Document ID: EPA-HQ-OPP-2003-0250-0011
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2004-03-11T05:00Z

1
Environmental
Fate
Prepared
for:

Regulatory
Management
Branch
II
Antimicrobial
Division
Office
of
Pesticide
Programs
U.
S.
Environmental
Protection
Agency
Arlington,
VA
22202
Prepared
by:

Risk
Assessment
and
Science
Branch
Antimicrobial
Division
Office
of
Pesticide
Programs
U.
S.
Environmental
Protection
Agency
Arlington,
VA
22202
2
Executive
Summary
The
major
exposure
from
the
use
of
chromated
and
non­
chromated
arsenical
wood
preservatives
is
to
three
environmental
compartments:
soil
/
sediments,
surface
and
ground
water
contamination
and
bioaccumulation
in
the
aquatic
and
benthic
organisms.
This
chapter
will
address
the
environmental
fate
of
arsenic
and
chromium
from
wood
treated
with
chromated
and
non­
chromated
arsenical
wood
preservatives.
The
environmental
fate
of
zinc,
which
leaches
from
wood
treated
with
ACZA,
was
previously
addressed
in
the
Zinc
Salts
RED
(
Case
4099,
August,
1992).
Although
copper
is
included
in
the
discussion
of
some
of
the
individual
studies
used
in
this
assessment,
below,
the
overall
environmental
fate
of
copper
will
be
addressed
in
the
forthcoming
Copper
RED.

The
leaching
of
arsenic
and
chromium
into
water
from
pressure­
treated
wood
has
been
widely
investigated
and
both
the
laboratory
and
field
studies.
These
studies
generally
indicate
that
leaching
of
the
metals
is
a
function
of
pH,
salinity
(
fresh
water,
sea
water,
estuaries,
natural
and
synthetic,
sterile
buffered
water),
temperature,
moisture
content
of
the
treated
wood,
wood
type,
and
wood
texture.
It
has
been
observed
that
most
of
the
leaching
takes
place
in
the
first
few
days
after
the
application.
Most
of
these
studies
have
shown
that
the
extent
and
rate
of
leaching
is:
As>
Cr.
Available
studies
were
conducted
under
different
conditions
and
the
exact
concentrations
of
preseravtive
solution
absorbed
by
wood
(
e.
g.
utility
poles)
are
not
known.
Sorption
constants
of
these
metals
are
high
for
various
soils.
Leaching
of
the
metals
into
soils
also
depends
on
the
pH
of
the
soil,
type
and
texture
of
the
soils,
organic
content
of
the
soils;
however,
studies
on
sorption
into
soils
from
utility
poles
have
shown
that
the
release
of
metals
into
soils/
sediments
from
the
base
of
treated
wood,
decks
or
utility
poles
or
from
the
pressure
treatment
facilities,
does
not
show
a
high
degree
of
downward
or
ground
level
migration.
In
most
cases,
after
migration
of
the
metals
a
few
meters
down
into
soil,
these
metals
attain
the
background
level
concentration
of
soil.
Chromium
is
released
into
water
and
soil
as
Cr(
III),
but
the
concentration
of
Cr(
III)
is
lower
than
arsernic,
partly
due
to
the
fixation
process
in
the
wood
structure.
Arsenic
is
leached
into
soil
and
water
as
As(
V).

In
general,
the
metals
in
water
exist
as
hydrated
species
(
coordinated
with
water),
or
hydroxy
species
or
the
metal
is
bound
to
inorganic
anions
like
FeF
6
­
3,
or
bonded
to
organic
ligands
to
form
metal
complexes
or
as
organometallics
(
contains
C­
Metal
bonds).
Fate
and
transport
processes,
and
interaction
with
aquatic
and
benthic
organisms
by
these
chemical
species
will
vary
from
one
of
type
of
organism
to
another.
The
metals
from
CCA
when
released
into
water
systems
usually
attain
background
concentrations.
In
view
of
the
fact
that
the
metals
attain
background
level
concentrations
in
soil
and
water,
and
the
tendency
of
the
metals
to
speciate,
it
is
hard
to
ascertain
the
source
of
contamination
in
water
and
soil.
Considering
absence
of
comprehensive
ground
water
monitoring
relative
to
the
leaching
of
metals
from
CCA
into
soils
and
water,
it
appears
no
significant
possibility
exists
for
ground
water
contamination
in
areas
where
utility
poles
have
been
placed
and
where
decks
have
been
built.
3
Environmental
Fate
Assessment
Chromium
and
arsenic
as
oxides
are
two
of
the
active
ingredients
of
the
water­
borne
wood
preservative
chromated
copper
arsenate
(
CCA).
As
a
wood
preservative
it
is
unique
in
more
than
one
way.
First,
it
is
a
mixture
of
inorganics
metal
species.
Second,
its
efficacy
as
a
wood
preservative
improves
if,
and
when,
it
goes
through
the
`
fixation'
process
during
wood
pressure
treatment.

The
physical
properties
and
the
chemistry
of
the
three
metals
(
arsenic,
chromium
and
copper)
of
the
water­
borne
wood
preservative
CCA
are
very
well
understood
in
aqueous
and
soil
compartments.
Most
of
the
Agency's
environmental
fate
guideline
studies
(
hydrolysis,
photolysis,
soil
aquatic
metabolism,
etc.)
cannot
be
conducted
on
the
individual,
or
a
mixture
of
these,
metallic
actives
due
to
their
complex
interactions
with
soil
and
water.

Chromium
is
a
transition
metals
and
has
a
tendency
to
exist
in
variable
oxidation
states
in
water
and
soils.
Common
oxidation
states
of
chromium
are
Cr(
III)
and
Cr(
VI).
Arsenic
is
a
metalloid
(
shows
the
characteristics
of
both
a
metal
and
a
non­
metal)
and
also
has
a
tendency
to
exist
in
variable
oxidation
states.
Common
oxidation
states
of
arsenic
are
As(
III)
and
As(
V).
In
addition,
the
pH
of
aqueous
media
or
soil,
nature
of
soil
(
texture
of
soil,
percent
of
organic
carbon
of
the
soil,
etc.),
salinity
of
water,
temperature
of
water,
and
soil
are
some
of
the
factors
that
give
rise
to
the
phenomenon
of
chemical
speciation
(
formation
of
different
metal
species)
which
is
a
common
phenomenon
in
these
environmental
compartments.
Because
of
these
parameters,
the
metal
ions
can
form
soluble
or
insoluble
substance
which
can
be
cationic
or
anionic
species
or
full
simple
molecules
or
complex
compounds.
In
general,
these
metal
ions
exist
in
water
and
soil
as:

A.
A
free
metal
ion,
which
in
aqueous
medium
is
aquated
(
solvated
or
complexed
with
water
molecules);
B.
Simple
inorganic
species
like
oxides,
hydroxides,
halides,
carbonates
etc.;
or
C.
Complexed
with
organic
and
inorganic
ligands.

Chromium:

Cr(
II)
is
unstable
in
water.
Cr(
III)
goes
through
hydrolysis
and
forms
various
species.
The
important
species
of
Cr(
III)
found
in
aqueous
systems
are:
CrOH+
2,
Cr(
OH)
2
+,
Cr(
OH)
4
­,
Cr(
OH)
3(
s).
In
addition,
polymeric
species
like:
Cr
2(
OH)
2
and
Cr
3(
OH)
4
+
5
are
also
formed
in
water.
All
these
species
are
present
in
aqueous
systems
in
the
absence
of
any
complexing
agents.
Similarly,
Cr(
VI)
also
hydrolyzes
in
water
and
forms
CrO
4
­
2,(
at
pH
>
6.5),
and
HCrO
4
­
and
Cr
2
O
7
­
2
in
acidic
medium.
In
fresh
water
at
pH
6
species
detected
are:
HCrO
4
­,
Cr(
OH)+
2,
Cr(
OH)
2
+,
CrO
4
­
2,
Cr+
3
and
Cr(
OH)
3(
s).
On
the
other
hand,
the
species
detected
in
sea
water
at
pH
8
are:
CrO
4
­
2,
Cr(
OH)+
2,
Cr(
OH)
3,
NaCrO
4
­,
Cr(
OH)+
2,
Cr(
OH)
4
­,
KCrO
4
­,
HCrO
4
­
.
Cr(
III)
is
kinetically
stable
and
Cr(
VI)
is
thermodynamically
stable
in
aqueous
medium.
Cr(
VI)
is
more
water
soluble,
and
more
mobile
and
can
easily
move
through
wet
soils
into
ground
water
and
may
become
more
bioavailable.
(
Lebow,
S.
1996).
The
half
life
of
Cr(
III)
in
water
has
been
estimated
from
being
4
one
month
to
20
months
and
this
shows
persistency
of
the
metal
(
Pettine,
M.
and
F.
J.
Millero,
1990)

Chromium
goes
through
oxidation­
reduction
reactions
when
sorbed
in
soils.
Organic
matter
in
soils,
which
has
a
high
sorption
capacity
for
chromium,
reduces
Cr(
VI)
to
Cr(
III)
spontaneously.
Manganese
oxides
in
the
soils,
on
the
other
hand,
oxidize
Cr(
III)
to
Cr(
VI).
Chromate
and
dichromate
ions
form
soluble
salts
and
increase
the
mobility
of
toxic
Cr(
VI)
in
soils.
Chromium
as
Cr(
VI)
reduces
to
Cr(
III)
under
anoxic
conditions.
In
water
at
neutral
conditions
(
pH
7),
formation
of
dichromate
ions
(
chromium
as
Cr(
VI))
is
minimized.
Cr(
VI)
is
adsorbed
less
and
less
by
hydrous
metal
oxides
and
soils
as
the
alkalinity
of
the
medium
increases.
The
presence
of
anions
like
sulfate
and
phosphate
decrease
the
sorption
phenomenon.
At
low
pH
and
low
concentrations
of
chromium,
however,
adsorption
of
Cr(
III)
on
iron
and
manganese
oxides
increases.

Arsenic:

The
common
and
important
arsenic
ores
are:
tenantite,
cobaltite,
arsenopyrite,
niccolite
and
enargite.
Arsenic
has
a
great
tendency
to
sorb
to
soils
and
sediments.
Its
sorption
capacity
(
µ
g
total
As/
g
soil)
with
silty
fine
sand
with
little
clay
ranges
from
1.0
to
252.
For
brown
clay
sand
it
is
between
1.0
to
80.0
and
with
fine
sand
the
sorption
capacity
varies
from
1.1
to
7.9.
Arsenic
sorption
is
dependent
on
pH,
redox
conditions,
competing
anions,
salinity
and
clay
content
and
hydrous
oxide
content
(
aluminum
or
iron).
Arsenic
mobility
in
clay
soils
is
low
to
moderate.
As(
V)
under
proper
conditions
can
reduce
to
As(
III).
In
aerobic
and
anaerobic
sediments,
arsenate
is
more
strongly
sorbed
than
methylarsenic
acid
(
Holm,
R.
T.
1979;
Wauchope,
R.
D.
1975).

As
the
sorption
of
arsenic
decreases
with
rising
pH,
the
mobility
of
arsenic
increases.
Organoarsenates
decrease
the
sorption
of
arsenic
and
increase
the
arsenic
mobility
Organoarsenates
are
more
mobile
than
arsenic.
Arsenic
mobility
in
clay
soils
is
low
to
moderate.
However,
in
loamy
and
sandy
soils,
mobility
increases
(
6­
10
cm/
day
for
loamy
sand).
Between
pH
2
and
11,
the
common
species
of
arsenic
present
in
aqueous
medium
are:
H
2
AsO
4
­
and
HAsO
4
2­.
Beyond
pH
12,
it
is
mostly
HAsO
3
2­
and
AsO
3
­
3.

Fixation:

Fixation
is
a
chemical
process
which
consists
of
a
series
of
chemical
reactions
that
ensue
after
the
wood
has
been
pressure
treated
with
CCA.
Fixation
precedes
the
actual
`
action'
of
CCA
to
act
as
a
wood
preservative.
It
depends
on
a
number
of
parameters:
temperature,
humidity
(
moisture
content
of
the
wood),
pH
and
drying
period
for
the
wood
after
the
pressure
treatment
has
been
completed.
Under
laboratory
conditions,
increasing
concentration
of
the
wood
preservative
will
lower
the
pH
of
the
solution
mixture
and
will
accelerate
the
rate
of
fixation
(
Anderson,
A.
G.
1990).
5
The
process
of
fixation
consists
of
a
series
of
chemical
reactions:

First,
`
an
initial
reaction'
of
absorption
of
the
preservative
to
the
cellulosic
and
lignin
components
of
the
wood.
Second,
a
primary
precipitation
reaction
which
converts
Cr(
VI)
to
Cr(
III)
and
this
process
continues
for
the
duration
of
fixation
period.
Lastly,
the
conversion
of
copper
arsenate
into
basic
copper
arsenate
(
Anderson,
A.
G.
1990).

Earlier
research
on
the
temperature
effect
on
the
fixation
process
on
scot
pine
and
beech
showed
that
increased
fixation
occurs
when
the
temperature
was
raised
to
30
oC
and
that
the
maximum
fixation
was
attained
in
42
hours
(
Wilson,
A.
1971).
In
another
study
on
fixation
(
Cooper,
et
al.
1992),
it
was
shown
that
for
western
red
cedar
the
fixation
process
was
best
achieved
at
70
oC
and
93%
relative
humidity
within
14.3
hours.
For
douglas
fir,
red
pine,
lodge
pole
pine,
southern
pine
and
jack
pine
the
fixation
at
the
same
temperature
and
humidity
conditions
was
best
achieved
between
5.9
to
8.3
hours.
In
a
study
on
red
pine
it
was
shown
a
freshly
treated
wood
when
freezed
dried
and
reequilibrated
with
moisture,
reduction
of
Cr(
VI)
to
Cr(
III)
took
place
even
at
low
moisture
contents
or
even
at
over
dried
conditions
(
Kaldas,
M.
and
P.
A.
Cooper,
1996).

Another
series
of
studies
on
hemlock,
grand
fir,
white
fir,
noble
fir,
pacific
silver
fir
and
douglas
fir
showed
when
the
wood
samples
were
removed
as
the
drying
process
was
on,
and
systemically
treated
with
CCA
by
a
full­
cell
process,
the
treatability
and
penetration
of
CCA
into
the
wood
depended
on
the
drying
rate
(
Lebow
et
al.,
1996).
In
a
related
study,
it
was
shown
that
the
fixation
process
is
temperature
dependent
(
McNamara
W.,
1989).

In
another
study,
the
fixation
rate
of
commercially
available
CCA
on
sawdust,
measured
by
arsenic
leaching,
showed
that
at
about
20
o
C,
98­
99%
CCA
was
fixated
by
day
five.
The
same
study
also
showed
that
as
the
fixation
process
proceeds,
the
pH
of
the
preservative
rises
(
Dalhgren
S.
E.,
1972).
Another
study
showed
that
rate
of
fixation
also
depended
on
the
type
of
wood
(
Wilson
A.,
1971).

The
process
of
fixation
has
been
traditionally
looked
upon
as
the
fixation
of
Cr(
VI)
changing
into
Cr(
III)
in
the
wood
tissues.
A
recent
work
on
southern
pine,
jack
pine,
and
red
pine
has
indicated
that
copper
and
arsenic
components
are
stabilized
(
fixated)
earlier
than
chromium
(
Cooper
et
al.,
1996).

Special
Leaching
or
Aqueous
Availability:

The
leaching
of
CCA
metals
and
subsequent
entrance
of
these
metal
ions
into
environmental
compartments
(
water,
soil,
plants,
and
animals)
is
an
important
process
for
environmental
fate
and
transport
assessment.
A
very
earlier
work
on
leaching
of
CCA
was
done
on
the
wood
used
in
residential
houses
to
build
foundations
and
this
study
showed
no
significant
leaching
of
CCA
components
and
the
conclusion
drawn
at
that
time
was
that
there
was
no
environmental
hazard
to
the
ground
water,
soil,
plants
or
animals
(
Arsenault,
R.
D.,
1975).
Later
6
studies
have
not
only
contradicted
this
observation
but
have
elucidated
the
mechanisms
of
leaching
and
also
estimate
the
amounts
of
leaching
of
CCA
metals
from
the
treated
wood.

To
elucidate
the
leaching
mechanism
of
arsenic
from
CCA­
treated
wood,
an
extensive
study
was
carried
out
in
the
presence
and
absence
of
electrolytes.
This
leaching
study
was
conducted
with
a
simulated
rainfall
(
rain
intensity:
1
±
0.15
inch/
hour).
Southern
pine,
kiln­
dried
plywood
specimen
(
29.2
cm
x
29.2
cm
x
1.9
cm)
were
selected
and
treated
with
4%
CCA
solutions
(
CCA­
A,
B
and
C)
in
the
presence
and
absence
of
electrolytes.
The
mean
absorption
of
the
preservation
solution
was
17.12
pounds
per
cubic
feet
(
pcf).
Initially
water
runoff
and
soil
leachate
samples
were
collected
after
15,
30,
45
and
60
minutes
of
simulated
rainfall
and
then
after
3,
9
and
27
hours
of
rainfall.

After
the
simulated
rainfall,
it
was
determined
that
plywood
samples
showed
a
significant
decline
of
arsenic
on
one
face
of
the
plywood
from
3.23
mg/
g
to
1.441
mg/
g
and
on
the
other
face
from
3.23
mg/
g
to
1.22
mg/
g.
Analysis
of
the
soils
(
sand
and
loam)
revealed
that
the
amounts
of
arsenic
were
not
different
for
the
soil
in
contact
with
the
treated
plywood
sample
than
the
soils
in
contact
with
untreated
(
blank)
plywood.
The
amounts
of
arsenic
in
the
surface
water
runoff
was
depended
on
the
texture
of
the
soil
and
the
time
of
exposure
to
the
rainfall.
Runoff
samples
collected
after
one
hour
of
simulated
rainfall
did
not
show
the
presence
of
arsenic.
The
samples
of
CCA­
C
in
the
presence
of
the
electrolyte
(
sodium
dichromate
and
copper
sulfate)
indicated
the
highest
arsenic
absorption
to
the
wood
but
also
the
highest
leaching.
The
surface
water
runoff
collected
from
the
loam
soil
had
a
higher
concentration
of
arsenic
(
44.5
µ
g/
L)
but
in
the
sand
the
amount
of
arsenic
was
only
7.3
µ
g/
L.
The
concentration
of
arsenic
increased
dramatically
for
the
first
three
hours
of
rainfall
and
then
slowly
decreased
thereafter.
The
soil
leachates
from
the
sand
after
the
first
hour
of
rainfall
with
the
CCA­
B
(
non­
electrolytic)
showed
the
higher
concentration
of
arsenic
(
98.6
µ
g/
L)
but
with
CCA­
C
(
electrolytic)
the
amount
was
61.3
µ
g/
l.
Loam
soil
leachates
for
CCA­
B
(
non­
electrolytic)
showed
the
presence
of
11.9
µ
g/
L
arsenic
and
for
CCA­
C
(
electrolytic)
the
arsenic
amount
was
22.2
µ
g/
L.
(
Chen
and
Walters,
1979).

In
another
study,
it
was
shown
that
from
the
southern
pine
wood
the
metals
from
CCA
leached
much
more
from
the
high­
temperature
pressure
treated
kiln­
dried
wood
than
the
air­
dried
pressure
treated
wood.(
Less
et
al.,
1993).

A
leaching
study
conducted
on
southern
pine,
pressure
treated
with
CCA­
C
wood
preservative,
was
submittted
by
the
registrants
to
the
Agency.
The
study
was
carried
out
at
three
pHs:
5,
7
and
9,
in
0.10M
HCl
and
in
simulated
sea
water
which
was
prepared
according
to
the
ASTM
Method
D1141­
90.
The
southern
pine
blocks
(
3.8
cm
x
3.8
cm
x
29
cm)
were
pressure
treated
upto
0.80
pounds
per
cubic
feet
(
pcf)
for
the
studies
in
pHs
5,7
and
in
0.10
M
HCl
while
the
for
simulated
sea
water,
the
blocks
were
pressure
treated
upto
2.5
pounds
per
cubic
feet
(
pcf).
The
pressure
treatment
was
carried
out
according
to
the
AWPA
Standards.
The
study
was
conducted
for
60
days
altogether.
The
amounts
of
the
metal
ions
leaching
was
found
highest
with
0.10
M
HCl
solutions:
total
arsenic
leaching
in
0.10M
HCl
on
day
1
was
170
µ
g/
cm2/
day
and
it
declined
to
27
µ
g
(
day
30).
However,
when
arsenic
was
examined
in
its
two
common
oxidation
7
states,
As(
III)
leached
at
a
rate
of
10
µ
g/
cm2/
day
(
day
21)
and
it
increased
to
38
µ
g/
cm2/
day
on
day
30
while
for
As(
V),
the
rate
was
10
µ
g/
cm2/
day
on
day
21
and
it
increased
to
22
µ
g/
cm2/
day
on
day
30.
The
rate
of
leaching
for
Cu(
II)
in
0.10M
HCl
was
149
µ
g/
cm2/
day
on
day
1
and
declined
to
22
µ
g/
cm2/
day
on
day
30.
The
rate
of
leaching
for
total
Cr
in
the
in
presence
of
0.10M
HCl
was
46
µ
g/
cm2/
day
for
day
5
and
declined
to
30
µ
g/
cm2/
day
on
day
30.
When
analyzed
for
Cr(
VI),
the
leaching
rate
in
0.10M
HCl
was
1.5
µ
g/
cm2/
day
for
day
21
and
reduced
to
1.0
µ
g/
cm2/
day
for
day
30
(
Stanley,
J.
S.,
1994).

In
a
40­
day
study
conducted
in
Canada
on
the
pressure­
treated
jack­
pine
with
CCA
at
various
pHs
of
3.5,
4.5,
5.5,
7.0
and
8.5
and
also
in
a
solution
containing
dilute
sulfuric
acid
(
0.10N).
The
pressure
treated
blocks
were
separated
into
two
sets:
One
set
was
kept
in
open
air
for
one
year
to
simulate
`
weathering'.
The
second
set
of
blocks
were
kept
in­
house
to
simulate
`
new
conditions'.
All
blocks
were
of
uniform
dimensions
of
5
cm2.
The
preservation
retention
of
the
blocks
was
close
to
but
not
exactly
like
CCA­
C
(
the
recommended
level
by
AWPA
Standards
is
0.40
pcf
(
6.4
kg/
m3).

`
Weathered'
blocks
leached
copper
significantly
more
at
pH
3.5,
4.5
and
5.5
than
the
`
fresh'
blocks.
Release
of
chromium
was
less
at
pH
3.5
and
4.5.
Arsenic
showed
a
higher
release
rate
at
pH
5.
Generally,
the
leaching
order
was
Cu
>
As>
Cr.
It
is
recognized
that
fixation
of
chromium
(
conversion
of
Cr(
VI)
to
Cr(
III)
)
prevents
the
leaching
of
chromium
from
the
wood.
The
pHs
in
this
study
were
maintained
using
citric
acid/
NaOH
mixture
solutions,
and
in
distilled
water
a
pH
of
7
was
maintained.
The
borax/
HCl
solution
resulted
in
pH
8.5.
A
similar
trend
was
observed
when
the
leaching
was
conducted
in
dilute
sulfuric
acid
solution
at
pHs
2.5,
3.5
and
4.5
(
preservation
retention
was
0.13
pcf
(
1.99
kg/
m3)
(
Warner,
J.
E.
&
K.
R.
Solomon,
1990).

A
13­
day
study
on
leaching
from
douglas­
fir,
redpine,
lodgepole
fir
and
western
red
cedar,
pressure
treated
with
2.3%
CCA
showed
and
confirmed
that
the
presence
of
citric
acid/
NaOH
buffer
increases
the
rate
of
leaching
from
the
wood
at
a
high
pHs
like
pH
7.
(
Cooper,
P.
A.,
1991).

A
twelve
month
study
was
conducted
on
leaching
of
CCA­
C
metals
from
pressure
treated
jack
pine
wood
with
1.8%
CCA­
C
treatment
solution
and
a
preservative
retention
of
0.40
pcf
(
6.4
kg/
m3
).
In
this
study,
the
CCA
metals
from
these
pressure
treated
wood
blocks
were
leached
into
four
different
compartments:
leaching
into
distilled
water,
leaching
into
natural
weathering
conditions,
leaching
into
soil
burial
and
leaching
into
compost
(
made
by
vegetable
matter).
It
was
observed
that
leaching
into
compost
was
higher
than
into
other
compartments:
13%
leaching
was
observed
in
the
compost,
in
soil
burial
it
was
1.3%,
weathering
sample
showed
about
a
1.5%
leaching
and
leaching
into
distilled
water
was
about
5%.
Leaching
order,
however,
was
the
same
as
with
other
studies:
Cu>
As>
Cr.
(
Cooper
et
al.,
1992).

A
similar
21­
day
leaching
study
with
southern
pine
sapwood,
pressure
treated
with
1.03%
CCA­
C
with
preservative
retention
of
0.3
pcf
(
4.8
kg/
m3
)
showed
a
leaching
rate
of
1
µ
g/
cm2/
day
for
Cu
and
As
and
0.01
µ
g/
cm2/
day
for
Cr
which
is
the
same
trend
(
copper

arsenic
8
>
chromium)
as
other
leaching
studies
have
shown
(
Merkle,
et
al.,
1993).

In
an
Australian
Study,
Tasmanian
Parks
and
Wildlife
Service
(
M.
Comfort,
Scientific
Rep.
93/
1,
1993),
conducted
a
leaching
study
on
Southern
Tasmanian
boardwalks
(
ages
1
to
14
years)
which
were
the
pressure
treated
with
CCA.
Soil
samples
collected
about
6
inches
and
a
few
meters
away
form
the
boardwalks
showed
that
the
chromium
(
88
ppm)
and
copper
levels
(
49
ppm)
in
the
close
proximity
samples
were
high
compared
to
the
distant
ones
which
were
not
different
from
the
blank
samples.
The
blank
samples
showed
chromium
at
20
ppm
and
copper
between
1­
3
ppm.
The
ages
of
the
boardwalks
did
appear
to
contribute
in
the
high
levels
of
the
metals.

In
a
European
study
(
Italy),
on
CCA
leaching
from
treated
wood,
rain
water
was
used
for
extraction.
CCA
treated
wood
samples
from
a
post
were
meshed
through
a
5
mesh,
25
springs/
cm2
sieve.
The
coarse
powder
so
obtained
was
digested
in
96%
sulfuric
acid
and
3%
hydrogen
peroxide
in
a
5:
1
ratio
and
the
analyses
showed
the
presence
of
As
(
1.602
mg/
g),
Cr(
1.345
mg/
g)
and
Cu(
0.813
mg/
g).
Before
the
extraction,
rainwater
which
was
collected
in
Turin
in
1994,
was
analyzed
for
the
presence
of
anions
and
cations
including
As,
Cr
and
Cu
and
the
amounts
of
these
respectively
were:
0.068,
0.029
and
0.021(
all
in
mg/
L).
This
rainwater
was
then
used
to
extract
the
coarse
powder
and
the
leachates
were
collected
at
different
times,
the
last
one
was
78­
hour
leachate.
The
78
hour
extraction
sample
contained
As
and
Cr
(
50
µ
g/
g)
and
Cu(
150
µ
g/
g).
The
same
study
also
conducted
the
extractions
at
pHs
6
down
to
3.
Maximum
amounts
of
metal
ions
were
released
at
pH
3.
A
similar
trend
was
observed
in
another
study.
The
CCA
solution
used
in
the
study
was
purchased
commercially
and
in
the
stock
solution
each
metal
ion
was
about
1000mg/
L
from
which
running
samples
were
prepared
(
Aceto,
M.
and
A.
Fedele,
1994).

In
a
study
in
simulated
sea
water,
it
was
observed
that
copper
leached
into
water
from
pressure
treated
full­
sized
pilings
at
529
mg
level
and
arsenic
level
was
measured
at
60
mg
and
little
or
no
chromium
was
measurable
(
Baldwin
et
al.,
1994).

In
a
freshwater
study
on
the
old
lockgates
and
freshly
constructed
lockgates
of
pressure
treated
wood
with
CCA
the
copper
concentrations
(
200
ppb)
were
high
at
the
newly
constructed
lockgates,
40
meters
downstream,
while
the
concentrations
of
copper
were
low
at
the
old
lockgates
(
40
ppb).
Chromium
concentrations
were
the
same
(
90
ppb)
at
both
locations
while
arsenic
was
90
ppb
level
at
the
new
lockgate
and
at
60
ppb
level
40
meters
downstream
(
Cooper,
P.
A.,
1991).

In
another
study,
the
leaching
of
the
metals
from
CCA
was
investigated
as
the
fixation
process
was
in
progress.
It
was
carried
out
on
the
pole
sections
(
8"
x
2'
diameter)
of
red
pine
poles
which
were
pressure
treated
with
CCA­
C
of
1.7%
and
3.5%
concentrations
as
well
as
with
pressure
treated
(
1.5%
CCA­
C)
the
jack
pine
boards
(
2"
x
6"
).
The
study
was
conducted
at
95%
humidity
and
60
o
C.
As
the
fixation
process
proceeds,
the
metals
from
the
CCA­
C
were
extracted
by
2­
hour
long
spray
of
simulated
rain
(
rainfall:
150
mm).
The
concentrations
of
the
9
metal
ions
in
the
leachates
progressively
declined
as
chromium
fixation
process
progressed.
Arsenic
stabilized
(
fixed)
faster
than
copper
fixation
which
in
turn
was
faster
than
chromium
fixation.
For
red
pine,
pressure
treated
with
1.7%
CCA­
C
at
95%
humidity
and
60
o
C,
the
preservation
retention
was
0.48
pcf
(
7.7
kg/
m3
)
and
1.02
pcf
(
16.4
kg/
m3
)
when
the
CCA­
C
solution
was
3.5%.
The
retention
for
jack
pine,
under
the
same
humidity
and
temperature
conditions,
the
preservation
retention
was
0.24
(
3.9
kg/
m3
)
when
the
wood
was
pressure
treated
with
2
%
CCA­
C
solution.

For
the
red
pine
pole
at
both
the
preservation
retentions
of
0.48
and
1.02
pcf
and
99.9%
chromium
fixation
level,
the
leaching
losses
from
the
wood
were:
4
µ
g/
cm2
for
Cr,
9
µ
g/
cm2
for
Cu
and
3
µ
g/
cm2
for
As.
For
the
jack
pine
wood,
on
the
other
hand,
at
99.9%
chromium
fixation
level,
the
leaching
losses
of
the
metal
ions
from
the
wood
were:
0.28
µ
g/
cm2
for
Cr,
0.88
µ
g/
cm2
for
Cu
and
0.62
µ
g/
cm2
for
As.
The
leaching
losses
continued
to
decline
as
the
Cr(
VI)
fixation
progressed
from
60­
70%
to
99.9%
level
(
Cooper
et.
al,
1995).

A
recent
estuarine
study
on
the
southern
yellow
pine,
pressure
treated
with
CCA­
C,
reaffirmed
the
results
from
previous
studies
that
the
leaching
of
the
metal
ions
from
the
wood
was
highest
for
Cu
and
lowest
for
Cr.
This
study
measured
the
laboratory
leaching
rates
for
copper,
arsenic
and
chromium
from
the
freshly
pressure
treated
southern
yellow
pine
as
well
as
the
actual
loss
of
these
metal
ions
from
a
weathered
CCA­
C
treated
lumber
which
had
been
service
for
14
years
as
a
bulkhead
in
Sayville,
New
York,
south
shore
estuarine
canal.
The
retention
level
of
the
CCA­
C
in
this
weathered
bulkhead
was
between
0.61
pcf
to
1.0
pcf
(
9.6
to
16.0
kg/
m3
)
as
communicated
by
S.
Roller
Lumber
Corp.
This
lumber
from
the
canal
was
chosen
as
it
had
experienced
4
types
of
weathering:
the
wood
surface
at
the
water
level
(
air
exposure),
the
wood
surface
exposed
to
tidal
water
off
and
on
(
air/
water
exposure),
the
wood
surface
continuously
submerged
in
water
(
water
exposure)
and
last,
the
wood
surface
buried
deep
in
the
sediment
below
the
canal.
(
soil
exposure).
The
CCA­
C
retention
level
for
the
weathered
lumber
was
0.20
pcf
(
3.1
kg/
m3
)
for
surface
exposed
to
air,
0.30
pcf
(
5.0
kg/
m3
)
for
the
wood
surface
exposed
to
tidal
water
off
and
on,
0.068
pcf
(
1.1
kg/
m3
)
for
the
wood
surface
submerged
under
water
and
0.60
pcf
(
9.9
kg/
m3
)
for
the
wood
surface
buried
in
the
sediment.
The
leaching
losses
of
the
metal
ions
from
these
weathered
surfaces
were
in
the
order
of:
subtidal
(
wood
surface
exposed
to
air
and
water)
>
tidal
(
wood
surface
submerged
in
water)
>
air
>
sediment.
The
extent
of
metal
ions
leaching
was
in
the
same
order
as
the
laboratory
leaching
studies:
Cu
>
As
>
Cr.

The
laboratory
leaching
study
by
the
same
group
showed
that
the
freshly
pressure
treated
southern
yellow
pine
(
CCA­
C),
the
leaching
rates
for
the
metal
ions
were:
5.71­
17.78
µ
g/
cm2/
day
for
Cu,
0.20­
0.98
µ
g/
cm2/
day
for
Cr
and
0.15­
0.90
µ
g/
cm2/
day
for
As,
for
the
initial
12­
hour.
This
laboratory
leaching
study
was
conducted
under
saline
conditions
(
3,13,
and
26
ppt)
which
generally
mimic
the
estuary
conditions.
The
preservation
retention
level
for
CCA­
C
in
the
southern
yellow
pine
was
between
0.29
pcf
to
4.0
pcf
(
4.6­
64.0
kg/
m3
)
when
measured
all
over
the
wood.
Overall,
the
preservation
retention
level,
however,
was
2.5
pcf
(
40.7
kg/
m3
).
The
analysis
of
the
metal
ions
in
the
leachates,
expressed
as
the
oxide
ratio
yielded:
48.8:
36:
15.4
10
(
CrO
3:
As
2
O
5:
CuO)
which
was
very
close
to
the
actual
ratio
of
47.5:
34:
18.5
which
is
the
recommended
ratio
by
AWPA
Standards.
The
Agency
has
noted
that
the
retention
level
of
CCAC
under
marine
water,
as
recommended
by
AWPA,
should
be
at
least
2.5
pcf
(
40.7
kg/
m3
).
However,
AWPA
recommends
that
retention
level
southern
yellow
pine
wood
in
some
areas
of
the
USA
like
north
of
New
Jersey
and
north
of
San
Francisco
can
be
about
1.5
pcf
(
24
kg/
m3
)
(
.
Breslin
and
Adler­
Ivanbrook,
1998).

Some
laboratory
and
field
studies
have
shown
that
the
leaching
process
is
aided
by
slow
or
drizzling
rain
than
by
heavy
showers
(
Evans,
F.
G.,
1987;
and
Cockroft
and
Laidlaw,
1978).

Most
of
the
leaching
from
the
treated
wood
in
the
field
and
laboratory
tests
take
place
in
the
first
few
days
after
the
application
of
the
wood
preservative.
Leaching
rates
depend
on
the
size
of
the
wood,
type
of
wood,
fixation
process.
I
has
been
shown
that
the
round
posts
show
a
higher
rate
of
leaching
than
the
saw
dust
of
the
lumber.
Hardwood
leach
more
than
softwood.
Pressure­
treated
red­
pine
leaches
at
a
higher
level
than
do
the
lodgepole,
Douglas
fir,
and
the
red
pine
(
Cooper,
P.
A.,
1990).

No
leaching
study
has
addressed
the
issue
of
whether
the
metals
leach
as
copper,
or
copper
arsenate,
or
chromium
arsenate
or
as
complexes
with
inorganic
or
organic
ligands
or
as
derivative
of
wood­
metal
moieties
or
as
water
soluble
wood
extracts.
If
the
metals
get
complexed
with
organic
ligands
and
become
more
mobile
in
soils
and
these
then
will
not
be
adsorbed
to
humic
substances.

Mobility
in
water
for
these
metal
ions
from
the
CCA
depend
on
many
factors
which
may
give
rise
to
a
number
of
pathways:
these
metals
can
first
diffuse
through
the
soils
as
complexes,
simple
salts,
or
free
ions,
or
percolate
through
the
soils
as
insoluble
substances
and
are
then
carried
to
the
water
systems.
Porous
soils
help
the
wood
preservative
components
to
move
through
into
water
and
this
increases
the
mobility
of
the
metals
in
water.
As
insoluble
and
having
been
deposited
on
the
sediments,
these
metals
can
be
of
environmental
concern
(
bioaccumulation)
for
the
benthic
organisms.
11
Migration
into
soils:

In
an
earlier
work
(
DeGroot,
et
al.,
1979)
on
CCA­
A,
CCA­
B
and
ACA­
treated
southern
pine
wood
stakes
which
were
installed
thirty
years
prior
to
the
leaching
study
in
acidic
porch
fine
sandy
soil
in
southern
Mississippi,
it
was
shown
that
the
amount
of
leaching
and
mobility
of
the
metal
ions
in
the
acidic
soil
is
not
significant.
Background
levels
of
As,
Cr
and
Cu
in
this
soil
core
depths
were
measured
and
are
shown
below:

Depth
As*
Cr*
Cu*
0­
6
in.
1.3
3.8
4.0
6­
12
in.
0.6
7.5
4.2
12­
18
in.
1.0
6.9
6.6
*
All
values
were
reported
in
ppm
and
at
95%
confidence
interval
The
preservation
retention
level
for
CCA­
A
was
0.70
pcf
(
10.6
kg/
m3
)
and
for
CCA­
B
it
was
0.55
pcf
(
8.8
kg/
m3
).

Table
1
summarizes
the
amounts
of
the
metal
ions
that
have
leached
into
the
soil
from
these
stakes
over
a
period
of
thirty
years.
The
data
includes
the
vertical
transfer
(
downward
migration
from
the
stake)
and
vertical
or
lateral
migration
from
the
base
of
the
stake
of
the
metal
ions.

TABLE
1
Levels4
of
As,
Cr
and
Cu
in
soil
core
after
vertical
(
downward)
and
lateral
transfer
from
the
stakes
Soil
core
location2
As
CCA­
I1
As
CCA­
II1
Cr
CCA­
I
Cr
CCA­
II
Cu
CCA­
I
Cu
CCA­
II
(
beneath)
0­
6
18.93
108.1
25.1
22.9
56.6
48.3
6­
12
1.6
21.4
8.2
7.4
6.9
8.2
12­
18
1.2
1.1
9.2
6.2
5.7
6.4
(
lateral
transfer)
0­
0
73.2
183.2
45.9
24.2
75.8
47.9
0­
3
5.6
117.7
9.4
8.2
11.8
15.3
Levels4
of
As,
Cr
and
Cu
in
soil
core
after
vertical
(
downward)
and
lateral
transfer
from
the
stakes
12
6
1.3
7.0
4.7
6.4
5.6
4.9
9
1.5
4.9
6.2
5.3
12.3
7.2
Notes:
1.
CCA­
A
and
CCA­
B
in
the
present
terminology
2.
Distance
reported
in
inches
3.
All
values
in
ppm
4.
At
95%
confidence
interval.

The
above
data
indicated
that
in
acidic
soil
the
leaching
and
migration
of
metal
ions
was
not
very
high
either
beneath
(
downward
migration)
the
soil
or
by
lateral
transfer
(
ground
level
migration)
of
the
metal
ions
from
the
stakes.

In
a
Nigerian
study,
on
soil
and
vegetable
contamination
in
and
around
a
CCA
wood
treatment
factory,
very
high
levels
of
the
metal
ions
were
detected
and
these
levels
progressively
decline
significantly
as
one
moves
away
from
the
treatment
and
storage
sites.
High
levels
of
the
metal
ions
were
also
detected
in
the
vegetables
and
crops
grown
within
the
premises
of
the
factory.
The
concentrations
of
the
metal
ions
were
measured
in
the
top
4
cm
of
soil
at
and
around
the
treatment/
storage
facility.
Table
2
summarizes
the
concentrations
of
the
metal
ions
at
various
location
in
and
outside
the
factory.
The
study
did
not
provide
the
information
of
the
type
of
soil
at
the
factory
premises
and
also
which
type
of
CCA
(
A,
B
or
C
type)
was
used
by
the
wood
treatment
factory.

Table
2
Measured
metal
ion
concentrations
in
top
4
cm
soil
in
a
wood
treatment
factory
&
background
level
concentrations
(
in
µ
g/
g,
dry
weight)

Sampling
Site
As(
conc.
range)
As
(
mean)
Cr(
conc.
range)
Cr(
mean)
Cu(
conc.
range)
Cu(
mean)

1
3456­
7148
5312
2154­
5810
3996
3817­
7216
5424
2
956­
4678
2552
868­
3740
2046
1618­
5478
3460
3
1092­
3508
2211
788­
3158
2005
2031­
5180
3710
4
238­
921
597
197­
764
498
407­
1062
763
5
8.4­
21
16.1
38­
78.6
59.3
67.4­
103
82.9
6
0.1­
40
6
5­
1500
70
2­
250
30
13
Notes:
Sampling
site
#
1:
soil
samples
from
the
preparation
and
mixing
sites
in
the
factory.
Sampling
site
#
2:
soil
samples
from
the
areas
in
the
factory
where
freshly
treated
wooden
poles
are
stacked.
Sampling
site#
3:
soil
samples
from
the
areas
where
sludge
is
deposited
inside
the
factory.
Sampling
site#
4:
soil
samples
from
12
randomly
selected
sites
inside
the
factory.
Sampling
site
5:
soil
samples
from
1
km
distance
from
the
factory
site.
Sampling
site
6:
Background
concentrations
as
reported
in
literature.
(
Bowen,
H.
C.,
1979)

In
a
recent
study,
85
samples
of
contaminated
soil
were
obtained
from
under
and
around
seven
decks
which
were
CCA
pressure
treated
and
the
ages
of
these
decks
were
from
4
years
to
15
years.
These
soil
samples
were
composites
of
the
upper
5
cm
soil
layers
and
the
soil
type
was
sandy
loam.
The
extraction
of
the
metal
ion
from
the
soil
samples
was
carried
out
by
digesting
into
conc.
nitric
acid
under
a
pressure
of
120
psi
in
a
microwave
oven
and
then
diluted
with
deionized
water.
The
concentration
of
the
metal
ions
were
determined
by
using
ICP­
AES
(
inductively
coupled
plasma
atomic
emission
spectrometry).
In
addition,
arsenic
also
determined
with
graphite
furnace
atomic
absorption
spectrometer
(
GFAAS).
The
average
amounts
(
in
mg/
kg)
were:
75
for
Cu,
43
for
Cr
and
76
for
As.
These
amounts
indicate
the
leaching
of
the
CCA
components
into
the
soil
is
high.
This
study
also
showed
that
the
amounts
of
the
metal
ions
increased
in
the
soil
with
the
age
of
a
deck.

The
same
study
also
indicated
that
soil
samples
taken
15
cm
from
the
deck
perimeter
showed
the
average
amounts
(
mg/
kg)
of
the
metals
to
be:
67
for
Cu,
46
for
Cr
and
32
for
As
which
indicates
that
the
soil
contamination
decreases
a
short
distance
away
from
the
deck
perimeter.
14
Table
3
summarizes
the
average
amounts
of
these
metal
ions
along
with
the
amounts
from
control
samples
as
well
as
EPA's
statutory
limits
on
these
metal
ions.

Table
3
Average
amounts
of
metal
ions
(
mg/
kg)
in
the
soil
samples
beneath
decks
and
statutory
limits
Location/
Statutory
Limits
Chromium
(
total)
Chromium(
VI)
Arsenic
Beneath
decks
43
nd
76
Control
soils
20
nd
4
EPA
503(
1993)
1200
­
41
State
of
CT
(
1996)
3900
100
10
This
study,
did
not
point
out
which
type
of
wood
was
used
for
the
decks
(
southern
pine
or
red
pine
etc.)
and
which
type
of
CCA
was
used
for
pressure
treatment
of
the
lumber
(
Stilwell,
D.
E.
and
K.
D.
Gorny,
1997).

Biotic
Transformations
&
Bioaccumulations:

An
earlier
study
(
Chou,
et
al.,
1973)
showed
that
between
3­
4%
of
the
metal
ions
were
taken
up
by
the
Poria
Monicola
Fungal
Hyphae
on
the
pressure
treated
southern
pine
veneers
with
CCA
which
contained
potassium
dichromate,
copper
sulfate
pentahydrate
and
arsenic
pentoxide
dihydrate
in
the
ratio
of
9:
7:
4.

Another
comprehensive
study
(
Irvine
and
Dahlgren
1976),
the
growth
of
number
of
marine
and
non­
marine
fungi
and
bacteria
were
affected
when
exposed
to
copper
­
chromearsenate
put
in
an
agar
media.
Table
4
summarizes
the
Minimum
Inhibition
Concentration
(
MIC)
of
the
CCA
components
needed
to
affect
the
growth
of
the
these
organisms.
15
Table
4
Minimum
Inhibition
Concentration
Values
for
Marine
&
Non­
Marine
Fungi
Type
of
Fungi
CuSO
4
(
mg/
L)
Na
2
Cr
2
O
7
(
mg/
L)
As
2
O
5
(
mg/
L)
CCA
%

Marine:

Corollospora
cristata
137
482
244
0.2
Lulworthia
sp.
274
482
488
0.1
Ceriosporopsis
halima
546
1,928
976
0.2
Asteromyces
cruciatus
546
2410
>
1220
0.4
Cladosporium
herbarum
>
1,370
482
>
1,220
0.2
Dendryphiella
salina
1,096
964
1,220
0.4
Monodictys
pelagica
274
482
244
0.1
Diplodia
oraemaris
274
964
122
0.1
Zalerion
maritimum
137
241
122
0.05
Cirrenalia
macrocephala
68.5
482
244
0.05
Non­
Marine:

Chaetomium
globosum
(
P117)
546
241
488
0.05
Chaetomium
globosum(
R24)
274
482
244
0.025
Leptosphaeria
sp.
546
120.5
488
0.025
Melogramma
sp.
1,096
241
61
0.0125
Botryosporium
sp.
1,370
120.5
244
0.4
Phoma
sp.
546
964
976
0.1
Fusarium
sp.
546
482
976
0.025
Doratomyces
sp.
137
120.5
488
0.025
Stachybotrys
atra
274
120.5
488
0.025
Graphium
sp.
274
60.3
244
0.0125
Note:
*
means
that
growth
of
the
fungi
were
stimulated
at
low
concentrations.
16
For
most
of
the
microorganisms
the
M.
I.
C.
values
for
chromium
ranges
from
120.5
to
964
mg/
L
except
for
Ceriosporopsis
halima
(
1928
mg/
L)
and
Asteromyces
cruciatus
(
2410
mg/
L).
In
case
of
arsenic
tolerance,
most
of
the
organisms
had
M.
I.
C.
values
between
244
to
976
mg/
L
except
for
Asteromyces
cruciatus
(
1220
mg/
L),
Cladosporium
herbarum
(
1220
mg/
L)
and
Dendryphiella
salina
(
1220
mg/
L).
The
majority
of
the
organisms
showed
M.
I.
C.
values
between
274
to
546
mg/
L
vis­
a­
vis
copper
except
for
Melogramma
sp.
(
1370
mg/
L)
and
Dendryphiella
salina
(
1370
mg/
L).
The
range
of
tolerance
for
arsenic
and
chromium
by
these
microorganisms
were
more
than
for
copper.

It
has
been
shown
that
in
an
estuary
there
are
different
pathways
by
which
the
CCA
components
leaching
from
the
treated
wood
can
impact
the
aquatic
biota..
CCA
components
can
dissolve
in
water
forming
aquated
cations.
These
species
can
then
be
taken
up
by
biota.
Epibiotic
organisms.
Fouling
organisms
that
live
directly
on
the
wood
have
the
highest
uptake
of
the
contaminants.
These
metallic
contaminants
can
be
absorbed
by
sediments
near
the
wood
(
e.
g.
docks).
These
can
then
are
taken
up
by
the
benthic
organisms.
These
could
be
biomagnified
through
the
food
chain.
The
uptake
(
bioaccumulation)
of
these
metallic
contaminants
depend
on
the
concentration
of
the
metallic
species
which
in
turn
depend
on
the
amount
of
water
flow
in
an
estuary,
amount
and
age
of
the
CCA
treated
wood.
Green
algae
Ulla
lactuca
and
Enteromorpha
intestinalis,
collected
from
the
CCA­
treated
bulkheads
in
Southhampton,
NY
showed
a
higher
degree
of
bioaccumulation
for
all
three
metal
ions
whereas
the
species
collected
from
the
nearby
rocks
showed
a
lower
degree
of
bioaccumulation.
Enteromorpha,
for
example,
collected
from
the
dock
showed
a
bioaccumulation
of
55
µ
g/
g
Cu,
6
µ
g/
g
of
Cr
and
4.7
µ
g/
g
of
As;
however,
the
same
microogranism
collected
from
the
nearby
rocks
showed
a
bioaccumulation
level
of
14
µ
g/
g
for
Cu,
2.5
µ
g/
g
of
Cr
and
1
µ
g/
g
of
As.
(
Weis
and
Weis,
1992a).

In
another
study,
(
Weis,
et
al.,
1993a)
it
was
shown
that
if
the
organisms
are
tested
for
bioacuumulation
in
a
body
water
where
the
water
flow
rates
are
different,
the
contaminants
are
bioaacuumulated
at
different
levels.
For
example,
algae
Cermium
sp.,
oysters
Crassostrea
virginica,
barnacles
balanus
eburneus,
and
mussles
Brachydontis
recurvis
were
collected
from
a
CCA­
treated
dock
in
an
open
water
environment
and
from
bulkheads
in
a
poorly
flushes
residential
canal
adjoining
Santa
Rosa
Sound,
Pensicola
Beach,
Florida
as
well
as
from
the
nearby
rocks
in
open
water.
Open­
water
docks
organisms
had
a
significantly
higher
level
of
bioaccumulation.
For
example
Ceramium,
living
in
open
water
area,
showed
a
copper
concentration
of
3
µ
g/
g
,
an
increase
of
2
µ
g/
g
from
non
exposed
organisms,
arsenic
showed
an
increase
from
3
µ
g/
g
(
non­
exposed
organism)
to
5.5
µ
g/
g.
The
same
study
showed
that
organisms
(
e.
g.
barnacles)
that
grew
on
rocks
nearby
the
dock,
had
a
1
µ
g/
g
of
copper
bioaccumulation,
those
on
the
open
water
dock
had
3
µ
g/
g
of
copper,
those
in
the
canal
(
poorly
flushed
areas)
has
about
10
µ
g/
g
of
Cu
and
those
that
grew
on
the
new
wood
docks
(
1
year
old)
inside
the
canal
had
a
bioaccumulation
of
80
µ
g/
g
Cu.
In
a
related
study
(
Weis,
et
al.,
1993
b),
it
was
shown
that
the
tissues
of
oysters
living
inside
a
canal
showed
the
concentration
of
Cu
to
be
150
µ
g/
g,
an
increase
of
12­
fold
over
the
controls.
The
same
oysters
did
not
show
an
increased
bioaccumulation
for
the
other
two
metals.
Other
studies
have
also
shown
the
same
trend,
oysters
have
a
tendency
of
bioacumulating
copper
more
than
other
metals
(
Schuster
&
Pringle,
1969).
17
A
study
on
the
sediments
adjacent
to
and
close
by
distances
to
CCA­
treated
bulkheads,
on
analyses
showed
a
higher
level
of
the
three
metal
ions.
Sediments
adjacent
to
bullheads
in
New
York
and
New
Jersey
estuaries
consist
of
fine­
grained
particles
(
silt
and
clay
often
less
than
one
percent).
These
sediments
in
these
locations
showed
a
very
high
concentration
of
the
metals
between
100­
2000
µ
g/
g.
Sediments
which
were
ten
meters
away
from
the
bulkheads,
consisted
of
higher
percentages
of
silt
and
clay
(
up
to
60%)
showed
a
lower
concentrations
of
the
metals.
Sediments
in
poorly
flushed
areas
showed
a
higher
concentrations
of
the
metals
then
the
ones
which
are
open
water
areas
with
regular
water
flows.
Again
the
sediments
around
the
newly
built
bulkheads
showed
the
highest
concentrations
of
the
metals.

These
sediments
can
possibly
become
a
pathway
of
exposure
to
the
benthic
biota
as
shown
in
another
study.
Fiddler
crabs
U.
Pugilator
showed
that
the
metal
concentrations
were
double
in
the
organisms
than
on
the
sediments
(
Weis
and
Weis,
1992
a).

In
1979,
The
Agency
published
a
document
Water­
Related
Environmental
Fate
of
129
Priority
Pollutants
(
EPA­
440/
4­
79­
029a)
which
summarized
the
open
literature
searches
the
fate
of
these
Priority
Pollutants
in
aqueous
medium.
The
fate
and
transport
of
arsenic,
chromium
and
copper
are
discussed
in
the
following
paragraphs:

Arsenic:

Table
5
summarizes
the
bioconcentration
factors
for
arsenic
in
various
taxa:

Table
5
Taxon
Bioconc.
Factor
Reference
Freshwater
Plants
333
Chapman,
et
al.,
1968
6000
Reay,
1973
FreshWater
fish
333
Chapman,
et
al.,
1968
Marine
Plants
333
Chapman,
et
al.,
1968
Marine
Invertebrates
333
Chapman,
et
al.,
1968
Marine
Fish
333
Chapman,
et
al.,
1968
Note
that
the
bioconcentration
factors
were
reported
as
the
ratio
of
the
concentration
of
the
element
in
the
aquatic
organism
(
in
ppm,
dry
weight)
to
the
concentration
of
the
element
in
water
(
in
ppm).

The
data
from
the
table
indicate
that
arsenic
does
show
a
tendency
to
accumulate
through
water
and
biomagnification
(
food).
The
bioconcentration
factors
are
not
large,
however,
The
EPA
document
also
reported
other
bioaccumulation
studies:
18
A.
Isensee
et
al.
(
1973)
conducted
a
microcosm
study
on
the
bioaccumulation
of
cacodylic
acid
derived
arsenical
and
dimethyl
arsine
for
32
days.
This
simulated
ecosystem
contained
algae,
snails,
daphnia
and
fish.
Fish
had
minimum
bioaccumulation
in
this
selected
group.
Snails
were
next
in
line
in
bioaccumulating
arsenic
while
the
algae
and
daphnia
showed
the
highest
tendency
to
bioaccumulate
arsenic.
At
the
end
of
the
study
period
(
32
days),
only
30%
of
arsenic
was
incorporated
by
the
biota.

B.
Green
sunfish
Lepomis
cyanellus
was
exposed
to
various
concentrations
of
sodium
arsenate
and
the
data
indicated
that
the
bioaccumulation
of
arsenic
(
presumbaly
as
As+
5)
was
a
function
of
the
sodium
arsenate
concentrations.
The
uptake
of
arsenic
by
liver,
gut
and
muscle
was
also
found
to
depend
on
the
temperature.

C.
A
sixteen
week
exposure
with
sodium
arsenate
to
young
and
adult
bluegills
Leomis
marchochirus
showed
that
the
concentration
of
arsenic
in
the
adult
bluegill
was
the
same
as
in
the
pond
but
the
arsenic
levels
in
the
young
bluegills
were
twice
as
high
as
in
the
adults.

D.
A
fish
in
a
pond
which
was
accidently
contaminated
with
arsenical
was
analyzed
and
arsenic
level
was
2.5
mg
As/
L;
fish
accumulated
6.6
µ
g
As/
g
in
muscle,
one
fifth
of
what
is
in
water.
Lake
Michigan
plankton
and
benthos
showed
a
concentration
factor
of
6.0
and
6.6
µ
g/
As
/
g
respectively.
Analysis
of
biota
in
Lake
Superior
showed
the
plankton
contained
30%
less
As
than
the
Lake
Michcigan
Plankton.

The
same
EPA
document
reported
bioaccumulation
and
bioconcentration
information
about
chromium
which
is
summarized
in
the
following:
19
Chromium:

Table
6
Bioconcentration
Factors
for
Chromium
Taxon
Bioconcentration
Factor
Reference
Freshwater
fish
200
Chapman
et
al.,
1968
Freshwater
invertebrates
2,000
Chapman
et
al.,
1968
Fresh
water
plants
4,000
Chapman
et
al.,
1968
Marine
fish
400
Chapman
et
al.,
1968
Marine
invertebrates
200
Chapaman
et
al.,
1968
Marine
plants
2,000
Chapman
et
al.,
1968
Benthic
algae
1,600
NAS*,
1974
Phytoplankton
2,300
NAS,
1974
Zooplankton
1,900
NAS,
1974
Mollusc
viscera
440
NAS,
1974
Crustacean
muscle
100
NAS,
1974
Fish
muscle
70
NAS,
1974
NAS
*
means
National
Academy
of
Sciences.

An
early
study
determined
the
chromium
partitioning
between
water,
sediment
and
chironomid
larvae
(
a
benthic
invertebrate).
Highest
concentration
of
chromium
was
found
in
the
sediment
(
7.64
µ
g/
g),
followed
by
bioaccumulation
of
2.96
µ
g/
g
of
Cr
in
the
chironomid
and
1.1
µ
g/
l
in
water
(
Namminga
and
Wilhm,
1977).
Another
study
showed
a
biomagnification
of
chromium
when
benthic
worm
(
tubificid)
when
fed
with
chromium
rich
bacteria
bioaccumulated
(
extracted)
the
metal
from
the
bacteria
(
Patrick
and
Loutit,
1976).
Radiolabed
Cr(
III)
was
found
to
biomagnify
through
the
food
chain
in
an
estuarine.
The
food
chain
consisted
of
phytoplankton,
brine
shrimp,
post­
larval
fish
and
mummichog.
The
concentration
of
the
radiolabeled
chromium
declined
in
the
food
chain
through
trophic
levels
(
Baptist
and
Lewis,
1969).
20
Another
study
was
conducted
on
the
bioaccumulation
of
metals
on
the
benthic
(
sediments
and
microorganisms)
impacted
by
the
CCA
treated
wood
bullheads
in
a
large
Atlantic
Coast
Estuaries.
Accumulation
of
metals
around
the
bulkheads
and
bioaccumulation
in
microorganisms
were
investigated
at
distance
zero
to
1,
3
and
10
meters
from
the
bulkheads.
Five
sites,
with
different
bulkhead
ages,
were
chosen:

A.
Middle
Pond
in
Southhampton,
New
York.
The
bulkhead
was
one
year
old.
Additionally,
two
reference
sites,
one
an
unbulkheaded
site
in
the
same
pond
and
the
second
a
bulkhead
made
up
of
aluminum
in
the
nearby
estuary
at
Bullhead
bay
in
Southampton,
N.
Y.

B.
Old
Fort
Pond,
also
in
Southampton.
This
was
an
eight
year­
old
bulkhead
in
a
poorly
flushed
location.
A
transect
from
the
opposite
shoreline
was
chosen
as
a
reference.

C.
Bulkheads
along
the
Debardaue
Canal,
at
the
North
Inlet
Research
Reserve
in
South
Carolina.
These
were
2
year­
old
bulkheads
with
intertidal
situation
and
the
Canal
itself
was
very
well­
flushed.
An
aluminum
bulkhead
in
the
same
vicinity
was
chosen
as
a
reference
site.

D.
A
two­
year
old
bulkhead
in
Osborn
Cove
off
the
Patuexent
River
in
the
Chesapeake
Bay,
Maryland.
This
was
a
poorly
flushed
location
and
the
natural
shoreline
was
used
as
a
reference
site,
30
m
across
the
cove.

E.
A
pair
of
adjacent
bullheads
at
the
Drum
Point
in
Solomon,
Maryland.
One
bulkhead
was
a
CCA­
treated
(
approximately
6­
8
year
old)
and
the
second
was
made
up
of
concrete.

Generally,
the
impact
of
CCA­
treated
wood
in
an
estuary
depended
on
the
surface
area
exposed
to
leaching,
the
leaching
rate
itself,
metal
speciation
(
type
of
metal
species
present
under
the
conditions),
rate
of
uptake
(
bioaccumulation)
by
epibiota,,
tidal
activity
(
well
or
poorlyflushed
locations,
adsorption
by
sediment
(
a
function
of
particle
size
of
the
soil),
trophic
transfer
to
grazers
and
predators.

In
the
following
the
data
summary
is
presented:

Middle
Pond:

Sediments
around
the
bulkhead
were
variable
and
made
up
of
coarse
and
fine
mixture.
Fine
sediment
fraction
was
more
at
10
meter
from
the
bulkhead
and
find
fractions
generally
retained
the
metals
more
tightly
than
the
coarse
fraction
of
the
sediment.
However,
the
percent
of
the
contaminants
(
the
metals
from
the
leaching
from
the
wood)
was
highest
at
distance
0
meter
from
the
bulkhead.
The
concentration
(
bioaccumulation)
was
highest
in
the
microrgansims
at
distance
0
meter
from
the
bulkhead
and
progressively
decreased
to
1
to
3
to
10
meters
away
form
the
bulkhead.
Comparatively,
the
metal
contamination
(
bioaccumulation)
of
mcirorganisms
at
the
reference
site
was
much
lower
than
at
the
experimental
site.
The
organisms
present
at
the
experimental
and
references
sites
were:
Marenzelleria
virdis,
Leitoscoloplos
sp.,
Neanthes
spp.,
Clymenella
torquada,
a
Capetillid
and
the
snail
Ilyanassa
obseleta.
Of
these
Neanthes
was
the
most
21
predominant
organism.

Old
Fort
Pond:

Chromium
levels
in
the
fine
fractions
of
the
sediment
remained
the
same
irrespective
of
the
distance
from
the
bulkhead,
while
the
copper
concentration
was
twice
as
high
at
zero
distance
from
the
bulkhead
than
at
a
distance
away
from
it.
Arsenic
levels
progressively
declined
moving
away
from
the
bulkhead.
The
change
in
the
percent
of
total
carbon
in
the
sediment
did
not
show
any
change
in
the
accumulation
numbers.

The
dominant
organisms
at
this
site
(
both
actual
and
reference)
were:
Marenzelleria
virdis,
Leitoscoloplos
sp.,
Neanthes
spp.,
Clymenella
torquada,
a
Capitellid
and
Hypaniola
gray
as
well
as
clams
Melaena
lateralis,
the
bubble
snail
Haminoea
and
Cyathura
polita.
The
data
analysis
for
the
bioaccumulation
in
these
species
was
difficult
as
it
did
not
show
any
trend
in
the
concentration
levels
of
metals
at
various
distances
from
the
bulkhead.

North
Inlet,
Debardeau
Canal:

The
highest
concentrations
of
the
metals
was
at
the
site
at
zero
meter
distance
from
the
bulkhead.
Since
this
site
consisted
of
the
wood
bulkhead
and
the
reference
site
was
aluminum,
the
analysis
showed
that
there
were
no
organsims
at
the
wood
bulkhead
at
distance
of
zero
and
one
meter
from
the
wood
bulkhead
while
at
3
meter
distance
Notomastus
was
the
main
organism
and
other
organisms
were
also
present
like
Neanthes,
a
nemertean
Lineus
socialis
At
the
Al
bulkhead
also
the
dominant
organism
was
Notomastus
and
besides
there
were
Clymenella,
Lineus,
Neanthes,
Melaena
lateralis
and
Mercenaria.

Osborne
Cove:

The
copper
accumulations
did
not
vary
much
from
zero
meter
distance
to
the
maximum
(
10
meters).
However,
arsenic
did
show
some
variations
with
distance.

The
type
of
organisms
existing
at
the
zero
meter
actual
site
were:
Lanonereis
culveri,
Hargeria
rapax,
Marenzerellia
virdis,
and
Hobsonia
florida.
Reference
sight
consisted
of,
in
addition
to
the
ones
mentioned,
the
follwoing:
Hypereteone
heteropoda,
Leitoscoloplos
fragilis,
Streblospio
benedecti,
Macoma
balthica,
M.
Mitchelli,
Lepidodactylus
dyticus,
Balanus
improvsus
and
Cyathura
polita.

Drum
Point
Both
copper
and
chromium
showed
a
declining
accumulation
moving
away
from
the
bulkhead.

The
organisms
present
on
this
site
were
predominantly:
Leitoscoloplos
fragilis,
marenzelleria
virdus,
Leptocheirus
plumulosus,
Gemma
gemmma.
No
significant
difference
bioacummulation
differences
were
observed
at
various
locations
on
this
site.
22
In
summary,
bioaccumulation
in
Middle
Pond
organisms
were
highest
in
the
organism
living
closest
to
the
wooden
bulkheads.
Bioaccumulation
in
tissues
declined
dramatically
at
a
3
meter
distance
from
the
bulkhead.
In
some
cases,
it
rose
again
by
10
meters
but
primarily
due
to
the
increase
in
the
fine
sediment
fraction
which
has
a
tendency
to
adsorb
and
retain
the
metals.

It
appears
at
all
bulkhead
sites
metals
are
retained
(
accumulated)
by
fine­
grained
sediments
and
a
reduction
ensues
in
the
nearby
biota.
Unbulkheaded
and
aluminum
bulkheads
do
not
show
this
tendency.
The
biota
at
10
meter
out
from
the
bulkhead
at
Middle
Pond
showed
reduction
because
of
percent
increase
of
fine­
grained
sediments
while
for
Old
Fort
Pond
the
same
phenomenon
was
observed
at
3
and
10
meters
away
from
the
bulkheads
because
of
the
same
reason.
At
all
sites,
the
impact
on
biota
was
highest
between
zero
and
1
meter
distance
from
the
bulkheads.
And
in
all
cases,
copper
was
observed
to
be
responsible
for
the
reduction
in
the
biota
around
the
bulkheads
(
Weis
et
al.,
1998)

A
recent
study
on
bioaccumulation
of
CCA
components
in
Blue
Mussels
Mytilus
Edulis
was
conducted
and
the
laboratory
and
field
expsoure
data
were
collected
over
a
period
of
one
year.
The
CCA­
treated
wood
was
of
the
Southern
Yellow
Pine
type.
CCA­
C
treated
wood
boards
(
4.4
cm
x
22.8
cm
x
3
m)
were
pressure­
treated
at
a
treatment
retention
of
2.5
pcf
(
40
kg/
m3.
).
Two
sets
of
blue
mussels,
one
4­
5
cm
long
and
the
other
3.5
to
4
cm
long
were
collected
from
the
east
jetty
at
the
Flax
Pond
inlet,
Old
field,
New
York.
the
laboratory
sea
tables
were
arrnged
in
such
a
way
that
one
set
of
blue
mussles
were
upstream
to
water
flow
and
the
other
downstream
to
water
flow.
The
mussles
were
sampled
form
each
sea
table
at
time
0,
one
week
and
one
month.
Similar
arrangements,
samples
of
blue
mussles,
submerges
in
water
and
were
placed
adjacent
to
the
wood.
After
the
experiment
was
terminated,
freeze­
dried
mussles
were
digested
in
nitric/
perchloric
acid
mixture
and
samples
collected
were
anlayzed
for
copper,
chromium
and
arsenic
by
flame
(
Cu)
and
graphite
furnace
(
Cr
and
As)
atomic
absorption
spectrophotometry.
The
laboratory
and
field
exposure
studies
showed
that
no
significant
difference
in
the
average
dry
tissue
weight
and
length
between
CCA­
C
treated
and
control
treatments.

Table
8
summarizes
the
concentrations
of
Cu,
Cr
and
As
in
the
tissues
of
blue
mussel.
Concentration
of
these
metals
obtained
by
Mussel
Watch,
organized
by
national
Status
&
Trends
sampling
stations
in
Long
Island
Sound
are
also
included
in
the
table
for
comparison
purposes.

TABLE
8
1
Contaminant
Lab.
Exposure
Field
Exposure
Mussel
Watch2
Cu
7.88
8.54
8.91
Cr
0.86
0.72
1.61
As
8.82
7.14
6.24
Notes:
1.
All
values
in
µ
g/
g
23
2.
Data
from
1990
reports
Note
that
the
measured
metal
contents
of
mussel
tissues
in
both
laboratory
and
field
exposure
studies
are
at
or
lower
than
the
average
values
obtained
from
the
national
or
regional
monitoring
studies.
The
species
of
these
elements
affect
their
bioaccumulation
in
mussel
tissues.
24
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