Page
1
of
8
UNITED
STATES
ENVIRONMENTAL
PROTECTION
AGENCY
WASHINGTON,
D.
C.
20460
OFFICE
OF
PREVENTION,
PESTICIDES
AND
TOXIC
SUBSTANCES
April
10,
2002
MEMORANDUM
SUBJECT:
Tolerance
Review
of
Compounds
of
Group
13,
Lignins,
Cellulose
and
Pines
as
Inert
Ingredients
in
Terrestrial
and/
or
Aquatic
Agricultural
and
Non­
Agricultural
Uses
FROM:
Sid
Abel,
Senior
Environmental
Scientist
Environmental
Fate
and
Effects
Division
(7507C)

TO:
Kathryn
Boyle,
Inerts
Team
Lead
Registration
Division
(7505C)

This
memorandum
transmits
the
Environmental
Fate
and
Effects
Division's
(EFED)
fate,
exposure
and
ecotoxicity
assessment
of
compounds
of
the
Lignins,
Cellulose
and
Pine
compounds
and
Furfural.
The
assessment
is
based
on
readily
available
information
from
the
Agency,
peer
reviewed
public
literature
sources
and
Structure
Activity
Relationships
(SAR).
Information
contained
in
these
sources
permits
EFED
to
conduct
a
qualitative
assessment
of
environmental
fate,
exposures
and
toxicity
of
these
compounds.

If
you
should
have
any
questions
concerning
the
information
within,
please
contact
me
at
305­
7346.
Page
2
of
8
Conclusions
A
review
of
the
readily
available
information
and
use
of
Structure
Activity
Relationships
(SAR)
on
the
compounds
that
make
up
the
ligninsulfonates,
cellulose
compounds,
pinenes
and
furfural
is
sufficient
to
conduct
a
qualitative
assessment
of
the
likely
fate,
exposures
and
toxicity
associated
with
their
use
as
pesticide
inert
ingredients.
Environmental
loadings
will
be
attributable
to
anthropogenic
(feedstock
for
chemical
syntheses
and
as
a
solvent
in
many
consumer
and
commercial
products)
and
natural
sources
(plants).

Available
data
and
SARs
indicate
that
the
ligninsulfonates,
cellulose
compounds,
pinenes,
and
furfural
will
undergo
primary
biologically
mediated
degradation
in
a
matter
of
days
to
weeks
and
ultimate
degradation
(mineralization)
in
a
matter
of
weeks
to
months.
Transformation
and/
or
degradation
via
hydrolysis
and
direct
soil
and
water
photolysis
is
not
expected
to
occur
for
any
of
these
compounds.
Atmospheric
photo­
oxidation
is
expected
to
occur
for
the
pinenes
and
furfural
and
represents
a
very
important
degradation
pathways
for
these
compounds.
Reaction
rates
halflives
range
from
hours
to
days.
With
the
exception
of
furfural,
this
group
of
compounds
are
expected
to
be
predominantly
found
in
the
sorbed
state
in
water,
while
furfural
will
be
mainly
in
dissolution.
Where
available,
literature
data
is
in
good
agreement
with
SAR
estimates.

Transport
to
surface
water
in
the
sorbed
state
is
expected
to
dominate
the
nondegradation
pathways
of
dissipation
for
all
but
furfural.
Furfural
will
reach
surface
water
in
dissolution
based
on
high
water
solubility
and
low
sorption
coefficients.
Groundwater
contamination
is
not
likely
to
be
significant
for
any
of
these
compounds.
In
water,
partitioning
to
the
sediment
is
likely
for
all
compounds
except
furfural.
Partitioning
to
air
from
water
surfaces
is
expected
to
be
high
for
all
compounds
based
Henry's
Law
constant
and
high
from
dryer
surfaces
such
as
soils
based
on
volatility.
Bioconcentration
is
expected
to
be
significant
for
the
pinenes
only.

Shallow
aquifer
ground
water
contamination
of
furfural
may
occur,
however,
biologically
mediated
degradation
under
aerobic
conditions
will
limit
loadings,
thus,
concentrations.
Based
on
the
high
volatility
of
these
compounds
and
aeration
sequences
used
in
many
drinking
water
treatment
utilities,
it
is
unlikely
that
most
of
these
compounds
will
be
found
in
treated
water
at
concentrations
equivalent
to
those
found
in
the
environment.
There
are
no
ambient
water
quality
criteria
or
drinking
water
maximum
contaminant
or
health
advisory
levels
for
these
compounds.

Based
on
the
Agency's
toxicity
categories
the
ligninsulfonates
and
cellulose
compounds
are
classified
as
practically
non­
toxic
to
aquatic
organisms
and
the
pinenes
are
classified
as
highly
toxic
to
very
highly
toxic
to
aquatic
organisms.
Furfural
is
classified
as
slightly
toxic.
Terrestrial
organisms
toxicity,
using
mammal
data
as
a
surrogate
in
the
absence
of
avian
data,
indicate
that
these
compounds
may
be
classified
as
practically
non­
toxic.
Page
3
of
8
LIGNINSULFONATES
The
available
chemical
structures,
physical­
chemical
properties,
environmental
fate,
and
aquatic
and
terrestrial
toxicity
of
these
compounds
are
somewhat
similar,
Table
1,
with
differences
mainly
attributable
to
differences
in
cation
group
(Ca,
Na,
NH4
,
Mg,
P,
Zn).
Major
uses
include
dispersants,
emulsion
stabilizer,
and
chelating
agents.
One
reference
indicated
sodium
lignonsulfonate
is
used
to
enhance
the
biodegradation
of
PCBs.
As
a
group,
the
ligninsulfonates
are
soluble
to
very
highly
water
soluble
depending
on
the
cation.
Once
in
water,
dissociation
of
the
cation
is
expected
depending
on
pH.
They
are
not
expected
to
be
mobile
in
terrestrial
environments,
moving
equally
with
the
water
and
sediment
phase
to
surface
water.
Ground
water
migration
is
not
likely.
Once
in
water,
the
dissociated
cation
and
anion
are
likely
to
remain
in
dissolution.
Volatility
from
soil
and
water
(Henry's
Law
Constant)
is
not
expected.
Primary
microbial
mediated
degradation
may
limit
transport
of
parent
material
to
surface
and
ground
water
from
applications
or
releases
to
land.
Fugacity
modeling
predicts
approximately
50%
of
releases
will
be
associated
with
the
water
phase
and
50%
with
soils.
Predicted
volatilization
half­
lives
in
rivers
and
lakes
is
on
the
order
of
decades.
Therefore,
the
data
suggest
that
the
ligninsulfonates
may
be
persistent
in
aquatic
environment
of
low
microbial
activity
and
much
less
persistent
in
environments
with
ample
microbial
activity.
According
to
the
MSDS
(Wesco
Technologies,
Ltd.,
2002),
pH
of
the
various
compounds
range
from
4
to
10
for
both
liquid
and
powder
forms,
Table
1.
Properties
for
zinc­
ligninsulfonate
cannot
be
determined
because
a
representative
structure
could
not
be
found.
MSDS
reports
the
compound's
pH
as
4
to
5
for
both
the
liquid
and
powder
form.

Estimated
ecotoxicity
data
for
aquatic
animals
are
available
Table
1.
The
ecotoxicity
estimates
indicate
that
these
compounds
are
practically
nontoxic
on
an
acute
basis.
Estimated
acute
toxicity
is
much
greater
than
1000
mg/
L
for
freshwater
fish,
Daphnia
magna,
and
green
algae.
Chronic
toxicity
levels
are
very
similar.
Terrestrial
animal
toxicity
based
on
available
rat
data
would
indicate
that
through
the
oral
route,
the
ligninsulfonates
are
practically
non­
toxic
on
an
acute
basis.

CELLULOSE
COMPOUNDS
The
chemical
structures,
physical­
chemical
properties,
environmental
fate
behavior,
and
aquatic
and
terrestrial
toxicity
of
these
compounds
is
expected
to
be
similar.
No
compound
specific
data
were
found
in
the
readily
available
information.
Structural
analyses
cannot
be
conducted
without
representative
structures
for
one
or
more
of
the
compounds.
Cellulose
is
a
glucose
polymer
of
high
molecular
weight
found
in
all
plants.
Glucose
units
are
joined
by
­
1,
4linkages
The
cellulose
compounds
are
the
most
abundant
compounds
found
in
nature.
Whether
simple
or
complex,
they
play
a
major
role
in
carbohydrate
metabolism
of
living
organisms.
As
a
result,
they
may
be
grouped
with
compounds
such
as
those
of
the
citric
acid
cycle
in
terms
of
importance,
environmental
behavior
and
toxicity.
Cellulose
compounds
are
polymer
compounds
with
cellulose
itself
being
unbranched.
Chemical
modification
of
cellulose
produces
polymeric
materials
that
are
familiar
commercial
products.
Adding
carbonyl
groups
and
cations,
such
as
Page
4
of
8
sodium,
will
tend
to
increase
solubility
and
reactivity
in
nature.
Carboxymethylcellulose
is
synthesized
when
cellulose
is
reacted
with
chloroacetate.
These
compounds
are
commonly
used
in
detergents.
A
carboxylic
acid,
carboxymethylcellulose
may
be
synthesized
to
the
sodium
or
ether
compound
listed
as
inert
ingredients.
Cellulose
compounds
are
expected
to
be
biodegradable
in
the
environment
as
primary
sources
of
energy.
Volatilization
is
expected
to
be
minimal.
Sorption
will
be
dependent
on
type
and
abundance
of
functional
groups,
e.
g.,
carbonyl
(R­
C=
O).

Terrestrial
animal
toxicity
based
on
available
rat
data
would
indicate
cellulose
compounds
are
practically
non­
toxic
on
an
acute
basis.

PINENES
AND
FURFURAL
The
physical­
chemical
properties,
environmental
fate
behavior,
and
aquatic
and
terrestrial
toxicity
of
­
pinene,
­
pinene
and
furfural
are
presented
in
Table
2.
­
Pinene
(turpentine)
is
naturally
occurring
in
a
wide
variety
of
plants
and
is
used
as
a
solvent,
fragrance,
flavoring
and
synthetic
intermediate.
­
Pinene
will
readily
volatilize
from
soil
and
moving
water
to
the
atmosphere
within
hours
and
within
days
from
lakes.
Once
in
the
atmosphere,
­
pinene
will
degrade
with
photochemically­
produced
hydroxyl
radicals
with
a
estimated
half­
life
of
4
hours.
Reaction
with
ozone
occurs
with
a
half­
life
of
approximately
40
minutes.
Night­
time
reactions
with
nitrate
radicals
occurs
with
a
half­
life
of
6
minutes.
Mobility
is
soil
is
expected
to
be
low.
Biologically
mediated
primary
degradation
is
expected
to
occur
rapidly
in
aerobic
soils.
Complete
removal
was
observed
in
three
different
soil
slurries
from
Georgia.
Degradation
is
seawater
samples
occurred
with
a
half­
life
of
approximately
6­
8
hours.
Bioconcentration
in
aquatic
organisms
may
occur
based
on
an
estimated
BFC
of
2800.
­
Pinene
has
been
detected
in
the
Black
Warrior
River
in
AL
and
in
sea
water
from
Resurrection
Bay,
AK.
Concentrations
were
reported
in
the
low
parts
per
billion
(<
100
ppb).
Based
on
the
above
information,
­
pinene
is
not
expected
to
persist
in
the
environment.

­
Pinene
(turpentine)
is
naturally
occurring,
with
­
pinene,
but
in
smaller
amounts,
in
a
wide
variety
of
plants
used
as
a
solvent,
fragrance,
flavoring
and
synthetic
intermediate.
­
Pinene
will
readily
volatilize
from
soil
and
moving
water
to
the
atmosphere
within
hours
and
within
days
from
lakes.
Once
in
the
atmosphere,
­
pinene
will
degrade
with
photochemically­
produced
hydroxyl
radicals
with
a
estimated
half­
life
of
4.
9
hours.
Reaction
with
ozone
occurs
with
a
halflife
of
approximately
22
hours.
Night­
time
reactions
with
nitrate
radicals
may
occur,
no
relevant
information
could
be
located
on
estimated
half­
lives.
Mobility
is
soil
is
expected
to
be
low.
Biologically
mediated
primary
degradation
is
expected
to
occur
rapidly
in
aerobic
soils.
Bioconcentration
in
aquatic
organisms
may
occur
based
on
an
estimated
BFC
of
444.
­
Pinene
has
been
detected
in
the
Black
Warrior
River
in
Alabama,
concentrations
were
not
reported.
Based
on
the
above
information,
­
pinene
is
not
expected
to
persist
in
the
environment.

Furfural
is
an
aldehyde
important
as
a
solvent
for
certain
petrochemical
processes
and
as
a
raw
material
for
preparation
of
polymers,
plastics,
and
tetrahydrofuran.
Furfural
will
volatilize
Page
5
of
8
from
soil
and
moving
water
to
the
atmosphere
within
days
and
within
months
from
lakes.
Once
in
the
atmosphere,
furfural
will
degrade
with
photochemically­
produced
hydroxyl
radicals
with
a
estimated
half­
life
of
3
to
4
hours.
Reaction
with
ozone
is
uncertain
and
may
not
occur.
Nighttime
reactions
with
nitrate
radicals
may
be
an
important
degradation
pathway,
however,
data
to
estimate
half­
lives
could
not
be
located.
Mobility
is
soil
is
expected
to
be
high,
with
ground
and
surface
contamination
likely.
Biologically
mediated
primary
degradation
is
expected
to
occur
in
aerobic
soils
within
days
and
ultimate
degradation
within
weeks.
Bioconcentration
in
aquatic
organisms
is
not
expected
to
occur.
Fugacity
modeling
suggest
that
approximately
55%
of
furfural
will
be
found
in
water
and
44
percent
on
soil.
Based
on
the
above
information,
furfural
is
not
expected
to
persist
in
the
environment.

Estimated
ecotoxicity
data
for
aquatic
animals
are
available
Table
2.
The
ecotoxicity
estimates
indicate
­
pine
is
very
highly
toxic
to
aquatic
organisms
on
an
acute
basis.
­
Pinene
may
present
an
acute
concern
for
marine/
estuarine
invertebrates
based
on
documented
environmental
concentrations
near
the
levels
of
predicted
toxicity.
Acute
toxicity
estimates
are
0.
72
mg/
L
for
freshwater
fish,
0.
51
mg/
L
for
marine/
estuarine
fish,
0.
93
mg/
L
for
Daphnia
magna,
0.
042
mg/
L
for
mysid
shrimp,
and
0.
66
mg/
L
for
green
algae.
Chronic
toxicity
estimates
for
freshwater
fish
is
0.
138
mg/
L.
Terrestrial
animal
toxicity
based
on
available
rat
data
would
indicate
that
­
pinene
is
practically
non­
toxic
on
an
acute
basis.

­
pine
very
highly
toxic
to
aquatic
organisms
on
an
acute
basis.
­
Pinene
may
present
an
acute
concern
for
marine/
estuarine
invertebrates
based
on
probable
environmental
concentrations
at
or
near
the
levels
of
predicted
toxicity.
Acute
toxicity
estimates
are
0.62
mg/
L
for
freshwater
fish,
0.
45
mg/
L
for
marine/
estuarine
fish,
0.
79
mg/
L
for
Daphnia
magna,
0.
034
mg/
L
for
mysid
shrimp,
and
0.56
mg/
L
for
green
algae.
Chronic
toxicity
estimates
for
freshwater
fish
is
0.117
mg/
L.
Terrestrial
animal
toxicity
based
on
available
rat
data
would
indicate
that
­
pinene
is
practically
non­
toxic
on
an
acute
basis.

Furfural
is
slightly
toxic
to
aquatic
organisms
on
an
acute
basis.
Acute
toxicity
estimates
are
18.8
mg/
L
for
freshwater
fish,
26.3
mg/
L
for
Daphnia
magna,
and
518
mg/
L
for
green
algae.
Chronic
toxicity
estimates
for
freshwater
fish
is
4
mg/
L.
Terrestrial
animal
toxicity
cannot
be
determine
at
this
time.

References
Meylan,
William
and
Philip
Howard,
1998.
ECOSAR
Class
Program,
Version
0.99d.
Syracuse
Research
Corporation,
Syracuse,
N.
Y.
For:
U.
S.
Environmental
Protection
Agency,
Office
of
Pollution
Prevention
and
Toxics,
Washington,
D.
C.

Meylan,
William
and
Philip
Howard,
2000.
Estimation
Program
Interface,
Version
3.
10.
Syracuse
Research
Corporation,
Syracuse,
N.
Y.
For:
U.
S.
Environmental
Protection
Agency,
Office
of
Page
6
of
8
Pollution
prevention
and
Toxics,
Washington,
D.
C.

TOXNET
2002.
Online
Scientific
Search
Engine,
National
Library
of
Medicine,
National
Institutes
of
Health.
Search
results
for
Lignins,
Cellulose
Compounds,
Pinenes,
Furfural
http://
toxnet.
nlm.
nih.
gov/.

Wesco
Technologies,
Ltd,
2002.
Material
Safety
Data
Sheets
(MSDS)
Wesco
Technologies,
Ltd.,
San
Clemente,
CA.
Internet
search
for
various
ligninsulfonates
at:
http://
www.
wtl.
com/
msds/
zl.
htm.
Page
7
of
8
Table
1.

Available
Estimated
(E)

and
Measured
(M)

Chemical
Properties
and
Ecotoxicological
Endpoints
of
Select
Lignins
Chemical
Property
Calcium
Lignosulfonate
Sodium
Lignosulfonate
Ammonium
Lignosulfonate
pH
4.5­
10
(liquid);

4­
10
(powder)

4.
5­
10
(liquid
and
powder)

~4.5
(liquid;
~6.
5
(powder)
Vapor
Pressure
(mmHg)

6.65x10
­20
@25
o
C
(E)

5.92x10
­27
@25
o
C
(E)

2.165.92x10
­24
@25
o
C
(E)
Log
Kow
0.

33(
E)

­3.
45
(E)

­0.
59
(E)
Koc
4.

63x10
4
(E)

1.

85x10
5
(E)

4.

63x10
4
(E)
Water
Solubility
(mg/
L)

236.2
(E)

5.22x10
5
@25
o
C
(E)

2050
@25
o
C
(E)
Henry's
Law
Constant
atm­
m
3
/mole
1.96x10
­22
(E)

7.

64x10
­33
(E)

4.

51x10
­33
(E)
Hydrolysis/

Photodegradation
NA
NA
NA
Biodegradation
Ultimate:
months;
Primary:
days
to
weeks
(E)

Ultimate:
months;
Primary:
days
to
weeks
(E)

Ultimate:
months;
Primary:
days
to
weeks
(E)
Fish
Acute
Toxicity
(96h­
LC50
)

FW:

>8000mg/
L
(E)
>7300
mg/
L
(48­
h
Rainbow
trout
­M)

FW:

>1.7x10
6
mg/
L
(E)

FW:

>29300
mg/
L
(E)
Daphnia
Acute
Toxicity
>1300
mg/
L
(48h­
EC50
)

(E)

>46700
mg/
L
(E)

>3130
mg/
L
(E)
Algae
Toxicity
(96h­
EC50
)

>79000
mg/
L
(E)

1.

7x10
8
mg/
L
(E)

4.

95x10
5
mg/
L
(E)
Fish
Chronic
Toxicity
(30­
day)

>130
mg/
L
(E)

2.

92x10
5
mg/
L
(E)

>4700
mg/
L
(E)
Daphnia
Chronic
Toxicity
(21­
day)

890
mg/
L
(E)

1.

8x10
5
mg/
L
(E)

>3100
mg/
L
(E)
E:

(SAR)

Structure
Activity
Relationship.
NA:
Not
Available.
pH:

Wesco
Technologies,
LTD,
San
Clemente,
CA,

http://
www.
wtl.

com/
msds/
zl.

htm
Page
8
of
8
Table
2.

Available
Estimated
(E)

and
Measured
(M)

Chemical
Properties
and
Ecotoxicological
Endpoints
of
Select
Pinene
Compounds
Furfural
Chemical
Property

­Pinene

­Pinene
Furfural
Vapor
Pressure
(mmHg)

4.75
@25
o
C
(M)

2.93
@25
o
C
(M)

2.21
@25
o
C
(M)
Log
Kow
4.83(
M)

4.35
(E)

0.

41
(M)
Koc
1204
(E)

1204
(E)

17.7
(E)
Water
Solubility
(mg/
L)

1.

891
@25
o
C
(M)

4.886
@25
o
C
(E)

0.5.36x104
@25
o
C
(E)
Henry's
Law
Constant
(atm­
m
3
/mole)

2.

94x10
­1
(M)

9.

2x10
­2
(E)

3.

37x10
­6
(M)
Hydrolysis
/Photodegradation
Not
Expected
to
Occur
Not
Expected
to
Occur
NA
Biodegradation
Ultimate:
weeks
to
months;
Primary:
days
to
weeks
(E
­

SAR)
Complete
removal
in
250
hours
in
3
different
soil
slurries
from
Georgia
Ultimate:
weeks
to
months;
Primary:
days
to
weeks
(E
SAR

Ultimate:
weeks;

Primary:
days
(E
­

SAR)
Fish
Acute
Toxicity
(96h­
LC50
)

FW:
0.72
mg/
L
(E)
M/
E:

0.51
mg/
L
(E)

FW:

0.

62
mg/
L
(E)
M/
E:

0.45
mg/
L
(E)

FW:

18.8mg/
L
(E)
Daphnia
Acute
Toxicity
0.93
mg/
L
(48h­
EC50
)

(E)

0.79
mg/
L
(48h­
EC50
)

(E)

26.3
mg/
L
(48h­
EC50
)(
E)
Mysid
Shrimp
Toxicity
(96h­
LC50
)

0.

042
mg/
L
(E)

0.

034
mg/
L
(E)

NA
Algae
Toxicity
(96h­
EC50
)

0.

66
mg/
L
(E)

0.56
mg/
L
(E)

517.7
mg/
L
Fish
Chronic
Toxicity
(30­
day)

0.138
mg/
L
(E)

0.

117
mg/
L
(E)

4.
0
mg/
L
(E)

(32­
day)
AS:

Activated
Sludge.

NA:
Not
Available.
SAR:

Structure
Activity
Relationship.
