MEMORANDUM
April
27,
2004
SUBJECT:
Science
Chapter
on:
Environmental
Fate
Studies
and
Environmental
Fate
Assessment
of
Pine
Oil
FROM
A.
Najm
Shamim,
Ph.
D.,
Chemist
Regulatory
Management
Branch
II
Antimicrobials
Division
(
7510C)

To:
Ben
Chambliss,
Acting
Team
Leader
Regulatory
Management
Branch
II
Antimicrobials
Division
(
7510C)

And
Michelle
Centra,
Pharmacologist,
And
Science
Coordinator
For
Dipropylene
Glycol
RED
Regulatory
Management
Branch
II
Antimicrobials
Division
(
7510C)

Thru:
Connie
Welch,
Chief
Regulatory
Management
Branch
II
Antimicrobials
Division
(
7510C)

Environmental
Fate
Science
Chapter
and
Fate
Assessment
on
Pine
Oil
is
submitted
for
Reregistration
Eligibility
Decision
(
RED).
Page
2
of
7
EXECUTIVE
SUMMARY
Environmental
Fate
Assessment
of
Pine
oil:

Pine
oil's
pesticidal
use
as
a
disinfectant,
santizer,
microbicide/
microbistat,
virucide,
and
insecticide
are
mainly
indoor
use
products
and
would
have
a
low
probability
of
surface
or
ground
water
contamination.
Pine
oil
as
registered
with
the
Agency
has
several
different
blends,
but
the
major
components
of
Pine
oil
are
alpha­
terpineol
and
alpha­
and
beta­
Pinene.
The
registrants
have
submitted
data
on
Pine
Oil
Blend
110990,
which
is
a
composite
blend
of
100%
pine
oil
MUPs
of
84%
terpene
alcohols
(
of
which
alpha
terpineol
is
a
major
constituent)
and
up
to
16%
terpene
hydrocarbons,
of
which
alpah/
beta
pinenes
are
a
major
constituent.
Since
the
registered
product
is
a
mixture
and
no
fate
data
were
submitted
and
since
no
open
literature
data
are
available
on
fate
characteristics
of
pine
oil,
the
Agency
decided
to
make
a
comparison
of
fate
properties
of
alpha/
beta
pinenes,
and
alpha
terpineol
and
extrapolate
these
to
pine
oil
under
consideration
for
reregistration.

Alpha­
and
beta­
pinene
may
exist
as
a
vapor
in
the
ambient
atmosphere
and
will
be
degraded
by
reaction
with
photochemically­
mediated
hydroxyl
radicals
with
a
half­
life
of
4
hours
and
4.9
hours,
respectively.
Alpha­
and
beta­
pinene
are
not
expected
to
directly
photolyze
due
to
the
lack
of
absorption
in
the
environmental
UV
spectrum.
Alpha­
and
beta­
pinene
volatilize
in
both
soil
and
surface
water.
These
undergo
biodegradation
readily
and
have
low
mobility
in
soil
possibly
have
low
probability
of
ground
and
surface
water
contamination.
Alpha­
and
betapinene's
bioconcentration
factors
of
2800
and
440,
respectively,
and
high
log
K
ow
values
may
result
in
bioaccumulation
or
bioconcentration
in
aquatic
organisms.
However,
a
recent
paper3
(
National
Park
Service
of
Colorado
and
Colorado
State
University)
suggests
that
turpentine
oil
(
of
which
alpha/
beta
pinenes
constitute
up
to
90%
do
not
appear
to
bioaccumulate,
possibly
due
to
readily
biodegradable
property.
Alpha­
and
beta­
pinene
have
also
been
shown
to
be
readily
biodegradable
in
the
soil
by
microorganisms,
although
both
alpha­
and
beta­
pinene
absorb
with
a
high
degree
to
suspended
particles
and
sediments
in
the
water
column
having
an
estimated
K
oc
(
1000
and
1200,
respectively).

Environmental
Fate
Assessment
(
alpha­
terpineol):

Alpha­
terpineol
most
likely
exists
as
a
vapor
in
the
ambient
atmosphere
and
is
degraded
by
reaction
with
photochemically­
mediated
hydroxyl
radicals
with
a
half­
life
of
4
hours.
Alphaterpineol
does
not
hydrolyze
or
go
through
direct
photolysis
due
to
the
lack
of
absorption
in
the
environmental
UV
spectrum.
Alpha­
Terpineol
volatilizes
in
both
soil
and
surface
water.
Along
with
volatilization,
it
is
highly
bio­
biodegradable
and
with
low
mobility
in
soil
it
is
not
likely
to
contaminate
ground
and
surface
water.
Alpha­
terpineol's
bioconcentration
factor
110
and
a
log
K
ow
value
may
possibly
result
in
moderate
bioaccumulation
and
bioconcentration
in
aquatic
organisms.
However,
no
data
on
aquatic
organisms
are
available.
Alpha­
terpineol
also
readily
degrades
in
the
soil
by
microorganisms.
Alpha­
terpineol
has
a
high
absorptitivty
to
suspended
particles
and
sediments
in
the
water
column
as
its
estimated
K
oc
(
1000).
Page
3
of
7
The
registered
product
of
pine
oil
appear
to
have
some
differences
in
physical
properties
like
it
is
not
water
soluble,
hence
no
Kow
can
be
estimated
and
is
not
known.
Similarly,
its
vapor
pressure
is
different
(
0.20
mm
Hg
at
20
o
C)
from
alpha/
beta
pinenes
or
alpha
terpineol,
(
4.93
and
2.98
for
alpha/
beta
pinenes
vs
4.2
x
10­
2
mm
Hg
for
alpha
terpineol).
Alpha/
beta
pinenes
and
alpha
terpineol
as
separate
entities
do
not
show
any
major
environmental
concerns,
and
the
Agency
at
this
time
has
determined
that
pine
oil
is
not
likely
to
have
any
major
environmental
concerns
Environmental
Fate
Chemistry
of
alpha­
and
beta­
pinene
:

The
Agency
does
not
have
a
database
on
alpha­
and
beta­
pinene
in
environmental
media.
For
the
reregistration
eligibility
decision
(
RED)
process
the
Agency
has
relied
on
open
literature
and
fate
properties
of
alpha­
and
beta­
pinene
obtained
from
open
literature.
The
following
fate
properties
from
an
open
literature
search
are
(
1,2)

Environmental
Fate
Properties
of
alpha­
and
beta­
pinene
alpha­
pinene
beta­
pinene
Vapor
Pressure
@
25o
C
(
mm
Hg)
4.75
2.93
Henry's
Law
Constant
(
air/
water
partition
coefficient)
(
atm­
cu
m/
mole)
0.107
0.160
K
OC
(
organic
carbon
ratio
in
soil)
1000
1200
Log
K
OW
(
octanol/
water
partition
coefficient)
4.83
4.35
BCF
2800
440
Alpha­
pinene
1.
Exists
solely
as
a
vapor
in
the
ambient
atmosphere
and
will
be
degraded
by
reaction
with
photochemically­
produced
hydroxyl
radicals
(
half­
life
for
reaction:
4
hrs).
2.
Degraded
in
atmosphere
by
reaction
with
ozone
(
half­
life
for
reaction:
40
minutes).
3.
Degraded
by
a
night­
time
reaction
with
nitrate
radicals
(
half­
life
for
reaction:
6
minutes)
4.
Not
expected
to
directly
photolyze
due
to
the
lack
of
absorption
in
the
environmental
UV
spectrum.

1.
Abiotic
Degradation:

a.
Hydrolysis:
Not
expected
to
occur
due
to
the
lack
of
hydrolyzable
functional
groups.
Page
4
of
7
b.
Photolysis:
Alpha­
pinene
not
expected
to
directly
photolyze
due
to
the
lack
of
absorption
in
the
environmental
UV
spectrum.
Products
from
the
reaction
of
alpha­
pinene
with
ozone
are
carbon
monoxide,
cabon
dioxide,
formaldehyde,
acetaldehyde,
formic
acid,
peroxyacteylnitrate,
cis­
pinonic
acid,
nopinene,
acetone,
pionaldehyde,
glyoxal,
and
hydroxyl
radicals.

2.
Biotic
Degradations:

a.
Aqueous
aerobic
degradation:
The
biodegradation
in
aerobic
waters
is
expected
to
be
rapid
based
on
the
results
of
screening
studies.
The
concentration
of
alphapinene
in
sea
water
samples
decreased
from
0.41
ng/
L
to
0.25
ng/
L
when
incubated
with
macrophytes
for
6
hours
at
10oC.
The
concentration
of
alphapinene
in
the
influent
to
a
kraft
mill
aerated
stabilization
basin
with
a
7­
8
day
retention
time
decreased
from
0.20
ppm
to
0.04
ppm.

b.
Aqueous
Anaerobic
degradation:
No
literature
studies
are
available.

c.
Aerobic
soil
degradation:
Rapid
degradation
is
expected
based
on
soil
slurry
samples
taken
from
three
different
Georgia
watersheds
that
were
found
to
readily
degrade
alpha­
pinene
under
aerobic
conditions
undergoing
complete
removal
within
250
hours
after
short
lag
period.

Bioaccumulation:
Log
K
ow
of
this
chemical
is
estimated
to
be
4.83,
and
is
likely
to
bioaccumalate.
A
bioconcentration
factor
of
2800
suggests
the
potential
for
bioconcentration
in
aquatic
organisms
is
very
high.
But
no
data
are
available
to
indicate
this
phenomenon.

A
Henry's
Law
Constant
of
0.107
atm­
cu
m/
mole
will
volatilize
from
most
moist
soil
and
may
volatilize
from
dry
soil.
Adsorption
to
soil
is
expected
to
attenuate
volatilization.
Alphapinene
is
also
expected
to
absorb
to
suspended
solids
and
sediments
in
the
water
column
based
on
the
estimated
K
oc
(
1000).
Volatilization
half­
lives
is
estimated
to
be
4
hours
in
a
model
river
and
5
days
in
a
model
lake.
Rapid
biodegradation
of
alpha­
pinene
occurs
in
both
soil
and
water
based
on
a
soil
slurry
study
and
screening
studies.

beta­
pinene
1.
Exists
solely
as
a
vapor
in
the
ambient
atmosphere
and
will
be
degraded
by
reaction
with
photochemically­
produced
hydroxyl
radicals
(
half­
life
for
reaction:
4.9
hrs).
2.
Not
expected
to
directly
photolyze
due
to
the
lack
of
absorption
in
the
environmental
UV
spectrum.

1.
Abiotic
Degradation:
Page
5
of
7
a.
Hydrolysis:
Not
expected
to
occur
due
to
the
lack
of
hydrolyzable
functional
groups.

b.
Photolysis:
beta­
pinene
not
expected
to
directly
photolyze
due
to
the
lack
of
absorption
in
the
environmental
UV
spectrum.

2.
Biotic
Degradations:

a.
Aqueous
aerobic
degradation:
The
biodegradation
in
aerobic
waters
is
expected
to
be
rapid
based
on
studies
performed
on
monoterpenes
and
alpha­
pinene.

b.
Aqueous
Anaerobic
degradation:
No
literature
studies
are
available.

c.
Aerobic
soil
degradation:
Pinene
is
degraded
by
microbiological
organisms
in
soil.

Bioaccumulation:
Log
K
ow
of
this
chemical
is
estimated
to
be
4.35,
and
therefore
is
expected
to
bioaccumalate.
A
bioconcentration
factor
of
440
suggests
some
potential
for
bioconcentration
in
aquatic
organisms.

A
Henry's
Law
Constant
of
0.160
atm­
cu
m/
mole
will
volatilize
from
most
moist
soil
and
may
volatilize
from
dry
soil.
Adsorption
to
soil
is
expected
to
attenuate
volatilization.
Betapinene
is
also
expected
to
absorb
to
suspended
solids
and
sediments
in
the
water
column
based
on
the
estimated
K
oc
(
1200).
Volatilization
half­
lives
is
estimated
to
be
1.2
hours
in
a
model
river
and
4.6
days
in
a
model
lake.
Rapid
biodegradation
of
beta­
pinene
occurs
in
both
soil
and
water
based
studies
performed
on
monoterpenes
and
alpha­
pinene.

Environmental
Fate
Data
For
alpha­
terpineol
:
Page
6
of
7
The
following
fate
properties
were
obtained
from
an
open
literature
search
for
alphaterpineol
1,2)

Environmental
Fate
Properties
of
alpha­
terpineol
Alpha­
Terpineol
Vapor
Pressure
@
25o
C
(
mm
Hg)
0.0423
Henry's
Law
Constant
(
air/
water
partition
coefficient)
(
atm­
cu
m/
mole)
1.2
×
10­
5
K
OC
(
organic
carbon
ratio
in
soil)
1000
Log
K
OW
(
octanol/
water
partition
coefficient)
2.98
BCF
110
alpha­
terpineol
3.
Exists
solely
as
a
vapor
in
the
ambient
atmosphere
and
will
be
degraded
by
reaction
with
photochemically­
produced
hydroxyl
radicals
(
half­
life
for
reaction:
4
hrs).
4.
Degraded
in
atmosphere
by
reaction
with
ozone
(
half­
life
for
reaction:
40
minutes).
5.
May
also
degrade
in
the
atmosphere
by
reaction
with
nitrate
radicals.
6.
Not
expected
to
directly
photolyze
due
to
the
lack
of
absorption
in
the
environmental
UV
spectrum.

1.
Abiotic
Degradation:

b.
Hydrolysis:
Not
expected
to
occur
due
to
the
lack
of
hydrolyzable
functional
groups.

c.
Photolysis:
alpha­
terpineol
not
expected
to
directly
photolyze
due
to
the
lack
of
absorption
in
the
environmental
UV
spectrum.

2.
Biotic
Degradations:

a.
Aqueous
aerobic
degradation:
Ninety­
nine
percent
removal
of
alpha­
terpineol,
at
an
initial
concentration
of
3.86
ppm,
was
incubated
for
168
­
192
hours
under
aerobic
conditions
using
sewage
inoculum
in
a
biological
treatment
study
utilizing
both
batch
and
continuous
digesters.
In
another
study,
alpha­
terpineol,
at
4000
ppm,
showed
no
biodegradation
after
about
23
days
under
aerobic
conditions
when
added
to
50
mL
of
mineral
salts
medium
and
0.2
mL
of
radioactive
waste
trench
leachate
inoculum.
Page
7
of
7
b.
Aqueous
Anaerobic
degradation:
No
literature
studies
are
available.

c.
Aerobic
soil
degradation:
Alph­
terpineol
is
readily
biodegraded
according
to
results
from
biological
treatment
simulation
and
a
standardized
screening
test
(
tests
not
specific
to
soil
media)

Bioaccumulation:
Log
K
ow
of
this
chemical
is
estimated
to
be
2.98,
and
therefore
has
potential
to
moderately
bioaccumalate.
A
bioconcentration
factor
of
110
suggests
the
potential
for
bioconcentration
in
aquatic
organisms
is
moderate
A
Henry's
Law
Constant
of
1.2
×
10­
5
atm­
cu
m/
mole
will
volatilize
from
most
moist
soil,
but
will
not
volatilize
from
dry
soil.
Alpha­
terpineol
is
also
expected
to
absorb
to
suspended
solids
and
sediments
in
the
water
column
based
on
the
estimated
K
oc
(
1000).
Volatilization
half­
lives
is
estimated
to
be
4
days
in
a
model
river
and
32
days
in
a
model
lake.
Rapid
biodegradation
of
alpha­
terpineol
should
occur
according
to
results
from
biological
treatment
simulation
and
a
standardized
screening
test.

Surface
and
Ground
Water
Contamination:

Pine
Oil
is
registered
for
indoor
uses
only
and
it
is
not
likely
to
contaminate
surface
or
ground
water.
In
an
event,
however,
if
Pine
oil
is
released
to
a
waste
stream,
the
three
major
constituents
namely:
alpha­
pinene,
beta
pinene
and
alpha
terpineol
volatilize
rapidly
from
surface
water,
are
highly
biodegradable,
they
have
short
half
lives
in
water,
and
have
low
mobility
in
soils.
Hence
there
is
low
probability
of
surface
and
ground
water
contamination.

BIBLIOGRAPHY
1.
Hazard
Substances
Databank
(
HSDB),
A
Database
of
the
National
Library
of
Medicine's
TOXNET
System.

2.
Environmental
Fate
Database.
A
Database
of
the
Syracuse
Research
Corporation
(
SRC).

References
1
and
2
use
estimated
fate
parameters.
In
a
number
of
cases,
these
parameters
may
be
on
the
high
end
of
estimation,
a
quantitative
fate
assessment
is
difficult
to
carry
out.

3.
Roy
Erwin,
National
Park
Service,
Water
Resource
Division,
Fort
Collins,
Colorado,
July
1997
