
Based
on
metiram's
use
on
apples,
acute
LOCs
are
exceeded
for
nonvascular
aquatic
plants
(
RQ
=
1.28).
This
exceedance
is
based
on
a
supplemental
green
algae
study.
EFED
has
not
received
studies
to
evaluate
the
risk
of
metiram
complexes
to
vascular
aquatic
plants.
There
is
inadequate
data
to
evaluate
acute
risks
to
freshwater
invertebrate,
estuarine/
marine
organisms,
aquatic
plants,
and
terrestrial
nontarget
plants
from
exposure
to
the
metiram
complex
and
metiram.
There
is
no
data
to
evaluate
metiram's
chronic
risks
to
freshwater
and
estuarine/
marine
organisms
from
exposure
to
the
metiram
complex.
12
Parent
metiram
is
insoluble
in
water
but
is
expected
to
decompose
rather
quickly,
by
hydrolytic
reactions,
into
a
multi
species
residue
(
the
metiram
complex)
consisting
of
transient
species
and
degradates
including
the
degradate
of
concern
ETU
and
its
degradates.
Metiram
has
low
octanol/
water
partition
coefficients
(
K
ow
),
especially
in
neutral
to
alkaline
aqueous
environments,
which
strongly
suggests
that
it
would
not
be
significantly
bio­
concentrated
by
aquatic
organisms.
Furthermore,
metiram
has
a
very
low
vapor
pressure,
thus
indicating
that
volatilization
is
not
an
important
dissipation
pathway.

Due
to
rapid
hydrolytic
decomposition,
parent
metiram
is
expected
to
exist
in
most
natural
environment
for
a
short
duration
(
few
days)
when
moisture
is
available.
Other
factors
that
affect
rate
of
hydrolytic
decomposition
of
the
parent
include:
particle
size,
molecular
weight
distribution
as
well
as
on
environmental
factors
such
as
oxygen
concentration,
pH,
moisture,
temperature
and
the
presence
of
metal
ions.
Relative
stability
of
the
parent
appears
to
be
relatively
high
in
alkaline
(
pH
9)
compared
to
neutral
to
acidic
conditions
(
pH
7­
5).

Most
of
the
species
present
in
the
metiram
complex
are
expected
to
partition
into
the
soil/
sediment
particles;
with
varied
strength
of
bonding.
These
soil
associated
materials
are
not
largely
affected
by
abiotic
degradation
but
are
susceptible
to
very
slow
bio­
degradation
possibly
further
producing
degradates,
including
ETU,
at
a
very
slow
rate.

b.
Key
Issues
and
Uncertainty
i.
Environmental
Fate
EECs
for
parent
metiram
were
estimated
for
water
bodies
using
hydrolysis
half­
lives.
The
same
water
hydrolysis
half­
lives
were
used
for
soils
assuming
sufficient
moisture
is
available
in
soil
pores
for
hydrolysis
to
occur
at
the
same
rate.
Uncertainty
exist
on
whether
half­
lives
used
are
applicable
because
soil
moisture
level
is
expected
to
impact
resultant
EECs.
Lower
EECs
are
expected
in
irrigated
and/
or
rain­
fed
soils
with
high
water
holding
capacity
(
WHC)
and
higher
EECs
are
expected
in
low
WHC
soils
under
dry
conditions.
Giving
the
fact
that
metiram
is
applied
to
growing
crops,
moisture
is
expected
to
be
available
for
parent
to
hydrolyze
at
an
adjusted
rate
near
or
just
below
that
determined
from
aqueous
hydrolysis
half­
lives.
Although
availability
of
moisture
is
the
limiting
factor
for
metiram
hydrolytic
stability,
other
factors
that
are
known
to
affect
this
process
include:
particle
size;
molecular
weight
distribution;
pH;
oxygen
and
metal
ion
concentrations.

EECs
for
the
metiram
complex
were
estimated
using
the
physicochemical
properties
and
hydrolysis
half­
lives
of
parent
metiram
in
addition
to
aerobic
soil
metabolism
half­
lives
and
sorption
coefficients
which
were
assigned
to
this
complex
rather
than
the
parent.
In
all
aerobic
soil
studies
two
separate
sets
of
experiments/
determinations
were
conducted:
the
first
was
to
obtain
data
for
calculating
halflives
using
the
CS
2
­
method
to
quantify
the
parent
while
the
second
was
to
characterize
the
degradation
process.
EFED
believes
that
half­
lives
calculated
from
the
first
set
of
experiments/
determinations
represent
hydrolytic
decomposition
of
parent
metiram
in
soils
rather
than
bio­
degradation.
Rapid
degradation
of
parent
metiram
produces
a
complex
(
the
metiram
complex)
which
appears
to
be
affected
by
slow
degradation
as
indicated
by
production
of
CO
2
.
Part
of
this
complex
may
contain
precursor(
s)
for
the
degradate
of
concern,
ETU.
Therefore,
EFED
used
the
second
set
of
experiments/
determinations
(
radioactivity
data)
for
calculating
half­
lives
and
assigned
13
it
to
the
metiram
complex.
Uncertainty
exists
in
these
complex
half­
lives
as
they
are
conservative
and
are
affected
by
the
validity
of
the
assumption
that
the
only
bio­
degradation
of
the
complex
was
represented
by
evolved
CO
2
.
Degradates
were
considered
as
part
of
the
complex
and
were
not
considered
separately
because
determined
concentrations
were
affected
by
impurities
in
the
test
materials,
hydrolytic
reactions
and
possible
artificial
degradation
during
extraction.

In
this
assessment,
aerobic
soil
half­
lives
(
calculated
from
the
CS
2
­
method)
are
considered
to
represent
hydrolysis
of
parent
metiram
into
its
complex
which
is
modified
by
soil
conditions
(
i.
e.
moisture
content,
pH
and
O
2
concentration).
In
contrast,
half­
lives
calculated
from
evolved
CO
2
are
considered
to
represent
bio­
degradation
of
the
metiram
complex
left
in
the
soil
which
appears
to
occur
in
parallel
with
hydrolytic
decomposition
of
the
parent.
Likewise,
calculated
adsorption/
desorption
characteristics
(
K
d
and
K
oc
)
are
thought
to
represent
the
metiram
complex
as
it
were
approximated
from
radioactivity
data
of
a
column
leaching
study;
with
no
1/
n
value
to
indicate
the
degree
of
non­
linearity
for
the
Freundlich
constant.

In
the
degradation
process
for
metiram,
Zn
ions/
salts
are
expected
to
dissipate
into
the
environment.
No
data
were
presented
to
evaluate
the
risk
that
might
be
associated
with
this
release
and
therefore,
uncertainty
exists
in
this
aspect
of
risk
assessment.

Complete
characterization
of
the
fate
of
the
metiram
complex
requires
more
information
on
the
various
species
that
constitute
this
complex
including
the
soil/
sediment
bound
species.
Information
needed
are
for
each
of
these
constituents
and
includes:
their
physicochemical
properties
and
the
nature
of
their
association
with
soil/
sediment
particles.

Additional
information
is
presented
in
Appendix
I
detailing
major
problems
in
EBDC
fate
studies
which
adds
a
degree
of
uncertainty
for
estimated
fate
parameters
for
parent
metiram
and
the
metiram
complex,
resultant
EECs,
and
surface
and
groundwater
modeling
results.

ii.
Ecological
Effects
What
does
EFED
expect
will
result
when
metiram
is
applied?
Metiram
is
applied
to
3
different
crops
(
that
is,
apples,
potatoes
and
tobacco)
and
has
uses
on
ornamental
plants
(
see
Table
II­
1)
to
control
plant
diseases.
Metiram
has
broad
use
across
areas
in
the
US
and
because
of
this
EFED
expects
metiram
to
come
in
contact
with
nontarget
organisms
across
many
taxa.
EFED
presumes
applications
of
the
metiram
will
occur
when
there
is
heavy
plant
disease
pressure.
Heavy
disease
pressure
to
plants
results
when
there
is
high
moisture
from
rains.
These
rains
promote
conditions
for
the
growth
and
propagation
of
fungal
species.
EFED
expects
metiram
applications
will
result
in
rapid
degradation
of
parent
metiram
to
metiram
complex
including
ETU
on
plant
surfaces.
EFED
figures
the
hydrolysis
of
the
metiram
will
be
variable
but
rather
fast.
Metiram
hydrolysis
half­
life
values
range
from
33
to
75
hours
(
see
Table
IV­
2).
EFED
assumes
rapid
degradation
will
occur
because
the
treated
plants
are
likely
to
either
be
wet
during
the
application
or
shortly
after
a
metiram
application.
All
the
metiram
uses
as
shown
in
Table
II­
1
need
repeat
applications
because
metiram
is
short­
lived
in
the
environment
as
shown
from
hydrolysis
studies.
Except
for
applications
to
dry
soils
in
dry
5
Dry
conditions
is
one
circumstance
that
may
explain
the
high­
end
(>
30
days)
foliar
dissipation
half­
life
values
for
the
EBDCs
in
general.
EFED
expects
differences
in
application
methods
such
as
application
rates,
differences
crops
such
as
morphology,
and
regional
differences
such
as
weather
also
affect
the
foliar
dissipation.
Another
reason
that
may
cause
longer
foliar
dissipation
half­
lives
is
sample
analysis.
Measurements
quantifying
the
foliar
dissipation
half­
life
routinely
use
measurements
of
the
evolved
CS
2
in
the
headspace
of
a
sealed
vial.
Such
measurements
quantify
the
sulfur
from
both
the
parent
EBDC
and
the
EBDC
complex
in
the
sample.
This
means
the
EBDC's
foliar
dissipation
half­
lives
result
from
the
presence
over
time
of
both
the
parent
EBDC
and
the
EBDC
complex.

14
environments,
EFED
expects
a
rapid
change
of
parent
metiram
into
metiram
complex.
5
Since
plants
receive
repeat
applications
of
metiram,
EFED
expects
wildlife
will
be
exposed
to
parent
metiram,
metiram
complex,
and
ETU
as
they
forage
on
food
items
in
metiram
treated
areas.
EFED
estimated
1.6%
of
the
applied
EBDCs
was
in
the
form
of
ETU
on
treated
foliage.
This
estimate
was
based
on
dislodgeable
foliar
residue
data
EFED
received
from
HED
(
Dole
and
Dawson,
2003a)
(
see
Table
II­
2,
from
EFED's
ETU
risk
assessment).

What
effect
does
EFED
expect
metiram
will
have
on
nontarget
terrestrial
species?
From
a
short­
term
or
acute
exposure
EFED
expects
metiram
is
a
low
risk
to
mammals
and
birds.
EFED
expects
the
acute
risk
to
mammals
from
metiram's
uses
to
be
low.
Metiram
is,
acutely,
practically
nontoxic
to
mammals
(
laboratory
rat
acute
LD
50
>
5,000
mg/
kg)
and
there
are
no
incident
data
in
EIIS
(
see
Appendix
VI
for
EIIS
background
information)
showing
metiram
adversely
mammals.
Metiram's
acute
avian
RQ
exceedances
are
due
mainly
to
exposure
estimates
because
metiram
is
only
slightly
toxic
(
bobwhite
quail
LC
50
=
3,712
ppm)
to
birds.
EFED
estimated
this
exposure
based
on
maximum
allowable
metiram
applications
at
maximum
application
rates
with
minimum
intervals
between
applications.
EFED
estimated
metiram's
total
foliar
residue
(
TFR)
dissipation
half­
life
was
35
days
since
this
half­
life
value
was
unknown
for
metiram.
EFED
used
these
estimates
to
calculate
the
RQs
based
on
the
most
conservative
high­
end
exposure
estimate.
Given
this
exposure
scheme,
the
largest
avian
acute
RQ
was
1.22
from
metiram's
use
on
tobacco.
Minor
departures
from
this
high­
end
exposure
estimate
resulting
from
decreases
in
the
number
of
application,
cuts
in
the
application
rate,
or
lessened
TFR
half­
life
estimates
would
likely
reduce
the
RQs
below
the
avian
acute
Endangered
Species
LOC
of
0.1.
Also,
there
are
no
avian
incident
reports
in
EIIS
showing
adverse
effects
to
birds
from
metiram's
use.
Given
the
long
historical
use
of
metiram
[
first
US
registration
date
was
October
7,
1983.
(
OPPIN.
2003.)],
EFED
does
not
expect
metiram's
acute
toxicity
to
be
a
major
risk
concern
to
birds
or
mammals.

EFED
expects
metiram's
long­
term
or
chronic
effects
on
birds
and
mammals
to
be
a
potential
major
risk.
This
expectation
is
supported
by
toxicological
studies
and
exposure
estimates.
EFED
expects
chronic
problems
that
affect
wildlife
from
the
use
of
metiram
would
go
unnoticed
in
the
field
and
thus
EFED
would
not
expect
incident
reports,
from
adverse
chronic
exposure.
Metiram's
uses
exceeds
chronic
LOCs
for
terrestrial
animals
(
birds
and
mammals)
for
all
metiram
use
patterns
for
all
food
categories
in
birds
and
mammals
except
for
some
seed
categories
from
metiram's
use
on
ornamentals
(
see
Figures
VII­
2
and
VII­
3).
These
exceedances,
based
on
modeling
using
a
35­
day
total
foliar
dissipation
half­
life,
occur
on
all
terrestrial
bird
and
mammal
food
items
(
that
is,
short
grass,
tall
grass,
broadleaf
forage,
insects,
fruits,
pods,
and
seeds).
These
chronic
exceedances
extend
throughout
the
application
periods
for
all
uses
ranging
from
more
than
42
days
for
tobacco
and
turf
to
more
than
65
days
for
potatoes
(
see
Table
VII­
2).
In
other
words,
there
are
potential
reproductive
risks
to
birds
and
mammals
from
the
first
application
through
the
last
application
and
beyond
for
all
metiram's
uses.
Revised
modeling
for
comparison,
using
a
3­
day
total
foliar
dissipation
half­
life
for
metiram,
shows
substantial
potential
chronic
risks
to
birds
(
see
VII­
7)
and
mammals
still
exist.
Available
dislodgeable
foliar
residue
(
DFR)
half­
life
data
from
the
Health
Effects
Division
(
HED)
showed
metiram's
half­
life
15
was
31.4
days
(
see
Table
II­
2).
This
single
metiram
half­
life
value,
from
one
DFR
study,
with
no
total
foliar
residue
(
TFR)
data
for
metiram
available
was
a
limitation.
Because
of
this
limited
data
EFED
felt
the
use
of
a
3­
day
half­
life
value
for
modeling
would
provide
an
EEC
range
for
comparing
metiram's
risks
to
birds
and
mammals.
EFED
selected
the
3­
day
half­
life
value
for
metiram
as
a
possible
low­
end
TFR
value.
DFR
and
TFR
values
for
maneb
and
mancozeb
(
two
EBDCs
chemically
related
to
metiram),
indicates
3
days
may
be
an
approximate
low­
end
foliar
dissipation
half­
life
estimate
for
the
EBDCs
in
general.
EFED
provides
a
brief
discussion
of
the
foliar
half­
life
values
ranges
for
maneb
and
mancozeb
in
Section
II­
Introduction,
Subsection
iii­
Analysis
Plan.
For
comparative
purposes,
EFED
also
provided
an
estimate
of
metiram's
risk
to
birds
and
mammals
based
on
lessened,
3­
day
TFR
half­
life
value
(
see
Appendix
IV).

EFED
used
metiram's
use
on
apples
as
an
example
(
see
Section
VII,
subsection
d.
Terrestrial
Risk
Assessment).
Metiram
can
be
applied
4
times
per
season
every
7
days
from
prebloom
through
the
foliar
stages
of
apples.
Bear,
ruffed
grouse,
snowshoe
hare,
pheasants,
Hungarian
partridges,
cottontail
rabbits,
deer,
fox,
opossums,
raccoons,
fox
squirrels,
songbirds,
and
elk
feed
on
apple
fruit
and/
or
foliage
(
Gusey
and
Maturdo,
1972).
Upland
game
birds
such
as
ruffed
grouse
and
ring­
necked
pheasant
feed
on
apple
fruit,
seeds
and
buds.
Songbirds
such
as
chestnut­
backed
chickadees,
redshafted
flickers,
robins,
starlings,
varied
thrushes,
tufted
titmouse,
cedar
waxwings
and
Lewis
woodpeckers
feed
on
apple
fruit
and
seeds.
Fur
and
game
mammals
such
as
black
bears,
foxes,
yellow­
bellied
marmots,
porcupines,
cottontail
rabbits,
and
red
squirrels
feed
on
apple
fruit
and
bark.
Hoofed
browsers
such
as
white­
tailed
deer
feed
on
apple
fruit,
twigs
and
leaves
(
Martin
and
others.,
1961).
Birds
such
as
morning
doves
and
valley
quail
use
apple
orchards
for
nesting
and
brood
rearing
(
Gusey
and
Maturdo,
1972).
These
wildlife
behaviors
in
apple
orchards
occur
throughout
the
year.
For
birds
and
mammals,
metiram's
chronic
risk
begins
on
Day
1
when
metiram
is
applied
and
continues
throughout
the
apple
growing
season
or
for
more
than
58
days
(
see
Figure
VII­
4).
During
this
time
period
there
would
be
potential
reproductive
risks
to
birds
and
mammals
feeding
on
short
grass,
broadleaf
or
forage
plants,
tall
grass,
fruit,
pods,
seeds
and
insects.
The
mallard
duck
study
used
to
calculate
the
RQs
for
this
assessment
showed
birds
chronic
reproductive
effects.
These
chronic
reproductive
effects
from
metiram
exposure
were
reduced
egg
production;
reduced
mean
egg
weight;
reduced
fertility
rate;
reduced
number
of
hatched
ducklings;
reduced
number
of
14­
day
old
survivors;
and
an
increased
rate
of
early
embryonic
deaths.
EFED
based
chronic
effects
in
mammals
on
a
3­
generation
reproduction
study
in
rats.
This
study
showed
parental
and
reproductive
toxicity.
The
parental
toxicity
resulted
in
decreased
body
weight
during
gestation
and
lactation
for
females.
The
reproductive
toxicity
resulted
in
decreased
mating
performance
(
increased
precoital
time
in
the
F2
generation).
Exposure
is
a
major
reason
for
these
chronic
risks
to
birds
and
mammals.
Reducing
the
chronic
risk
below
LOCs
for
birds
and
mammals
from
metiram's
use
on
apples
would
require
a
96­
fold
rate
cut
in
the
maximum
application
rate
of
metiram
to
apples
(
see
figure
VII­
5).
Using
a
combination
of
application
rate
cuts
and
multiple
application
decreases
would
require
a
28­
fold
cut
in
the
maximum
application
rate
with
a
decrease
to
1
application
per
season.
Metiram's
current
labeling
allows
4
applications
per
season
on
apples
(
see
figure
VII­
6).

Metiram
is
practically
nontoxic
to
the
honeybee
from
acute
contact
exposure.
EFED
does
not
perform
risk
quotient
assessments
for
terrestrial
insects.
Based
on
the
lack
of
acute
metiram
toxicity
to
honeybees,
EFED
expects
a
low
acute
risk
to
nontarget
terrestrial
insects.
There
are
no
data
to
evaluate
metiram's
risk
to
terrestrial
nontarget
plants.
EFED
is
uncertain
about
metiram's
risk
to
nontarget
terrestrial
plants
and
needs
testing
performed
at
metiram's
maximum
rate
of
application
in
the
environment.
6
Based
on
green
algae,
(
Pseudokirchneriella
subcapitata)
testing.

7
The
highest
ETU
RQ
is
0.0005
(
see
EFED's
ETU
chapter).

16
probit
k
=
(
log
LC
­
log
LC
)
*
slope
+
probit
50%

k
=
new
percentage
mortality
k
50
Equation
III­
1
What
is
the
likelihood
of
adverse
acute
effects
to
individual
terrestrial
organisms?
Lacking
slope
information,
EFED
was
not
able
to
predict
the
likelihood
of
individual
acute
effects
in
birds,
from
metiram's
exposure
representing
the
highest
bird
acute
RQ
(
that
is,
1.22).
A
dose­
response
slope
value
for
the
bobwhite
quail
acute
dietary
toxicity
(
that
is,
LC
50
=
3,712
ppm
metiram)
was
not
determined.
In
this
dietary
toxicity
study,
5
of
10
birds
died
at
the
highest
concentration
tested
with
no
mortality
at
the
lower
concentrations
tested.
Since
only
one
concentration
provided
a
percent
mortality
between
0
and
100%,
a
slope
value
could
not
be
determined
through
probit
analysis.

What
effect
does
EFED
expect
metiram
will
have
on
nontarget
aquatic
species?
EFED
expects
metiram
to
reach
aquatic
environments
through
drift
and
runoff
since
metiram
is
not
labeled
for
direct
application
to
aquatic
environments.
Metiram
is
insoluble
in
water
but
EFED
expects
it
to
decompose
rather
quickly,
by
hydrolytic
reactions,
into
a
multispecies
residue
(
metiram
complex)
consisting
of
transient
species
and
degradates
including
the
degradate
of
concern
ETU.
Once
metiram
reaches
the
aquatic
environment
EFED
believes
the
metiram
complex
will
be
the
portion
of
the
metiram
that
is
biologically
available
to
aquatic
organisms.
EFED
expects
most
of
the
transient
species
present
in
the
metiram
complex
to
partition
into
the
sediment
particles
with
varied
strength
of
bonding.
Over
time
ETU
is
an
important
transformation
product
of
the
metiram
complex.
The
residues
from
this
complex
are
short­
lived
in
aquatic
media
and
ETU
is
persistent
in
this
media
unless
ETU
is
subjected
to
rapid
degradation
by
microbes
and/
or
indirect
photolysis.
The
ETU
acute
RQs
for
nonvascular
aquatic
plants6,
freshwater
fish
and
freshwater
invertebrates
were
well
below7
the
lowest
LOC
(
that
is,
the
Endangered
Species
LOC
=
0.05)
for
aquatic
organisms.
EFED
does
not
know
how
acutely
toxic
ETU
is
to
estuarine/
marine
fish
or
invertebrates
because
no
data
has
been
submitted
for
evaluating
this
hazard.
This
means
the
metiram
complex,
other
than
ETU,
is
responsible
for
the
acute
toxicity
to
freshwater
fish
and
nonvascular
aquatic
plants.
EFED
expects
the
acute
toxicity
to
freshwater
fish
and
nonvascular
aquatic
plants,
from
exposure
to
the
metiram
complex,
will
not
last
long.
The
acute
fish
studies
have
a
duration
of
96
hours,
while
the
nonvascular
aquatic
plant
studies
are
120
hours
in
duration.
Acceptable
aquatic
half­
life
data
is
unavailable
for
most
products
of
the
metiram
complex.
Once
exposed
to
water,
parent
metiram
is
not
expected
to
be
present
in
significant
amounts
in
the
environment
except
for
short
duration
because
it
will
hydrolyze
rather
quickly
into
its
complex.
Based
on
this
information,
EFED
expects
the
metiram
complexexs'
acute
toxicity
to
these
aquatic
organisms
will
last
for
120
hours
but
suspects
this
toxicity
will
rapidly
decline
after
this
time
period
as
these
residues
degrade
to
ETU.

What
is
the
likelihood
of
adverse
acute
effects
to
individual
aquatic
organisms?
Based
on
laboratory
studies
and
modeled
EECs,
calculated
RQs
show
that
metiram
complex
is
a
potential
acute
risk
to
freshwater
fish
and
nonvascular
aquatic
plants.
Based
on
freshwater
fish
toxicity,
metiram
exceeds
acute
restricted
use
and
acute
endangered
species
LOCs
for
freshwater
fish
(
RQ
=
0.43
for
apples
and
0.24
for
potatoes).
The
likelihood
of
individual
effects,
from
metiram
exposure,
at
the
freshwater
fish
endangered
species
LOC,
is
1
in
500.
EFED
calculated
this
chance
estimate
using
a
freshwater
fish
acute
LC
50
=
0.23
ppm
with
a
slope
=
2.23
from
17
MRID
No.
43525001
and
an
endangered
species
LOC
or
LC
k
=
0.0115
ppm
(
that
is,
0.05
of
the
LC
50
)
using
the
equation
III­
1.
The
peak
metiram
aquatic
EEC
expected
from
drift
and
runoff
is
98.9
ppb.
This
value
is
the
estimated
aquatic
concentrations
based
on
metiram's
applications
to
apples.
At
this
concentration
the
likelihood
of
adverse
metiram
effects
to
individual
freshwater
fish
is
1
in
5.
At
the
peak
aquatic
EEC
expected
(
that
is,
98.9
ppb)
the
likelihood
of
an
acute
adverse
effect
to
individual
aquatic
plants
is
1
in
2.
This
chance
estimate
is
based
on
a
slope
of
1.65
and
a
green
algae
(
Ankistrodesmus
bibraianus)
EC
50
of
77
ppb
(
MRID
No.
43199601).

c.
Endangered
Species
Conclusions
Based
on
available
screening
level
information
there
is
a
potential
concern
for
acute
effects
on
listed
birds
and
freshwater
fish
species
and
chronic
effects
on
listed
birds
and
mammals
should
exposure
actually
occur.
Even
though
metiram
is
only
slightly
toxic
to
birds,
RQs
exceed
the
endangered
species
LOC
(
RQ
range
from
0.11
to
1.22)
at
maximum
EEC
levels.
EFED
does
not
expect
metiram
exposure
to
pose
acute
risk
to
nontarget
insects
because
metiram
is
practically
nontoxic
to
honeybees
(
acute
contact
LD
50
=
437
µ
g/
bee)
and
there
are
no
incident
data
reporting
adverse
effects
to
honeybees.
The
Agency
does
not
currently
have
enough
data
to
perform
a
screening
level
assessment
for
metiram's
effects
on
listed
nontarget
terrestrial
plants,
freshwater
invertebrates,
estuarine/
marine
fish,
or
vascular
aquatic
plants.
There
are
no
nonvascular
aquatic
plants
or
estuarine/
marine
invertebrate
species
on
the
endangered
species
list.

d.
Endocrine
Disruption
Concerns
The
Federal
Food,
Drug,
and
Cosmetic
Act
(
FFDCA)
requires
EPA,
as
amended
by
the
Food
Quality
Protection
Act
(
FQPA),
to
develop
a
screening
program.
This
program
is
to
decide
whether
certain
substances
(
including
all
pesticide
active
and
other
ingredients)
"
may
have
an
effect
in
humans
that
is
similar
to
an
effect
produced
by
a
naturally­
occurring
estrogen,
or
other
such
endocrine
effects
as
the
Administrator
may
designate.
"
Following
the
recommendations
of
its
Endocrine
Disruptor
Screening
and
Testing
Advisory
Committee
(
EDSTAC),
EPA
determined
there
was
scientific
basis
for
including,
as
part
of
the
program,
the
androgen
and
thyroid
hormone
systems,
as
well
as
the
estrogen
hormone
system.
EPA
also
adopted
EDSTAC's
recommendation
including
in
the
Program
evaluations
of
potential
effects
in
wildlife.
For
pesticide
chemicals,
EPA
will
use
FIFRA
and
FFDCA
authority
to
require
the
wildlife
evaluations.
EPA
will
use
FFDCA
authority
to
evaluate
effects
in
wildlife
from
tests
that
Food
and
Drug
Administration
uses
to
discover
effects
in
humans.
As
the
science
develops
and
allows,
EPA
may
add
screening
of
more
hormone
systems
to
the
Endocrine
Disruptor
Screening
Program
(
EDSP).

Avian
reproduction
studies
reviewed
by
EFED
revealed
effects
such
as
reduced
egg
production,
mean
egg
weight,
fertility
rate,
number
of
hatched
ducklings,
number
of
14­
day
old
survivors,
and
an
increased
rate
of
early
embryonic
deaths.
Mammalian
reproductive
effects
study
included
parental
toxicity
resulting
in
decreased
body
weight
during
gestation
and
lactation
for
females.
Also,
the
reproductive
toxicity
resulted
in
decreased
mating
performance
(
increased
precoital
time)
in
the
F2
generation
(
two
generations
removed
from
the
original
parent
generation).
In
a
3
month
feeding
study
submitted
to
The
Agency
(
MRID
42590­
01),
there
was
a
significant
decrease
in
total
serum
thyroxine
(
T4)
concentrations
in
both
sexes
of
mice.
These
effects,
noted
in
both
birds
and
mammals,
may
be
a
result
of
possible
hormonal
disruptions.
Based
on
these
effects
in
birds
and
mammals,
EFED
recommends
metiram
be
subjected
to
more
definitive
testing
to
better
characterize
effects
18
related
to
its
endocrine
disruptor
influences.
EFED
recommends
such
testing
when
EDSP
develops
suitable
screening
or
testing
protocols.
EFED
has
limited
aquatic
toxicological
data,
based
on
mortality
effects,
to
evaluate
aquatic
organisms
for
endocrine
induced
effects.
EFED
cannot
evaluate
potential
endocrine
disrupting
influences
to
aquatic
organisms
until
EFED
receives
more
testing
on
taxa.
19
IV.
Environmental
Fate
and
Transport
Assessment
The
fate
of
parent
metiram
was
evaluated
by
considering
data
on
its
hydrolytic
stability.
Practically,
parent
metiram
is
short­
lived,
therefor
it
was
important
to
evaluate
the
fate
and
transport
of
the
resultant
metiram
complex
by
its
degradation
processes
in
aqueous
phases
as
well
as
soil
and
field
environments.
Transformation
products
identified
in
fate
studies
were
also
given
the
required
emphasis
here
and
in
the
accompanied
document
for
ETU,
EBDCs'
common
degradate.

a.
Chemical
Identity
and
Physicochemical
Properties
Table
IV­
1
summarizes
important
properties
of
parent
metiram.
It
is
a
high
molecular­
weight
polymer
that
is
insoluble
in
water.
As
a
complete
chain
polymer,
it
has
a
solubility
of
2
ppm
accompanied
by
complete
hydrolytic
decomposition
or
degradation.
There
is
evidence
that
solubility
is
related
to
particle
size
as
the
latter
probably
determines
the
presence
of
easily
soluble
monomeric
and
broken
polymer
chains
(
i.
e
low
molecular
weight
polymer
chains).
Solubility
is
expected
to
increase
with
reduction
in
polymer
particle
size
and
in
presence
of
highly
acidic
and
alkaline
conditions
(
pH
3
and
9).
Presence
of
certain
metal
ions
is
expected
to
affect
solubility
as
these
ions
may
replace
metal
ions
present
in
the
structure
causing
a
change
in
solubility.

The
low
vapor
pressure
of
polymeric
metiram
suggests
partitioning
into
the
air
will
not
be
an
important
route
of
its
dissipation
in
the
environment.
Metiram
has
low
K
ow
values
at
most
natural
aquatic
environments
(
pH
.
5­
8.5)
suggesting
that
it
will
not
be
significantly
bio­
concentrated
by
aquatic
organisms
such
as
fish.

Table
IV­
1.
Nomenclature
and
physical
chemical
identity
of
the
metiram
complex
and
ETU.

CAS
Name
tris[
ammine­[
ethylen
bis(
dithiocarbamate)]
zinc(
II)]
[
tetrahydro­
1,2,4,7­
dithiadiazocine­
3,8­
dithione]
polymer
Structure
of
Metiram
and
its
Main
Degradate
ETU
CAS
Registry
No.
9006­
42­
2
PC
Code
014601
Molecular
Weight
1088.6
(
C16H33N11S16Zn3)

Formulated
Products
Wettable
powder,
dust
K
OW
2.9­
03.2
@
pH
5
(
Log
KOW=
0.46­
0.50)
6.0­
83.2
@
pH
7
(
Log
KOW=
0.78­
1.92)
1.6­
06.8
@
pH
9
(
Log
KOW=
0.19­
0.83)

Vapor
Pressure
9.9x10­
11
atm.
@
20
°
C
Henry's
Law
constant
7.0X10­
8
atm.
m3
mole­
1
(
Calculated)

Boiling
Point
Decomposes
@
140
°
C
Water
Solubility
Decomposes
in
water
at
concentrations
<
2
ppm*

*
higher
solubility
or
decomposition
is
expected
with
reduction
in
particle
size
and
can
vary
with
pH,
and
presence
of
metal
ions.
20
b.
Fate
Processes
Submitted
guideline
studies
suggest
that
under
typical
application
rates
into
natural
environment,
parent
metiram
is
expected
to
decompose
(
within
a
week)
by
hydrolytic
reactions
and
resists
both
water/
soil
photolysis
or
volatilization.
Therefore,
hydrolytic
reactions
are
extremely
important
in
the
fate
of
parent
metiram
and
its
decomposition
to
metiram
complex.

Metiram
complex
consists
of
transient
species,
degradates
and
other
un­
identified
materials.
Based
on
data
summarized
in
Table
IV­
2,
the
main
process
involved
in
parent
metiram
dissipation
in
the
environment
is
hydrolysis.
In
contrast,
the
main
processes
involved
in
the
fate
of
resultant
metiram
complex
is
its
strong
affinity
for
adsorption
to
the
soil/
sediment
followed
by
limited
biotic
degradation.
As
a
result
of
bio­
degradation
of
the
residue,
slow
and
continuous
release
of
degradates
including
ETU
(
at
low
concentrations)
is
expected
to
occur
over
time.
Mobility
of
metiram
complex
in
the
natural
environment
is
expected
to
be
limited
because
of
its
strong
affinity
to
adsorption.
In
contrast,
the
degradate
of
concern
(
ETU)
is
predicted
to
be
susceptible
to
leaching
due
to
its
high
solubility
and
mobility.
In
the
soil
environment
ETU
lacks
stability
which
can
limit
its
leaching,
however,
its
possible
slow
and
steady
formation
from
metiram
complex
can
overcome
the
lack
of
stability
and
make
it
available
for
leaching
at
low
concentrations.

Table
IV­
2.
Parent
metiram
hydrolysis/
photolysis
half­
lives
and
environmental
fate
data
summary
for
metiram
complex.

Parameter
Value
Source
(
MRID
)

Hydrolysis
Extrapolated
t1/
2
depends
on
the
pH
of
the
aqueous
media
as
follows:
Acidic:
33
Hours
@
pH
5
Neutral:
44
Hours
@
pH
7
Basic:
75
Hours
@
pH
9
001467­
64
Photo
lysis
Stable
in
water
(
direct
photolysis),
No
data
for
indirect
photolysis
001551­
90
001619­
38
Stable
on
soil
001570­
31
Aerobic
Soil
Metabolism
t1/
2
=
387
days
(
R2=
0.70)
in
Cashmere
loamy
sand
soil
(
77%
sand,
16%
silt,
7%
clay,
pH
6.6,
0.8%
organic
carbon,
and
CEC
of
12
meq/
100g
soil)
459069­
01
t1/
2
=
390
days
(
R2=
0.89)
in
Collamer
silt
loam
soil
(
29%
sand,
61%
silt,
10%
clay,
pH
6.1,
2.09%
organic
carbon,
and
CEC
of
13
meq/
100g
soil)
451452­
03
t1/
2
=
388
days
(
R2=
0.89)
in
a
loam
soil
(
11%
sand,
72%
silt,
17%
clay,
pH
7.1,
1.0%
organic
carbon,
and
CEC
of
13
meq/
100g
soil)
001552­
88
t1/
2
=
454
days
(
R2=
0.89)
in
a
loamy
sand
soil
(
44%
sand,
52%
silt,
4%
clay,
pH
6.1,
2.9%
organic
carbon,
and
CEC
of
9
meq/
100g
soil)

Anaerobic
Soil
Metabolism
The
anaerobic
portion
of
the
study
was
not
acceptable
001552­
88
Aerobic
Aquatic
Metabolism:
Refer
to
text
4593344­
01
Anaerobic
Aquatic
Metabolism;
and
Bioaccumulation
Factor
:
No
data
Parameter
Value
Source
(
MRID
)

8
No
complete
report
was
found
for
these
experiments
and
ultrasound
was
used
in
preparing
zero
time
suspensions.

Ultrasound
can
cause
reduction
in
particle
size
which
can
create
artificial
instability
of
polymeric
metiram.

21
Adsorption
Coefficients
(
L
Kg­
1)
Sandy
Soil
Kd
=
0.58
and
KOC
=
111
Sandy
Loam
Kd
=
1.68
and
KOC
=
578
Silty
Loam
Kd
=
6.17
and
KOC
=
1,061
Clay
Soil
Kd
=
48.50
and
KOC
=
1,738
405763­
01
Loamy
sand
soil:
Very
High
Kd
as
sum
radioactivity
in
all
soil
segments
combined
was
99.2%.
Radioactivity
was
not
analyzed
in
the
leachate;
thus
a
Kd
could
not
be
calculated.
001552­
88
Field
Dissipation
DT50
=
143
days
in
upstate
New
York
on
sugar­
beets
DT50
=
20
days
in
California
on
sugar­
beets
414408­
01
414408­
02
i.
Aqueous
Solutions
The
behavior
of
metiram
and
the
free
EBDC
ligand
in
water
is
complex
and
difficult
to
interpret
given
the
formation
of
transient
species
and
further
reactions
of
degradates,
which
make
chemical
analysis
very
difficult.
Parent
metiram
is
practically
a
water
insoluble
compound.
When
it
is
suspended
in
an
aqueous
medium
at
high
concentrations,
only
a
fraction
is
solubilized
by
hydrolytic
decomposition
into
transient
species
and
degradates.
Hydrolytic
decomposition
appears
to
occur
due
to
breakage
of
bonds
between
Zn+
2
and
S
in
coordination
with
the
EBDC
ligand.
The
detached
free
ligand
then
undergoes
reaction
with
water
to
produce
transient
species
and
degradates
including
ETU.
As
with
any
dithiocarbamate,
the
EBDC
ligand
has
the
potential
to
form
monosulfide
and
disulfide
oxidation
products.
Given
the
complexity
of
EBDC,
these
oxidation
products
could
show
complex
structures.
Transformation
products
formed
as
a
results
of
the
process
of
hydrolytic
decomposition
are
dominated
by
ETU.
Studies
with
aqueous
sterilized
buffered
suspensions
of
metiram
suggest
that
particle
size
reduction
can
cause
further
instability
of
polymeric
metiram.

Calculated
first
order
hydrolysis
half­
lives
were
33,
44
and
75
hours
for
polymeric
metiram
in
buffered
suspensions
at
pH
5,
7
and
9,
respectively
(
MRID
001467­
64).
Zero
concentrations
for
these
4
to
10­
day
experiments
were
near
17
ppm.
Identified
hydrolysis
products
were
said
to
include
CS
2
and
H
2
S
in
acid
conditions
and
none
were
reported
in
alkaline
conditions.
Data
obtained
from
these
experiments
(
MRID
001467­
64)
were
the
only
available
data
to
calculate
half­
lives
although
it
contain
a
degree
of
uncertainty8.
Data
from
other
experiments
(
MRID
001551­
89
and
addendum
MRID
001619­
37)
can
not
be
used
for
this
purpose
because
polymeric
metiram
was
suspended
in
aqueous
sterilized
buffered
medium
starting
with
extremely
high
zero
time
concentrations
(
1,600­
2,160
ppm).
Such
concentrations
are
not
expected
to
occur
in
aquatic
nor
soil
environments
even
with
maximum
single
application
being
applied
directly
into
such
environments
(<
1
and
14
ppm,
respectively).

Two
important
conclusions
can
be
drawn
from
both
studies.
First,
metiram
is
highly
insoluble
in
water
and
will
only
solublize,
by
decomposition,
when
present
at
relatively
low
concentrations.
At
these
concentrations,
rather
quick
decomposition
occurs
and
appears
to
be
affected
by
the
physical
state
of
metiram
and
to
a
lesser
extent
on
the
pH
of
the
medium.
Second,
ETU
is
a
major
degradation
product
of
hydrolysis
in
aqueous
media.
22
The
results
of
a
direct
photolysis
study
(
MRID
001551­
90
and
addendum
MRID
001619­
38)
with
metiram
in
water
suggest
that
degradation
is
generally
controlled
by
hydrolysis
rather
than
photolysis.
It
was
concluded
that
photo­
transformation
does
not
appear
to
be
a
significant
mode
of
degradation
for
metiram
in
water.
High
photon
energy
(
i.
e
much
higher
than
mid­
day
sunlight)
appears
to
affect
the
stability
of
metiram
suspended
in
aqueous
solutions.
However,
the
extent
of
such
effect
can
not
be
estimated
from
this
study.
There
are
no
acceptable
data
on
the
degradation
of
metiram
in
the
presence
of
photo­
sensitizers
to
assess
the
contribution
of
indirect
photolysis
in
surface
water.
Therefore,
the
photolytic
behavior
of
metiram
in
surface
water
is
uncertain.

ii.
Soil
Photolysis
on
soil
study
(
MRID
001570­
31)
suggests
that
soil
photolysis
does
not
appear
to
be
a
significant
mode
of
degradation
for
metiram.
Observed
metiram
degradation
was
only
slightly
more
significant
in
irradiated
samples
compared
to
those
maintained
in
the
dark
preventing
calculation
of
a
half­
life.
The
results
obtained
on
degradation/
degradation
products
are,
at
least
in
part,
a
result
of
extraction
and
impurities
in
the
active
ingredient
used.
However,
Xenon
light
appears
to
facilitated
the
degradation
process
of
the
parent
and
resultant
complex.

Several
aerobic
soil
studies
were
submitted
for
metiram
and
classified
by
EFED
as
supplemental
due
to
impurities
in
the
test
material,
possible
artificial
degradation
during
extraction,
incomplete
characterization
of
the
bound
species,
duration
and
questions
concerning
species
quantified
by
the
CS
2
­
method.
EFED
agrees
with
the
registrant
estimated
short
half­
life
for
parent
metiram
in
soils
but
believes
that
its
rapid
disappearance
is
mainly
attributed
to
hydrolytic
decomposition
rather
than
aerobic
soil
bio­
transformation.
This
conclusion
is
supported
by
reported
instability/
vulnerability
to
hydrolysis
(
half­
life=
1.8
days,
MRID
001467­
64)
and
presence
of
relatively
high
concentrations
of
transient
species
and
degradates
at
time
zero.
Two
parallel
process
are
suggested
by
EFED
to
explain
the
fate
of
metiram
in
aerobic
soil;
very
rapid
hydrolysis
and
very
slow
bio­
degradation.
The
first
transforms
parent
metiram
into
a
multi
species
residue
(
metiram
complex)
while
the
second
transforms
metiram
complex
into
further
degradates
and
CO
2
.
EFED
agrees
with
registrant
calculated
half­
lives
for
the
parent
metiram
which
are
believed
to
be
hydrolysis
half­
lives
that
are
modified
by
soil
conditions
(
moisture,
O
2
content,
pH
and
other
characteristics).
However,
a
second
set
of
half­
lives
were
calculated
by
EFED
for
the
metiram
complex
as
species
present
in
this
complex
can
be
precursors
for
the
degradate
of
concern,
ETU.
For
this
purpose,
EFED
used
the
mass
balance
data
(
radioactivity
data)
and
assumed
that
the
only
bio­
degradation
of
the
complex
was
represented
by
evolved
CO
2
.
It
is
important
to
note
that
these
estimated
half­
lives
are
conservative
as
estimates
are
based
on
complete
mineralization
of
the
metiram
complex
as
a
whole.

Registrant
calculated
half­
lives
using
the
CS
2
data
are
considered,
by
EFED,
to
represent
hydrolysis
rather
than
bio­
degradation
of
parent
metiram
in
the
soil
system.
The
results
are
summarized
in
Table
IV­
3
and
indicate
parent
metiram
is
not
persistent
(
short
half­
lives
in
the
range
of
<
1
to
7
days).
Variation
in
the
results
could
be
a
reflection
of
many
factors
including:
test
substance
used,
moisture
maintained,
procedure
used
in
the
calculation,
and
variations
in
EBIS
concentration
(
a
contributor
to
evolved
CS
2
).
In
contrast,
EFED
calculated
conservative
first
order
half­
lives
for
metiram
complex
are
summarized
in
Table
IV­
2
and
indicate
that
the
complex
is
persistent
(
long
half­
lives
in
the
range
of
387­
454
days).
23
Table
IV­
3.
Calculated
half­
lives
using
CS
2
data
in
soil
systems
with
varied
characteristics
(
half­
lives
are
considered
by
EFED
to
be
Parent
metiram
hydrolysis).

Soil
Texture
Concentration
Applied
(
ppm)
Moisture
Applied
(%
of
WHC)
Incubation
Temperature
Half­
life
Study
MRID
No.
(
Days)
Calculation
Procedure
Loamy
Sand
7.5
70%
25
±
1
oC
1
Model*
459069­
01
Silt
Loam
20.0
70%
25
±
1
oC
7
non­
linear
regression
451452­
03
Loamy
Sand
10.0
40%
Not
Reported
1
Time
for
50%
dissipation
001552­
88
Loam
9.9
40%
<
1
*
Compartment
model
and
the
ModelMaker
program.

Initial
degradation
of
parent
metiram
was
not
tested
under
anaerobic
conditions.
However,
anaerobic
degradation
pattern/
rate
for
the
complex
of
metiram
after
30­
day
aerobic
aging
(
i.
e
the
metiram
complex)
were
similar/
slower
to
aerobic
conditions
(
MRID
001552­
88).

iii.
Sediment/
Water
Systems
The
aerobic
bio­
transformation
of
[
ethylene­
14C]
metiram,
was
studied
in
a
water/
loamy
sand
sediment
system
(
system
A:
water
pH
8.4,
organic
carbon
11.4
mg/
L;
sediment
pH
8.3,
organic
carbon
0.52%)
from
a
pond
and
a
stream
water­
loamy
sand
sediment
system
(
system
B:
water
pH
7.6,
organic
carbon
3.1
mg/
L;
sediment
pH
7.0,
organic
carbon
0.57%)
from
a
small
stream,
both
located
in
Germany,
for
100
days
in
darkness
at
20
±
1
°
C.
Metiram
was
applied
at
the
rate
of
0.60
mg
a.
i./
L
water
(
MRID
4593344­
01).
Aerobic
conditions
were
maintained
in
the
water
layer
of
the
watersediment
systems,
but
the
sediment
layer
remained
anaerobic
throughout
the
study.
In
preparing
the
test
substance,
<
1
ppm
of
metiram
was
suspended
in
water;
a
concentration
below
the
reported
solubility
of
metiram
(<
2
ppm).
Due
to
the
reported
hydrolytic
decomposition
of
metiram
at
concentrations
below
2
ppm,
applied
material
at
time
zero
may
have
contained
little,
if
any
metiram;
metiram
has
never
been
verified.

This
study
provided
data
confirming
that
parent
metiram
is
short­
lived
in
aquatic
systems
especially
when
present
at
low
concentrations.
Author
calculated
half­
lives
for
the
entire
systems
were
0.9
and
0.5
days
for
systems
A
and
B,
respectively.
In
this
calculation,
the
author
used
CS
2
­
data
to
represent
parent
metiram
assuming
that
evolved
CS
2
is
unique
to
parent
which
is
not
the
case
because
CS
2
can
also
evolve
from
metiram
degradates.
These
short
half­
lives
are
probably
a
result
of
hydrolysis
occurring
in
these
water/
sediment
systems.
Calculated
first
order
hydrolysis
half­
lives
were
1.4
to
3.1
days
for
polymeric
metiram
in
buffered
suspensions
between
at
pH
5
and
9,
7
and
9,
respectively
(
MRID
001467­
64).
As
stated
previously,
hydrolysis
results
in
the
formation
of
the
multi
species
residue
referred
to
as
metiram
complex.
Therefore,
the
results
of
this
study
is
used
to
provide
useful
data
on
distribution/
fate
of
the
complex
as
a
whole
as
well
as
the
species
that
constitute
this
complex.
For
the
complex
as
a
whole
(
metiram
complex),
EFED
calculated
its
half­
lives
based
on
radioactivity
data
and
on
the
assumption
that
the
only
bio­
degradation
of
the
complex
is
represented
by
evolved
CO
2
.
EFED
calculated
half­
lives
for
metiram
complex
in
the
entire
systems
were
858
days
(
r2
=
0.99)
and
173
days
(
r2
=
1.00)
for
systems
A
and
B,
respectively.
24
In
system
A,
ETU
was
the
major
transformation
product
with
minor
quantities
of
EU,
EBIS
and
CO
2
.
In
contrast,
ETU,
EBIS
and
CO
2
were
the
major
transformation
product
in
system
B
with
minor
quantities
of
EU.
In
order
to
establish
a
common
base
for
interpreting
change
in
various
materials
with
time,
reported
data
were
recalculated
by
EFED
based
on
determined
radioactivity
in
the
system
with
100%
material
balance
(
referred
to
as
100%
transformed
data).
Resultant
100%
transformed
data
were
plotted
for
radioactivity
distribution
and
the
distribution
of
the
constituents.
In
system
A,
radioactivity
partitioned
equally
between
the
water
and
the
sediment
within
two
weeks
of
the
application
date
and
stayed
almost
constant
over
the
100­
day
experiment
showing
only
slight
biodegradation
as
indicated
by
the
slight
increase
in
evolved
CO
2
.
In
contrast,
partition
of
radioactivity
between
the
water
and
sediment
phases
in
the
system
B
reached
the
50%
level
within
two
weeks
for
the
water
and
within
50
days
for
the
sediment.
A
pronounced
decline
of
the
level
of
radioactivity
in
the
water
phase
and
an
increase
in
evolved
CO
2
were
apparent
indicating
much
higher
biodegradation
occurring
in
this
stream
system
B
compared
to
the
pond
system.
Data
indicate
that
the
major
degradate
in
both
systems
was
ETU
and
appears
to
partition
into
the
water
phase.
In
system
A,
ETU
reached
a
maximum
of
60%
of
the
applied
at
day
1,
decreased
to
46%
at
day
7
followed
by
only
very
slight
decrease
towards
the
end
of
the
experiment.
In
system
B,
ETU
reached
a
maximum
of
50%
of
the
applied
at
day
1,
decreased
to
41%
at
day
14
followed
by
a
significant
decrease
towards
the
end
of
the
experiment.
In
both
systems,
the
decrease
in
ETU
appears
to
coincide
in
quantity
and
time
with
CO
2
production
indicating
possible
ETU
degradation
in
the
water
phase.

No
acceptable
data
are
available
for
anaerobic
sediment­
water
systems;
as
no
studies
were
submitted
to
characterize
the
behavior
of
metiram
in
such
systems.

iv.
Bound
Species,
CS2­
data
and
Half­
life
Determination
for
EBDCs
EFED
used
the
CS
2
­
data
for
calculating
conservative
parent
metiram
half­
lives
in
aqueous
hydrolysis
studies.
Hydrolysis
half­
lives
are
considered
conservative
because
CS
2
evolves
from
parent
metiram
and
most
of
its
degradates.
In
addition,
EFED
suggested
that
calculated
half­
lives,
on
the
basis
of
CS
2
­
data,
are
acceptable
as
parent
hydrolysis
rather
than
bio­
degradation
half­
lives
in
soil
and
water/
sediment
systems.
This
means
that
EFED
did
not
consider
the
significant
bound
species,
in
aerobic
and
aquatic
studies,
to
be
included
(
i.
e.
quantified)
as
part
of
the
species
determined
by
the
CS
2
­
method.
In
the
absence
of
characterization
data
on
these
significant
bound
species,
EFED
has
no
other
way
to
calculate
bio­
degradation
half­
lives
other
than
the
use
of
evolved
CO
2
­
data.
EFED
recognizes
that
resultant
bio­
degradation
half­
lives
would
be
conservative
as
it
represents
complete
mineralization
of
the
metiram
complex
as
a
whole.
Giving
the
fact
that
parent
metiram
is
short­
lived,
it
was
necessary
to
assign
these
half­
lives
to
all
of
the
hydrolytic
products
which
were
referred
to
as
the
metiram
complex.
EFED
believes
that
it
is
justified
to
use
the
term
metiram
complex
and
to
use
CO
2
for
calculating
its
half­
lives
in
soil
and
water/
sediment
systems.

In
few
of
the
submitted
fate
studies,
only
limited
data
were
provided
on
the
significant
bound
species
found
in
soil
and
water/
sediment
studies.
Fractionation
of
the
bound
species
was
performed
into
fulvic
and
humic
fractions
with
no
further
determination
of
identity/
quantity
of
species
present.
Without
presenting
direct
evidence,
the
registrant
suggested
that
the
"
bound
EBDC'
is
probably
ethylenediamine
"
EDA".
In
submitted
soil/
sediment
studies,
sulfur
balance
appears
to
decrease
with
time
coinciding
with
the
observed
increase
in
bound
species
which
would
suggest
that
the
bound
species
contain
sulfur.
EDA
has
no
structural
sulfur
and
its
presence
as
a
major
part
of
the
bound
25
species
can
not
explain
the
observed
sink
in
sulfur
balance.
This
sink
may,
however,
be
explained
by
the
presence
of
EBDC
species
with
high
affinity
to
soil/
sediment
and
in
which
structural
sulfur
resists
being
evolved,
as
CS
2
,
by
reagents/
heat
used
in
the
CS
2
­
method.
Therefore,
EFED
is
proposing
that
the
bound
species
are
probably
sulfur
containing
compounds
that
can
be
"
ETU
precursors".
It
is
noted
that
EDA
was
not
identified,
as
a
degradate
of
metiram,
in
any
abiotic
or
biotic
fate
studies
and
that
rapid
degradation
was
predicted
for
EDA
in
water/
soils
using
US
EPA
EPI
suite
program
v3.10.
It
is
also
noted
that
the
observed
sulfur
sink
may
be
related
to
a
reason
other
than
that
suggested
by
EFED
(
ETU
precursors).
This
reason
may
be
related
to
the
fact
that
sulfur
bearing
compounds
may
have
formed,
but
were
not
tracked,
in
submitted
fate
studies.
These
sulfur
bearing
compounds
may
include:
elemental
sulfur,
sulfates,
CS
2
,
H
2
S
and
others.

In
order
to
solve
the
problem
of
the
identity
of
bound
species,
EFED
proposes
that
the
registrant
conduct
one
complete
aerobic
soil
study.
In
the
proposed
study,
greater
efforts
should
be
exercised
to
try
to
characterize
bound
species.
In
addition,
EDA;
and
ETU,
EBIS,
and
all
types
of
sulfur
bearing
compounds
should
be
tracked
(
possibly
by
labeling
structural
sulfur
in
parent
metiram).
A
sterile
soil
treatment
should
also
be
included
in
order
to
determine
the
relative
importance
of
the
active
dissipation/
degradation
processes
in
aerobic
soils
(
binding
to
soil/
hydrolysis
compared
to
biodegradation

c.
Mobility
The
only
mobility
data
for
metiram
were
obtained
from
a
soil
column
leaching
study
on
four
soils
(
MRI
D
405763­
01,
Table
IV­
4)
and
represent
mobility
of
metiram
complex.
Low
to
slight
mobility
of
the
complex
is
indicated
from
K
oc
values
approximated
for
sandy
loam,
silt
loam
and
clay
soils
while
high
mobility
is
indicated
for
a
sandy
soil.
Since
K
d
and
K
oc
for
metiram
complex
are
approximated
from
a
soil
column
leaching
study
there
is
not
a
1/
n
value
indicating
the
degree
of
nonlinearity
for
the
Freundlich
constant.
Based
on
radio­
activity
leaching
profiles,
39­
87%
of
the
radioactivity
remained
in
the
top
1"
of
three
soils
(
MD
clay,
MS
SiL
and
CA
SL)
and
was
positively
related
to
%
clay,
%
organic
carbon
and
cation
exchange
capacity.
In
contrast,
59%
of
the
radioactivity
was
leached
from
the
12"
column
of
the
coarse
textured
fourth
soil
(
MD
sand)
which
contains
low
organic
matter
and
clay
and
has
a
low
cation
exchange
capacity.
Leached
radioactivity
from
the
first
three
soils
was
in
the
range
of
2
to
31%.
This
indicates
the
high
affinity
of
metiram
complex
for
adsorption
to
the
clay
and
organic
matter
fractions
of
the
soil.

Leaching
of
a
30
day
aerobically
aged
metiram
complex
over
a
column
of
the
same
soil
(
loamy
sand)
resulted
in
no
significant
movement
(
MRID
001552­
88).
Radioactivity
in
the
top
5
cm
accounted
for
94.13%
of
the
complex
and
was
96.3%
in
the
top
10
cm.
The
results
indicate
metiram
complex,
as
a
whole,
is
immobile.
26
Table
IV­
4.
Soil
adsorption/
desorption
study
results
for
metiram
complex
(
MRID
405763­
01).

Soil
Name/
Source
Maryland
(
MD)
California
(
CA)
Mississippi
(
MS)
Maryland
(
MD)

Textural
class
sand
sandy
loam
(
SL)
silt
loam
(
SiL)
clay
Clay
(%)
2.2
6.4
6.3
42.0
Organic
Carbon
(%)*
1
0.52
0.29
0.58
2.79
pH
(
Water)
6.5
6.3
7.5
5.9
C.
E.
C
(
meq/
100g)
2
5
10
25
Adsorption
Coefficient
(
Kd)
0.58
1.68
6.17
48.5
Organic­
C
Adoration
Coefficient
Koc)
111
578
1,061
1,738
Mobility
Class
high
Low
Slight
*
1
Organic
Carbon
(%)=
Organic
matter
(%)/
1.724.

d.
Field
Dissipation
In
a
study
conducted
in
upstate
New
York
on
sugar­
beets,
metiram
(
applied
as
Polyram
80WP)
dissipated
with
a
DT
50
of
143
days
while
a
study
conducted
in
California
on
the
same
crop
reported
a
DT
50
of
20
days
(
MRID
414408­
01/
02).
For
the
same
studies,
reported
DT
50
s
for
ETU
were
45
and
16
days,
respectively.
Data
on
vertical
downwards
movement
of
metiram
and
ETU
was
limited
by
the
low
sensitivity
of
the
analytical
method
(
LOD
of
0.05
and
0.01
ppm,
respectively).
Other
major
deficiencies
of
the
studies
were
inadequate
storage
stability
data
and
the
fact
that
chemical
analysis
was
generally
delayed
after
sampling.
While
data
suggested
movement
of
metiram
and
ETU,
the
registrant
claimed
that
such
detections
were
the
result
of
contamination
of
samples,
which
posed
further
questions
about
the
validity
of
the
studies.
However,
the
concern
of
ETU
leaching
to
groundwater
would
probably
be
better
addressed
by
the
required
monitoring
studies.

e.
Bio­
accumulation
Data
requirement
were
waived
for
metiram
because
the
K
ow
is
below
100
(
Table
IV­
1).
At
such
low
K
ow
bio­
accumulation
is
not
expected
to
occur
in
aquatic
organisms
such
as
fish.

f.
Transformation
Products
Several
degradates
and
metabolites
were
identified
during
hydrolytic
decomposition
of
metiram
in
aqueous
media
and
in
soil/
field
degradation
studies.
In
addition
to
CO
2
the
following
transformation
products
were
reported:

(
1)
Transient
Species
which
included:

(
a)
Carbimid
or
ETT=
IUPAC
Name:
1
H
imidazol­
2­
thion,
4,5
dihydro,
1
thioformamido)
27
(
b)
EBIS=
ethylene
bis
isothiocyanate
sulfide
(
Other
names:
ETM=
ethylene
thiuram
monosulfide
and
IUPAC
Name:
(
DIDT)
5,6­
dihydro­
3H­
imidazo[
2,1­
C]­
1,2,4­
dithiazole­
3­
thione,
CAS
No.:
33813­
20­
6).

(
c)
TDIT=
2,3,7,8­
tetrahydrodiimidazo[
2,1­
b:
1,2­
e][
1,3,5]
thiadiazine­
5­
thione.

(
2)
Degradates
produced
from
parent
through
transient
species:
ETU=
ethylenethiourea
(
IUPAC
Name:
2­
Imidazolidinethione,
CAS
No.:
96­
45­
7)

(
3)
Degradates
produced
from
ETU:

(
a)
EU=
ethyleneurea
(
IUPAC
Name:
2­
Imidazolidone
CAS
No.:
120­
93­
4
(
b)
HYD=
Hydantoine
or
Glycolylurea
(
IUPAC
Name:
2,4­(
3H,
5H)­­
Imidazoledione,
CAS
No.:
461­
72­
3)

The
principal
transient
species
identified
was
ETT
or
carbimid
in
abiotic
studies
as
it
was
>
1%
only
in
the
first
few
days
followed
by
no
detection
in
a
hydrolysis
study
(
MRIDs
001551­
89
and
addendum
MRID
001619­
37).
In
biotic
studies,
EBIS
was
the
transient
species
as
it
was
reported
to
reach
up
to
13%
at
4
days
and
to
declined
to
<
1%
at
59
days
in
an
aerobic
soil.
ETU
is
the
degradate
of
concern
for
metiram
and
was
identified
in
both
laboratory
and
field
studies.
ETU
was
the
dominant
degradate
in
hydrolysis
studies
reaching
a
maximum
of
4,
6,
8
and
13%
at
pH
5,
6,
3
and
9,
28
respectively
at
the
end
of
a
40­
day
hydrolysis
study
(
MRIDs
001551­
89
and
addendum
MRID
001619­
37).
In
contrast,
ETU
reached
only
a
maximum
of
4%
in
the
first
4days
and
declined
to
<
1%
at
the
end
of
a
59­
day
aerobic
soil
study
(
MRID
451452­
03).
Both
EU,
HYD
were
identified
as
in
minor
amount
(<
1%)
at
some
time
intervals
in
aqueous
hydrolysis
studies
along
with
un­
identified
low
molecular
weight
polar
and
non­
polar
materials.
Only
EU
was
identified
in
the
aerobic
soil
study
in
minor
amounts
(<
1%)
at
all
time
intervals.
Uncertainties
exists
for
quantities
reported
for
transient
species
and
degradation
products
due
to
apparent
anomalies
present
in
various
studies
in
regard
to
the
purity
of
test
substance
and
formation
of
various
transient
species
(
i.
e.,
EBIS)
and
degradation
products
(
i.
e.,
ETU
and
EU)
during
extraction.
These
uncertainties
are
discussed
in
details
in
the
Appendix
I.
29
V.
Water
Resource
Assessment
Once
exposed
to
water,
parent
metiram
is
not
expected
to
be
present
in
significant
amounts
in
the
environment
except
for
short
duration
because
it
will
hydrolyze
rather
quickly
into
its
complex.
In
dry
conditions
and
in
soils
with
low
water
holding
capacity
parent
metiram
will
persist.
More
details
about
parent
metiram
EECs
are
presented
in
Appendix
I
(
section
c.
i).

This
water
resource
assessment
is
for
metiram
complex;
the
resultant
residue
from
expected
rapid
hydrolysis
of
parent
metiram
in
the
natural
environment.
Metiram
complex
was
determined
to
consist
of
a
suite
of
chemical
species:
transient
species
(
EBIS,
carbimid
and
TDIT),
ETU,
ETU
degradates
(
EU,
hydantoine
and
others),
and
the
significant
unknown
bound
species
(
suspected
of
containing
persistent
precursors
for
ETU).
Among
the
constituents
of
metiram
complex,
ETU
is
the
species
of
concern
(
US
EPA,
2002).
Therefore,
a
complete
water
resource
assessment
was
performed
for
ETU
while
only
surface
water
modeling
was
necessary
for
metiram
complex.
The
resultant
EECs
were
used
in
the
ecological
risk
assessment
of
metiram
complex.

a.
Surface
Water
Monitoring
and
Modeling
EFED
is
not
aware
of
surface­
water
monitoring
data
for
metiram.
Monitoring
data
were
submitted
to
the
Agency
by
the
EBDC
Task
Force
only
for
the
degradate
of
concern
ETU,
this
data
will
be
discussed
separately
in
the
accompanied
chapter
for
ETU.
The
surface
water
assessment
of
metiram
complex
is
therefore
based
upon
computer
modeling.

The
surface
water
assessment
was
carried
out
using
the
linked
PRZM
and
EXAMS
models.
PRZM/
EXAMS
input
values
are
listed
in
Table
V.
1
and
the
results
in
Table
V.
2.
This
data
were
used
for
estimating
EECs
necessary
for
the
ecological
risk
assessment
of
metiram
complex.

Table
V.
1.
PRZM/
EXAMS
Input
Parameters
for
metiram
complex*.

Input
Parameter
Value
Reference
Molecular
Weight
(
grams)
1088.6
Registrant
data
Vapor
Pressure
(
torr)
7.52e­
8
Registrant
data
Bacterial
Bio­
lysis
in
the
water
column
(
days)
0
(
Stable)
Note:
A
new
study
was
submitted
in
which
EFED
calculated
half­
lives
for
metiram
complex
in
the
entire
systems
were
858
days
(
r2
=
0.99)
for
one
system
and
173
days
(
r2
=
1.00)
for
another
(
MRID
459069­
01).

Bacterial
Bio­
lysis
in
benthic
sediment
(
days)
0
(
Stable)
Guidance**
because:
No
anaerobic
aquatic
metabolism
study/
significant
hydrolysis
Aerobic
Soil
Metabolism
Half­
life
(
days)
432
Upper
confidence
bound
on
the
mean
for
four
soils
(
MRIDs
451452­
03,
001552­
88,
and
459069­
01).

Application
Method
Aerial
Product
Label
Depth
of
Incorporation
(
inches)
0
Product
Label
30
Application
Efficiency
(
fraction)
0.95
Guidance**

Spray
Drift
(
fraction)
0.05
Guidance**

Solubility
(
mg/
L
or
ppm)
2
Registrant
data
Koc
(
L
Kg­
1)
872
Average
for
four
soils
(
MRID
405763­
01)

pH
7
Hydrolysis
Half­
life
(
days)
1.8
MRID
001467­
64
Photolysis
Half­
life(
days)
0
(
Stable)
MRIDs
001551­
90
and
001619­
38
*
Parent
metiram
Parameters
for
Molecular
Weight
(
grams);
Vapor
Pressure
(
torr);
Solubility
(
mg/
L
or
ppm);
and
pH
7
Hydrolysis
Half­
life
were
used.
**
Guidance
for
Chemistry
and
Management
Practice
Input
Parameters
For
Use
in
Modeling
the
Environmental
Fate
and
Transport
of
Pesticides,
Version
2/
November
7,
2000.

Table
V.
2.
PRZM/
EXAMS
output
EECs
(
ppb)
for
metiram
complex*

Crop
Rate
(
lbs/
Acre)
Number
of
Applications
Interval
Peak
96
Hour
21
Day
60
Day
90
Day
Annual
Average
Apples(
NC)
4.8
4
7
98.9
55.4
20.7
9.4
5.3
1.6
Potatoes
(
ME)
1.6
7
5
54.5
28.1
10.2
5.6
3.8
1.4
b.
Ground
Water
Monitoring
and
Modeling
EFED
is
not
aware
of
ground
water
monitoring
data
for
metiram.
Monitoring
data
were
submitted
to
the
Agency
by
the
EBDC
Task
Force
only
for
the
degradate
of
concern
ETU,
this
data
will
be
discussed
separately
in
the
accompanied
ETU
RED
chapter.
No
ground
water
modeling
was
performed
for
metiram
complex
because
the
only
species
of
concern
is
ETU
for
which
modeling
can
be
found
in
the
accompanied
ETU
chapter.

c.
Drinking
Water
Assessment
Assessments
for
surface/
ground
drinking
water
were
only
performed
for
the
degradate
of
concern,
ETU.
This
assessment
can
be
found
in
the
accompanied
chapter
for
ETU.
31
VI.
Aquatic
Exposure
and
Risk
Assessment
a.
Hazards
Summary
The
limited
toxicity
data
for
metiram
consists
of
a
core
coldwater
fish
acute
toxicity
study,
a
supplemental
freshwater
invertebrate
acute
toxicity
study,
and
a
supplemental
aquatic
plant
study.
Acutely,
metiram
is
highly
toxic
to
coldwater
freshwater
fish
(
rainbow
trout
LC
50
=
0.23
ppm
based
on
measured,
filtered
samples).
The
guideline
(
72­
1c)
is
fulfilled.
The
supplemental
acute
daphnid
study
shows
metiram
to
have
a
freshwater
aquatic
invertebrates
EC
50
value
>
0.358
ppm
based
on
measured,
unfiltered
samples.
EFED
basis
the
indecisive
toxicity
classification
of
daphnid
on
a
supplemental
study
and
EFED
needs
a
core
study
to
fulfill
this
guideline
(
72­
2b)
(
see
Appendix
III).
EFED
classified
the
study
supplemental
because
the
study
failed
to
fix
an
EC
50
,
and
because
samples
were
not
filtered
before
analytical
measurement.
The
supplemental
study
using
freshwater
green
algae,
Ankistrodesmus
bibraianus
shows
metiram
to
be
toxic
to
aquatic
plants
(
EC
50
=
0.077
ppm
based
on
nominal
concentrations).
EFED
classified
the
study
supplemental
because
inappropriate
cell
inoculum
levels
were
used
and
the
lighting
regime
was
inappropriate.
EFED
is
recommending
core
studies
to
fulfill
this
aquatic
non­
target
plant
guideline
(
either
Tier
I,
122­
2
or
Tier
II,
123­
2)
(
see
Appendix
III).
There
are
many
studies
classified
invalid
because
test
concentrations
were
not
measured
(
as
EFED
requires
for
poorly
soluble
compounds)
and
other
flaws.
Examples
are
bluegill
acute
study
(
MRID
40945501);
bluegill
acute
study
(
MRID
44224401);
rainbow
trout
acute
study
(
40497011);
and
daphnid
acute
study
(
MRID
40497003).
There
are
several
other
studies
classified
invalid
due
to
various
study
design
flaws.
Examples
of
these
are
an
acute
daphnid
study
(
MRID
43525002);
a
rainbow
trout
early
life
stage
study
(
MRID
43770401);
daphnid
life
cycle
tests
(
MRID
43770402)
and
(
MRID
44301102);
and
a
bluegill
acute
study
(
MRID
44224401).
For
a
more
detailed
listing
and
explanation
of
metiram's
hazards
to
aquatic
organisms
and
a
listing
of
more
aquatic
guideline
studies
EFED
needs,
see
Appendix
III.

The
EBDCs
(
metiram,
mancozeb,
and
maneb),
unlike
most
pesticide
active
ingredients
are
not
welldefined
monomeric
substances
(
DÇtzer,
1994).
The
EBDCs
are
polymeric
complexes
and
are
nearly
insoluble
in
water
with
a
high
affinity
to
adsorption
by
soil
or
sediment
particles.
The
EBDC
portion
that
dissolves
in
water
and
breaks
up
into
a
suite
of
transient
species
and
degradates,
is
the
EBDC
complex.
This
complex
is
not
the
parent
material
by
itself.
Over
time
ETU
is
an
important
transformation
product
of
the
EBDCs;
unless
it
is
subjected
to
rapid
degradation
by
microbial
activity
and/
or
indirect
photolysis.

Studies
provided
estimates
of
the
Parent
EBDC
material
in
test
concentrations
used
for
evaluating
the
toxicity
to
aquatic
organisms.
These
studies
showed
low
recoveries
of
the
test
substance.
For
example,
measuring
carbon
disulfide
(
CS
2
)
containing
residues,
using
gas
chromatography,
one
study
found
roughly
a
40%
±
10%
average
of
nominal
levels
of
the
"
parent
residues".
Through
filtering
and
measuring
the
treatment
water,
the
recovery
of
"
parent
residues"
was
around
15%
±
10%
average
of
nominal
levels
(
MRID
No.
43525001).
Filtering
of
the
test
solution
before
analytical
measurement
increases
the
accurate
measurement
of
the
test
material
in
solution
because
this
removes
the
undissolved
material
in
the
solution.
This
remaining,
soluble
portion
of
the
chemical
is
more
biologically
available
to
aquatic
organisms
and
represents
a
more
conservative
estimate
of
the
toxicity
to
these
organisms.
These
filtered
and
measured
"
parent
residues",
are
the
portion
of
the
parent
material
that
is
available
to
aquatic
organisms
in
the
environment
(
see
Figure
VI­
1).
The
EPA's
32
Rejection
Rate
Analysis
determined
that
studies,
testing
materials
having
poor
water
solubility,
were
to
use
measured
as
opposed
to
nominal
concentrations.
Studies
were
to
use
measured
concentrations
for
fixing
aquatic
toxicological
endpoints
for
compounds
with
poor
solubility
(
US
EPA.
December,
1994).
EFED
believes
filtered
and
measured
samples
provide
a
more
conservative
estimate
of
the
EBDCs'
toxicity
to
aquatic
organisms.
Also,
EFED
believes
the
filtered
and
measured
samples
provide
a
more
true
estimate
of
aquatic
organism
exposure
to
the
EBDC
complexes
in
the
environment.

Modeling
estimates
using
PRZM­
EXAMS
are
also
estimating
EBDC
complex
by
predicting
the
EECs
using
the
physicochemical
properties
of
the
EBDC,
parent
aerobic
soil
metabolism
half­
lives
and
sorption
coefficients.
Appendix
VII
shows
the
toxicity
to
aquatic
organisms
found
from
the
various
EBDC
aquatic
toxicological
studies.
These
endpoints
are
an
estimate
of
the
EBDC
complex
that
fixes
the
toxicities
(
that
is,
LC
50
s,
EC
50
s,
and
NOAECs).
The
modeling
EECs
are
also
estimates.
Influences
such
as
particle
size,
conditions
of
storage,
degree
of
decomposition,
pH,
and
the
presence
of
other
cations
(
see
Figure
VI­
1)
would
always
cause
difficulty
in
providing
definite
aquatic
toxicological
endpoints
for
the
EBDCs.
33
Table
VI­
1:
Toxicological
Endpoints
Used
to
Determine
Aquatic
Risk
Quotients
(
RQs)
for
Metiram
Type
of
Toxicity
Organism
Species
Toxicological
Endpoint
Acute
Freshwater
fish
rainbow
trout
(
Salmo
gairdneri)
LC
50
=
230
ppb
Chronic
no
data
no
data
Acute
Freshwater
invertebrate
waterflea
(
Daphnia
magna)
LC
50
>
358
ppb
Chronic
no
data
no
data
Acute
Estuarine/
marine
fish
no
data
no
data
Chronic
no
data
no
data
Acute
Estuarine/
marine
invertebrate
no
data
no
data
Chronic
no
data
no
data
Acute
Aquatic
plant
green
algae
(
Ankistrodesmus
bibraianus)
EC
50
=
77
ppb
b.
Exposure
and
Risk
Quotients
EFED
performed
Tier
II
modeling
(
PRZM/
EXAMS)
for
metiram's
use
on
apples
and
potatoes,
the
main
crop
uses
for
metiram.
Modeling
values
used
(
Table
V­
1)
and
resulting
EECs
(
Table
V­
2)
for
Tier
II
modeling
are
in
section
V­
Water
Resource
Assessment,
above.

EFED
did
not
evaluate
acute
risks
to
estuarine/
marine
animals
because
of
the
lack
of
data
(
acute
toxicity
endpoints).
EFED
did
not
evaluate
chronic
risks
for
freshwater
aquatic
animals
from
exposure
to
the
metiram
complex
because
no
data
(
chronic
toxicity
endpoints)
were
available
to
evaluate
these
risks.
EFED
is
requiring
these
missing
data
through
this
document.
EFED
is
reserving
the
need
for
chronic
studies,
for
estuarine/
marine
aquatic
organisms,
until
EFED
receives
and
reviews
the
acute
studies
for
estuarine/
marine
organisms.
Chronic
assessments
to
nontarget
aquatic
plants
are
not
currently
being
performed.
Below
(
figure
VI­
2)
are
graphs
representing
metiram's
acute
aquatic
risks
to
freshwater
fish
and
nonvascular
aquatic
plants
from
exposure
to
the
metiram
complex.
EFED
bases
these
potential
risks
on
metiram's
current
use
patterns
at
maximum
application
rates,
maximum
number
of
applications
allowed
each
growing
cycle
or
year,
minimum
intervals
between
applications
and
maximum
predicted
EECs
from
modeling.
For
a
more
detailed
listing
and
explanation
of
metiram's
risk,
see
Appendix
IV.
34
0
0.2
0.4
0.6
0.8
1
1.2
1.4
Risk
Quotient
Apples
Potatoes
Sites
Acute
RQ
for
Nonvascular
Aquatic
Plant
Acute
RQ
for
Freshwater
Fish
Metiram
Acute
Aquatic
Risk
Based
on
Tier
II
PRZM­
EXAMS
Modeling
Figure
VI­
2
RQ
greater
or
equal
to
1.0
exceeds
aquatic
plant
acute
and
acute
endangered
species
LOCs.
RQ
greater
or
equal
to
0.5
exceeds
aquatic
animal
acute,
acute
restricted
use
and
acute
endangered
species
LOCs.
RQ
greater
or
equal
to
0.1
exceeds
aquatic
animal
acute
restricted
use
and
acute
endangered
species
LOCs
RQ
greater
or
equal
to
0.05
exceeds
aquatic
animal
acute
endangered
species
LOCs
There
are
no
known
nonvascular
aquatic
plant
species
on
the
endangered
species
list.
35
Figure
VI­
3
­
Frequency
of
Organism
Classes
in
Reported
Incidents
in
EIIS
(
Mastrota,
2001)
c.
Aquatic
Risk
Assessment
The
limited
acceptable
ecotoxicological
data
and
numerous
data
gaps
for
metiram
as
well
as
it's
major
toxicological
degradate
of
concern,
ETU
(
see
ETU
chapter),
makes
it
impossible
to
render
a
complete
assessment
concerning
metiram's
potential
aquatic
environmental
risk.
Based
on
limited
data,
metiram
is
likely
to
pose
a
potential
acute
restricted
use
and
acute
endangered
species
risk
to
freshwater
fish
(
highest
RQ
=
0.43
for
freshwater
fish
on
apple
use)
and
an
acute
risk
to
nonvascular
aquatic
plants
(
highest
RQ
=
1.28
from
metiram's
use
on
apples)
since
risk
LOCs
have
been
exceeded
(
see
Figure
VI­
2).
No
adverse
aquatic
incidents
concerning
metiram's
use
(
see
below)
have
been
reported.
The
major
uncertainties
concerning
metiram's
risk
to
aquatic
organisms
revolves
around
the
lack
of
data
and
in
particular
the
lack
of
chronic
data.
The
data
being
used
to
assess
the
risk
to
aquatic
nonvascular
plants
is
supplemental
and
core
data
is
needed.
Additional
aquatic
plant
studies
need
to
be
submitted
for
a
vascular
aquatic
plant,
a
marine
diatom,
a
blue­
green
algae
and
a
freshwater
diatom
to
fully
evaluate
metiram's
risk
to
aquatic
plants.
Core
studies
to
evaluate
the
acute
risks
to
estuarine/
marine
organisms
need
to
be
submitted
and
there
are
no
chronic
studies
available
upon
which
to
conduct
aquatic
chronic
risk
assessments
for
metiram.

i.
Incidents
The
Ecological
Incident
Information
System
(
EIIS)
indicated
there
were
no
adverse
aquatic
incidents
reported
in
association
with
metiram
use.

Although
more
than
50%
of
the
incidents
reported
in
EIIS
deal
with
plant
and
fish
issues
(
see
Figure
VI­
3),
most
of
the
plant
incidents
involve
spray
drift
damage
to
terrestrial
plants
and
most
of
the
fish
incidents
are
fish
kill
reports.
Chronic
problems
that
affect
wildlife
from
the
use
of
metiram
and
it's
degradate,
ETU,
would
be
expected
to
be
largely
unnoticed
in
the
field
and
thus
incident
reports,
as
a
result
of
chronic
exposure,
would
not
be
expected.
Since
metiram
has
been
used
in
the
US
since
1983,
the
lack
of
metiram
reported
aquatic
related
incidents
would
support
the
expectation
that
metiram
is
a
low
acute
aquatic
risk
concern.
However,
EIIS
would
not
be
expected
to
p
r
o
vide
info
rma
t
io
n
concerning
chronic
problems
associated
with
pesticidal
use
in
the
environment.
36
ii.
Endocrine
Disruptors
Metiram's
aquatic
toxicological
data
are
limited
to
acute
testing,
based
on
mortality
effects.
Evaluating
metiram's
effects
on
aquatic
organisms
for
endocrine
induced
effects
is
uncertain.
EFED
needs
more
testing
over
more
taxa
to
evaluate
metiram's
potential
to
act
as
endocrine
disruptors
in
aquatic
organisms.

iii.
Endangered
Species
Based
on
available
screening
level
information
there
is
a
potential
concern
for
acute
effects
on
listed
freshwater
fish
species
should
exposure
actually
occur.
The
Agency
does
not
currently
have
data
on
which
to
fully
evaluate
the
toxicity
of
metiram
to
endangered/
threatened
species
of
freshwater
organisms,
estuarine/
marine
organisms,
or
aquatic
vascular
plants.
To
date,
there
are
no
known
nonvascular
aquatic
plant
or
estuarine/
marine
invertebrate
species
on
the
endangered
species
list.
37
VII.
Terrestrial
Exposure
and
Risk
a.
Hazards
Summary
(
Acute/
Chronic)

Acutely,
metiram
is
practically
nontoxic
to
birds
(
Northern
bobwhite
quail
acute
oral
LD
50
>
2,150
mg/
kg).
Avian
subacute
dietary
tests
were
conducted
using
Northern
bobwhite
quail
and
mallard
duck
as
test
species.
The
formulated
product
LC
50
values
for
bobwhite
and
mallard
were
4,640
ppm
(
3,712
ppm
ai
)
and
>
4,640
ppm
(>
3,712
ppm
ai
),
respectively.
This
classifies
metiram
as
slightly
toxic
to
avian
species
from
subacute
dietary
exposure.

In
a
metiram
avian
reproduction
study
using
the
mallard
duck,
chronic
toxic
effects
were
seen.
These
effects
in
birds
included:
reduced
egg
production;
reduced
mean
egg
weight;
reduced
fertility
rate;
reduced
number
of
hatched
ducklings;
reduced
number
of
14­
day
old
survivors;
and
an
increased
rate
of
early
embryonic
deaths.
The
reproduction
NOAEC/
LOAEC
is
50/
300
ppm.
EFED
classified
a
Northern
bobwhite
quail
reproduction
study
as
supplemental
because
of
mortality
and
a
high
number
of
cracked
eggs
(>
18%)
in
the
control
group.
A
NOAEC
of
>
500
ppm
was
established
at
the
highest
dose
tested
in
this
study
(
MRID
No.
41082001)
with
no
LOAEC
determination
because
no
adverse
effects
were
noted
at
the
concentrations
tested.
A
waiver
for
additional
reproductive
testing
on
Northern
bobwhite
quail
was
requested
(
Barcode
No.
D223505;
3/
96)
based
on
similarity
to
testing
results
for
the
EBDC's,
and
the
registrant
was
informed
testing
would
be
held
in
abeyance
and
reconsidered
at
reregistration.
Collectively,
the
mallard
is
the
more
sensitive
species
for
the
EBDCs,
and
EFED
will
use
results
from
the
mallard
reproductive
study
for
risk
assessment
purposes.
Therefore,
a
repeat
of
this
study
(
MRID
No.
41082001)
is
not
necessary.

Acutely,
metiram
is
practically
nontoxic
to
small
mammals
with
an
oral
LD
50
>
5,000
mg/
kg
in
tests
done
on
laboratory
rats.
Results
from
a
chronic
3­
generation
reproduction
study
in
rats
for
metiram
show
a
parental
and
reproductive
toxicity
at
a
LOAEL
of
320
ppm
(
NOAEL
=
40
ppm).
Parental
toxicity
resulted
in
decreased
body
weight
during
gestation
and
lactation
for
females.
Reproductive
toxicity
resulted
in
decreased
mating
performance
(
increased
precoital
time)
in
the
F2
generation
(
two
generations
removed
from
the
original
parent
generation).

Currently,
EFED
does
not
assess
risk
to
non­
target
insects
using
risk
quotients.
Results
of
acceptable
studies
are
used
for
recommending
appropriate
label
precautions.
Since
metiram
was
determined
to
be
practically
nontoxic
to
honey
bees
(
LD
50
=
437
µ
g/
bee)
no
bee
precautionary
labeling
is
required
on
metiram
product
labeling.

EFED
has
not
received
any
nontarget
terrestrial
plant
studies
and
is
unable
to
assess
the
risk
to
nontarget
terrestrial
plants
as
a
result
of
metiram's
uses.
The
submission
of
Tier
I
seedling
emergence
and
vegetative
vigor
studies
for
a
TEP
are
needed
to
evaluate
this
risk.

For
a
more
detailed
listing
and
explanation
of
metiram's
hazards
to
all
terrestrial
organisms,
see
Appendix
III.
38
Table
VII­
1:
Toxicological
Endpoints
Used
to
Determine
Risk
Quotients
(
RQs)
for
Metiram
Type
of
Toxicity
Organism
Species
Toxicological
Endpoint
Subacute
dietary
Bird
Northern
Bobwhite
Quail
(
Colinus
virginianus)
LC
50
 

3,712
ppm
Chronic
Bird
mallard
duck
(
Anas
platyrhynchos)
NOAEC
=
50
ppm1
Chronic
Mammal
laboratory
rat
(
Rattus
norvegicus)
NOAEL
=
40
ppm2
1
LOAEC
based
on
reduced
egg
production,
reduced
mean
egg
weight,
reduced
fertility
rate,
reduced
number
of
hatched
ducklings,
reduced
number
of
14­
day
old
survivors;
and
an
increased
rate
of
early
embryonic
deaths
2
Reproductive
study
LOAEL
based
on
parental
toxicity
resulting
in
decreased
body
weight
during
gestation
and
lactation
for
females
and
reproductive
toxicity
resulting
in
decreased
mating
performance
(
increased
precoital
time)
in
the
F2
generation
(
two
generations
removed
from
the
original
parent
generation).

b.
Exposure
Summary
EFED
evaluated
terrestrial
exposure
using
EECs
produced
from
the
FATE
version
5.0
model
that
calculates
the
decay
of
a
chemical
applied
to
foliar
surfaces
for
single
or
multiple
applications.
The
model
assumes
initial
concentrations
on
plant
surfaces
based
on
Kenaga
predicted
maximum
and
mean
residues
as
modified
by
Fletcher
et
al.
(
1994)
and
assumes
1st
order
dissipation.
Kenaga
estimates
and
an
explanation
of
the
model
with
sample
output
are
presented
in
Appendix
VII.
Without
available
total
foliar
dissipation
half­
life
data
for
metiram,
EFED
used
a
35­
day
half­
life.
EFED
based
this
half­
life
selection
on
the
upper
limit
of
pesticide,
foliar
dissipation
half­
lives
provided
in
the
half­
life
listing
of
Willis
and
McDowell,
1987.
EFED
uses
this
value
as
a
default
value
when
the
foliar
dissipation
for
a
particular
pesticide
is
unknown.

c.
Risk
Quotients
Below
are
graphs
representing
metiram's
potential
acute
and
chronic
risks
to
nontarget
terrestrial
animals.
These
potential
risks
are
based
on
metiram's
current
use
patterns
at
maximum
application
rates
and
minimum
intervals
between
applications.
These
graphs
show
the
acute
and
chronic
Risk
Quotients
(
RQs)
that
can
be
expected
from
terrestrial
animals
feeding
on
the
food
items
listed.
These
acute
and
chronic
RQs
are
derived
from
estimated
environmental
concentrations
(
EECs)
based
on
the
maximum
and
mean
residue
estimates
(
see
Appendix
II)
that
are
expected
on
these
food
items
following
metiram's
applications
to
various
sites
indicated.

Metiram's
avian
acute
dietary
RQs
exceed
acute,
acute
restricted
use
and
acute
endangered
species
LOCs
for
tobacco,
apple,
and
potato
uses.
The
RQs
range
from
0.56
to
1.22
(
see
Figure
VII­
1,
below).
Avian
acute
endangered
species
levels
of
concern
(
LOCs)
are
exceeded
for
all
metiram
use
patterns
at
maximum
EEC
levels
(
RQ
range
from
0.11
to
1.22).
The
chronic
RQs
for
multiple
broadcast
spray
applications
of
metiram
are
tabulated
below
in
Figure
VII­
2.
The
results
show,
for
multiple
spray
applications
of
metiram,
the
avian
chronic
LOCs
are
exceeded
for
all
uses
patterns.
RQs
exceed
chronic
LOCs
ranging
from
a
high
of
91
from
the
tobacco
use
to
a
low
of
1
from
metiram's
uses
on
potatoes
and
ornamental
nonflowering
plants.

Chronic
concerns
to
terrestrial
animals
are
exceeded
when
the
RQ
reaches
1.0.
For
example,
the
chronic
RQ
for
birds
feeding
on
short
grass
as
a
result
of
metiram
being
applied
to
tobacco
is
91
at
maximum
residue
levels
and
32
at
mean
residue
levels.
As
can
be
seen
from
these
graphs,
nearly
all
39
0
0.2
0.4
0.6
0.8
1
1.2
1.4
Risk
Quotient
(
RQ)

Tobacco
Apples
Potatoes
Ornamental
(
nonflowering
plants)
Ornamental
(
woody
shrubs
&
vines)

Sites
Max.
for
Short
grass
Max.­
Broadleaf/
ForagePlants/
Sm.
Insec
Max.
for
Tall
grass
Mean
for
Short
grass
Mean­
Broadleaf/
ForagePlants/
Sm.
Inse
Mean
for
Tall
grass
Max.­
Fruits/
Pods/
Seeds/
Large
Insects
Mean­
Fruits/
Pods/
Seeds/
Large
Insects
Metiram
Acute
Avian
Risk
Maximum
and
Mean
Exposure
Risk
Figure
VII­
1
RQ
greater
or
equal
to
0.5
exceeds
acute,
acute
restricted
use
and
acute
endangered
species
LOCs.
RQ
greater
or
equal
to
0.2
exceeds
acute
restricted
use
and
acute
endangered
species
LOCs
RQ
greater
or
equal
to
0.1
exceeds
acute
endangered
species
LOCs.
metiram's
uses
exceed
chronic
LOCs
for
birds
and
mammals.
Based
on
the
estimated
mean
residues
on
fruits,
pods,
seeds,
and
large
insects
the
avian
and
mammalian
chronic
LOCs
would
not
be
exceeded
as
a
result
of
metiram's
use
on
ornamentals.
The
chronic
exceedances
to
birds
range
from
a
high
RQ
of
91
on
tobacco
to
a
low
of
1
on
ornamentals.
For
mammals
(
Figure
VII­
3),
the
range
of
RQ
exceedance
is
from
a
high
of
113
on
tobacco
to
a
low
of
1
on
ornamentals.

For
a
more
detailed
listing
and
explanation
of
metiram's
risk
to
all
terrestrial
organisms,
see
Appendix
IV.
40
1
10
100
Risk
Quotient
(
RQ)

Tobacco
Apples
Potatoes
Ornamental
(
nonflowering
plants)
Ornamental
(
woody
shrubs
&
vines)
Sites
Mean­
Fruits/
Pods/
Seeds/
Large
Insects
Max.­
Fruits/
Pods/
Seeds/
Large
Insects
Mean
for
Tall
grass
Mean­
Broadleaf/
ForagePlants/
Sm.
Insects
Mean
for
Short
grass
Max.
for
Tall
grass
Max.­
Broadleaf/
ForagePlants/
Sm.
Insects
Max.
for
Short
grass
Metiram
Chronic
Avian
Risk
Maximum
and
Mean
Exposure
Risk
Figure
VII­
2
(
Based
on
a
35­
day
foliar
dissipation
half­
life)
RQ
greater
or
equal
to
1
exceeds
chronic
LOCs.
41
1
10
100
1000
Risk
Quotient
(
RQ)

Tobacco
Apples
Potatoes
Ornamental
(
nonflowering
plants)
Ornamental
(
woody
shrubs
&
vines)

Sites
Mean­
Fruits/
Pods/
Seeds/
Large
Insects
Max.­
Fruits/
Pods/
Seeds/
Large
Insects
Mean
for
Tall
grass
Mean­
Broadleaf/
ForagePlants/
Sm.
Insects
Mean
for
Short
grass
Max.
for
Tall
grass
Max.­
Broadleaf/
ForagePlants/
Sm.
Insects
Max.
for
Short
grass
Metiram
Chronic
Mammalian
Risk
Maximum
and
Mean
Exposure
Risk
Figure
VII­
3
(
Based
on
a
35­
day
foliar
dissipation
half­
life)
RQ
greater
or
equal
to
1
exceeds
chronic
LOCs.
42
Metiram's
Residue
from
Apple
Use
Based
on
Fate
v.
5
Modeling
1
10
100
1000
10000
1
4
7
10
13
16
19
22
25
28
31
34
37
40
43
46
49
52
55
58
Day
ppm
Metiram's
Avian
NOAEC
=
50
ppm
Metiram's
Mammalian
NOAEL
=
40
ppm
Maximum
Residue
on
Short
Grass
Maximum
Residue
on
Broadleaf
/
Forage
Plants
&
Small
Insects
Maximum
Residue
on
Tall
grass
Mean
Residue
on
Short
grass
Mean
Residue
on
Broadleaf
/
Forage
Plants
&
Small
Insects
Mean
Residue
on
Tall
grass
Maximum
Residue
on
Fruits,
Pods,
Seeds,
and
Large
Insects
Mean
Residue
on
Fruits,
Pods,
Seeds,
and
Large
Insects
Figure
VII­
4
d.
Terrestrial
Risk
Assessment
A
dose­
response
slope
value
for
the
bobwhite
quail
acute
dietary
toxicity
(
that
is,
LC
50
=
3,712
ppm
metiram)
was
not
determined.
In
this
dietary
toxicity
study,
5
of
10
birds
died
at
the
highest
concentration
tested
with
no
mortality
at
the
lower
concentrations
tested.
Since
only
one
concentration
provided
a
percent
mortality
between
0
and
100%,
a
slope
value
could
not
be
determined
through
probit
analysis.
Lacking
slope
information,
EFED
was
not
able
to
predict
the
likelihood
of
individual
acute
effects
in
birds,
from
metiram's
exposure.

Approximately
460,000
lbs
ai
of
metiram
is
applied
annually
to
US
apples
with
11%
of
the
total
apple,
U.
S.
planted,
acres
being
treated
with
metiram
(
EPA
use
data
1992
through
2001)
(
BEAD's
Quantitative
Usage
Analysis
for
Metiram
dated
November
1,
2002).
Metiram
can
be
applied
4
times
per
season
every
7
days
from
pre­
bloom
through
the
foliar
stages
of
apples.
Bear,
ruffed
grouse,
snowshoe
hare,
pheasants,
Hungarian
partridges,
cottontail
rabbits,
deer,
fox,
opossums,
raccoons,
fox
squirrels,
songbirds,
and
elk
feed
on
apple
fruit
and/
or
foliage
(
Gusey
and
Maturdo,
1972).
Upland
gamebirds
such
as
ruffed
grouse
and
ring­
necked
pheasant
feed
on
apple
fruit,
seeds
and
buds.

Songbirds
such
as
chestnut­
backed
chickadees,
red­
shafted
flickers,
robins,
starlings,
varied
thrushes,
tufted
titmouse,
cedar
waxwings
and
Lewis
woodpeckers
feed
on
apple
fruit
and
seeds.
Fur
and
game
mammals
such
as
black
bears,
foxes,
yellow­
bellied
marmots,
porcupines,
cottontail
rabbits,
and
red
squirrels
feed
on
apple
fruit
and
bark
with
hoofed
browsers
such
as
white­
tailed
deer
feeding
on
apple
fruit,
twigs
and
leaves
(
Martin
et.
al.,
1961).
Birds
such
as
morning
doves
and
valley
quail
utilize
apple
orchards
for
nesting
and
brood
rearing
(
Gusey
and
Maturdo,
1972).
These
wildlife
9
Rate
reductions
determined
by
randomly
imputing
application
rates
into
ELL­
Fate
spreadsheet
program
until
the
mammalian
chronic
risk
to
15
gram
body
weight
small
mammal
from
metiram
residues
on
short
grass
is
less
than
or
equal
to
1.

43
activities
in
apple
orchards
occur
throughout
the
year.
Figure
VII­
4
shows
the
residue
levels
(
ppm)
that
can
be
expected
on
various
avian
and
mammalian
food
items
as
a
result
of
metiram's
use
on
apples.
These
metiram
residues
are
based
on
metiram
being
applied
4
times
every
7
days
at
a
maximum
application
rates
(
4.8
lb
ai/
A).
This
figure
also
shows
the
NOAEC
(
50
ppm)
for
birds
and
the
NOAEL
(
40
ppm)
for
mammals
as
horizontal
lines.
Metiram
levels
at
or
above
these
horizontal
lines
pose
a
potential
risk
of
adverse
reproductive
effects
to
the
birds
and
mammals
feeding
on
these
food
items.
For
birds
and
mammals
this
potential
risk
begins
on
Day
1
when
metiram
range
from
72
ppm
on
fruits,
pods,
seeds,
and
large
insects
to
1,152
ppm
on
short
grass
for
any
and
all
food
items
the
birds
may
ingest
and
continues
throughout
the
apple
production
season
or
for
more
than
58
days.
On
Day
58
the
metiram
would
range
from
54
ppm
as
the
mean
residue
on
fruit,
pods,
seeds,
and
large
insects
to
1,857
ppm
as
the
maximum
residue
on
short
grass.
Although
apples
is
being
used
as
an
example
of
the
wildlife
exposure
that
can
be
expected
from
metiram's
registered
use,
all
the
sites
metiram
is
currently
being
used
on
(
see
Table
II­
1)
would
have
comparable
exposure
levels
with
similar
potential
risks
to
wildlife.

In
this
screening
level
assessment,
metiram's
high
application
rates
combined
with
repeat
applications
are
a
major
reason
why
avian
and
mammalian
LOCs
are
exceeded.
Single
application
rates
range
from
1.2
lb
ai/
A
on
Ornamentals
(
woody
shrubs
&
vines)
to
6.8
lb
ai/
A
on
tobacco.
Labeling
allows
repeat
applications
at
these
maximum
rates
for
all
metiram's
uses.
These
high
applications
rates
with
repeat
applications
increases
the
exposure
of
metiram
to
nontarget
organism.
High
exposure
is
the
reason
for
high
RQs.
One
way
to
grasp
the
impact
of
the
high
exposure
is
to
use
modeling
to
estimate
the
reductions
needed
to
reduce
the
EECs
below
the
LOCs.
Using
modeling
to
calculate
EECs
below
LOCs
is
simply
a
rough
estimate
but
does
provide
some
insight
into
the
extent
metiram's
application
rates
contributes
to
potential
chronic
risk
to
birds
and
mammals.

To
reduce
the
exposure
to
birds
and
mammals
from
metirams's
use
on
apples,
the
maximum
single
application
rate
would
need
to
be
reduced
from
the
current
4.8
lb
ai/
A
to
0.05
lb
ai/
A
(
see
figure
VII­
5)
9.
This
calls
for
a
96­
fold
decrease
in
the
maximum
application
rate
of
metiram
to
apples.
A
combination
of
rate
drops
with
a
decrease
in
the
number
of
applications
per
growing
season,
could
also
be
used
to
lessen
the
EECs.
However,
to
reduce
the
potential
chronic
EEC
exposure
risk,
essentially
only
1
metiram
application
could
be
made
to
apples
at
a
maximum
application
rate
of
0.17
lb
ai/
A
(
see
figure
VII­
6).
This
translates
to
a
28­
fold
application
rate
decrease
and
cuts
out
all
multiples
applications.
Current
labeling
allows
4
metiram
applications
to
apples.
44
Metiram
Chemical
Name:
Apples
Use
non­
granular
Formulation
Inputs
lbs
a.
i./
acre
0.05
Application
Rate
days
35
Half­
life
days
7
Application
Interval
4
Maximum
#
Apps./
Year
Outputs
56
Day
Average
Maximum
Concentration
Concentration
(
PPM)
(
PPM)
25.74
39.46
Short
Grass
11.80
18.08
Tall
Grass
14.48
22.20
Broadleaf
plants/
Insects
1.61
2.47
Seeds
4650
Acute
LC50
(
ppm)
Avian
50
Chronic
NOAEC
(
ppm)

Chronic
RQ
Acute
RQ
(
Max.
res.
mult.
apps.)
0.79
0.01
Short
Grass
0.36
0.00
Tall
Grass
0.44
0.00
Broadleaf
plants/
Insects
0.05
0.00
Seeds
5000
Acute
LD50
(
mg/
kg)
Mammalian
40
Chronic
NOAEL
(
mg/
kg
1000
g
mammal
35
g
mammal
15
g
mammal
Chronic
RQ
Chronic
RQ
Chronic
RQ
(
Max.
res.
)
Acute
RQ
(
Max.
res.
)
Acute
RQ
(
Max.
res.
)
Acute
RQ
mult.
apps.)
(
mult.
apps)
mult.
apps.)
(
mult.
apps)
mult.
apps.)
(
mult.
apps)
0.15
0.00
0.65
0.01
0.94
0.01
Short
Grass
0.07
0.00
0.30
0.00
0.43
0.00
Tall
Grass
0.08
0.00
0.37
0.00
0.53
0.00
Broadleaf
plants/
Insects
0.01
0.00
0.04
0.00
0.06
0.00
Seeds
Figure
VII­
5:
Metiram
Mitigation
Based
on
Reduction
in
Application
Rate
to
Apples.
(
Libelo.
1999)
45
Metiram
Chemical
Name:
Apples
Use
non­
granular
Formulation
Inputs
lbs
a.
i./
acre
0.17
Application
Rate
days
35
Half­
life
days
7
Application
Interval
1
Maximum
#
Apps./
Year
Outputs
56
Day
Average
Maximum
Concentration
Concentration
(
PPM)
(
PPM)
24.90
40.80
Short
Grass
11.41
18.70
Tall
Grass
14.01
22.95
Broadleaf
plants/
Insects
1.56
2.55
Seeds
4650
Acute
LC50
(
ppm)
Avian
50
Chronic
NOAEC
(
ppm)

Chronic
RQ
Acute
RQ
(
Max.
res.
mult.
apps.)
0.82
0.01
Short
Grass
0.37
0.00
Tall
Grass
0.46
0.00
Broadleaf
plants/
Insects
0.05
0.00
Seeds
5000
Acute
LD50
(
mg/
kg)
Mammalian
40
Chronic
NOAEL
(
mg/
kg)

1000
g
mammal
35
g
mammal
15
g
mammal
Chronic
RQ
Chronic
RQ
Chronic
RQ
(
Max.
res.
)
Acute
RQ
(
Max.
res.
)
Acute
RQ
(
Max.
res.
)
Acute
RQ
mult.
apps.)
(
mult.
apps)
mult.
apps.)
(
mult.
apps)
mult.
apps.)
(
mult.
apps)
0.15
0.00
0.67
0.01
0.97
0.01
Short
Grass
0.07
0.00
0.31
0.00
0.44
0.00
Tall
Grass
0.09
0.00
0.38
0.00
0.55
0.00
Broadleaf
plants/
Insects
0.01
0.00
0.04
0.00
0.06
0.00
Seeds
Figure
VII­
6:
Metiram
Mitigation
Based
on
Reduction
in
Application
Rate
and
Number
of
Applications
to
Apples.
(
Libelo.
1999)

Besides
metiram's
use
on
apples,
metiram
is
also
used
on
potatoes,
tobacco,
ornamental
nonflowering
plants
and
ornamental
woody
shrubs
and
vines
(
see
Table
II­
1,
above).
Each
of
these
groupings
represent
a
unique
use
pattern.
The
potential
exposure
cuts,
using
apples
as
an
example,
could
be
extended
to
each
of
these
separate
crop
groupings.
The
conclusions
for
these
other
crop
groupings
would
be
similar
to
the
conclusions
drawn
from
the
example
of
metiram's
use
on
apples.
In
other
words,
all
metiram's
uses
represent
a
potential
extended
chronic
risk
to
birds
and
mammals.
Decreases
in
the
amounts
of
metiram
applied
would
need
to
be
large
to
allay
metiram's
potential
chronic
risk
to
birds
and
mammals.
The
temporal
chronic
risks
to
birds
and
mammals
from
metiram's
current
uses
are
provided
in
Table
VII­
2.
As
with
the
apple
use,
the
potential
chronic
risks
to
birds
and
mammals
begins
with
the
first
application
of
metiram
to
the
crop
or
site
and
continues
throughout
the
crop/
site
cycle.
In
Table
VII­
2,
the
times
of
potential
extended
chronic
risks
to
birds
and
mammals
is
based
on
maximum
application
rates,
maximum
number
of
applications
and
minimum
intervals
between
application.
As
can
be
seen
from
the
range
of
metiram
on
avian
and
mammalian
46
food
items
(
Table
VII­
2),
the
potential
risk
to
birds
and
mammals
extends
across
all
food
items
at
maximum
or
mean
residue
levels.

Table
VII­
2.
Temporal
Chronic
Risks
as
a
Result
of
Metiram
on
Avian/
Mammalian
Food
Items.
1
Crop
Number
of
Days
Metiram
Exceed
Birds'
Chronic
NOAEC
(
50
ppm)
&
Mammals'
Chronic
NOAEL
(
40
ppm)
(
days)
Range
of
Average,
Daily,
Maximum
Metiram
on
Short
Grass
to
Average,
Daily,
Mean
Metiram
residues
on
Fruits,
Pods,
Seed
&
Large
Insects
(
ppm)

Apples
>
58
2,451
to
71
for
58
days
Potatoes
>
65
1,310
to
38
for
65
days
Tobacco2
>
42
3,138
to
92
for
42
days
Ornamentals
(
nonflowering
plants)
2
>
51
667
to
19
for
51
days
Ornamentals
(
woody
shrubs
&
vines)
2
>
51
500
to
15
for
51
days
1.
Based
on
FATE
v
5.0
modeling
with
a
total
foliar
residue
half­
life
of
35
days.
2.
Maximum
number
of
applications/
year
or
crop
cycle
not
specified
on
labeling.
Assumed
3
applications
per
crop
cycle.

It
is
unknown
if
the
scenario
chosen
for
tobacco
is
truly
"
typical".
Selection
could
have
been
based
on
the
label
specification
to
make
two
applications
per
week
from
seedling
stage
to
transplant.
Assuming
70­
75
days
from
planting
seeds
to
transplant,
10­
14
days
from
seed
to
plant
emergence,
and
2
applications
per
week
over
the
period
of
plant
growth
in
the
beds,
the
number
of
applications
could
be
as
high
as
16.
The
assumption
in
this
risk
assessment
assumed
3
applications
during
the
crop
cycle
and
even
at
this
low
number
of
applications
the
use
of
metiram
on
tobacco
exceeds
both
acute
and
chronic
LOCs.
As
shown
in
Figure
VII­
1,
above,
acute
avian
LOCs
are
exceeded.
As
shown
in
Figures
VII­
2
and
VII­
3,
chronic
LOCs
are
greatly
exceeded
for
birds
and
mammals.

The
avian
acute
and
chronic
RQ
values
are
exceeded
for
all
scenarios.
Metiram's
avian
acute
RQ
exceedances
are
due
mainly
to
exposure
estimates.
Acutely,
metiram
is
only
slightly
toxic
(
Bobwhite
quail
LC
50
=
3,712
ppm)
to
birds.
Metiram's
chronic
RQ
exceedances
are
triggered
on
toxicity
(
mallard
duck
NOAEC
=
50
ppm)
and
exposure.
However
there
is
a
degree
of
uncertainty
in
the
exposure
values
used.
In
the
modeling,
EFED
assumed
a
total
foliar
residue
dissipation
half­
life
of
thirty
five
(
35)
days.
EFED
used
this
value
as
a
default
value
because
metiram's
total
foliar
residue
half­
life
is
unknown.
Uncertainty
exists
because
metiram
(
complete
polymeric
chains)
is
nonpersistentt
in
most
of
the
natural
environments.
EFED
expects
metiram
to
decompose
rapidly
(
within
days)
by
hydrolytic
reactions
in
the
main
compartments
of
the
natural
environment.
Whereas
soil/
sediment
associated
residue
appear
to
biodegrade
at
a
slow
rate
producing
metiram
degradates
including
ETU.
EFED
expects
hydrolytic
breakdown
of
metiram
because
most
plant
disease
problems
are
the
result
of
rain
events
and
metiram
(
a
fungicide)
would
be
applied
between
these
rain
events
to
plant
surfaces
for
disease
control.
Data
from
laboratory
studies
show
metiram
may
degrade
rapidly.
However,
there
are
supplemental
data
that
suggests
that
terrestrial
field
dissipation
(
DT
50
)
for
metiram
can
range
from
20
to
143
days.
Finally,
the
need
for
frequent
reapplications
(
at
4
to
7­
day
intervals)
of
metiram
provides
grounds
that
protective
nature
of
metiram
is
limited
pointing
to
added
uncertainty
in
assuming
a
35­
day
half­
life.

EFED
understands
the
35­
day
TFR
half­
life
used
in
calculating
avian
and
mammalian
RQs
represents
an
uncertainty
because
metiram's
TFR
half­
life
range
is
unknown.
DFR
and
TFR
values
for
maneb
and
mancozeb
(
two
EBDCs
chemically
related
to
metiram),
indicates
3
days
may
be
an
approximate
low­
end
foliar
dissipation
half­
life
estimate
for
the
EBDCs
in
general.
EFED
provides
a
brief
47
1
10
100
Risk
Quotient
(
RQ)

Tobacco
Apples
Potatoes
Ornamental
(
nonflowering
plants)
Ornamental
(
woody
shrubs
&
vines)

Sites
Mean­
Fruits/
Pods/
Seeds/
Large
Insects
Max.­
Fruits/
Pods/
Seeds/
Large
Insects
Mean
for
Tall
grass
Mean­
Broadleaf/
ForagePlants/
Sm.
Insects
Mean
for
Short
grass
Max.
for
Tall
grass
Max.­
Broadleaf/
ForagePlants/
Sm.
Insects
Max.
for
Short
grass
Metiram
Chronic
Avian
Risk
Maximum
and
Mean
Exposure
Risk
Figure
VII­
7
(
Based
on
3­
day
foliar
dissipation
half­
life)
RQ
greater
or
equal
to
1
exceeds
chronic
LOCs.
discussion
of
the
foliar
half­
life
values
ranges
for
maneb
and
mancozeb
in
Section
II­
Introduction,
Subsection
iii­
Analysis
Plan.
For
comparative
purposes,
EFED
also
provided
an
estimate
of
metiram's
risk
to
birds
and
mammals
based
on
a
3­
day
TFR
half­
life
value
(
see
Appendix
IV).

Revised
modeling,
using
a
3­
day
foliar
dissipation
half­
life
for
metiram,
yields
the
avian
chronic
RQs
shown
in
Figure
VII­
7.
When
compared
with
the
chronic
RQs
provided
in
Figure
VII­
2
above,
based
on
a
35­
day
foliar
dissipation
half­
life,
potential
chronic
risks
to
birds
still
exist.
This
means
EFED
expects
potential
avian
chronic
risk
from
metiram's
uses
regardless
of
the
foliar
dissipation
half­
life
value
used.
EFED
expects
a
similar
result
for
the
potential
chronic
risks
to
mammals
(
see
Appendix
IV
for
RQs).
A
listing
of
avian
and
mammalian
acute
and
chronic
RQs
for
metiram
based
on
a
3­
day
foliar
dissipation
half­
life
can
be
found
in
Appendix
IV.

EFED
does
not
assess
risk
to
non­
target
insects
using
risk
quotients.
Results
of
acceptable
studies
are
used
for
recommending
appropriate
label
precautions.
Since
metiram
was
determined
to
be
practically
nontoxic
to
honey
bees
(
LD
50
=
437
µ
g/
bee)
no
bee
precautionary
labeling
is
required
on
metiram
product
labeling.
48
EFED
does
not
have
sufficient
data
to
evaluate
metiram's
risk
to
non­
target
terrestrial
plants.
Tier
I
seedling
emergence
[
guideline
122­
1(
a)]
and
vegetative
vigor
[
guideline
122­
1(
b)]
studies
for
metiram
have
not
been
received
and
submission
of
these
studies
for
review
by
the
EFED
are
recommended.

EFED
expects
metiram's
potential
acute
risk
to
birds
and
mammals
to
be
low.
There
are
potential
chronic
risks
to
birds
and
mammals
from
metiram's
use
on
apples,
potatoes,
tobacco
seed
beds
(
although
to
a
lesser
extent
for
tobacco
seed
beds
because
of
limited
acreage)
ornamental
nonflowering
plants,
and
ornamental
woody
shrubs
and
vines.
EFED
expects
high
potential
chronic
avian
and
mammalian
risk
from
metiram's
uses.
The
chronic
RQs
are
exceeded
as
shown
in
Figures
VII­
2
and
3.
Not
only
are
the
RQ
values
exceeded
for
the
shortgrass
scenario,
but
also
for
broadleaf
plants,
insects
and
seeds.
Both
maximum
and
mean
EECs
for
these
food
items
exceed
avian
and
mammalian
chronic
LOCs
for
all
metiram's
uses.
The
number
of
days
the
terrestrial
application
residues
exceed
the
avian
chronic
NOAEC
(
50
ppm)
and
mammalian
chronic
NOAEC
(
40
ppm)
is
also
high
(
from
>
42
days
on
tobacco
to
>
65
days
on
potatoes,
(
see
table
VII­
2).
Thus,
it
appears
metiram's
exposure
is
of
sufficient
magnitude
and
duration
to
pose
a
potential
reproductive
risk
to
both
birds
and
mammals.

i.
Incidents
There
are
no
incidents
for
metiram
listed
in
the
Ecological
Incident
Information
System
(
EIIS)
data
base
dealing
with
adverse
effects
to
terrestrial
nontarget
organisms.

Acutely,
metiram,
appears
to
pose
a
low
risk
to
terrestrial
animals.
The
chronic
LOCs
to
terrestrial
animals
(
birds
and
mammals)
are
exceeded
for
all
metiram
use
patterns.
The
incident
reports
filed
with
EPA
mainly
deal
with
field
mortality
of
wildlife.
EFED
expects
chronic
problems
affecting
wildlife
from
the
use
of
metiram
would
be
largely
unnoticed
in
the
field.
Because
of
this,
EFED
doesn't
expect
incident
reports,
from
chronic
exposure.

ii.
Endocrine
Disruption
EPA
is
required
under
the
Federal
Food,
Drug,
and
Cosmetic
Act
(
FFDCA),
as
amended
by
the
Food
Quality
Protection
Act
(
FQPA),
to
develop
a
screening
program
to
determine
whether
certain
substances
(
including
all
pesticide
active
and
other
ingredients)
"
may
have
an
effect
in
humans
that
is
similar
to
an
effect
produced
by
a
naturally­
occurring
estrogen,
or
other
such
endocrine
effects
as
the
Administrator
may
designate."
Following
the
recommendations
of
its
Endocrine
Disruptor
Screening
and
Testing
Advisory
Committee(
EDSTAC),
EPA
determined
that
there
was
scientific
basis
for
including,
as
part
of
the
program,
the
androgen­
and
thyroid
hormone
systems,
in
addition
to
the
estrogen
hormone
system.
EPA
also
adopted
EDSTAC's
recommendation
that
the
Program
include
evaluations
of
potential
effects
in
wildlife.
For
pesticide
chemicals,
EPA
will
use
FIFRA
and,
to
the
extent
that
effects
in
wildlife
may
help
determine
whether
a
substance
may
have
an
effect
in
humans,
FFDCA
authority
to
require
the
wildlife
evaluations.
As
the
science
develops
and
resources
allow,
screening
of
additional
hormone
systems
may
be
added
to
the
Endocrine
Disruptor
Screening
Program
(
EDSP).

The
avian
reproductive
studies
reviewed
by
EFED
noted
metiram
reproductive
effects
such
as
reduced
egg
production,
reduced
mean
egg
weight,
reduced
fertility
rate,
reduced
number
of
hatched
49
ducklings,
reduced
number
of
14­
day
old
survivors,
and
an
increased
rate
of
early
embryonic
deaths.
Metiram
mammalian
effects,
from
a
reproductive
study,
were
noted
such
as
parental
toxicity
resulting
in
decreased
body
weight
during
gestation
and
lactation
for
females
and
reproductive
toxicity
resulting
in
decreased
mating
performance
(
increased
precoital
time)
in
the
F2
generation
(
two
generations
removed
from
the
original
parent
generation).
In
a
3
month
feeding
study
submitted
to
The
Agency
(
MRID
42590­
01),
there
was
a
significant
decrease
in
total
serum
thyroxine
(
T4)
concentrations
in
both
sexes
of
mice.
These
effects
noted
in
both
birds
and
mammals
may
be
a
result
of
hormonal
disruption
and
might
support
the
concern
that
metiram
may
be
a
potential
endocrine
disrupting
compound.
Based
on
these
effects
in
birds
and
mammals,
EFED
recommends
that
when
appropriate
screening
and/
or
testing
protocols
being
considered
under
the
Agency's
EDSP
have
been
developed,
metiram
be
subjected
to
more
definitive
testing
to
better
characterize
effects
related
to
its
endocrine
disruptor
activity.

iii.
Endangered
Species
Based
on
available
screening
level
information
there
is
a
potential
concern
for
acute
effects
on
listed
birds
species
and
chronic
effects
on
listed
birds
and
mammals
should
exposure
actually
occur.
Even
though
metiram
is
only
slightly
toxic
to
birds,
metiram's
uses
exceed
the
endangered
species
LOC
(
RQ
range
from
0.11
to
1.22)
at
maximum
EEC
levels.
EFED
expects
metiram
poses
a
low
acute
risk
to
nontarget
insects
because
metiram
is
practically
nontoxic
to
honeybees,
(
acute
contact
LD
50
=
437
µ
g/
bee).
Also,
there
is
no
incident
data
reporting
adverse
effects
to
honeybees
from
metiram's
use.
The
Agency
does
not
currently
have
enough
data
to
perform
a
screening
level
assessment
for
metiram's
effects
on
listed
nontarget
terrestrial
plants.
50
APPENDIX
I:
Metiram
Registered
Uses
&
Notes
on
Fate
Studies
and
Modeling
a.
Metiram
Registered
Uses
Table
1.
Registered
uses
for
metiram.

Metiram
Product
Crop
(
disease)
Registered
Maximum
Application
Rate
and
Application
Methods
Polyram
80
DF
(
Dry
Flowable)

(
EPA
Reg.
No.
7969­
105)

(
Company:
BASF)
Apples
(
Apple
scab
and
apple
rust)
Pre­
bloom­
4.8
lb
ai/
acre
(
max.
seasonal
total
is
19.2
lb
ai/
acre)
4
applications;
7­
10
day
application
schedule
through
bloom;
ground
or
aerial
(
see
note
below
this
Table)
or
extended­
2.4
lb
ai/
acre
(
maximum
seasonal
total
16.8
lb
ai/
acre)
7
applications;
7­
10
day
application
schedule;
ground
or
aerial
with
chemigation
permitted
(
minimum
of
5
GPA
water
by
air)
(
Do
not
combine
pre­
bloom
and
extended
schedules)

Potatoes
(
Early
and
late
blight)
1.6
lb
ai/
acre
(
max.
seasonal
total
11.2
lb
ai/
acre)
7
applications;
5­
10
day
application
schedule;
not
to
exceed
2
applications
per
week
Roses
(
Cercospora
leaf
spot
and
black
spot)
0.8­
1.2
lb
ai/
acre
(
no
max
seasonal
rate
established)
Weekly
as
needed;
two
applications
per
week
if
rainy;
knapsack
or
other
suitable
small
area
spray
equipment
FL­
980001
Polyram
80
DF
Leatherleaf
fern
(
Anthracnose)
1.6
lb
ai/
acre
(
single
weekly
application);
0.8
lb
ai/
acre
(
2­
3
applications
per
week)
weekly
applications;
increase
to
2­
3
apps
per
week
if
heavy
disease
pressure
or
periods
of
heavy
rain
ground
application
only;
may
use
chemigation
Potato
Seed
Treater
Fungicide
(
7.04%
dust)

(
EPA
Reg.
No.
34704­
731)

(
Company:
Platte
Chemical
Co.)
Cut
potato
(
fusarium
seed
piece
decay;
seed­
borne
common
scab)
0.105
lb
ai
cwt
(
cut
seed
pieces
to
average
1
3/
4
to
2
ounces
each;
seed
requirements
will
vary
from
12.5
to
36
cwt
per
acre
"
36
inch
rows
with
seed
pieces
spaced
9
inches;
cover
seed
pieces
at
least
4
inches";
0.105
lb
ai
cwt
X
36
cwt
per
acre
is
equivalent
to
3.78
lb
ai/
a)

Royal
Brand
Polyram
3.5
Dust
Fungicide
(
3.5%
dust)

(
EPA
Reg.
No.
5481­
264)

(
Company:
AMVAC)
Tobacco
seedling
plants
(
Blue
mold)
6.776
lb
ai/
acre
(
2­
4
lb
of
product
per
900
sq.
ft.)
2
times
weekly
until
transplant
time;
apply
with
a
dusting
machine
that
will
give
good
coverage
to
plant
51
b.
Notes
on
Fate
Studies
i.
Aqueous
medium
studies
Guidance
for
hydrolysis
and
aqueous
photolysis
require
Parent
EBDC
to
be
applied
at
concentrations
within
the
solubility
range.
It
was
established
that
any
part
of
Parent
EBDC
that
goes
into
solution
will
completely
decompose,
by
hydrolytic
reactions,
into
a
suite
of
multi
species
residue;
the
EBDC
complex.
Reported
levels
of
Parent
EBDCs
that
decompose
in
water
were
near
2
ppm
for
metiram
and
in
the
range
of
6­
22
ppm
for
mancozeb
and
6­
200
ppm
for
maneb.
Additionally,
particle
size
reduction
(
i.
e.
sonication)
is
believed
to
cause
an
increase
in
the
level
susceptibility
of
parent
EBDCs
to
decomposition.
In
most
studies,
levels
used
in
aqueous
media
studies
were
near
this
critical
range
of
susceptibility,
parent
was
determined
by
CS
2
and
suspensions
were
prepared
using
ultrasonic.
Therefore,
calculated
hydrolysis
and/
or
photolysis
half­
lives
are
affected
by:

(
1)
Occurrence
of
hydrolytic
decomposition
during
preparation
of
stock
solution;
indicated
by
the
presence
of
high
concentrations
of
transient
species
and
degradates
at
time
zero.

(
2)
An
increase
of
hydrolytic
reactions
caused
by
reduction
of
particle
size
by
sonication;
and
(
3)
Nonspecificity
of
CS
2
­
determination
for
Parent
EBDC
in
the
presence
of
its
hydrolytic
complex
because
it
was
experimentally
proven
that
CS
2
evolves
from
at
least
one
of
its
constituents;
EBIS.

(
4)
influence
of
the
presence
of
metal
ions
on
solubility
of
Parent
EBDC
(
i.
e
decomposition
to
EBDC
complex).
These
metal
ions
are
introduced
to
the
system
from
chemicals
present
in
buffer
solutions.

In
studies
were
solvents
DMSO
is
used,
no
half­
life
could
be
calculated
for
EBDCs
because
no
Parent
EBDC
would
be
present
at
time
zero.
This
solvent
appears
to
cause
complete
breakage
of
the
EBDC
complex
into
various
transformation
products
dominated
by
ETU.
This
means
that
such
study
can
only
be
used
to
identify
effects
of
pH
or
photon
energy
and
aging
on
the
suite
of
EBDC
complex
present
at
time
zero.

ii.
Soil/
sediment
studies
Problems
associated
with
soil
sediment/
studies
include:

(
1)
Degradation
of
Parent
EBDC,
by
decomposition
in
water,
before
time
zero
and
when
the
application
suspension
is
prepared.
In
most
cases,
resultant
application
suspensions
were
dominated
by
the
EBDC
complex.
Analysis
was
not
always
performed
for
suspensions
just
before
application.

(
2)
Extraction
systems
(
i.
e.,
acetonitrile/
water
or
methanol/
water)
appear
to
affect
the
integrity
of
the
parent.
Therefore,
resultant
suite
of
EBDC
complex
(
in
the
extraction
solution)
was
at
least
partly
artificial
and
can
not
be
used
to
represent
the
suite
that
might
form
in
the
environment.
The
use
of
different
extraction
systems
made
it
difficult
to
compare
results
obtained
from
different
soils.

(
3)
EBDC
complex
has
high
affinity
to
soil
and
no
characterization
was
conducted
for
the
resultant
bound
species.
Therefore,
EBDCs
bound
species
is
suspicious
of
containing
active
species
that
can
52
0
7
14
Time
(
days)
30.0%
40.0%
50.0%
60.0%
70.0%
80.0%
90.0%

Of
Applied
Radioactivity
Loam
(
Germany)
LS
(
Germany)
Collamer
SiL
(
USA)
Cashmere
LS
(
USA)
Approximation
0
100
200
300
400
Time
(
days)
50.0%
60.0%
70.0%
80.0%

Of
Applied
Radioactivity
Loam
(
Germany)
LS
(
Germany)
Collamer
SiL
(
USA)
Cashmere
LS
(
USA)
Approximation
be
precursors
for
the
degradate
of
concern
ETU.
For
example,
In
metiram
aerobic
soil
studies,
bound
species
degraded
after
reaching
a
plateau
in
the
range
of
70­
85%.
Production
of
degradates
and
CO
2
,
increased
after
the
bound
species
reach
the
described
plateau.
Figure
1
shows
bound
radioactivity
distribution
with
time
as
reported
for
soils
in
four
aerobic
soil
studies.

(
4)
Nonspecificity
of
CS
2
­
determination
for
Parent
EBDC
in
the
presence
of
its
hydrolytic
complex
because
it
was
experimentally
proven
that
CS
2
evolves
from
at
least
one
of
its
constituent;
EBIS.

(
5)
Chromatographic
separation
between
Parent
EBDC
and
various
species
in
its
complex
was
not
conclusive
and
solvents
used
appear
to
affect
the
integrity
of
parent
and
some
degradates
and/
or
transient
species.

Figure
1.
Change
of
bound
radioactivity
with
time
in
four
aerobic
soils
treated
with
metiram.
53
Therefore,
the
above
mentioned
difficulties
should
be
taken
in
consideration
in
determining
species
present
in
fate
studies
and
those
expected
to
be
present
in
the
natural
environment.
For
example,
in
metiram,
it
is
expected
that
species
present
in
fate
studies
are
those
shown
in
Figure
2
and
those
in
compartments
of
the
natural
environment
are
those
shown
in
Figure
3.
54
Metiram
a.
i
Main
consituents:
Metiram
"
MT­
P"
+
Minor
constituents:
"
MT­
C"

Air
Water
Run­
off
"
MT­
C"
mainly
ETU
Metiram
a.
i
with
minimal
change
will
eventually
be
deposited
onto
soil/
plant
/
water
bodies
Plant
Metiram
a.
i
can
be
affected
by
hydrolytic
decomposition
increasing
"
MT­
C"
(
process
is
water
availability
and
resident
time
dependent)
Application
"
MT­
P"

Solid
phase
(
Soil
particles)

"
MT­
C"
unkown
sp.
Drift
Liquid
phase
(
Pore
water)

"
MT­
C"
mainly
ETU
Solid
phase
(
Sediment
particles)

"
MT­
C"
unkown
sp.
Liquid
phase
(
Water)

"
MT­
C"
mainly
ETU
Hydrolytic
Decomposition
Soil
"
MT­
P"
Wash­
off
Water
Bodies
"
MT­
P"

Hydrolytic
Decompos
ition
Erosion
(
Adsorped
"
MT­
C"
unknown
species)
Figure
3.
Identity
of
various
species
expected
to
exist
in
various
compartments
of
the
natural
environment.
c.
Notes
on
Modeling
i.
EECs
for
Parent
metiram
EECs
for
Parent
metiram
are
presented
in
the
Figure
4.
Data
for
EECs
were
calculated
using
the
slope
of
the
line
for
1.8
days
(
Table
IV.
2);
the
estimated
hydrolysis
half.
Other
assumptions
included:

­
Application
rate
of
4.8
lbs
a.
i/
Acre
applied
four
times
at
7­
day
intervals;

­
All
applied
material
reached
the
soil
and
mixed
in
the
top
2"
giving
a
zero
time
concentration
of
7.1
ppm.

­
Enough
moisture
is
present
to
complete
hydrolytic
reactions.

Data
indicate
that
soil
EECs
of
metiram
are
expected
to
be
below
1
ppm
(.
14%
of
the
applied)
one
day
before
the
second
application.
The
same
is
repeated
after
each
of
the
four
application
causing
an
accumulation
of
nearly
0.6
ppm
(.
9%
of
the
applied)
just
before
the
last
application.
Amounts
being
left
following
all
four
applications
degrades
to
negligible
amounts
within
two
weeks
from
the
last
application.
This
data
are
believed
to
represent
concentrations
in
soil
environments
where
most
of
the
pesticide
is
applied.
However,
higher
EECs
are
expected
in
dry
conditions
and
in
soils
with
very
low
water
holding
capacity.
55
0
7
14
21
28
35
42
Time
(
days);
Four
Applications
at
days:
0,
7,
14
and
21
0
1
2
3
4
5
6
7
8
EECs
of
Metiram
Parent
(
ppm)

Parent
EECs
based
on
Hydrolysis
half­
life=
1.8
days
Considering
that
only
a
small
fraction
of
the
applied
material
would
reach
water
bodies
by
drift,
metiram
complex,
not
parent,
is
the
species
expected
to
be
found
in
water
bodies
affected
by
drift.

Figure
4.
EECs
for
parent
metiram
following
four
applications
of
4.8
lbs
a.
i/
acre
applied
four
times
at
7­
day
intervals.

ii.
Background
Information
on
the
PRZM
and
EXAMS
models
&
the
Index
Reservoir
Scenario
The
linked
PRZM
and
EXAMS
models
are
used
in
this
case
as
a
second
tier
screen
designed
to
estimate
the
pesticide
concentrations
found
in
water
for
use
in
drinking
water
assessments.
They
provide
high­
end
values
on
the
concentrations
that
might
be
found
in
a
small
drinking
water
reservoir
due
to
the
use
of
pesticide.
The
Drinking
Water
Index
Reservoir
scenario
includes
a
427
acres
field
immediately
adjacent
to
a
13
acres
reservoir,
9
feet
deep,
with
continuous
site­
specific
flow.
This
amount
can
be
reduced
due
to
degradation
in
field
and
the
effect
of
binding
to
soil.
Spray
drift
is
equal
to
6.4%
of
the
applied
concentration
from
the
ground
spray
application
and
16%
for
aerial
applications.

The
PRZM/
EXAMS
modeling
system
with
the
Index
Reservoir
scenario
also
makes
adjustments
for
the
percent
cropped
area.
While
it
is
assumed
that
the
entire
watershed
would
not
be
treated,
the
use
of
a
PCA
is
still
a
screen
because
it
represents
the
highest
percentage
of
crop
cover
of
any
large
watershed
in
the
US,
and
it
assumes
that
the
entire
crop
is
being
treated.
Various
other
conservative
assumptions
of
this
scenario
include
the
use
of
a
small
drinking
water
reservoir
surrounded
by
a
runoff­
prone
watershed,
the
use
of
the
maximum
use
rate
and
no
buffer
zone.

iii.
Background
Information
on
SCIGROW
SCI­
GROW
is
a
screening
model
which
the
Office
of
Pesticide
Programs
(
OPP)
in
EPA
frequently
uses
to
estimate
pesticide
concentrations
in
vulnerable
ground
water.
The
model
provides
an
exposure
value
which
is
used
to
determine
the
potential
risk
to
the
environment
and
to
human
health
from
drinking
water
contaminated
with
the
pesticide.
The
SCI­
GROW
estimate
is
based
on
environmental
fate
properties
of
the
pesticide
(
aerobic
soil
degradation
half­
life
and
linear
adsorption
coefficient
normalized
for
soil
organic
carbon
content),
the
maximum
application
rate,
and
existing
data
from
56
small­
scale
prospective
ground­
water
monitoring
studies
at
sites
with
sandy
soils
and
shallow
ground
water.

Pesticide
concentrations
estimated
by
SCI­
GROW
represent
conservative
or
high­
end
exposure
values
because
the
model
is
based
on
ground­
water
monitoring
studies
which
were
conducted
by
applying
pesticides
at
maximum
allowed
rates
and
frequency
to
vulnerable
sites
(
i.
e.,
shallow
aquifers,
sandy,
permeable
soils,
and
substantial
rainfall
and/
or
irrigation
to
maximize
leaching).
In
most
cases,
a
large
majority
of
the
use
areas
will
have
ground
water
that
is
less
vulnerable
to
contamination
than
the
areas
used
to
derive
the
SCI­
GROW
estimate.
SCIGROW
provides
a
groundwater
screening
exposure
value
to
be
used
in
determining
the
potential
risk
to
human
health
from
drinking
water
contaminated
with
the
pesticide.
SCIGROW
estimates
likely
groundwater
concentrations
if
the
pesticide
is
used
at
the
maximum
allowable
rate
in
areas
where
groundwater
is
exceptionally
vulnerable
to
contamination.
In
most
cases,
a
large
majority
of
the
use
area
will
have
groundwater
that
is
less
vulnerable
to
contamination
than
the
areas
used
to
derive
the
SCIGROW
estimate.
57
APPENDIX
II:
Terrestrial
Modeling
a.
Hoerger­
Kenaga
Estimates
EFED
uses
Hoerger
and
Kenaga
estimates
(
1972)
as
changed
by
Fletcher
and
other
researchers
(
1994)
to
estimate
the
residues
on
plants
and
insects.
Hoerger­
Kenaga
categories
represent
preferred
foods
of
various
terrestrial
vertebrates.
Upland
game
birds
prefer
fruits
and
bud
and
shoot
tips
of
leafy
crops.
Hares
and
hoofed
mammals
consume
leaves
and
stems
of
leafy
crops.
Rodents
consume
seeds,
seedpods
and
grasses;
and
various
birds,
mammals,
reptiles
and
terrestrial­
phase
amphibians
consume
insects.
Terrestrial
vertebrates
also
may
contact
pesticides
applied
to
soil
by
swallowing
pesticide
granules
or
pesticide­
laden
soil
when
foraging.
Rich
in
minerals,
soil
comprises
5
to
30%
of
dietary
intake
by
many
wildlife
species
(
Beyer
and
Conner).

Hoerger
and
Kenaga
based
pesticide
environmental
concentration
estimates
on
residue
data
correlated
from
more
than
20
pesticides
on
more
than
60
crops.
These
estimates
are
representative
of
many
geographic
regions
(
7
states)
and
a
wide
array
of
cultural
practices.
Hoerger­
Kenaga
estimates
also
considered
differences
in
vegetative
yield,
surface
to
mass
ratio
and
interception
causes.
In
1994,
Fletcher,
Nellessen
and
Pfleeger
reexamined
the
Hoerger­
Kenaga
simple
linear
model
(
y=
B1x,
where
x=
application
rate
and
y=
pesticide
residue
in
ppm)
to
decide
whether
the
terrestrial
EEC's
were
accurate.
They
compiled
a
data
set
of
pesticide
day­
0
and
residue­
decay
data
involving
121
pesticides
(
85
insecticides,
27
herbicides,
and
9
fungicides
from
17
different
chemical
classes)
on
118
species
of
plants.
After
analyzes,
their
conclusions
were
that
Hoerger­
Kenaga
estimates
needed
only
minor
changes
to
increase
the
predictive
values.
They
recommended
an
increase
for
forage
and
fruit
categories
from
58
to
135
ppm
and
from
7
to
15
ppm,
respectively.
Otherwise,
the
Hoerger­
Kenaga
estimates
were
accurate
in
predicting
the
maximum
residue
values
after
a
1
lb
ai/
acre
application.
Mean
values
represent
the
arithmetic
mean
of
values
from
samples
collected
the
day
of
pesticide
treatment.
The
values
in
the
table
below
are
the
predicted
0­
day
maximum
and
mean
residues
of
a
pesticide
that
may
occur
on
selected
avian,
mammalian,
reptilian
or
terrestrial­
phase
amphibian
food
items.
These
predicted
residues
occur
immediately
following
a
direct
single
application
at
a
1
lb
ai/
acre
application
rate.
For
pesticides
applied
as
a
nongranular
product
(
for
example,
liquid
or
dust),
EFED
compared
the
estimated
environmental
concentrations
(
EECs)
on
food
items
following
product
application
to
LC
50
values
to
assess
risk.
EFED
based
the
estimated
environmental
concentrations
of
metiram
on
food
items
on
Kenaga
maximum
and
mean
predicted
values.

Table
1:
Estimated
Environmental
Concentrations
on
Avian
and
Mammalian
Food
Items
(
ppm)
Following
a
Single
Application
at
1
lb
ai/
A)

Food
Items
EEC
(
ppm)
Predicted
Maximum
Residue1
EEC
(
ppm)
Predicted
Mean
Residue1
Short
grass
240
85
Tall
grass
110
36
Broadleaf
plants
and
small
insects
135
45
Fruits,
pods,
seeds,
and
large
insects
15
7
1
Predicted
maximum
and
mean
residues
are
for
a
1
lb
ai/
a
application
rate
and
are
based
on
Hoerger
and
Kenaga
(
1972)
as
modified
by
Fletcher
and
others.
(
1994).
58
b.
Fate
v.
5.0
Model
Terrestrial
Exposure
Values
The
model
assumes
a
first
order
decay
to
fix
the
concentration
at
each
day
after
first
application
based
on
the
concentration
resulting
from
the
first
and
more
applications.
The
model
calculates
decay
from
the
first
order
rate
equation:

CT
=
Cie­
kT
or
in
integrated
form:
ln
(
CT/
Ci)
=
­
kT
Where:

CT
=
concentration
at
time
T
on
day
zero
Ci
=
concentration
in
parts
per
million
(
ppm)
present
initially
(
on
day
zero)
on
the
surfaces.
The
model
calculates
Ci
based
on
Kenaga
and
Fletcher
by
multiplying
the
application
rate,
in
pounds
active
ingredient
per
acre.
The
model
multiplies
the
application
rate
by
240
(
mean
of
85)
for
short
grass,
110
(
mean
of
36)
for
tall
grass,
and
135
(
mean
of
45)
for
broad­
leaf
plants
and
insects
and
15
(
mean
of
7)
for
seeds.
The
model
converts
extra
applications
from
pounds
active
ingredient
per
acre
to
PPM
on
the
plant
surface
and
the
addition
mass
added
to
the
mass
of
the
chemical
still
present
on
the
surfaces
on
the
day
of
application.

k=
degradation
rate
constant
determined
from
studies
of
hydrolysis,
photolysis,
microbial
degradation,
etc.
Since
degradation
rate
is
reported
by
half­
life,
the
model
calculates
the
rate
constant
from
the
half­
life
(
k
=
ln
2/
T1/
2).
Choosing
the
degradation
rate
and
half­
life
to
use
in
terrestrial
exposure
calculations
is
open
for
debate
and
should
be
done
by
a
qualified
scientist.

T=
time,
in
days,
since
the
start
of
the
simulation.
The
first
application
is
on
day
0.
The
simulation
runs
for
the
number
of
days
entered
by
the
modeler.

The
program
calculates
concentration
on
each
surface
on
a
daily
interval
for
the
number
of
days
entered
by
the
modeler.
The
modeler
chooses
the
days
based
on
the
guidance
provided
in
Urban,
2000.
The
modeler
uses
the
following
formula
with
acute
exposure
addition
of
30
days
or
the
chronic
exposure
addition
of
60
days:

maximum
number
of
applications
crop
cycle
or
season
minimum
interval
between
applications
(
days)
+
30
or
60
days
*

The
model
calculates
maximum
and
mean
EECs
based
on
the
maximum
and
mean
Kenaga­
Fletcher
values
listed
in
Table
1
above.
These
EECs
are
the
maximum
amounts
collecting
on
each
day
during
the
interval
chosen.
The
model
calculates
these
EECs
for
the
different
food
item
groupings.
59
c.
Fate
v.
5.0
Model
Sample
Output
for
Metiram
RUN
No.
1
FOR
Metiram
ON
Apples
***
INPUT
VALUES
***
­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­
RATE(#/
AC)
APPLICATIONS
HALF­
LIFE
AVIAN(
ppm)
MAMMALIAN(
mg/
kg)
ONE(
MAX)
NO.­
INTERVAL
(
DAYS)
LC50
NOAEC
LD50
NOAEL
­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­
4.800(
15.783)
4
7
35.0
*******
50.000
1.000
40.000
MAXIMUM
&
58
DAY
AVERAGE
KENAGA/
FLETCHER
RESIDUES:
95th%
(
mean)
in
ppm
­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­­
SHORT
BROADLEAF
TALL
SEED
GRASS
&
INSECTS
GRASS
FRUIT
____________________
________________
________________
________________
MAX3787.96(
1341.57)
2130.73(
710.24)
1736.15(
568.19)
236.75(
110.48)

Below
are
lists
of
daily
Kenaga­
Flether
pesticide
residue
values
for
four
avian/
mammalian
food
groupings
for
Metiram
use
on
Apples
Values
are
in
parts
per
million
(
ppm).

SHORT
BROADLEAF
TALL
SEED
GRASS
&
INSECTS
GRASS
FRUIT
DAILY
DAILY
DAILY
DAILY
VALUES
VALUES
VALUES
VALUES
DAY
95%
MEAN
95%
MEAN
95%
MEAN
95%
MEAN
___
_______________
_______________
_______________
_______________

1
1152.00
408.00
648.00
216.00
528.00
172.80
72.00
33.60
2
1129.41
400.00
635.29
211.76
517.65
169.41
70.59
32.94
3
1107.26
392.16
622.84
207.61
507.50
166.09
69.20
32.30
4
1085.55
384.47
610.62
203.54
497.54
162.83
67.85
31.66
5
1064.26
376.93
598.65
199.55
487.79
159.64
66.52
31.04
6
1043.39
369.54
586.91
195.64
478.22
156.51
65.21
30.43
7
1022.93
362.29
575.40
191.80
468.84
153.44
63.93
29.84
8
2154.87
763.18
1212.12
404.04
987.65
323.23
134.68
62.85
9
2112.62
748.22
1188.35
396.12
968.28
316.89
132.04
61.62
10
2071.19
733.55
1165.05
388.35
949.30
310.68
129.45
60.41
11
2030.58
719.16
1142.20
380.73
930.68
304.59
126.91
59.23
12
1990.76
705.06
1119.80
373.27
912.43
298.61
124.42
58.06
13
1951.72
691.23
1097.84
365.95
894.54
292.76
121.98
56.93
14
1913.45
677.68
1076.31
358.77
877.00
287.02
119.59
55.81
15
3027.93
1072.39
1703.21
567.74
1387.80
454.19
189.25
88.31
16
2968.55
1051.36
1669.81
556.60
1360.59
445.28
185.53
86.58
17
2910.34
1030.75
1637.07
545.69
1333.91
436.55
181.90
84.88
18
2853.27
1010.53
1604.96
534.99
1307.75
427.99
178.33
83.22
19
2797.32
990.72
1573.49
524.50
1282.10
419.60
174.83
81.59
20
2742.47
971.29
1542.64
514.21
1256.96
411.37
171.40
79.99
21
2688.69
952.24
1512.39
504.13
1232.31
403.30
168.04
78.42
22
3787.96
1341.57
2130.73
710.24
1736.15
568.19
236.75
110.48
23
3713.68
1315.26
2088.95
696.32
1702.11
557.05
232.11
108.32
24
3640.86
1289.47
2047.98
682.66
1668.73
546.13
227.55
106.19
25
3569.47
1264.19
2007.82
669.27
1636.01
535.42
223.09
104.11
26
3499.47
1239.40
1968.45
656.15
1603.92
524.92
218.72
102.07
27
3430.85
1215.09
1929.85
643.28
1572.47
514.63
214.43
100.07
28
3363.57
1191.26
1892.01
630.67
1541.64
504.54
210.22
98.10
29
3297.61
1167.90
1854.91
618.30
1511.41
494.64
206.10
96.18
30
3232.95
1145.00
1818.53
606.18
1481.77
484.94
202.06
94.29
31
3169.55
1122.55
1782.87
594.29
1452.71
475.43
198.10
92.45
32
3107.40
1100.54
1747.91
582.64
1424.23
466.11
194.21
90.63
33
3046.47
1078.96
1713.64
571.21
1396.30
456.97
190.40
88.86
60
34
2986.73
1057.80
1680.03
560.01
1368.92
448.01
186.67
87.11
35
2928.16
1037.06
1647.09
549.03
1342.07
439.22
183.01
85.40
36
2870.74
1016.72
1614.79
538.26
1315.76
430.61
179.42
83.73
37
2814.45
996.78
1583.13
527.71
1289.95
422.17
175.90
82.09
38
2759.26
977.24
1552.08
517.36
1264.66
413.89
172.45
80.48
39
2705.15
958.07
1521.65
507.22
1239.86
405.77
169.07
78.90
40
2652.10
939.29
1491.81
497.27
1215.55
397.82
165.76
77.35
41
2600.10
920.87
1462.55
487.52
1191.71
390.01
162.51
75.84
42
2549.11
902.81
1433.87
477.96
1168.34
382.37
159.32
74.35
43
2499.12
885.11
1405.76
468.59
1145.43
374.87
156.20
72.89
44
2450.12
867.75
1378.19
459.40
1122.97
367.52
153.13
71.46
45
2402.07
850.73
1351.17
450.39
1100.95
360.31
150.13
70.06
46
2354.97
834.05
1324.67
441.56
1079.36
353.25
147.19
68.69
47
2308.79
817.70
1298.69
432.90
1058.20
346.32
144.30
67.34
48
2263.52
801.66
1273.23
424.41
1037.44
339.53
141.47
66.02
49
2219.13
785.94
1248.26
416.09
1017.10
332.87
138.70
64.72
50
2175.61
770.53
1223.78
407.93
997.16
326.34
135.98
63.46
51
2132.95
755.42
1199.79
399.93
977.60
319.94
133.31
62.21
52
2091.13
740.61
1176.26
392.09
958.43
313.67
130.70
60.99
53
2050.12
726.08
1153.19
384.40
939.64
307.52
128.13
59.80
54
2009.92
711.85
1130.58
376.86
921.21
301.49
125.62
58.62
55
1970.50
697.89
1108.41
369.47
903.15
295.58
123.16
57.47
56
1931.86
684.20
1086.67
362.22
885.44
289.78
120.74
56.35
57
1893.98
670.79
1065.36
355.12
868.08
284.10
118.37
55.24
58
1856.84
657.63
1044.47
348.16
851.05
278.53
116.05
54.16
___
_______________
_______________
_______________
_______________

SHORT
BROADLEAF
TALL
SEED
GRASS
&
INSECTS
GRASS
FRUIT
AVERAGE
AVERAGE
AVERAGE
AVERAGE
VALUES
VALUES
VALUES
VALUES
DAY
95%
MEAN
95%
MEAN
95%
MEAN
95%
MEAN
___
_______________
_______________
_______________
_______________

2450.95
868.04
1378.66
459.55
1123.35
367.64
153.18
71.49
61
APPENDIX
III:
Ecological
Hazards
Assessment
a.
Scope
The
toxicity
testing
required
does
not
test
all
species
of
birds,
fish,
mammals,
invertebrates,
and
plants.
EFED
uses
only
two
surrogate
species
for
birds
(
Bobwhite
quail
and
mallard
ducks)
to
represent
all
bird
species
(
over
900
in
the
US).
EFED
uses
three
species
of
freshwater
fish
(
rainbow
trout,
bluegill
sunfish
and
fathead
minnow)
to
act
as
surrogate
test
species
for
all
freshwater
fish
species
(
over
900
in
the
US).
One
estuarine
fish
species
(
sheepshead
minnow)
serves
as
surrogate
for
all
estuarine
and
marine
fish
(
over
300
in
the
US).
The
surrogate
species
for
terrestrial
invertebrates
is
the
honeybee.
For
freshwater
invertebrates
the
surrogate
species
is
usually
the
waterflea
(
Daphnia
magna).
For
estuarine
and
marine
invertebrates
the
surrogate
species
are
mysid
shrimp
and
eastern
oyster.
EFED
uses
these
four
species
to
represent
all
invertbrates
species
(
over
10,000
in
the
US).
For
plants,
there
are
ten
surrogate
species
used
for
all
terrestrial
plants
and
five
surrogate
species
used
for
all
aquatic
plants.
There
are
over
20,000
plant
species
in
the
US
which
includes
flowering
plants,
conifers,
ferns,
mosses,
liverworts,
hornworts
and
lichens.
There
are
over
27,000
species
of
algae
worldwide.

The
surrogate
species
testing
scheme
used
in
this
assessment
assumes
that
a
chemical's
method
of
action
and
toxicity
found
for
avian
species
is
similar
to
that
in
all
reptiles
(
over
300
species
in
the
US).
The
same
assumption
applies
to
amphibians
(
over
200
species
in
the
US)
and
fish.
EFED
assumes
the
tadpole
stage
of
amphibians
has
the
same
sensitivity
as
a
fish.
Therefore,
EFED
considers
the
results
from
toxicity
tests
on
surrogate
species
are
applicable
to
other
member
species
within
their
class
and
extrapolates
this
toxicity
to
reptiles
and
amphibians.
EFED
got
the
US
species
numbers
noted
in
this
section
from:
http://
www.
natureserve.
org/
summary
(
NatureServe:
An
online
encyclopedia
of
life
[
web
application].
2000)
and
the
worldwide
species
number
from
Ecological
Planning
and
Toxicology,
Inc.
1996.

b.
Toxicity
to
Terrestrial
Animals
i.
Birds,
Acute,
Subacute
and
Chronic
EFED
requires
an
acute
oral
toxicity
study
using
the
technical
grade
of
the
active
ingredient
(
TGAI)
to
find
out
the
toxicity
of
metiram
to
birds.
The
avian
oral
LD
50
test
is
an
acute,
single­
dose
laboratory
study
designed
to
estimate
the
quantity
of
toxicant
needed
to
cause
50%
mortality
in
a
test
population
of
birds.
The
preferred
test
species
is
either
the
mallard
duck,
a
waterfowl,
or
Bobwhite
quail,
an
upland
game
bird.
Adult
birds
receive
the
TGAI
by
oral
intubation
with
results
expressed
as
LD
50
in
milligrams
(
mg)
active
ingredient
(
a.
i.)
per
kilogram
(
kg).
Toxicity
category
descriptions
are
the
following
(
Brooks,
1973):

If
the
LD50
is
less
than
10
mg
a.
i./
kg,
then
the
test
substance
is
very
highly
toxic.
If
the
LD50
is
10­
to­
50
mg
a.
i./
kg,
then
the
test
substance
is
highly
toxic.
If
the
LD50
is
51­
to­
500
mg
a.
i./
kg,
then
the
test
substance
is
moderately
toxic.
If
the
LD50
is
501­
to­
2,000
mg
a.
i./
kg,
then
the
test
substance
is
slightly
toxic.
62
If
the
LD50
is
greater
than
2,000
mg
a.
i./
kg,
then
the
test
substance
is
practically
nontoxic.

Based
on
the
study
listed
in
Table
1,
metiram,
taken
orally,
is
practically
nontoxic
to
birds.
MRID
No.
40656901
fulfills
guideline
71­
1(
a).

Table
1:
Avian
(
also
Reptilian
and
Terrestrial­
Phase
Amphibian)
Acute
Oral
Toxicity
­
Metiram
Technical
Species
%
ai
LD
50
(
mg
ai/
kg)
Toxicity
Category
MRID
No.
Author/
year
Classification1
Northern
bobwhite
(
Colinus
virginianus)
95
>
2150
practically
nontoxic
40656901/
Fletcher,
D./
1988
Core
1
Core
(
study
satisfies
guideline).
Supplemental
(
study
is
scientifically
sound,
but
does
not
satisfy
guideline)

EFED
requires
two
dietary
studies
using
the
TGAI
to
find
out
the
toxicity
of
metiram
to
birds.
These
avian
dietary
LC
50
tests,
using
the
Mallard
Duck
and
Bobwhite
Quail,
are
acute,
eight­
day
dietary
laboratory
studies
designed
to
estimate
the
quantities
of
toxicant
needed
to
cause
50%
mortality
in
the
two
respective
test
populations
of
birds.
Juvenile
birds
received
the
TGAI
mixed
in
their
diet
for
five
days
followed
by
three
days
of
"
clean"
diet.
The
results,
expressed
as
LC
50
,
is
in
parts
per
million
(
ppm)
active
ingredient
(
a.
i.)
of
the
diet.
Toxicity
category
descriptions
are
the
following
(
Brooks,
1973):

If
the
LC50
is
less
than
50
ppm
a.
i.,
then
the
test
substance
is
very
highly
toxic.
If
the
LC50
is
50­
to­
500
ppm
a.
i.,
then
the
test
substance
is
highly
toxic.
If
the
LC50
is
501­
to­
1,000
ppm
a.
i.,
then
the
test
substance
is
moderately
toxic.
If
the
LC50
is
1001­
to­
5,000
ppm
a.
i.,
then
the
test
substance
is
slightly
toxic.
If
the
LC50
is
greater
than
5,000
ppm
a.
i.,
then
the
test
substance
is
practically
nontoxic.

Taken
orally,
metiram
mixed
in
the
diet,
is
slightly
toxic
to
birds
(
see
Table
2).
MRID
Nos.
00108004
and
00108005
have
fulfilled
guidelines
71­
2(
a
and
b).
EFED
will
use
the
toxicity
value
(
LC
50
)
appearing
in
the
shaded
area
of
the
table
to
calculate
the
acute
avian
risk
quotients
(
RQs).

Table
2:
Avian
(
also
Reptilian
and
Terrestrial­
Phase
Amphibian)
Subacute
Dietary
Toxicity
­
Metiram
Technical
Species
%
ai
LC50(
ppm
ai)
Toxicity
Category
MRID/
Accession
(
AC)
No.
Author/
Year
Study
Classification
Mallard
Duck
(
Anas
platyrhynchos)
80
>
3712
slightly
toxic
00108005//
Fink,
R./
1974
Core
Northern
Bobwhite
Quail
(
Colinus
virginianus)
80
37121
slope
not
determined
slightly
toxic
00108004/
Fink,
R./
1974
Core
1
Only
highest
dose
showed
percent
mortality
(
50%),
therefore
the
LC50
determined
is
not
statistically
sound.

EFED
requires
avian
reproduction
studies
using
the
Bobwhite
Quail
and
Mallard
Duck
to
estimate
the
quantity
of
toxicant
needed
to
adversely
affect
reproduction
in
a
test
population
of
birds.
Breeding
birds
receive
the
TGAI
mixed
in
their
diet
throughout
their
breeding
cycle.
Test
birds
are
63
approaching
their
first
breeding
season
and
are
18­
to­
23
weeks
old.
The
onset
of
the
exposure
period
is
at
least
10
weeks
before
egg
laying.
The
exposure
period
during
egg
laying
is
10
weeks
with
a
withdrawal
period
of
three
added
weeks
if
the
observer
notes
a
decrease
in
egg
laying.
The
No
Observed
Adverse
Effect
Concentration
(
NOAEC)
and
various
observable
effect
levels,
expressed
as
the
Lowest
Observable
Adverse
Effect
Concentration
(
LOAEC)
are
the
results
determined
from
these
studies.
These
results
are
in
parts
per
million
of
active
ingredient
(
ppm
a.
i.)
in
the
diet.

EFED
requires
avian
reproduction
studies
for
metiram
because
birds
may
be
subject
to
repeated
or
continuous
exposure
to
the
pesticide,
especially
preceding
or
during
the
breeding
season.
In
addition,
the
pesticide
is
stable
in
the
environment
and
potentially
toxic
amounts
may
persist
in
animal
feed.
Finally,
information
gathered
from
mammalian
reproduction
studies
shows
metiram's
use
may
adversely
affect
reproduction
in
terrestrial
vertebrates.
The
preferred
test
species
are
mallard
duck
and
bobwhite
quail.
Table
3
shows
the
results
of
these
tests.
EFED
will
use
the
toxicity
value
(
NOAEC)
appearing
in
the
shaded
area
of
the
table
to
calculate
the
chronic
avian
risk
quotients
(
RQs).

MRID
No.
42539102,
in
Table
3,
showed
chronic
toxic
effects
in
mallard
ducks.
These
effects
included:
reduced
egg
production;
reduced
mean
egg
weight;
reduced
fertility
rate;
reduced
number
of
hatched
ducklings;
reduced
number
of
14­
day
old
survivors;
and
an
increased
rate
of
early
embryonic
deaths.
The
reproduction
NOAEC
and
LOAEC
were
50
and
300
ppm,
respectively.
MRID
No.
42539102
fulfills
guideline
71­
4(
b).

EFED
classified
a
bobwhite
quail
reproduction
study
(
MRID
No.
41082001)
supplemental
because
of
high
mortality
and
a
high
number
of
cracked
eggs
(
that
is,
greater
than
18%)
in
the
control
group.
This
study
showed
an
NOAEC
greater
than
500
ppm
(
the
highest
dose
tested).
In
a
3­
26­
96
memorandum
from
A.
Maciorowski
(
EFED)
to
W.
Waldrop
(
SRRD),
EFED
made
the
following
decision
about
the
need
for
a
core
bobwhite
quail
reproductive
study:

"
Core
mallard
reproduction
studies
exist
for
metiram,
mancozeb,
and
maneb...
Collectively,
these
studies
indicate
that
the
mallard
is
more
sensitive
than
the
bobwhite
quail
to
the
EBDCs.
Therefore,
additional
bobwhite
quail
reproduction
testing
with
metiram
is
not
required..."

Mallard
duck
reproduction
NOAECs
for
mancozeb
and
maneb
are
10
ppm
and
20
ppm,
respectively.
Bobwhite
quail
NOAECs
are
125
to
300
ppm
for
mancozeb
and
>
500
ppm
for
maneb.
64
Table
3:
Avian
(
Reptilian
&
Terrestrial­
Phase
Amphibian)
Reproduction
Chronic
Toxicity
­
Metiram
Technical
Species/
Study
Duration
%
ai
NOAEC/
LOAEC
(
ppm
ai)
LOAEC
Endpoints
MRID
No.
Author/
year
Classification1
Northern
bobwhite
(
Colinus
virginianus)
/
22
weeks
93
>
500/
not
determined
Not
applicable
41082001/
Fletcher,
D.&
C.
Pedesen/
1989
Supplemental
Mallard
Duck
(
Anas
platyrhynchos)
/
22
weeks
97
50/
300
Reduced
egg
production;
reduced
mean
egg
weight;
reduced
fertility
rate;
reduced
number
of
hatched
ducklings;
reduced
number
of
14­
day
old
survivors;
and
an
increased
rate
of
early
embryonic
deaths.
42539102/
Munk,
R./
1992
Core
1
Core
(
study
satisfies
guideline).
Supplemental
(
study
is
scientifically
sound,
but
does
not
satisfy
guideline)

ii.
Mammals,
Acute
and
Chronic
EFED
needs
for
wild
mammal
testing
depends
on
the
results
of
lower
tier
laboratory
mammalian
studies,
intended
use
pattern
and
environmental
fate
characteristics.
Usually,
rat
or
mouse
toxicity
values
received
from
the
Agency's
Health
Effects
Division
(
HED)
substitute
for
wild
mammal
testing.
EFED
took
the
toxicity
values
used
in
this
assessment
(
see
tables
that
follow)
from
HED.
This
assessment
used
HED's
Tox
One­
Liner,
the
metiram
toxicological
chapter
dated
1/
6/
00
(
D249581),
the
final
Hazard
Identification
Assessment
Review
Committee
(
HIARC)
report
on
metiram
dated
November
15,
1999
(
HED
document
number
013838),
and
a
draft
revised
endpoint
selection
table
from
a
9/
18/
01
HIARC
meeting.
This
assessment
will
use
the
toxicity
values
(
LD
50
and
NOAEL)
appearing
in
the
shaded
areas
of
the
tables
to
calculate
the
acute
and
chronic
mammalian
risk
quotients
(
RQ's)
in
later
sections.
Toxicity
category
descriptions
are
the
following
(
Brooks,
1973):

If
the
LD50
is
less
than
10
mg
a.
i./
kg,
then
the
test
substance
is
very
highly
toxic.
If
the
LD50
is
10­
to­
50
mg
a.
i./
kg,
then
the
test
substance
is
highly
toxic.
If
the
LD50
is
51­
to­
500
mg
a.
i./
kg,
then
the
test
substance
is
moderately
toxic.
If
the
LD50
is
501­
to­
2,000
mg
a.
i./
kg,
then
the
test
substance
is
slightly
toxic.
If
the
LD50
is
greater
than
2,000
mg
a.
i./
kg,
then
the
test
substance
is
practically
nontoxic.

The
results
show
that
metiram
is
practically
nontoxic
to
mammals
from
acute
oral
exposure
(
Table
4).

Table
4:
Mammalian
Acute
Oral
Toxicity
­
Metiram
Species
%
ai
LD50
(
mg
ai/
kg)
Toxicity
Category)
Affected
Endpoints
MRID
or
Accession
(
AC)
No.

Technical
laboratory
rat
(
Rattus
norvegicus)
technical
>
10,000
(
male)
8,000
(
female)
practically
nontoxic
mortality
009768
laboratory
rat
(
Rattus
norvegicus)
80
>
5,000
(
male
&
female)
practically
nontoxic
mortality
009926
65
1.
Acute
Dermal
and
Inhalation
Toxicity
Testing
As
well
as
acute
oral
routes
of
exposure,
terrestrial
vertebrates
entering
a
treatment
area
may
also
receive
dermal
and
inhalation
exposure
to
metiram.
Toxicity
category
descriptions
associated
with
dermal
routes
of
exposure
include
(
US
EPA
CFR.
Part
156):

If
the
LD50
is
less
than
or
equal
to
200
mg/
kg,
then
the
test
substance
is
in
Toxicity
Category
I.
If
the
LD50
is
greater
than
200
through
2,000
mg/
kg,
then
the
test
substance
is
in
Toxicity
Category
II.
If
the
LD50
is
greater
than
2,000
through
5,000
mg/
kg,
then
the
test
substance
is
in
Toxicity
Category
III
If
the
LD50
is
greater
than
5,000
mg/
kg,
then
the
test
substance
is
in
Toxicity
Category
IV.

The
results
show
that
metiram
is
a
Category
III
toxicant
to
mammals
from
dermal
exposure
(
Table
5).

Table
5:
Mammalian
Acute
Dermal
Toxicity
­
Metiram
Technical
Surrogate
Species
%
ai
LD50
(
mg
ai/
kg)
Toxicity
Category
Affected
Endpoints
MRID
or
Accession
(
AC)
No.

laboratory
rat
(
Rattus
norvegicus)
97.6
>
2,000
Category
III
mortality
009768
Table
6
shows
metiram's
acute
inhalation
toxicity
results.
Toxicity
category
descriptions
associated
with
inhalation
routes
of
exposure
include
(
US
EPA
CFR.
Part
156):

If
the
LC50
is
less
than
or
equal
to
0.05
mg/
liter,
then
the
test
substance
is
in
Toxicity
Category
I.
If
the
LC50
is
greater
than
0.05
mg/
liter
through
0.5
mg/
liter,
then
the
test
substance
is
in
Toxicity
Category
II.
If
the
LC50
is
greater
than
0.5
mg/
liter
through
2.0
mg/
liter,
then
the
test
substance
is
in
Toxicity
Category
III
If
the
LC50
is
greater
than
2.0
mg/
liter,
then
the
test
substance
is
in
Toxicity
Category
IV.

Metiram
is
a
Category
IV
toxicant
to
mammals
based
on
acute
inhalation
exposure.

Table
6:
Mammalian
Acute
Inhalation
Toxicity
­
Metiram
Technical
Surrogate
Species/
Formulation
%
A.
I.
LC50
(
mg/
liter)
Toxicity
Category
Affected
Endpoints
MRID
or
Accession
(
AC)
No.

laboratory
rat
(
Rattus
norvegicus)
technical
>
5.7
Category
IV
mortality
009768
2.
Mammalian
Sub­
chronic
Toxicity
Testing
66
Table
7
shows
the
filed
mammalian
subchronic
feeding
studies
in
rats.
These
studies
show
results
from
extended
exposure
(
that
is,
3­
month
feeding
studies).
The
result
show
metiram
residues
in
the
diet
at
levels
of
80
ppm
will
cause
reduced
forelimb
strength
in
female
rats.
Levels
of
1,000
ppm,
in
mice,
will
decrease
total
serum,
thyroxine
(
T
4
,
a
thyroid
hormone)
concentration
in
both
sexes.

Table
7:
Mammalian
Sub­
chronic
Toxicity
­
Metiram
Surrogate
Species/
%
ai
NOAEL/
LOAEL
(
ppm)
LOAEL
Endpoints
MRID
or
Accession
(
AC)
No.

Laboratory
rat
(
Rattus
norvegicus)/
feeding­
3
months
94.8
5.0/
80.0
Reduced
forelimb
strength
in
females.
42539101
Laboratory
mouse
(
Mus
musculus)/
feeding­
3
months
95.0
300/
1,000
Decrease
in
total
serum,
thyroxine
(
T
4
,
a
thyroid
hormone)
concentration
in
both
sexes.
42595001
3.
Mammalian
Reproductive
and
Developmental
Toxicity
Testing
Table
8
shows
treatment­
related
developmental
effects
caused
by
metiram.
The
developmental
effects
in
rats
include
increased
pre­
and
post­
implantation
losses,
decreased
litter
size,
and
decreased
litter
weight
at
an
exposure
of
1,600
ppm
(
LOAEL)
(
AC
No.
242188).
This
same
study
showed
maternal
decreases
in
body
weight
gains
at
an
exposure
of
3,200
ppm
(
LOAEL).
A
metiram
developmental
study,
using
rabbits
as
the
test
species,
showed
an
increased
incidence
of
abortions
at
a
1,320
ppm
(
LOAEL)
exposure
level.
However,
because
of
inadequate
examination
of
the
aborted
fetuses,
this
study
showed
no
developmental
defects
(
MRID
No.
40711401).
A
3­
generational
reproductive
study
with
metiram,
using
rats
as
the
test
species,
indicated
there
was
a
maternal
decrease
in
body
weight
during
gestation
and
lactation
of
the
treatment
groups,
as
compared
to
the
controls,
at
exposure
levels
of
320
ppm
(
LOAEL).
At
this
same
level
(
320
ppm)
reproductive
toxicity
was
noted
based
on
decreased
mating
performance
(
increased
precoital
time)
in
the
F2
generation
(
two
generations
removed
from
the
original
parent
generation).
There
were
no
direct
adverse
effects
noted
in
the
offspring
(
no
dose
related
effect
on
litter
sizes,
no
significant
cumulative
losses
in
any
gerneration,
no
adverse
body
weight
changes
and
no
histological
findings
attributed
to
treatment)
of
this
reproductive
study
at
the
highest
dose
tested
(
320
ppm)
(
AC
No.
247214).

Table
8:
Mammalian
Developmental
and
Reproductive
Chronic
Toxicity
­
Metiram
Technical
Species/
Study
Duration
%
ai
Test
Type
NOAEL/
LOAEL
Toxicity
Value
(
mg/
kg/
day)
Affected
Endpoints
MRID
or
Accession
(
AC)
No.

laboratory
rat
(
Rattus
norvegicus)/
from
gestation
day
6
through
gestation
day
15
96.8
Developmental
80/
160
(
1600/
3200
ppm)
1
(
maternal)
80/
160
(
800/
1600ppm)
1
(
developmental)
mat.
­
decreased
body
weight
gain
dev.
­
increased
pre­
and
postimplantation
losses,
decreased
litter
size,
and
decreased
litter
weight
242188
Table
8:
Mammalian
Developmental
and
Reproductive
Chronic
Toxicity
­
Metiram
Technical
Species/
Study
Duration
%
ai
Test
Type
NOAEL/
LOAEL
Toxicity
Value
(
mg/
kg/
day)
Affected
Endpoints
MRID
or
Accession
(
AC)
No.

67
laboratory
rabbit
(
Sylvivlagus
sp.)/
from
gestation
day
7
through
gestation
day
19
97.9
Developmental
10/
40
(
330/
1320
ppm)
1
(
maternal)
not
determined
(
developmental)
mat.
­
abortions
dev.
­
not
determined
40711401
laboratory
rat
(
Rattus
norvegicus)/
3­
generation
96.8
Reproductive
2.2/
19.8
(
40/
320
ppm)
2
females
(
parental)
1.8(
m)
2.2(
f)/
14.2(
m)
19.9(
f)
(
40/
320
ppm)
2
14.2(
m)
19.8(
f)/
not
applicable
(
320/
not
applicable)
2
(
reproductive)
parental
­
decreased
body
weight
during
gestation
&
lactation
for
females
reproductive
­
decreased
mating
performance
in
the
F2
generation
offspring
­
no
adverse
effects
were
observed
at
the
highest
dose
tested
247214
1
ppm
conversion
based
on:
1
mg/
kg/
day
=
20
ppm
in
adult
rats,
10
ppm
in
younger
rats,
and
33
ppm
in
rabbits.
(
Nelson,
1975)
2
ppm
value
provided
in
study
review
iii.
Insect
Acute
Contact
A
honey
bee
acute
contact
study
using
the
TGAI
is
required
for
metiram
because
its
outdoor
use
will
result
in
honey
bee
exposure.
The
acute
contact
LD
50
,
using
the
honey
bee,
Apis
mellifera,
is
an
acute
contact,
single­
dose
laboratory
study
designed
to
estimate
the
quantity
of
toxicant
required
to
cause
50%
mortality
in
a
test
population
of
bees.
The
TGAI
is
administered
by
one
of
two
methods:
whole
body
exposure
to
technical
pesticide
in
a
nontoxic
dust
diluent;
or,
topical
exposure
to
technical
pesticide
via
micro­
applicator.
The
median
lethal
dose
(
LD
50
)
is
expressed
in
micrograms
of
active
ingredient
per
bee
(:
g
a.
i./
bee).
Results
of
this
test
are
tabulated
below
(
Table
9).
Toxicity
category
descriptions
are
the
following
(
Atkins,
1981):

If
the
LD50
is
less
than
2
:
g
a.
i./
bee,
then
the
test
substance
is
highly
toxic.
If
the
LD50
is
2
to
less
than
11
:
g
a.
i./
bee,
then
the
test
substance
is
moderately
toxic.
If
the
LD50
is
11
:
g
a.
i./
bee
or
greater,
then
the
test
substance
is
practically
nontoxic
The
LD
50
for
metiram
was
437
µ
g
per
bee
which
categorizes
metiram
as
practically
nontoxic
to
bees.
The
guideline
(
141­
1)
is
fulfilled
(
MRID
No.
00066220).

Table
9:
Non­
target
Insect
Acute
Contact
Toxicity
­
Metiram
Species
%
ai
LD50
(
µ
g
a.
i./
bee)
Toxicity
Category
MRID/
Accession
(
AC)
No.
Author/
Year
Study
Classification1
Honey
bee
(
Apis
mellifera)
80
437
practically
nontoxic
00066220/
Atkins,
E.
et
al./
1977
Core
1
Core
(
study
satisfies
guideline).
Supplemental
(
study
is
scientifically
sound,
but
does
not
satisfy
guideline)
68
iv.
Insect
Residual
Contact
A
honey
bee
toxicity
of
residues
on
foliage
study
is
required
on
an
end­
use
product
for
any
pesticide
intended
for
outdoor
application
when
the
proposed
use
pattern
indicates
that
honey
bees
may
be
exposed
to
the
pesticide
and
when
the
formulation
contains
one
or
more
active
ingredients
having
an
acute
contact
honey
bee
LD
50
which
falls
in
the
moderately
toxic
or
highly
toxic
range.
The
purpose
of
this
guideline
study
is
to
develop
data
on
the
residual
toxicity
to
honey
bees.
Bee
mortality
determinations
are
made
from
bees
exposed
to
treated
foliage
harvested
at
various
time
periods
after
treatment.
Metiram,
as
indicated
in
the
acute
toxicity
test
in
Table
9,
above,
is
practically
nontoxic
to
honey
bees.
Because
of
this,
a
honey
bee
toxicity
of
residues
on
foliage
(
guideline
141­
2)
is
not
required
for
metiram.

v.
Terrestrial
Field
Testing
No
studies
were
submitted
and
no
studies
are
required
c.
Aquatic
Organism
Toxicity
i.
Toxicity
to
Freshwater
Animals
1.
Freshwater
Fish,
Acute
Two
freshwater
fish
toxicity
studies
using
the
TGAI
are
required
to
establish
the
toxicity
of
metiram
to
fish.
The
preferred
test
species
are
rainbow
trout
(
a
coldwater
fish,
Guideline
72­
1c)
and
bluegill
sunfish
(
a
warmwater
fish;
Guideline
72­
1a).
Results
of
these
tests
are
tabulated
below.
The
toxicity
category
descriptions
for
freshwater
and
estuarine/
marine
fish
and
aquatic
invertebrates,
are
defined
below
in
parts
per
million
(
ppm),
the
standard
units
of
measure.
The
toxicity
category
descriptions
for
freshwater
and
estuarine/
marine
fish
and
aquatic
invertebrates,
are
defined
below
in
parts
per
million
(
ppm),
the
standard
units
of
measure
(
Brooks,
1973).
The
toxicity
values
(
LC
50
)
appearing
in
the
shaded
area
of
the
tables
will
be
used
to
calculate
the
acute
aquatic
risk
quotients
(
RQ's)
in
subsequent
sections.

If
the
LC50
is
less
than
0.1
ppm
a.
i.,
then
the
test
substance
is
very
highly
toxic.
If
the
LC50
is
0.1­
to­
1.0
ppm
a.
i.,
then
the
test
substance
is
highly
toxic.
If
the
LC50
is
greater
than
1
and
up
through
10
ppm
a.
i.,
then
the
test
substance
is
moderately
toxic.
If
the
LC50
is
greater
than
10
and
up
through
100
ppm
a.
i.,
then
the
test
substance
is
slightly
toxic.
If
the
LC50
is
greater
than
100
ppm
a.
i.,
then
the
test
substance
is
practically
nontoxic.

Metiram
is
highly
toxic
to
coldwater
freshwater
fish
on
an
acute
basis
(
rainbow
trout
LC
50
=
0.23
ppm
based
on
measured,
filtered
samples)
(
see
Table
10
below).
The
guideline
(
72­
1c)
is
fulfilled
(
MRID
43525001).
There
are
numerous
studies
classified
invalid
because
test
concentrations
were
not
measured;
as
is
required
for
poorly
soluble
compounds
[
e.
g.,
bluegill
LC
50
>
160
ppm
(
MRID
40945501);
bluegill
LC
50
<
42
and
>
26
ppm
(
MRID
44224401);
and
rainbow
trout
LC
50
of
46.7
ppm
(
40497011).
The
freshwater
fish
acute
toxicity
guideline
requirement
for
a
a
warmwater
fish
(
Guideline
72­
1a)
has
not
been
fulfilled
and
a
Core
study
is
required
to
be
submitted.
69
An
outdoor,
multiple
application
(
4
applications
every
7
days)
study
exposed
juvenile
(
3
months
old)
rainbow
trout
to
metiram
(
MRID
No.
45933402).
The
trout
were
exposed
under
static
conditions
while
contained
in
0.55
cu.
meter
stainless
steel
basins.
The
test
basins
contained
~
2
cm.
of
natural
lake
sediment
in
the
bottom.
The
28­
day
nominal
LC
50
based
on
mortality
was
0.276
ppm
ai.
A
chronic
NOAEC
of
0.07
ppm
ai
based
on
weight
loss
and
reduced
growth
were
also
determined
in
this
study.
This
study
was
determined
to
be
scientifically
sound
and
categorized
as
supplemental
because
the
study
did
not
fulfill
any
guideline
study
requirement.

Table
10:
Freshwater
Fish
96­
hr
Acute
Toxicity
­
Metiram
Technical
Species/
Flow­
through
or
Static/
Duration
%
ai
LC
50
/
(
ppm
ai)/
(
measured/
nominal)
Toxicity
Category
MRID
/
Accession
No./
Author/
Year
Study
Classification1
Rainbow
Trout
(
Salmo
gairdneri)/
flowthrough
96­
hour
71.04
0.23
(
measured)
Slope
=
2.23
highly
toxic
43525001/
Monk,
R./
1994
Core
Rainbow
Trout
(
Oncorhynchus
mykiss)/
static/
28
day
68.5
0.276
(
nominal)
highly
toxic
45933402/
Junker,
M./
2002
Supplemental
1
Core
(
study
satisfies
guideline).
Supplemental
(
study
is
scientifically
sound,
but
does
not
satisfy
guideline)

2.
Freshwater
Fish,
Chronic
A
freshwater
fish
early
life­
stage
test
using
the
TGAI
is
required
for
metiram
because
the
end­
use
product
is
expected
to
be
transported
to
water
from
the
intended
use
site,
and
the
following
conditions
are
met:
(
1)
the
pesticide
is
intended
for
use
such
that
its
presence
in
water
is
likely
to
be
continuous
or
recurrent,
(
2)
an
aquatic
acute
LC
50
or
EC
50
is
less
than
1ppm,
and
(
3)
the
EEC
in
water
is
equal
to
or
greater
than
0.01
of
any
acute
LC
50
or
EC
50
value.
Acceptable
freshwater
test
species
are
rainbow
trout,
brook
trout,
coho
salmon,
Chinook,
bluegill,
brown
trout,
lake
trout,
northern
pike,
fathead
minnow,
white
sucker
and
channel
catfish.
The
fish
early
life­
stage
is
a
laboratory
test
designed
to
estimate
the
quantity
of
toxicant
required
to
adversely
effect
the
reproductive
capabilities
of
a
test
population
of
fish.
The
test
should
be
performed
using
flowthrough
conditions.
The
TGAI
is
administered
into
water
containing
the
test
species,
providing
exposure
throughout
a
critical
life­
stage,
and
the
results
are
expressed
as
a
No
Observed
Adverse
Effect
Concentration
(
NOAEC)
and
LOAEC
(
Lowest
Observed
Adverse
Effect
Concentration)
in
parts
per
billion
(
ppb)
of
active
ingredient.
The
No
Observed
Adverse
Effect
Concentration
represents
an
exposure
concentration,
at
or
below
which
biologically
significant
effects
will
not
occur
to
species
of
similar
sensitivities.
A
rainbow
trout
early
life
stage
study
submitted
with
a
reported
NOAEC
of
31.6
ppb
(
MRID
No.
43770401)
was
categorized
as
invalid
due
to
study
design
flaws.
The
EFED
does
not
have
a
study
to
fulfill
this
required
freshwater
fish
early
life­
stage
test
(
Guideline
72­
4a)
for
metiram.
A
guideline
study
is
required
to
be
submitted.

A
freshwater
fish
early
life­
cycle
test
(
Guideline
72­
5)
using
the
TGAI
of
metiram
is
held
in
reserve
pending
the
results
of
the
required
freshwater
fish
early
life­
stage
test
(
Guideline
72­
4a)
for
metiram
mentioned
above.

3.
Freshwater
Invertebrates,
Acute
A
freshwater
aquatic
invertebrate
toxicity
test
using
the
TGAI
is
required
to
establish
the
acute
toxicity
of
metiram
to
aquatic
invertebrates.
The
preferred
test
organism
is
Daphnia
magna,
but
early
70
instar
amphipods,
stoneflies,
mayflies,
or
midges
may
also
be
used.
A
supplemental
acute
daphnid
study
(
MRID
No.
44301101)
indicates
metiram's
freshwater
aquatic
invertebrates
EC
50
value
is
greater
than
0.358
ppm
based
on
measured,
unfiltered
samples.
The
study
was
classified
supplemental
because
an
EC
50
was
not
established,
and
because
samples
were
not
filtered
prior
to
analytical
measurement.
Results
of
this
test
are
tabulated
below
(
Table
11).
Guideline
72­
2(
a)
for
the
TGAI
of
metiram
is
not
fulfilled.
A
core
study
to
fulfill
this
guideline
is
required.

There
was
one
acute
toxicity
daphnid
study
classified
invalid
because
test
concentrations
were
not
measured
(
MRID
No.
40497003)
as
is
required
for
poorly
soluble
compounds
and
another
daphnid
acute
toxicity
study
(
MRID
No.
43525002)
also
categorized
as
invalid
because
of
study
design
flaws.

Table
11:
Freshwater
Invertebrate
Acute
Toxicity
­
Metiram
Technical
Species/
Static
or
Flowthrough
Duration
%
ai
LC50/
EC50
(
ppm)/
(
nominal/
measured)
Toxicity
Category
MRID/
Accession
(
AC)
No.
Author/
Year
Study
Classification1
Daphnid
(
Daphnia
magna)/
static
(
48
hr.)
70
>
0.358
(
measured­
unfiltered)
Slope
=
not
applicable
highly
toxic
44301101/
Maisch/
1997
Supplemental
1
Core
(
study
satisfies
guideline).
Supplemental
(
study
is
scientifically
sound,
but
does
not
satisfy
guideline)

4.
Freshwater
Invertebrate,
Chronic
A
freshwater
aquatic
invertebrate
life­
cycle
test
using
the
TGAI
is
required
for
metiram
since
the
enduse
product
is
expected
to
be
transported
to
water
from
the
intended
use
site,
and
the
following
conditions
are
met:
(
1)
the
pesticide
is
intended
for
use
such
that
its
presence
in
water
is
likely
to
be
continuous
or
recurrent,
(
2)
the
aquatic
acute
LC
50
or
EC
50
is
less
than
1.0
ppm,
and
(
3)
the
EEC
in
water
is
equal
to
or
greater
than
0.01
of
any
acute
EC
50
or
LC
50
value.
The
preferred
test
species
is
Daphnia
magna.
Daphnid
life­
cycle
tests
(
MRID
Nos.
43770402
and
44301102
)
were
submitted
to
fulfill
this
guideline
requirement
but
were
classified
as
invalid
due
to
study
design
flaws.
A
core
freshwater
aquatic
invertebrate
life­
cycle
test
using
the
TGAI
is
required
to
be
submitted
for
metiram.
Guideline
72­
4(
b)
for
metiram
is
not
fulfilled.

5.
Freshwater
Whole
Sediment
Toxicity
Invertebrates,
Acute
Whole
Sediment
Acute
Toxicity
(
Guideline
850.1735)
testing
using
the
TGAI
is
required
to
determine
the
toxicity
and
bioaccumulation
potential
of
chemicals
in
sediments
in
benthic
organisms.
This
test
is
a
28­
day
study
and
the
preferred
test
species
are
the
amphipod,
Hyalella
azteca
and
the
midge,
Chironomus
tentans.
Natural
sediment
is
spiked
with
different
concentrations
of
test
chemical
and
the
results
from
the
sediment
toxicity
tests
can
be
used
to
determine
causal
relationships
between
the
chemical
and
biological
response.
Reported
endpoints
from
whole
sediment
toxicity
tests
may
include
the
LC
50
or
EC
50
,
NOAEC,
or
the
LOAEC.
Whole
Sediment
Acute
Toxicity
Invertebrates,
Freshwater
(
Guideline
850.1735)
testing
is
required
for
metiram
because
metiram
is
toxic
to
aquatic
invertebrates,
persistent
in
the
environment,
and
binds
to
sediment.
This
guideline
has
not
been
fulfilled
and
a
guideline
study
is
required
to
be
submitted.
71
6.
Freshwater
Field
Studies
No
studies
were
submitted
and
no
studies
are
required.

ii.
Toxicity
to
Estuarine
and
Marine
Animals
1.
Estuarine
and
Marine
Fish,
Acute
Acute
toxicity
testing
with
estuarine
and
marine
fish
using
the
TGAI
is
required
for
metiram
because
the
end­
use
product
is
expected
to
reach
the
marine/
estuarine
environment
because
of
its
use
in
coastal
counties.
The
preferred
test
organism
is
the
sheepshead
minnow.
The
EFED
does
not
have
an
estuarine/
marine
fish
acute
toxicity
test
to
fulfill
this
guideline
requirement
for
metiram.
A
core
study
for
acute
toxicity
testing
of
TGAI
metiram
on
estuarine/
marine
fish
(
Guideline
72­
3a)
is
required
to
be
submitted.

2.
Estuarine
and
Marine
Fish,
Chronic
An
estuarine/
marine
fish
early
life­
stage
toxicity
test
using
the
TGAI
is
required
when
the
end­
use
product
is
expected
to
be
transported
to
the
estuarine/
marine
environment
from
the
intended
use
site,
and
the
following
conditions
are
met:
the
pesticide
is
intended
for
use
such
that
its
presence
in
water
is
likely
to
be
continuous
or
recurrent
and
the
EEC
in
water
is
equal
to
or
greater
than
0.01
of
any
acute
LC
50
or
EC
50
value.
The
preferred
test
species
is
sheepshead
minnow.
The
guideline
(
72­
4a)
estuaine/
marine
fish
is
not
fulfilled
for
metiram.
An
early
life­
stage
test
using
the
TGAI
(
Guideline
72­
4a)
for
metiram
is
held
in
reserve
pending
the
results
of
the
required
acute
toxicity
testing
(
Guideline
72­
3a)
for
metiram
mentioned
above.

3.
Estuarine
and
Marine
Invertebrates,
Acute
Acute
toxicity
testing
with
estuarine/
marine
invertebrates
using
the
TGAI
is
required
for
metiram
because
the
end­
use
product
is
expected
to
reach
the
marine/
estuarine
environment
because
of
it
use
in
coastal
counties.
The
preferred
test
species
are
mysid
shrimp
and
eastern
oyster.
The
EFED
does
not
have
an
estuarine/
marine
invertebrate
acute
toxicity
tests
to
fulfill
this
guideline
requirement
for
metiram.
Core
studies
for
acute
toxicity
testing
of
TGAI
metiram
on
estuarine/
marine
invertebrates
(
Guidelines
72­
3b
&
c)
are
required
to
be
submitted.

4.
Estuarine
and
Marine
Invertebrate,
Chronic
An
estuarine/
marine
invertebrate
life­
cycle
toxicity
test
(
Guideline
72­
4b)
using
the
TGAI
is
required
when
the
end­
use
product
is
expected
to
be
transported
to
the
estuarine/
marine
environment
from
the
intended
use
site,
the
pesticide
is
intended
for
use
such
that
its
presence
in
water
is
likely
to
be
continuous
or
recurrent,
any
aquatic
acute
LC
50
or
EC
50
is
less
than
1.0
ppm,
and
the
EEC
in
water
72
is
equal
to
or
greater
than
0.01
of
any
acute
LC
50
or
EC
50
value.
The
preferred
test
species
is
mysid
shrimp.
An
estuarine/
marine
invertebrate
life­
cycle
toxicity
test
(
Guideline
72­
4b)
for
metiram
is
held
in
reserve
pending
the
results
of
the
required
acute
toxicity
testing
(
Guidelines
72­
3b
&
c)
for
metiram
mentioned
above.

5.
Estuarine
and
Marine
Whole
Sediment
Toxicity
Invertebrates,
Acute
Whole
sediment
toxicity
testing
with
estuarine/
marine
invertebrates
using
the
TGAI
is
being
required
for
metiram
because
metiram
has
a
high
affinity
for
sediment
and
the
end­
use
product
is
expected
to
reach
the
marine/
estuarine
environment
because
of
it
use
in
coastal
counties.
This
test
lasts
10
or
more
days
and
the
preferred
test
species
are
four
species
of
estuarine/
marine
amphipods;
Ampelisca
abdita,
Eohaustorius
estuarius,
Rhepoxynius
abronius,
and
Leptocheirus
plumulosus.
The
EFED
does
not
have
an
estuarine/
marine
invertebrate
whole
sediment
toxicity
tests
to
fulfill
this
guideline
requirement
for
metiram.
A
core
study
for
Whole
Sediment
Acute
Toxicity
Invertebrates,
Marine
(
Guideline
850.1740)
testing
of
TGAI
metiram
on
estuarine/
marine
invertebrates
is
required
to
be
submitted.

6.
Estuarine
and
Marine
Field
Studies
No
studies
were
submitted
and
no
studies
are
required.

iii.
Toxicity
to
Plants
1.
Terrestrial
Plants
Terrestrial
plant
Tier
I
seedling
emergence
and
vegetative
vigor
testing
of
a
metiram
TEP
is
currently
recommended
for
all
pesticides
having
outdoor
uses.
For
seedling
emergence
and
vegetative
vigor
testing
the
following
plant
species
and
groups
should
be
tested:
(
1)
six
species
of
at
least
four
dicotyledonous
families,
one
species
of
which
is
soybean
(
Glycine
max)
and
the
second
is
a
root
crop,
and
(
2)
four
species
of
at
least
two
monocotyledonous
families,
one
of
which
is
corn
(
Zea
mays).
Tier
I
tests
measure
the
response
of
plants,
relative
to
a
control,
at
a
test
level
that
is
equal
to
the
highest
use
rate
(
expressed
as
lbs
ai/
A).
Tier
II
studies
are
required
if
the
Tier
I
studies
indicate
any
of
the
test
species,
when
exposed
to
the
test
material,
displayed
a
$
25%
inhibition
of
various
growth
parameters
as
compared
to
the
control.

Tier
I
seedling
emergence
[
guideline
122­
1(
a)]
and
vegetative
vigor
[
guideline
122­
1(
b)]
studies
for
the
metiram
have
not
be
received
and
submission
of
these
studies
for
review
by
the
EFED
are
recommended.
The
submission
recommendation
for
Tier
II
seedling
emergence
[
guideline
123­
1(
a)]
and
vegetative
vigor
[
guideline
123­
1(
b)]
testing
for
the
metiram
is
being
held
in
reserve
pending
the
results
of
Tier
I
testing.

2.
Aquatic
Plants
Aquatic
plant
testing
is
recommended
for
all
pesticides
having
outdoor
uses
(
Keehner.
July
1999).
The
tests
are
performed
on
species
from
a
cross­
section
of
the
non­
target
aquatic
plant
population.
73
The
preferred
test
species
are
duckweed
(
Lemna
gibba),
marine
diatom
(
Skeletonema
costatum),
blue­
green
algae
(
Anabaena
flos­
aquae),
freshwater
green
alga
(
Selenastrum
capricornutum),
and
a
freshwater
diatom.
Tier
I
aquatic
plant
testing
is
a
maximum
dose
test
designed
to
quickly
evaluate
the
toxic
effects
to
the
test
species
in
terms
of
growth
and
reproduction
and
to
determine
the
need
for
additional
aquatic
plant
testing.
Tier
II
aquatic
plant
testing
is
a
multiple
dose
test
of
the
plants
species
that
showed
a
phytotoxic
effect
to
the
pesticide
being
tested
at
the
Tier
I
level.
Tier
II
testing
is
aimed
to
determine
the
detrimental
effect
levels
of
the
chemical
on
the
aquatic
plants
which
showed
a
greater
than
50%
detrimental
effect
in
Tier
I
testing.

For
metiram,
one
Tier
II
supplemental
study
has
been
submitted
for
Ankistrodesmus
bibraianus,
a
freshwater
green
alga.
Results
of
Tier
II
toxicity
testing
on
the
technical
material
are
tabulated
in
Table
12,
below.
The
EC
50
for
Ankistrodesmus
bibraianus
was
77.0
ppb
a.
i.
based
on
nominal
concentrations;
the
NOAEC
was
13.0
ppb.
This
study
was
classified
as
supplemental
principally
because
inappropriate
cell
inoculum
levels
were
used,
the
concentrations
used
were
not
measured,
and
the
lighting
regime
was
inappropriate.
The
toxicity
value
(
EC
50
)
appearing
in
the
shaded
area
of
the
table
will
be
used
to
calculate
the
acute
risk
quotients
(
RQ's)
in
subsequent
sections.
Guideline
123­
2
(
Tier
II)
has
been
not
been
fulfilled.
Core
Tier
I
or
Tier
II
aquatic
plant
growth
testing
need
to
be
submitted
for
duckweed
(
Lemna
gibba),
marine
diatom
(
Skeletonema
costatum),
blue­
green
algae
(
Anabaena
flos­
aquae),
freshwater
green
alga
(
Selenastrum
capricornutum),
and
a
freshwater
diatom.

Table
12:
Non­
target
Aquatic
Plant
Toxicity
(
Tier
II)
­
Metiram
Species/
duration
%
A.
I.
EC50/
NOAEC
(
ppb
ai)
MRID
No.
Author/
year
Classification1
Nonvascular
Plants
freshwater
green
algae
(
Ankistrodesmus
bibraianus)
/
72
hrs.
80
77.0/
13.0
(
nominal)
Slope
=
1.65
43199601/
Dohmen,
G./
1990
Supplemental
1
Core
(
study
satisfies
guideline).
Supplemental
(
study
is
scientifically
sound,
but
does
not
satisfy
guideline).

3.
Aquatic
Plant
Field
Studies
No
studies
were
submitted
and
no
studies
are
required.
74
APPENDIX
IV:
Environmental
Exposure
Assessment
a.
Review
of
Risk
Quotients
(
RQs)

Risk
characterization
integrates
the
results
of
the
exposure
and
ecotoxicity
data
to
evaluate
the
likelihood
of
adverse
ecological
effects.
The
Agency
calls
this
integration
the
quotient
method.
The
Agency
calculates
risk
quotients
(
RQs)
by
dividing
exposure
estimates
by
acute
and
chronic
ecotoxicity
values.

RQ
=
EXPOSURE/
TOXICITY
EFED
compares
RQs
to
OPP's
levels
of
concern
(
LOCs).
OPP
uses
these
LOCs
to
analyze
potential
risk
to
non­
target
organisms
and
the
need
to
consider
regulatory
action.
This
method
signals
that
a
pesticide
used
as
directed
has
the
potential
to
cause
adverse
effects
on
non­
target
organisms.
LOCs
currently
address
the
following
risk
presumption
categories:
(
1)
acute
risks
­
the
risks
warrant
regulatory
action
as
well
as
restricted
use
classification;
(
2)
acute
restricted
use
­
the
potential
for
acute
risk
exists,
but
the
restricted
use
classification
may
mitigate
the
risk;
(
3)
acute
endangered
species
­
the
risk
may
adversely
affect
endangered;
and
(
4)
chronic
risk
­
the
risk
may
warrant
regulatory
action
because
there
is
a
potential
for
chronic
risk.
Currently,
EFED
does
not
perform
assessments
for
chronic
risk
to
plants,
acute
or
chronic
risks
to
non­
target
insects,
or
chronic
risk
from
granular
or
bait
formulations
to
birds
or
mammals.

The
Agency
gets
ecotoxicity
test
values
(
measurement
endpoints)
used
in
the
acute
and
chronic
risk
quotients
from
required
studies.
Examples
of
ecotoxicity
values
gathered
from
short­
term
laboratory
studies
that
assess
acute
effects
are:
(
1)
LC
50
(
fish
and
birds);
(
2)
LD
50
(
birds
and
mammals);
(
3)
EC
50
(
aquatic
plants
and
aquatic
invertebrates);
and
(
4)
EC
25
(
terrestrial
plants).
Examples
of
toxicity
test
effect
levels
drawn
from
the
results
of
long­
term
laboratory
studies
that
assess
chronic
effects
are:
(
1)
LOAEL
or
LOAEC
(
birds,
fish,
and
aquatic
invertebrates)
and
(
2)
NOAEL
or
NOAEC
(
birds,
fish
and
aquatic
invertebrates).
For
birds,
mammals,
fish
and
aquatic
invertebrates,
the
Agency
uses
the
NOAEL
or
NOAEC
as
the
ecotoxicity
test
value
in
assessing
chronic
effects,
although
the
Agency
may
use
other
values
when
justified.
Tabulated
below
are
risk
presumptions
and
the
matching
RQs
and
LOCs.

Risk
quotients
are
index
or
reference
values
used
to
show
potential
ecological
risk.
There
are
limits
with
the
use
of
risk
quotients
in
assessing
the
risk
to
non­
target
animals
and
plants.
The
likelihood
of
an
adverse
effect
does
not
increase
with
the
size
of
the
risk
quotient.
(
Urban,
2000).
An
LOC
defined
as
1
(
see
table
below)
provides
the
reference
point
for
estimating
the
exposure
to
toxicity
risk
(
that
is,
risk
quotient).
Values
at
or
above
this
reference
point
trigger
risk
concerns.
A
risk
quotient
value
of
100
compared
to
a
value
of
50
does
not
suggest
a
greater
risk
or
a
risk
that
is
more
likely
to
occur.
Both
these
values
are
above
the
reference
point
for
risk
of
1.
The
risk
quotient
value
of
100
reflects
an
exposure
level
that
is
twice
has
high
as
the
risk
quotient
value
of
50.
The
"
exposure"
in
the
"
RQ
=
Exposure/
Toxicity"
ratio
is
twice
has
high
for
RQ
of
100
as
for
the
RQ
of
50.
Risk
quotients
are
non­
probabilistic
and
have
numerical
and
dichotomous
results.
The
numerical
result
75
drawn
from
the
calculation
either
exceeds
a
fixed
LOC
or
does
not
exceed
it.
(
US
EPA.
June
30,
1995).

Table
1.
Risk
presumptions
for
terrestrial
animals
based
on
risk
quotients
(
RQ)
and
levels
of
concern
(
LOC).

Risk
Presumption
RQ
LOC
Birds
Acute
High
Risk
EEC1/
LC
50
or
LD
50
/
ft2
or
LD
50
/
day3
0.5
Acute
Restricted
Use
EEC/
LC
50
or
LD
50
/
ft2
or
LD
50
/
day
(
or
LD
50
<
50
mg/
kg)
0.2
Acute
Endangered
Species
EEC/
LC
50
or
LD
50
/
ft2
or
LD
50
/
day
0.1
Chronic
Risk
EEC/
NOEC
1
Wild
Mammals
Acute
High
Risk
EEC/
LC
50
or
LD
50
/
ft2
or
LD
50
/
day
0.5
Acute
Restricted
Use
EEC/
LC
50
or
LD
50
/
ft2
or
LD
50
/
day
(
or
LD
50
<
50
mg/
kg)
0.2
Acute
Endangered
Species
EEC/
LC
50
or
LD
50
/
ft2
or
LD
50
/
day
0.1
Chronic
Risk
EEC/
NOEC
1
1
abbreviation
for
Estimated
Environmental
Concentration
(
ppm)
on
avian/
mammalian
food
items
2
mg/
ft2
3
mg
of
toxicant
consumed/
day
LD
50
*
wt.
of
bird
LD
50
*
wt.
of
bird
Table
2.
Risk
presumptions
for
aquatic
animals
based
on
risk
quotients
(
RQ)
and
levels
of
concern
(
LOC).

Risk
Presumption
RQ
LOC
Acute
High
Risk
EEC1/
LC
50
or
EC
50
0.5
Acute
Restricted
Use
EEC/
LC
50
or
EC
50
0.1
Acute
Endangered
Species
EEC/
LC
50
or
EC
50
0.05
Chronic
Risk
EEC/
or
NOEC
1
1
EEC
=
(
ppm
or
ppb)
in
water
Table
3.
Risk
presumptions
for
plants
based
on
risk
quotients
(
RQ)
and
levels
of
concern
(
LOC).

Risk
Presumption
RQ
LOC
Terrestrial
and
Semi­
Aquatic
Plants
Acute
High
Risk
EEC1/
EC
25
1
Acute
Endangered
Species
EEC/
EC
05
or
NOEC
1
Aquatic
Plants
Acute
High
Risk
EEC2/
EC
50
1
Acute
Endangered
Species
EEC/
EC
05
or
NOEC
1
1
EEC
=
lbs
ai/
A
2
EEC
=
(
ppb/
ppm)
in
water
76
b.
Exposure
and
Risk
to
Terrestrial
Animals
i.
Birds
Metiram's
acute
dietary
RQs
exceed
acute,
acute
restricted
use
and
acute
endangered
species
LOCs
for
tobacco,
apple,
and
potato
uses.
The
RQs
range
from
0.56
to
1.22
(
see
Table
4,
below).
Acute
endangered
species
levels
of
concern
(
LOCs)
are
exceeded
for
all
metiram
use
patterns
at
maximum
EEC
levels
(
RQ
range
from
0.11
to
1.22
for
a
35­
day
metiram
half­
life
value
estimate).
The
chronic
risk
quotients
for
multiple
broadcast
applications
of
nongranular
metiram
products
are
also
tabulated
below
in
Table
4.
The
results
indicate,
for
multiple
applications
of
metiram,
the
avian
chronic
LOCs
are
exceeded
for
all
uses
patterns.
RQs
exceed
chronic
LOCs
ranging
from
a
high
of
91
from
the
tobacco
use
to
a
low
of
1
from
metiram's
uses
on
potatoes
and
ornamental
nonflowering
plants.
77
Table
4:
Avian
Acute
and
Chronic
Risk
Quotients
for
Multiple
Broadcast
Applications
of
Nongranular
Metiram
based
on
a
Bobwhite
Quail
(
Colinus
virginianus)
LC50
of
3,712
ppm
and
a
Mallard
Duck
(
Anas
platyrhynchos)
NOAEC
of
50
ppm
a
.
Application
Rate
Chronic
RQ
Chronic
RQ
Acute
RQ
Acute
RQ
(
lbs
ai/
A)/

Based
on
Based
on
Based
on
Based
on
Number
of
Mean
EECs
Maximum
EECs
Mean
EECs
Maximum
EECs
Mean
Maximum
Applications/
Site/

(
Mean
EEC/
NOAEC)
3
(
Max.
EEC/
NOAEC)
3
(
Mean
EEC/
LC50)
2
(
Max.
EEC/
LC50)
2
EEC
(
ppm)
1
EEC
(
ppm)
1
Food
Items
Interval
Application
Method
27
76
0.36
1.02
1,342
3,788
Short
grass
4.8/
4
Apples
11
35
0.15
0.47
568
1,736
Tall
grass
7­
day
interval
ground
&
aerial
14
43
0.19
0.57
710
2,131
Broadleaf
plants/
Insects
2
5
0.03
0.06
110
237
Seeds
14
41
0.19
0.55
721
2,037
Short
grass
1.6/
7
Potatoes
6
19
0.08
0.25
305
933
Tall
grass
5­
day
interval
ground
&
aerial
8
23
0.10
0.31
382
1,146
Broadleaf
plants/
Insects
1
3
0.02
0.03
59
127
Seeds
32
91
0.43
1.22
1,605
4,533
Short
grass
6.8/
3b
Tobacco
14
42
0.18
0.56
680
2,077
Tall
grass
4­
day
interval
ground
17
51
0.23
0.69
850
2,550
Broadleaf
plants/
Insects
3
6
0.04
0.08
132
283
Seeds
7
20
0.10
0.27
357
1,009
Short
grass
1.6/
3b
Ornamental
3
9
0.04
0.12
151
463
Tall
grass
7­
day
interval
(
nonflowering
plants)

4
11
0.05
0.15
189
568
Broadleaf
plants/
Insects
ground
0.6
1
0.01
0.02
29
63
Seeds
5
15
0.07
0.20
268
757
Short
grass
1.2/
3b
Ornamental
2
7
0.03
0.09
114
347
Tall
grass
7­
day
interval
(
woody
shrubs
&
vines)

3
9
0.04
0.11
142
426
Broadleaf
plants/
Insects
ground
0.4
0.9
0.006
0.01
22
47
Seeds
1
Assumes
degradation
using
FATE
version
5.0
program
with
a
half­
life
of
35
days.
EFED
uses
this
value
as
a
default
value
when
the
foliar
dissipation
for
a
particular
pesticide
is
unknown.

2
RQ
greater
or
equal
to
0.5
exceeds
acute,
acute
restricted
use
and
acute
endangered
species
LOCs.

RQ
greater
or
equal
to
0.2
exceeds
acute
restricted
use
and
acute
endangered
species
LOCs.

RQ
greater
or
equal
to
0.1
exceeds
acute
endangered
species
LOCs.
3
RQ
greater
or
equal
to
1.00
exceeds
chronic
LOC.

a
Due
to
reduced
egg
production,
reduced
mean
egg
weight,
reduced
fertility
rate,

reduced
number
of
hatched
ducklings,
reduced
number
of
14­
day
old
survivors,

and
an
increased
rate
of
early
embryonic
deaths.
b
Maximum
number
of
applications/
year
or
crop
cycle
not
specified
(
assumed
3
applications).
78
The
35­
day
foliar
dissipation
half­
life
used
in
calculating
RQs
in
Table
4
represents
an
uncertainty.
Metiram's
total
foliar
dissipation
half­
life
is
unknown.
For
comparative
purposes,
EFED
is
providing
an
estimate
of
metiram's
risk
to
birds
based
on
lessened
half­
life
value.
Table
4a
shows
modeling
using
a
3­
day
foliar
dissipation
half­
life
for
metiram.
Assuming
a
3­
day
foliar
dissipation
half­
life
acute,
acute
restricted
use
and
acute
endangered
species
LOCs
are
exceeded
for
only
the
tobacco
use
(
RQ
=
0.68
for
short
grass).
The
acute
endangered
species
LOC
are
still
exceeded
for
all
metiram's
uses
(
RQ
range
from
0.1
to
0.68)
with
most
uses
exceeded
for
birds
feeding
on
shortgrass
only.
Assuming
a
3­
day
foliar
dissipation
half­
life,
the
avian
chronic
RQs
are
still
exceeding
the
LOC
for
all
metiram's
uses.
RQs
exceed
chronic
LOCs
ranging
from
a
high
of
50.7
from
the
tobacco
use
to
a
low
of
1.8
from
metiram's
uses
on
apples.
79
Table
4a:
Avian
Acute
and
Chronic
Risk
Quotients
for
Multiple
Broadcast
Applications
of
Nongranular
Metiram
based
on
a
Bobwhite
Quail
(
Colinus
virginianus
)
LC50
of
3,712
ppm
and
a
Mallard
Duck
(
Anas
platyrhynchos
)
NOAEC
of
50
ppma
.
Application
Rate
Chronic
RQ
Chronic
RQ
Acute
RQ
Acute
RQ
(
lbs
ai/
A)/

Based
on
Based
on
Based
on
Based
on
Number
of
Mean
EECs
Maximum
EECs
Mean
EECs
Maximum
EECs
Mean
Maximum
Applications/
Site/

(
Mean
EEC/
NOAEC)
3
(
Max.
EEC/
NOAEC)
3
(
Mean
EEC/
LC50)
2
(
Max.
EEC/
LC50)
2
EEC
(
ppm)
1
EEC
(
ppm)
1
Food
Items
Interval
Application
Method
10.2
28.7
0.14
0.39
508
1,435
Short
grass
4.8/
4
Apples
4.3
13.2
0.06
0.18
215
658
Tall
grass
7­
day
interval
ground
&
aerial
5.4
16.1
0.07
0.22
269
807
Broadleaf
plants/
Insect
0.8
1.8
0.01
0.02
42
90
Seeds
4.0
11.2
0.05
0.15
198
560
Short
grass
1.6/
7
Potatoes
1.7
5.1
0.02
0.07
84
257
Tall
grass
5­
day
interval
ground
&
aerial
2.1
6.3
0.03
0.08
105
315
Broadleaf
plants/
Insect
0.3
0.7
0.00
0.01
16
35
Seeds
18.0
50.7
0.24
0.68
898
2,537
Short
grass
6.8/
3b
Tobacco
7.6
23.3
0.10
0.31
381
1,163
Tall
grass
4­
day
interval
ground
9.5
28.5
0.13
0.38
476
1,427
Broadleaf
plants/
Insect
1.5
3.2
0.02
0.04
74
159
Seeds
3.4
9.5
0.05
0.13
168
475
Short
grass
1.6/
3b
Ornamental
1.4
4.4
0.02
0.06
71
218
Tall
grass
7­
day
interval
(
nonflowering
plants)

1.8
5.3
0.02
0.07
89
267
Broadleaf
plants/
Insect
ground
0.3
0.6
0.00
0.01
14
30
Seeds
2.5
7.1
0.03
0.10
126
356
Short
grass
1.2/
3b
Ornamental
1.1
3.3
0.01
0.04
53
163
Tall
grass
7­
day
interval
(
woody
shrubs
&
vines
1.3
4.0
0.02
0.05
67
201
Broadleaf
plants/
Insect
ground
0.2
0.4
0.003
0.01
10
22
Seeds
1
Assumes
degradation
using
FATE
version
5.0
program
with
a
total
foliar
residue
dissipation
half­
life
of
3
days.

2
RQ
greater
or
equal
to
0.5
exceeds
acute,
acute
restricted
use
and
acute
endangered
species
RQ
greater
or
equal
to
0.2
exceeds
acute
restricted
use
and
acute
endangered
species
LOCs.

RQ
greater
or
equal
to
0.1
exceeds
acute
endangered
species
LOCs.
3
RQ
greater
or
equal
to
1.00
exceeds
chronic
LOC.

a
Due
to
reduced
egg
production,
reduced
mean
egg
weight,
reduced
fertility
ra
reduced
number
of
hatched
ducklings,
reduced
number
of
14­
day
old
survivors
and
an
increased
rate
of
early
embryonic
deaths.
b
Maximum
number
of
applications/
year
or
crop
cycle
not
specified
(
assumed
3
applications).
80
Table
5:
Mammalian
Chronic
Risk
Quotients
for
Multiple
Applications
of
Metiram
Nongranular
(
Broadcast)
Based
on
a
labaratory
rats
(
Rattus
norvegicus)
NOAEL
of
40
ppm
a
Application
Rate
Chronic
RQ
Chronic
RQ
(
lbs
ai/
A)/

Based
on
Based
on
Number
of
Mean
EECs
Maximum
EECs
Mean
Maximum
Applications/
Site/

(
Mean
EEC/
NOAEL)
2
(
Max.
EEC/
NOAEL)
2
EEC
(
ppm)
1
EEC
(
ppm)
1
Food
Items
Interval
Application
Method
34
95
1,342
3,788
Short
grass
4.8/
4
Apples
14
43
568
1,736
Tall
grass
7­
day
interval
ground
&
aerial
18
53
710
2,131
Broadleaf
plants/
Insects
3
6
110
237
Seeds
18
51
721
2,037
Short
grass
1.6/
7
Potatoes
8
23
305
933
Tall
grass
5­
day
interval
ground
&
aerial
10
29
382
1,146
Broadleaf
plants/
Insects
1
3
59
127
Seeds
40
113
1,605
4,533
Short
grass
6.8/
3b
Tobacco
17
52
680
2,077
Tall
grass
4­
day
interval
ground
21
64
850
2,550
Broadleaf
plants/
Insects
3
7
132
283
Seeds
9
25
357
1,009
Short
grass
1.6/
3b
Ornamental
4
12
151
463
Tall
grass
7­
day
interval
(
nonflowering
plants)

5
14
189
568
Broadleaf
plants/
Insects
ground
0.7
2
29
63
Seeds
7
19
268
757
Short
grass
1.2/
3b
Ornamental
3
9
114
347
Tall
grass
7­
day
interval
(
woody
shrubs
&
vines)

4
11
142
426
Broadleaf
plants/
Insects
ground
0.6
1
22
47
Seeds
1
Assumes
degradation
using
FATE
version
5.0
program
with
a
half­
life
of
35
days.
EFED
uses
this
value
as
a
default
value
when
the
foliar
dissipation
for
a
particular
pesticide
is
unknown.

2
RQ
greater
or
equal
to
1.0
exceeds
chronic
risk
LOCs.

a
Reproductive
study,
dueto
parental
toxicity
resulting
in
decreased
body
weight
during
gestation
and
lactation
for
females
and
reproductive
toxicity
resulting
in
decreased
mating
performance
(
increased
precoital
time)
in
the
F2
generation
(
two
generations
removed
from
the
original
parent
generation)
b
Maximum
number
of
applications/
year
or
crop
cycle
not
specified
(
assumed
3
applications).
ii.
Mammals
As
identified
in
Appendix
III,
metiram
is
practically
nontoxic
(
rat
LD
50
>
5,000
mg/
kg)
to
mammals
on
an
acute
basis.
Because
of
this,
there
is
a
minimal
concern
that
the
acute
exposure
to
metiram
presents
a
risk
to
mammals,
so
RQs
for
acute
exposure
were
not
determined.
The
chronic
mammalian
risk
quotients
for
multiple
broadcast
applications
of
nongranular
products
are
tabulated
below
in
table
5.
The
results
indicate
that
chronic
mammalian
LOCs
are
exceeded
for
all
metiram
use
patterns
listed.
81
82
Table
5a:
Mammalian
Chronic
Risk
Quotients
for
Multiple
Applications
of
Metiram
Nongranular
(
Broadcast)
Based
on
a
labaratory
rats
(
Rattus
norvegicus
)
NOAEL
of
40
ppm
a
Application
Rate
Chronic
RQ
Chronic
RQ
(
lbs
ai/
A)/

Based
on
Based
on
Number
of
Mean
EECs
Maximum
EECs
Mean
Maximum
Applications/
Site/

(
Mean
EEC/
NOAEL)
2
(
Max.
EEC/
NOAEL)
2
EEC
(
ppm)
1
EEC
(
ppm)
1
Food
Items
Interval
Application
Method
12.7
35.9
508
1,435
Short
grass
4.8/
4
Apples
5.4
16.4
215
658
Tall
grass
7­
day
interval
ground
&
aerial
6.7
20.2
269
807
Broadleaf
plants/
Insects
1.0
2.2
42
90
Seeds
5.0
14.0
198
560
Short
grass
1.6/
7
Potatoes
2.1
6.4
84
257
Tall
grass
5­
day
interval
ground
&
aerial
2.6
7.9
105
315
Broadleaf
plants/
Insects
0.4
0.9
16
35
Seeds
22.5
63.4
898
2,537
Short
grass
6.8/
3b
Tobacco
9.5
29.1
381
1,163
Tall
grass
4­
day
interval
ground
11.9
35.7
476
1,427
Broadleaf
plants/
Insects
1.8
4.0
74
159
Seeds
4.2
11.9
168
475
Short
grass
1.6/
3b
Ornamental
1.8
5.4
71
218
Tall
grass
7­
day
interval
(
nonflowering
plants)

2.2
6.7
89
267
Broadleaf
plants/
Insects
ground
0.3
0.7
14
30
Seeds
3.2
8.9
126
356
Short
grass
1.2/
3b
Ornamental
1.3
4.1
53
163
Tall
grass
7­
day
interval
(
woody
shrubs
&
vines
1.7
5.0
67
201
Broadleaf
plants/
Insects
ground
0.3
0.6
10
22
Seeds
1
Assumes
degradation
using
FATE
version
5.0
program
with
a
half­
life
of
3
days.

2
RQ
greater
or
equal
to
1.0
exceeds
chronic
risk
LOCs.

a
Reproductive
study,
dueto
parental
toxicity
resulting
in
decreased
body
weight
during
gestation
and
lactation
for
females
and
reproductive
toxicity
resulting
in
decreased
mating
performance
(
increased
precoital
time)
in
the
F2
generation
(
two
generations
removed
from
the
original
parent
generation)
b
Maximum
number
of
applications/
year
or
crop
cycle
not
specified
(
assumed
3
applications)
Revised
modeling,
using
a
3­
day
foliar
dissipation
half­
life
for
metiram,
yields
the
mammalian
chronic
RQs
for
metiram
in
Table
5a.
When
compared
to
the
chronic
RQs
provided
in
Table
5
above,
based
on
a
35­
day
foliar
dissipation
half­
life,
substantial
chronic
risks
to
birds
still
exist.

iii.
Insects
Currently,
EFED
does
not
assess
risk
to
non­
target
insects.
Results
of
acceptable
studies
are
used
for
recommending
appropriate
label
precautions.
Since
metiram
was
determined
to
be
practically
83
nontoxic
to
honey
bees
(
LD
50
=
437
µ
g/
bee)
no
bee
precautionary
labeling
is
required
on
metiram
product
labeling.

c.
Exposure
and
Risk
to
Aquatic
Organisms
i.
Overview
Because
monitoring
data
from
field
locations
are
not
available
for
metiram,
the
surface
water
exposure
EECs
of
metiram
are
based
on
results
of
screening
models.
Surface
water
concentrations
of
metiram
were
modeled
using
the
Pesticide
Root
Zone
Model
version
3.1.2
beta
(
Carsel
et
al.,
1997)
and
Exposure
Analysis
Modeling
System
version
2.98.04
(
Burns,
1997)
(
PRZM/
EXAMS)
for
Tier
II
estimates.

The
PRZM/
EXAMS
modeling
tools
used
by
EFED
are
designed
to
be
conservative
tools;
90%
of
simulated
sites
are
expected
to
have
environmental
concentrations
which
are
lower
than
the
Tier
II
estimates.
EFED
uses
environmental
fate
and
transport
computer
models
to
calculate
refined
EECs.
PRZM
simulates
pesticide
surface
water
runoff
on
daily
time
steps,
incorporating
runoff,
infiltration,
erosion,
and
evaporation.
The
model
calculates
foliar
dissipation
and
runoff,
pesticide
uptake
by
plants,
soil
microbial
transformation,
volatilization,
and
soil
dispersion
and
retardation.
EXAMS
simulates
pesticide
fate
and
transport
in
an
aquatic
environment
(
one
hectare
body
of
water,
two
meters
deep
with
no
outflow).
The
EECs
have
been
calculated
so
that
in
any
given
year,
there
is
a
10%
probability
that
the
maximum
average
concentration
of
that
duration
in
that
year
will
equal
or
exceed
the
EEC
at
the
site.
The
Tier
II
model
uses
a
single
site
which
represents
a
high
exposure
scenario
for
the
use
of
the
pesticide
on
a
particular
crop
use
site.
The
weather
and
agricultural
practice
are
simulated
at
the
site
over
multiple
years
so
that
the
probability
of
an
EEC
occurring
at
that
site
can
be
estimated.
The
PRZM/
EXAMS
modeling
approach
is
an
uncertain
predictor
of
water
concentrations
in
estuarine/
marine
systems.
It
is
expected,
though
not
empirically
demonstrated,
that
flushing
and
exchange
rates
within
these
systems
may
differ
from
those
assumed
in
the
existing
surface
water
modeling.
In
some
cases,
flushing
and
exchange
may
be
greater
than
accounted
for
in
the
EXAMS
model
and
actual
estuarine/
marine
water
concentrations
may
be
lower.
In
other
cases
tidal
entrapment
of
pollutants
may
contribute
to
higher
effective
pesticide
concentrations
than
have
been
predicted.

The
EECs
are
used
for
assessing
acute
and
chronic
risks
to
aquatic
organisms.
Acute
risk
assessments
are
performed
using
peak
EEC
values
for
single
and
multiple
applications.
Chronic
risk
assessments
are
performed
using
the
21­
day
EECs
for
invertebrates
and
60­
day
EECs
for
fish.

Input
parameters
used
in
Tier
II
(
PRZM
version
3.1.2
beta/
EXAMS
version
2.90.04)
modeling
were
selected
using
Agency
guidance
(
WQTT/
EFED/
OPP.
August,
2000)
and
EFED
calculated
degradation
rate
constants
from
review
of
registrant
submitted
environmental
fate
studies.
A
summary,
with
the
environmental
fate
parameters
used
in
the
model
for
metiram
and
the
output
EECs,
is
provided
in
Appendix
II.
For
a
discussion
of
these
parameters
see
the
Surface­
Water
Monitoring
and
Modeling
section,
above,
of
this
assessment
84
Table
6:
Metiram
Acute
Risk
Quotients
for
Freshwater
Fish
Based
On
a
Rainbow
Trout
(
Salmo
gairdneri
)
LC50
of
230
ppb.
Application
Rate
(
lbs
ai/
A)/

Number
of
Acute
RQ
Applications/
Site/
(
Peak
EEC/
LC50)
2
EEC
Peak
(
ppb)
1
Interval
Application
Method/

0.43
98.9
4.8/
4
Apples
7­
day
interval
ground
&
aerial
0.24
54.5
1.6/
7
Potatoes
5­
day
interval
ground
&
aerial
1
Based
on
PRZM
version
3.12/
EXAMS
version
2.97.5
modeling.
2
RQ
greater
or
equal
to
0.5
exceeds
acute
high
risk,
acute
restricted
use
and
acute
endangered
species
LOC
RQ
greater
or
equal
to
0.1
exceeds
acute
restricted
use
and
acute
endangered
species
LOCs.

RQ
greater
or
equal
to
0.05
exceeds
acute
endangered
species
LOCs.
ii.
Freshwater
Fish
Metiram
acute
risk
quotients
for
freshwater
fish
are
tabulated
below
in
Table
6.
The
results
indicate
that
acute
restricted
use
and
acute
endangered
species
LOCs
are
exceeded
for
uses
on
apples
and
potatoes.
Modeling
was
only
performed
on
these
two
(
2)
metiram
uses
since
these
are
the
major
crop
uses
for
metiram
and
scenarios
for
performing
PRZM­
EXAMS
modeling
for
ornamental
plantings
have
not
been
developed.
85
Table
7:
Metiram
Acute
Risk
Quotients
for
Freshwater
Invertebrates
Based
On
a
water
flea
(
Daphnia
magna)
EC50
of
>
358
ppb.
Application
Rate
(
lbs
ai/
A)/

Number
of
Acute
RQ
Applications/
Site/
(
Peak
EEC/
LC50)
2
EEC
Peak
(
ppb)
1
Interval
Application
Method/

0.28
98.9
4.8/
4
Apples
7­
day
interval
ground
&
aerial
0.15
54.5
1.6/
7
Potatoes
5­
day
interval
ground
&
aerial
1
Based
on
PRZM
version
3.12/
EXAMS
version
2.97.5
modeling.
2
RQ
greater
or
equal
to
0.5
exceeds
acute
high
risk,
acute
restricted
use
and
acute
endangered
species
LO
RQ
greater
or
equal
to
0.1
exceeds
acute
restricted
use
and
acute
endangered
species
LOCs.

RQ
greater
or
equal
to
0.05
exceeds
acute
endangered
species
LOCs.
iii.
Freshwater
Invertebrates
Metiram's
acute
risk
quotients
for
freshwater
invertebrates
are
presented
in
Table
7.
The
results
indicate
that
the
freshwater
invertebrate
acute
restricted
use
and
acute
endangered
species
LOCs
are
exceeded
for
uses
on
apples
and
potatoes.
It
should
be
noted
that
the
metiram
EC
50
for
daphnia
is
expected
to
be
greater
than
358
ppb
since
this
was
the
largest
concentration
tested
in
MRID
No.
44301101
and
an
EC
50
was
not
truly
established
on
this
supplemental
study.
Based
on
this
supplemental
study
it
is
uncertain
whether
or
not
metiram
would
pose
an
acute
risk
to
aquatic
invertebrates,
since
the
study
did
not
provide
a
definitive
EC
50
.
A
core
study
is
being
required
to
fulfill
this
guideline
requirement.
86
Table
8:
Metiram
Acute
Risk
Quotients
for
Aquatic
Non­
Vascular
Plants
Based
Upon
a
Green
Algae
(
Ankistrodesmus
bibraianus
)
EC50
of
77
ppb
Application
Rate
(
lbs
ai/
A)/
Number
of
Non­
Target
Plant
Applications/
Site/

RQ
(
EEC/
EC50)
3
EEC
Peak
(
ppb)
1
Interval
Application
Method/

1.28
98.9
4.8/
4
Apples
7­
day
interval
ground
&
aerial
0.71
54.5
1.6/
7
Potatoes
5­
day
interval
ground
&
aerial
1
Based
on
PRZM
version
3.12/
EXAMS
version
2.97.5
modeling.

2
RQ
greater
or
equal
to
1.0
exceeds
acute
risk
LOCs.
d.
Exposure
and
Risk
to
Non­
target
Plants:
Aquatic
Plants
Exposure
to
non­
target
aquatic
plants
may
occur
through
runoff
or
spray
drift
from
adjacent
treated
sites.
An
aquatic
plant
risk
assessment
for
acute
risk
is
usually
made
for
aquatic
vascular
plants
from
the
surrogate
duckweed
Lemna
gibba.
Non­
vascular
acute
risk
assessments
are
performed
using
either
algae
or
a
diatom,
whichever
is
the
most
sensitive
species.
An
aquatic
plant
risk
assessment
for
acute
endangered
species
is
usually
made
for
aquatic
vascular
plants
from
the
surrogate
duckweed
Lemna
gibba.
To
date,
there
are
no
known
non­
vascular
plant
species
on
the
endangered
species
list.
Runoff
and
drift
exposure
is
computed
from
PRZM­
EXAMS.
The
risk
quotient
is
determined
by
dividing
the
pesticide's
initial
or
peak
concentration
in
water
by
the
plant
EC
50
value.

Acute
risk
quotients
for
freshwater,
non­
vascular
green
alga
(
Ankistrodesmus
bibraianus)
plants
are
presented
in
Table
8.
The
results
indicate
that
the
non­
vascular,
non­
target
plant
acute
risk
LOCs
are
exceeded
for
metiram's
use
patterns
on
apples.
87
e.
Endangered
Species
Based
on
available
screening
level
information
there
is
a
potential
concern
for
acute
effects
on
listed
birds
and
freshwater
fish
species
and
chronic
effects
on
listed
birds
and
mammals
should
exposure
actually
occur.
Even
though
metiram
is
only
slightly
toxic
to
birds,
RQs
exceed
the
endangered
species
LOC
(
RQ
range
from
0.11
to
1.22)
at
maximum
EEC
levels.
EFED
does
not
expect
metiram
exposure
to
pose
acute
risk
to
nontarget
insects
because
metiram
is
practically
nontoxic
to
honeybees
(
acute
contact
LD
50
=
437
µ
g/
bee)
and
there
are
no
incident
data
reporting
adverse
effects
to
honeybees.
The
Agency
does
not
currently
have
enough
data
to
perform
a
screening
level
assessment
for
metiram's
effects
on
listed
nontarget
terrestrial
plants,
freshwater
invertebrates,
estuarine/
marine
fish,
or
vascular
aquatic
plants.
There
are
no
nonvascular
aquatic
plants
or
estuarine/
marine
invertebrate
species
on
the
endangered
species
list.

f.
Ecological
Incidents
The
Ecological
Incident
Information
System
(
EIIS)
(
see
Appendix
VI
for
background
information)
indicated
there
were
no
adverse
effect
incidents
to
terrestrial
or
aquatic
non­
target
organisms
reported
in
association
with
metiram's
use.
88
APPENDIX
V:
Relevant
Eco­
toxicity
Data
Correspondence
UNITED
STATES
ENVIRONMENTAL
PROTECTION
AGENCY
WASHINGTON,
D.
C.
20460
OFFICE
OF
PREVENTION,
PESTICIDES
AND
TOXIC
SUBSTANCES
DP
Barcode:
D261917
Filename:
DCTM_
ARP.
wpd
MEMORANDUM
2/
24/
00
Subject:
Request
to
Upgrade
Four
Ecotoxicity
Studies
Using
Metiram
To:
Patricia
Moe,
Chemical
Review
Manager
Special
Review
and
Reregistration
Division
(
7508W)

From:
Joanne
Edwards,
Entomologist
Ecological
Hazards
Branch
Environmental
Fate
and
Effects
Division
(
7507C)

Through:
Tom
Bailey,
Chief
Ecological
Hazards
Branch
Environmental
Fate
and
Effects
Division
(
7507C)

EFED
has
considered
BASF's
response
to
EFED's
review
of
four
aquatic
ecotoxicity
studies
(
MRIDs
44224401,
44301101,
4430102,
and
43199601;
see
D234011,
D237041
and
D177394
).
The
additional
information
provided
by
BASF
does
not
allow
for
upgrading
of
these
studies.
The
primary
issue
with
aquatic
testing
of
metiram
has
been
how
to
deal
with
its
poor
solubility
(
i.
e.,
variously
reported
at
2
ppm
or
less)
.
EFED
and
BASF
had
an
understanding
that
all
aquatic
ecotoxicity
test
results
would
be
based
on
measured
and
filtered
samples.

To
date,
there
are
no
"
core"
aquatic
studies
using
ETU
as
the
test
substance,
and
only
one
"
core"
study,
a
rainbow
trout
acute
study,
using
metiram
as
the
test
substance
.
The
rainbow
trout
LC50
was
0.55
ppm
based
on
measured
concentrations.
When
correcting
for
dissolved
material
(
filtered),
the
LC50
was
0.2
ppm
(
MRID
43525001).
These
results
show
metiram
to
be
highly
toxic
to
the
fish,
and
indicate
the
need
for
label
precautionary
language,
and
higher
tier
testing.
These
results
are
in
strong
contrast
to
results
from
previously
submitted
studies
conducted
with
metiram
and
ETU,
in
which
the
results
were
based
on
nominal
concentration,
and
showed
ETU
and
metiram
to
be
practically
nontoxic
to
aquatic
animals.
These
studies
have
been
reclassified
invalid
(
e.
g.,
bluegill
LC50
metiram
>
160
ppm
(
MRID
40945501);
bluegill
LC50
metiram
between
26
and
42
ppm
(
MRID
89
44224401);
daphnid
EC50
metiram
=
2.53
ppm.
(
MRID
4097003);
rainbow
trout
ETU
LC50>
490
ppm
(
Acc.
071589)
and
daphnid
ETU
LC50
=
49
ppm
(
Acc.
071589).

The
registrant
is
referred
to
the
guidance
for
how
to
deal
with
poorly
soluble
compounds
in
EPA's
Rejection
Rate
Analysis
(
EPA­
738­
R­
94­
0235),
in
particular
to
why
the
Agency
considers
measured
concentrations,
rather
than
nominal
concentrations,
necessary.
The
registrant
is
referred
to
the
individual
Data
Evaluation
Records
for
the
other
reasons
the
studies
do
not
warrant
reclassification.

In
the
case
of
the
green
algae
study
(
MRID
43199601),
additional
reasons
for
asking
for
a
repeat
study,
not
listed
in
the
DER,
include
an
inappropriate
lighting
regime
(
2x
recommended)
and
inappropriate
cell
inoculum
levels
(
4x
recommended).
The
registrant
is
referred
to
the
guidance
in
EPA's
Pesticide
Rejection
Rate
Analysis
(
see
pg.
158).

If
you
have
any
questions
regarding
this
memorandum,
you
may
contact
Joanne
Edwards
(
308­
6736)
or
Tom
Bailey
(
308­
6666).
90
UNITED
STATES
ENVIRONMENTAL
PROTECTION
AGENCY
WASHINGTON,
D.
C.
20460
OFFICE
OF
PREVENTION,
PESTICIDES
AND
TOXIC
SUBSTANCES
DP
Barcode:
D234011;
D237041;
D177394
Filename:
DCTM_
ARP.
wpd
MEMORANDUM
4/
12/
99
Subject:
Ecotoxicity
Studies
for
Metiram
To:
Anne
Overstreet,
Chemical
Review
Manager
Special
Review
and
Reregistration
Division
(
7508W)

From:
Joanne
Edwards,
Entomologist
Ecological
Hazards
Branch
Environmental
Fate
and
Effects
Division
(
7507C)

Through:
Tom
Bailey,
Chief
Ecological
Hazards
Branch
Environmental
Fate
and
Effects
Division
(
7507C)

Attached
to
this
memorandum
are
Data
Evaluation
Records
(
DERs)
for
ecotoxicity
studies
conducted
with
metiram.
A
synopsis
of
each
study
review
is
provided
below.

MRID
40656901.
D.
W.
Fletcher.
1988.
Metiram
Technical:
21­
Day
Acute
Oral
LD50
Study
in
Bobwhite
Quail;
Bio­
Life
Associates
LTD;
Sponsor:
Metiram
Task
Force;
Laboratory
Report
ID
87
QD
99;
no
DP
barcode
This
study
is
classified
core,
and
fulfills
the
guideline
requirement
for
an
acute
oral
toxicity
study
with
an
upland
gamebird.
The
bobwhite
LD50
is
>
2150
ppm,
classifying
metiram
as
practically
nontoxic
to
bobwhite
on
an
acute
oral
basis.

MRID
44224401.
R.
Munk.
1996.
BAS
222
28
F­
Acute
Toxicity
Study
on
the
Bluegill
Sunfish
(
Lepomis
macrochirus
RAF.)
In
a
Flow­
through
System
(
96
Hours);
BASF
Aktiengesellschaft,
Ludwigshafen,
Germany;
Sponsor
BASF
Corp.,
Research
Triangle
Park,
NC;
Laboratory
Report
ID
14F0265/
965056;
D234011
91
This
study
is
not
scientifically
sound,
and
does
not
fulfill
the
guideline
requirement
for
an
acute
LC50
with
a
warmwater
fish
(
Gdln
72­
1).
The
study
is
classified
invalid
because
the
analytical
data
were
questionable
and
stability/
solubility
problems
were
encountered
with
the
test
material.
The
study
must
be
repeated.

MRID
44301101.
Maisch.
1997.
Determination
of
the
Acute
Effect
of
BAS
222
28
F
(
Metiram)
on
the
Swimming
Ability
of
the
Water
Flea,
Daphnia
magna;
BASF
Aktiengesellschaft,
Ludwigschafen/
Rhine,
FRG;
Sponsor:
BASF
Corp.,
Research
Triangle
Park,
NC;
Laboratory
Report
ID
97/
10538;
D237041
This
study
is
scientifically
sound,
but
does
not
fulfill
the
guideline
requirement
for
an
acute
LC50
with
a
freshwater
invertebrate
(
Gdln
72­
2).
The
study
is
classified
supplemental
because
(
1)
an
EC50
was
not
established;
(
2)
there
was
a
high
variability
in
analytical
results;
and
(
3)
analytical
measurements
were
not
made
on
new
solutions
in
this
static
renewal
test.
Based
on
the
median
analytical
recover
rate
of
all
tested
concentrations
(
51.1%),
the
reported
48­
hour
EC50
was
>
358
ppb,
which
classifies
metiram
as
highly
toxic
to
Daphnia
magna.
The
study
must
be
repeated.

MRID
443011­
02.
Maisch.
1997.
Determination
of
the
Chronic
Effects
of
BAS
222
28
F
on
the
Reproduction
of
the
Water
Flea
Daphnia
magna
STRAUS
in
a
Flow­
Through
Test
System;
BASF
Aktiengesellschaft,
Ludwigshafen/
Rhine,
Germany;
Sponsor:
BASF
Corp.,
Research
Triangle
Park,
NC;
Laboratory
Report
ID
97/
10521;
D237041
This
study
is
not
scientifically
sound,
and
does
not
fulfill
the
requirements
for
a
freshwater
invertebrate
life­
cycle
test
(
Gdln
72­
4).
The
study
is
classified
invalid
because:
(
1)
the
measured
concentrations
were
highly
variable
(
measured
6
to
106%
of
the
nominals);
(
2)
the
control
concentrations
appeared
to
be
contaminated;
(
3)
ephippia
were
produced
in
the
control
group;
and;
(
4)
dry
weight
was
not
measured.
The
study
must
be
repeated.

MRID
43199601.
G.
P.
Dohmen.
1990.
Effects
of
BAS
222
28
F
on
the
Growth
of
the
Green
Alga
Ankistrodesmus
bibraianus;
BASF
Aktiengesellschaft,
Limburgerhof,
Germany;
Sponsor:
BASF
Corp.,
Research
Triangle
Park,
NC;
Laboratory
Project
ID:
P
9
0
­
E008
This
study
is
scientifically
sound
but
does
not
fulfill
the
guideline
requirements
for
an
algal
toxicity
test
because
the
test
was
only
conducted
for
72
hours
and
the
test
species
was
not
the
required
green
alga
species.
The
study
is
classified
supplemental.
The
72­
hour
EC
50
and
NOEC
for
A.
bibraianus
exposed
to
metiram
were
0.077
and
0.013
ppm,
respectively.

To
date,
only
one
EPA
aquatic
guideline
requirement
(
rainbow
trout
LC50;
MRID
43525001)
is
satisfied
for
this
chemical.
It
is
apparent
that
the
problems
in
conducting
acceptable
aquatic
testing
stem
from
metiram's
low
solubility
in
water.
For
guidance
on
how
to
deal
with
poorly
soluble
materials,
the
registrant
is
referred
to
Appendix
A
of
EPA's
Pesticide
Reregistration
Rejection
Rate
Analysis
(
EPA­
738­
R­
94­
0235).
If
you
have
any
questions
regarding
this
memorandum,
you
may
contact
Joanne
Edwards
(
308­
6736)
or
Tom
Bailey
(
308­
6666).
92
APPENDIX
VI:
US
EPA
Ecological
Incident
Information
System
The
Office
of
Pesticide
Programs
(
OPP)
has
tracked
incidents
reports,
given
to
EPA
since
about
1994,
by
assigning
identification
number
in
an
Incident
Data
System
(
IDS)
and
microfiching
the
reports.
The
Environmental
Fate
and
Effects
Division
(
EFED)
then
enters
the
ecological
related
incident
reports
into
a
second
database,
the
Ecological
Incident
Information
System
(
EIIS).
This
second
database
has
some
85
fields
for
potential
data
entry.
EFED
has
also
made
an
effort
to
enter
information
into
EIIS
on
incident
reports
received
before
establishment
of
current
databases.
Although
EFED
has
added
many
of
these
reports,
EIIS
does
not
yet
provide
a
listing
of
all
incident
reports
received
by
EPA.
OPP
does
not
receive
incident
reports
in
a
consistent
format.
For
example,
states
and
various
labs
usually
have
their
own
report
formats.
The
incidents
reports
may
involve
multiple
incidents
involving
multiple
chemicals
in
one
report,
and
may
report
on
only
part
of
an
incident
investigation
(
for
example,
residues).
EFED
has
made
some
progress
in
recent
years,
both
in
getting
incident
reports
sent
and
entered.
However,
there
has
never
been
enough
staff
time
and
effort
assigned
to
recording
incidents.
For
example,
the
staff
time
and
effort
assigned
to
tracking
and
reviewing
laboratory
toxicity
studies
are
greater
than
those
assigned
to
tracking
incidents.

EFED
classifies
EIIS
entered
incidents
into
one
of
several
certainty
levels:
highly
probable,
probable,
possible,
unlikely,
or
unrelated.
In
brief,
"
highly
probable"
incidents
usually
need
carcass
residues,
show
large
cholinesterase
inhibition
(
for
chemicals
such
as
organophosphates
that
depress
brain
and
blood
cholinesterase),
or
clear
circumstances
about
the
exposure.
"
Probable"
incidents
include
those
where
residues
were
not
available
or
circumstances
were
less
clear
than
for
"
highly
probable."
"
Possible"
incidents
include
those
where
multiple
chemicals
may
have
been
involved
and
it
is
not
clear
what
the
contribution
was
of
a
given
chemical.
OPP
use
the
"
unlikely"
category,
for
example,
where
a
given
chemical
is
almost
nontoxic
to
the
category
of
organism
killed
or
the
chemical
was
tested
for
but
not
detected
in
samples.
"
Unrelated"
incidents
are
those
that
OPP
confirms
as
not
pesticiderelated

EFED
also
classes
EIIS
entered
incidents
as
use
or
misuse.
Unless
specifically
confirmed
by
a
state
or
federal
agency
to
be
misuse,
or
there
was
clear
misuse
such
as
intentional
baiting
to
kill
wildlife,
EFED
would
not
typically
consider
incidents
to
be
misuse.
For
example,
data
entry
personnel
often
do
not
have
a
copy
of
the
specific
label
used
in
a
given
application,
and
would
not
usually
be
able
to
detect
various
label­
specific
violations.

EFED
believes
the
number
pesticide
related
incidents
reported
in
EIIS,
while
large,
are
a
small
fraction
of
pesticide
incidents.
EIIS
entered
incidents
requires
that
mortality
incidents
be
seen,
reported,
examined,
and
have
investigation
reports
sent
to
EPA.
Incidents
often
are
not
seen,
because
of
scavenger
removal
of
carcasses,
decay
in
a
field,
or
simply
because
carcasses
may
be
hard
to
see
on
many
sites.
Poisoned
wildlife
may
also
move
off­
site
to
less
visible
areas
before
dying.
Incidents
often
are
not
seen
because
few
people
are
systematically
looking.
Finders,
seeing
incidents,
may
not
report
incidents
to
suitable
authorities
to
examine
the
incident.
The
finder
may
not
know
that
it
is
important
to
report
incidents
or
may
not
know
who
to
contact.
He
or
she
may
not
feel
they
have
the
time
or
wish
to
make
a
telephone
call,
may
hesitate
to
call
because
of
their
own
involvement
in
the
kill,
or
the
call
may
be
long­
distance
which
may
discourage
the
caller.
Incidents
reported
may
not
93
get
examined
if
time
or
people
are
limited
or
may
not
get
examined
thoroughly,
with
residue
and
cholinesterase
analyzes,
for
example.
Also,
if
kills
are
not
reported
and
examined
at
once,
there
will
be
little
chance
of
documenting
the
cause,
since
tissues
and
residues
may
decay
quickly.
States
often
do
not
send
reports
of
examined
incidents
to
EPA,
since
reporting
by
states
is
voluntary
and
some
investigators
may
believe
that
they
don't
have
the
time
or
people
to
send
incident
reports
to
EPA.
(
Felkel.
2000)
94
APPENDIX
VII:
EBDC
Aquatic
Studies
EBDC
Aquatic
Studies
Used
for
Calculating
Risk
Quotients
With
Associated
Study
Parameters
­
3/
13/
2003
MRID
No.
Chemical
Species
Tested
Water
type
Water
Analysis
(
cations,
anions,

EC)
Test
Type1
Nominal
Test
Concentrations
Range
(
ppm)
Measured
(
unfiltered)

Test
Concentrations
Range
(
ppm)
Measured
(
filtered)

Test
Concentrations
Range
(
ppm)
and
Filter
Size
(
µ
m)
Test
Aquaria
Size
(
L)
Chemical
Analyses
(
Parent
or
Other?)
Toxicity
Endpoint
(
ppm)
Exposure
Time
(
hours)
Study
Categorization
43525001
metiram
Rainbow
trout
freshwater
mixture
of
tap
water,
unchlorinated
water,
deionized
water
(
chemical
analysis
­
not
reported)
F
0.01
­
1.0
ND2
­
0.527
ND2
­
0.233
filter
size
=

0.05
60
GC3
for
CS
2
LC
50
=

0.2294
96
core
44301101
metiram
water
flea
freshwater
deionized
water,

EDTA
free,
and
HCL
fortified
samples
for
analysis
S
0.1
­
1.0
0.051
­
0.511
Not
applicable
0.25
GC3
for
CS
2
EC
50
>

0.3586
(
highest
concentr
a­
tion
tested)
48
supplemental
43199601
metiram
green
algae
freshwater
Na
2
EDTA
S
0.001
­

1.0
Not
applicable
Not
applicable
0.1
Not
applicable
EC
50
=

0.0775
72
supplemental
40706001
maneb
Rainbow
trout
freshwater
softwater
and
well
water
(
chemical
analysis
­
not
reported)
S
0.08
­
1.0
0.009
­
0.225
Not
applicable
30
GC3
for
CS
2
LC
50
=
0.04166
96
supplemental
41346301
maneb
fathead
minnow
freshwater
EDTA
F
0.0013
­

0.020
0.00096
­

0.012
Not
applicable
11.5
GC3
for
CS
2
NOAEC
=
0.00616
35
days
core
40749402
maneb
water
flea
freshwater
softwater
and
well
water
S
0.08
­
1.0
ND2
­
0.39
Not
applicable
0.1
GC3
for
CS
2
LC
50
=

0.126
48
core
EBDC
Aquatic
Studies
Used
for
Calculating
Risk
Quotients
With
Associated
Study
Parameters
­
3/
13/
2003
MRID
No.
Chemical
Species
Tested
Water
type
Water
Analysis
(
cations,
anions,

EC)
Test
Type1
Nominal
Test
Concentrations
Range
(
ppm)
Measured
(
unfiltered)

Test
Concentrations
Range
(
ppm)
Measured
(
filtered)

Test
Concentrations
Range
(
ppm)
and
Filter
Size
(
µ
m)
Test
Aquaria
Size
(
L)
Chemical
Analyses
(
Parent
or
Other?)
Toxicity
Endpoint
(
ppm)
Exposure
Time
(
hours)
Study
Categorization
95
40943101
maneb
Atlantic
silverside
Estuari
ne/
mar
ine
filtered
(
0.5
µ
m)

seawater
(
salinity
~
20%)

&
EDTA
F
0.12
­
1.5
ND2
­
1.10
Not
applicable
9
GC3
for
CS
2
LC
50
=

0.186
96
core
41000002
maneb
mysid
shrimp
Estuari
ne/
mar
ine
filtered
(
0.5
µ
m)

seawater
(
salinity
~
20%)

&
EDTA
F
0.005
­

0.060
ND2
­
0.0064
Not
applicable
6.4
GC3
for
CS
2
LC
50
=

0.0036
96
supplemental
40943501
maneb
green
algae
freshwater
Na
2
EDTA
S
0.0026
­

0.040
0.0004
­

0.0067
Not
applicable
0.25
GC3
for
CS
2
EC
50
=
0.01348
120
core
40118502
mancozeb
Rainbow
trout
freshwater
Not
reported
S
0.22
­
4.5
Not
applicable
Not
applicable
Not
reported
Not
applicable
LC
50
=

0.465
96
core9
43230701
mancozeb
fathead
minnow
freshwater
EDTA
added
F
0.0003
­

0.02
0.000236
­

0.01910
ND2
­
0.007973
Not
applicable
~
12.2
GC3
for
CS
2
&

LSC10
for
14C
NOAEC
=
0.002196
for
GC
&

0.00237
for
LSC
28
days
core
40118503
mancozeb
water
flea
freshwater
Not
reported
S
0.026
­

2.0
Not
applicable
Not
applicable
Not
reported
Not
applicable
EC
50
=

0.585
48
core9
40953802
mancozeb
water
flea
freshwater
EDTA
added
F
0.003
­

0.05
0.0029
­

0.053
Not
applicable
1.0
GC3
for
CS
2
&

LSC10
for
14C
NOAEC
=
0.00736
for
LSC
21
days
core
41844901
mancozeb
sheepshead
minnow
Estuari
ne/
mar
ine
filtered
seawater
with
well
water
(
salinity
~
20%)

Na
3
EDTA
added
F
0.6
­
7.7
0.28
­
3.7
Not
applicable
9
GC3
for
CS
2
LC
50
=

1.66
96
supplemental
EBDC
Aquatic
Studies
Used
for
Calculating
Risk
Quotients
With
Associated
Study
Parameters
­
3/
13/
2003
MRID
No.
Chemical
Species
Tested
Water
type
Water
Analysis
(
cations,
anions,

EC)
Test
Type1
Nominal
Test
Concentrations
Range
(
ppm)
Measured
(
unfiltered)

Test
Concentrations
Range
(
ppm)
Measured
(
filtered)

Test
Concentrations
Range
(
ppm)
and
Filter
Size
(
µ
m)
Test
Aquaria
Size
(
L)
Chemical
Analyses
(
Parent
or
Other?)
Toxicity
Endpoint
(
ppm)
Exposure
Time
(
hours)
Study
Categorization
96
41822901
mancozeb
mysid
shrimp
Estuari
ne/
mar
ine
filtered
seawater
with
well
water
(
salinity
~
20%)

Na
3
EDTA
added
F
0.003
­

0.04
0.0034
­

0.017
Not
applicable
6
GC3
for
CS
2
LC
50
=
0.01056
96
supplemental
43664701
mancozeb
green
algae
freshwater
Na
2
EDTA
S
0.033
­

0.50
0.022
­
0.376
Not
applicable
0.1
GC3
for
CS
2
EC
50
=

0.047
120
core
1.
For
aquatic
organisms
(
fish,
zooplankton,
and
phytoplankton),
tests
are
carried
out
using
either
static
(
S)
or
flow­
through
(
F)
methods.
In
the
static
method,
the
pesticide
and
test
organisms
are
added
to
the
test
solution
and
kept
there
for
the
remainder
of
the
study
time.
In
the
flow­
through
method,
a
freshly
prepared,
pesticide­
spiked
test
solution
flows
through
the
test
chamber
continuously
for
the
duration
of
the
test.
The
flow­
through
method
provides
a
higher
continuous
dose
of
the
pesticide;
however,
the
static
method
does
not
remove
waste
products
and
may
accumulate
toxic
pesticide
breakdown
products
and
metabolites.
Neither
method
exactly
mimics
a
natural
system.
(
http://
docs.
pesticideinfo.
org/
documentation4/
ref_
ecotoxicity4.
html
)
Flow­
through
system
allows
the
testing
of
volatile
and
instable
chemicals,
problematic
in
static
test
systems.

2.
None
detected
3.
Gas
chromatography
4.
Based
on
filtered
and
measured
concentration.

5.
Based
on
nominal
concentration.

6.
Based
on
measured
(
unfiltered)
concentration.

7.
Measured
estimate
is
based
on
15%
of
nominal
test
concentrations
remaining
at
end
of
test.
No
actual
values
were
provided
in
DER
and
the
limits
of
detection
at
lower
values
is
questionable.
Measured
EC
50
was
based
on
actual
mean
green
algae
cell
counts
at
end
of
study.
Aquatic
plant
studies
base
the
test
concentrations
on
the
0­
hour
concentrations
because
the
plants
will
take­
up
test
material
during
the
study
period
and
loss
of
test
material
is
not
necessarily
due
to
instability
of
test
material.

8.
Based
on
actual
cell
counts,
not
on
measured
concentration
levels.

9.
Categorization
based
on
acceptance
in
1987
Mancozeb
Standard
EBDC
Aquatic
Studies
Used
for
Calculating
Risk
Quotients
With
Associated
Study
Parameters
­
3/
13/
2003
MRID
No.
Chemical
Species
Tested
Water
type
Water
Analysis
(
cations,
anions,

EC)
Test
Type1
Nominal
Test
Concentrations
Range
(
ppm)
Measured
(
unfiltered)

Test
Concentrations
Range
(
ppm)
Measured
(
filtered)

Test
Concentrations
Range
(
ppm)
and
Filter
Size
(
µ
m)
Test
Aquaria
Size
(
L)
Chemical
Analyses
(
Parent
or
Other?)
Toxicity
Endpoint
(
ppm)
Exposure
Time
(
hours)
Study
Categorization
97
10.
LSC
detection.
The
process
by
which
radioactive
decay
energy
is
converted
to
visible
light
and
measured
in
an
organic
liquid
environment
is
called
LIQUID
SCINTILLATION
COUNTING
(
LSC).
In
Liquid
Scintillation
Counting,
the
amount
of
light
produced
is
proportional
to
the
amount
of
radiation
present
in
the
sample
and
the
energy
of
the
light
produced
is
proportional
to
the
energy
of
the
radiation
that
is
present
in
he
sample.
This
makes
LSC
a
very
convenient
tool
to
measure
radioactivity.
http://
www.
sfu.
ca/~
rsafety/
APPEND9.
pdf
98
REFERENCES
a.
Environmental
Fate
00146764
BASF
AG
(
1981)
Hydrolytical
Stability:
?
MetiramF.
Unpublished
00155189
Klein,
W.
(
1985)
Report
on:
Hydrolysis
of
the
EBDC
Fungicide
Metiram".
Unpublished
study
prepared
by
Fraunhofer
Institut
fur
Umweltchemie
und
Oekotoxikologie.
97
p.

00155190
Klein,
W.
(
1985)
Report
on:
Water
Photolysis
of
the
EBDC
Fungicide
Metiram".
Unpublished
study
prepared
by
Fraunhofer
Institut
fur
Umweltchemie
und
Oekotoxikologie.
97
p.
study.
4
p.

00157031
Klein,
W.
(
1986)
Report
on
Soil
Photolysis
of
the
EBDC
Fungicide
Metiram­
complex.
Unpublished
study
prepared
by
Fraunhofer
In­
titut
fuer
Umweltchemie
und
Oekotoxikologie.
93p.

00161937
Regenstein
(
1986)
Hydrolysis
of
the
EBDC
Fungicide
Metiram
­
Complex:
?
AddendumF.
Unpublished
study
prepared
by
BASF
Aktienge­
sellschaft.
4
p.

00161938
Regenstein
(
1986)
Water
Photolysis
of
the
EBDC
Fungicide
Metiram
Complex:

?
AddendumF.
Unpublished
study
prepared
by
BASF
Aktien­
gesellschaft.
5
p.

40576301
Spare,
W.
(
1988)
Leaching
Characteristics
of
Parent
Metiram:
Project
No.
2501.
Unpublished
study
prepared
by
Agrisearch
Inc.

41440801
Bookbinder,
M.
(
1990)
Metiram
and
Ethylenethiorea:
Dissipation
in
Soil
After
Application
to
Sugar
Beets
in
California
by
Ground
Equipment:
Lab
Project
Number:
42­
MET/
90014.
Unpublished
study
prepared
by
Orius
Associates
Inc.,
in
cooperation
wtih
Morse
Laboratories,
Inc.,
and
others.
200
p.

41440802
Bookbinder,
M.
(
1990)
Metiram
and
Ethylenethiourea:
Dissipation
in
Soil
After
Application
to
Sugar
Beets
in
New
York
by
Ground
Equipment,
1988­
1989:
Lab
Project
Number:
42­
MET/
90029.
Unpublished
study
prepared
by
Orius
Associates
Inc.,
in
cooperation
with
Morse
Laboratories,
Inc.,
and
others.
132
p.
118
p.

00155162
Keller,
E.;
Huber,
R.
(
1985)
Summary
of
Metiram
Soil
Metabolism
Studies
Unpublished
study.
8
p.

00155288
Keller,
E.;
Huber,
R.
(
1985)
?
The
Fate
of
Metiram
in
SoilF:
Rep.
No.
2208.
Unpublished
compilation
prepared
by
BASF
AG.
29
p.

00161935
Novak,
R.
(
1986)
Polyram
Soil
Dissipation:
Determination
of
Polyram
and
Ethylenethiourea
Residues:
NPC
Project
No.
86­
2001.
Unpublished
study
prepared
by
NPC,
Inc.
in
cooperation
with
Enviro­
Bio­
Tech,
Ltd.
22
p.
99
00088894
Lyman,
W.
R.
(
1977)
The
Fate
of
Ethylenebisdithiocarbamate
Fungicides
in
the
Environment.
(
Unpublished
study
received
Dec
9,
1981
under
707­
78;
submitted
by
Rohm
&
Haas
Co.,
Philadelphia,
Pa.;
CDL:
070520­
A)

b.
Ecological
Effects
Valid
Ecotoxicity
Studies
00066220
Atkins,
E.;
Anderson,
L.;
Kellum,
D.;
et
al.
(
1977)
Protecting
Honey
Bees
from
Pesticides.
Riverside,
CA;
Univ.
Of
California.
(
Leaflet
2883).

00108004
Fink,
R.
(
1974)
Final
Report:
Eight­
day
Dietary
LC450­
Bobwhite
Quail:
Project
No.
104­
105.
(
Unpublished
study
received
Apr
2,
1974
under
279­
2032;
prepared
by
Truslow
Farms,
Inc.,
submitted
by
FMC
Corp.,
Philadelphia,
Pa.;
CDL:
132451­
A)

00108005
Fink,
R.
(
1974)
Final
Report:
Eight­
day
Dietary
LC450­
Mallard
Ducks:
Project
No.
104­
106.
(
Unpublished
study
received
Apr
2,1974
under
279­
2032;
prepared
by
Truslow
Farms,
Inc.,
submitted
by
FMC
Corp.,
Philadelphia,
Pa.;
CDL:
132451­
B)

40656901
Fletcher,
D.
(
1988)
Metiram
Technical:
21­
day
Acute
Oral
LD50
Study
in
Bobwhite
Quail:
Laboratory
Project
ID:
87
QD
99.
Unpublished
study
prepared
by
Bio­
Life
Associates,
Ltd.
25
p.

41082001
Fletcher,
D.;
Pedesen,
C.
(
1989)
Metiram
Premix
95%:
Toxicity
and
Reproduction
Study
in
Bobwhite
Quail:
BLAL
No.
87
QR
29.
Unpublished
study
prepared
by
Bio­
Life
Associates,
Ltd.
90
p.

42539102
Munk,
R.
(
1992)
1­
generation
Reproduction
Study
with
Metiram
Premix
on
the
Mallard
Duck
by
Administration
in
the
Diet:
Lab
Project
Number:
72W0698/
90059:
92/
11151.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
214
p.

43199601
Dohmen,
G.
(
1990)
Effects
of
BAS
222
28
F
on
the
Growth
of
the
Green
Alga
Ankistrodesmus
bibraianus:
Lab
Project
Number:
P90/
E008:
90/
0114:
2985.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
27
p.

43525001
Monk,
R.
(
1994)
Acute
Toxicity
Study
on
the
Rainbow
Trout
of
BAS
222
28
F
in
a
Flow­
Through
System
for
96
Hours:
Lab
Project
Numbers:
94/
10920:
PCP03089:
94/
161.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
47
p.

44301101
Maisch
(
1997)
Determination
of
the
Acute
Effect
of
BAS
222
28
F
(
Metiram)
on
the
Swimming
Ability
of
the
Water
Flea,
Daphnia
magna
Straus:
Final
Report:
Lab
Project
Number:
97/
10538:
PCP04287:
96/
0599/
50/
1.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
27
p.
100
Invalid
Ecotoxicity
Studies
40497003
Mueller,
?.
(
1981)
Metiram
BAS
222­
F­­
Acute
Toxicity
to
the
Water­
flea
Daphnia
magna
Straus:
Laboratory
Project
ID
1/
0020/
X/
81:
Reg.
Doc.
#
BASF
81/
0339.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
12
p.

40497011
Munk,
R.
(
1986)
Report
on
the
Study
of
the
Acute
Toxicity:
Name
of
Test
Substance:
BAS
222
28
F/
Polyram
Combi
DF.
Animal
Species:
Rainbow
Trout
(
Salmo
gaidneri
Rich.):
Laboratory
Project
ID85/
400
(
12F400/
85):
Reg.
Doc.
#
BASF
88/
0475.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
23
p.

40945501
Bowman,
J.
(
1988)
Acute
Toxicity
of
[
Carbon
14]­
Metiram
to
Bluegill
Sunfish
(
Lepomis
macrochirus):
ABC
Lab.
Proj.
ID
36982.
Unpublished
study
prepared
by
Analytical
Bio­
Chemistry
Laboratories,
Inc.
123
p.

41156101
Munk,
R.
(
1989)
One
Generation
Reproduction
Study
with
Metiram­
Premix
95%
on
the
Mallard
Duck
(
Anas
platyrhynchos
L.)
by
Admin
istration
in
the
Diet:
Project
No.
72W0116/
88006:
BASF
Registration
Document
No.
BASF:
89/
0227.
Unpublished
study
prepared
by
Basf
Aktiengesellschaft.
124
p.

43525002
Jatzek,
?.
(
1994)
Determination
of
the
Acute
Toxicity
of
BAS
222
28
F
to
the
Water
Flea
Daphnia
magna
Straus
for
48
Hours:
Lab
Project
Numbers:
94/
10671:
94/
0839/
50/
1:
94/
082.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
31
p.

43770401
Monk,
R.
(
1990)
Sublethal
Toxic
Effects
of
Polyram
WG
(
BAS
22228
F)
on
Rainbow
Trout
(
Oncorhynchus
mykiss
Walbaum)
in
a
Flow­
Through
System
for
28
Days:
Lab
Project
Number:
90/
10320:
90/
10319:
42F0724/
895238.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
88
p.

43770402
Fritsch,
H.
(
1990)
Determination
of
the
Longterm
Effects
of
Polyram
WG
BAS
222
28
F
Prod.­
Nr.
81708
on
the
Parthenogenetic
Reproduction
Rate
of
Daphnia
magna
for
21
Days:
Lab
Project
Number:
90/
0310:
1891809:
3/
1809/
89­
1891809.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
63
p.

44224401
Munk,
R.
(
1996)
BAS
222
28
F­­
Acute
Toxicity
Study
on
the
Bluegill
Sunfish
(
Lepomis
macrochirus
RAF.)
in
a
Flow­
Through
System
(
96
Hours):
Lab
Project
Number:
14F0265/
965056:
96/
10978.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
46
p.

44301102
Maisch
(
1997)
Determination
of
the
Chronic
Effect
of
BAS
222
28F
(
Metiram)
on
the
Reproduction
of
the
Water
Flea,
Daphnia
magna
Straus
in
a
Flow­
Through
Test
System:
Final
Report:
Lab
Project
Number:
97/
10521:
96/
0599/
52/
1:
97/
10537.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
42
p.
{
OPPTS
850.1300}
101
Other
Ecotoxicity
Literature
Cited
Atkins,
E.
L.
et
al.
Reducing
Pesticide
Hazards
to
Honey
Bees.
(
1981).
Univ.
of
California.
Division
of
Agricultural
Science
.
Leaflet
2883.
URL:
http://
bees.
ucr.
edu/
tox.
html
Beyer,
W.
N..
and
E.
E.
Connor,
"
Estimates
of
Soil
Ingestion
by
Wildlife,"
U.
S.
Fish
and
Wildlife
Service,
Patuxent
Wildlife
Research
Center
at
Laurel,
MD
and
S.
Gerould,
U.
S.
Geological
Survey,
Reston,
VA.

Brooks,
H.
L.
et
al.
1973.
Insecticides.
Cooperative
Extension
Service.
Kansas
State
Univ.
Manhattan,
Kansas.

Burns,
L.
A.
1997.
EXAMS
2.98.04
Users
Manual.
National
Exposure
Research
Lab,
Office
of
Research
and
Development,
U.
S.
Environmental
Protection
Agency.
Athens,
Georgia.
URL:
http://
www.
epa.
gov/
oppefed1/
models/
water/
index.
htm
Carsel,
R.
F.,
Imhoff,
J.
C.,
Hummel,
P.
R.,
Cheplick,
J.
M.
and
Donigan,
A.
S.
1997.
PRZM
3.1
Users
Manual.
National
Exposure
Research
Lab,
Office
of
Research
and
Development,
U.
S.
Environmental
Protection
Agency.
Athens,
Georgia.
URL:
http://
www.
epa.
gov/
oppefed1/
models/
water/
index.
htm
Dole,
Tim
and
Jeff
Dawson.
Issued:
12/
05/
2003.
Metiram:
Occupational
and
Residential
Exposure
Assessment
and
Recommendations
for
the
Reregistration
Eligibility
Decision
Document.
PC
Code
014601;
DP
Barcode:
D287664.

Dole,
Tim
and
Jeff
Dawson.
Issued:
5/
15/
2003a.
Mancozeb:
Occupational
and
Residential
Exposure
Assessment
and
Recommendations
for
the
Reregistration
Eligibility
Decision
Document.
PC
Code
014504;
DP
Barcode:
D286871.

DÇtzer,
R.
1994.
Statement
on
the
Analytical
Determination
of
Polyram
DF
(
Active
Ingredient:
Metiram)
in
Water
for
Ecotoxicological
Tests.
Attachment
to
MRID
No.
43525001:
Acute
Toxicity
Study
on
the
Rainbow
Trout
of
BAS
222
28
F
in
a
Flow­
Through
System
for
96
Hours:
Lab
Project
Numbers:
94/
10920:
PCP03089:
94/
161.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.

Felkel,
J.
2000.
Reregistration
Eligibility
Document
(
RED)
for
Diazinon.
US
EPA,
OPP,
EFED
URL:
http://
www.
epa.
gov/
pesticides/
reregistration/
status.
htm#
D
Fletcher,
J.
S.,
J.
E.
Nellessen,
and
T.
G.
Pfleeger.
1994.
Literature
review
and
evaluation
of
the
EPA
food­
chain
(
Kenaga)
nomogram,
an
instrument
for
estimating
pesticide
residues
on
plants.
Environ.
Toxicol.
Chem.
13:
1383­
1391.

Gusey,
W.
F.
and
Z.
D.
Maturgo.
November,
1972.
Wildlife
Utilization
of
Croplands.
Environmental
Conservation
Dept.
Shell
Oil
Co.
Houston,
TX.
102
Hoerger,
F.
and
E.
E.
Kenaga.
1972.
Pesticide
residues
on
plants:
Correlation
of
representative
data
as
a
basis
for
estimation
of
their
magnitude
in
the
environment.
In
F.
Coulston
and
F.
Korte
(
eds),
Environmental
Quality
and
Safety:
Chemistry,
Toxicology
and
Technology.
Georg
Thieme
Publishers,
Stuttgart,
pp.
9­
28.

Libelo,
L.
Feb.
1999.
ELL­
Fate:
A
spreadsheet
based
model
that
calculates
the
decay
of
a
chemical
applied
to
foliar
surfaces
for
single
or
multiple
applications.
Environmental
Fate
and
Effects
Division,
Office
of
Pesticides
Programs,
U.
S.
Environmental
Protection
Agency.

Libelo,
L.
Jul.
2001.
ELL­
Fate
Version
1.2:
A
spreadsheet
based
model
that
calculates
the
decay
of
a
chemical
applied
to
foliar
surfaces
for
single
or
multiple
applications.
Environmental
Fate
and
Effects
Division,
Office
of
Pesticides
Programs,
U.
S.
Environmental
Protection
Agency.

Keehner,
D.
Jul.
1999.
Memorandum
dated
7­
1­
99
to
Environmental
Fate
and
Effects
Division/
OPP/
EPA
concerning
the
interim
policy
on
data
requirements
for
non­
target
plant
testing.

Martin,
A.
C.,
A.
L.
Nelson,
and
H.
S.
Zim.
1961.
American
Wildlife
&
Plants:
A
Guide
to
Wildlife
Food
Habits.
Dover
Publications,
Inc.

Mastrota,
N.
Nov.
2001.
Frequency
of
Organism
Classes
in
Reported
Incidents
from
the
US
EPA
Ecological
Incident
Information
System
(
EIIS).
Environmental
Fate
and
Effects
Division,
Office
of
Pesticides
Programs,
U.
S.
Environmental
Protection
Agency.

MRID
No.
43525001.
Monk,
R.
(
1994)
Acute
Toxicity
Study
on
the
Rainbow
Trout
of
BAS
222
28
F
in
a
Flow­
Through
System
for
96
Hours:
Lab
Project
Numbers:
94/
10920:
PCP03089:
94/
161.
Unpublished
study
prepared
by
BASF
Aktiengesellschaft.
47
p.

NatureServe:
An
online
encyclopedia
of
life
[
web
application].
2000.
Version
1.2
.
Arlington,
Virginia,
USA:
Association
for
Biodiversity
Information.
Available:
http://
www.
natureserve.
org/.
(
Accessed:
March
28,
3901
).
URL:
http://
www.
natureserve.
org/
summary
Nelson,
A.
N.
1975.
Appraisal
of
the
Safety
of
Chemicals:
Approximate
Relation
of
Parts
Per
Million
in
Diet
to
Mg/
Kg/
Day.
Quarterly
Report
to
the
Editor
on
Topics
of
Current
Interest.
Association
of
Food
and
Drug
Officials
of
the
United
States.

Office
of
Pesticide
Programs
Information
Network
(
OPPIN).
2003.
A
in­
house
database
for
regulatory
and
scientific
data,
workflow
tracking,
and
electronic
document
management.
Office
of
Pesticides
Programs,
U.
S.
Environmental
Protection
Agency.

Parker,
R.
D.
2001.
GENEEC
Users
Manual:
Tier
One
Screening
Model
for
Pesticide
Aquatic
Ecological
Exposure
Assessment
Version
2.0.
Environmental
Fate
and
Effects
Division,
Office
of
Pesticides
Programs,
U.
S.
Environmental
Protection
Agency.
103
URL:
http://
www.
epa.
gov/
oppefed1/
models/
water/
index.
htm
Urban,
Douglas
J.
Apr.
28,
2000.
Guidance
for
Conducting
Avian
Risk
Assessments
for
Spray
Applications
of
Pesticides.
Environmental
Fate
&
Effects
Division.
Office
of
Pesticide
Programs.
U.
S.
Environmental
Protection
Agency.
Washington,
D.
C.

U.
S.
EPA
40
Code
of
Federal
Regulations
(
CFR).
Part
156,
Subpart
A,
Section
156.10.(
h)(
1)
Labeling
Requirements.
URL:
http://
www.
epa.
gov/
oppfead1/
labeling/
lrm/
chap­
08.
htm
US
EPA.
April,
1998.
Guidelines
for
Ecological
Risk
Assessment.
Risk
Assessment
Forum.
Washington,
DC.
EPA/
630/
R­
95/
002F
US
EPA.
Oct.
6,
1997.
Announcement
of
the
Draft
Drinking
Water
Contaminant
List.
FR
Vol.
62,
No.
193.
pp
52193­
52219
URL:
http://
www.
epa.
gov/
ogwdw000/
ccl/
dwccl.
html
US
EPA.
June
30,
1995.
EEB
Guidance
Document
Number
A­
02.
What
Are
Our
Levels
of
Concern
and
How
Are
They
Used.
Office
of
Pesticide
Programs.
Environmental
Fate
&
Effects
Division.
Washington,
D.
C.

US
EPA.
December,
1994.
Pesticide
Reregistration
Rejection
Rate
Analysis:
Ecological
Effects.
Office
of
Prevention,
Pesticides
and
Toxic
Substances
(
OPPTS).
Washington
DC,
20460,
US.
EPA­
738­
R­
94­
0235.

US
EPA
December,
2002.
TXR#
0050408.
Ethylene
bisdithiocarbamates
(
EBDCs):
Mancozeb,
Maneb,
and
Metiram.
Outcome
of
the
HED
Metabolism
Assessment
Review
Committee
(
MARC)
Meeting.
Office
of
Pesticide
Programs.
Health
Effects
Division.
Washington,
D.
C.

US
EPA.
2005.
Environmental
Fate
and
Ecological
Risk
Assessment
for
Maneb,
Section
4
Reregistration
for
Control
of
Fungal
Diseases
on
Numerous
Crops,
Ornamental
Plantings,
and
Turf
(
Phase
3
Response).
Office
of
Pesticide
Programs.
Environmental
Fate
&
Effects
Division.
Washington,
D.
C.

US
EPA.
2005a.
Environmental
Fate
and
Ecological
Risk
Assessment
for
Mancozeb,
Section
4
Reregistration
for
Control
of
Fungal
Diseases
on
Numerous
Crops,
a
Forestry
Use
on
Douglas
Firs,
Ornamental
Plantings,
and
Turf
(
Phase
3
Response).
Office
of
Pesticide
Programs.
Environmental
Fate
&
Effects
Division.
Washington,
D.
C.

Willis,
G.
and
L.
McDowell.
1987.
Pesticide
Persistence
on
Foliage.
Review
of
Environmental
Contamination
and
Toxicology,
Volume
100.
Springer­
Verlag,
New
York.
pp.
24­
73
WQTT/
EFED/
OPP
(
Water
Quality
Technical
Team/
Environmental
Fate
and
Effects
Division/
Office
of
Pesticides
Programs).
August
6,
2000.
Guidance
for
Chemistry
and
Management
Practice
Input
104
Parameters
For
Use
in
Modeling
the
Environmental
Fate
and
Transport
of
Pesticides:
GENEEC,
PRZM/
EXAMS/
SCI­
GROW.
URL:
http://
www.
epa.
gov/
oppefed1/
models/
water/
index.
htm