9010C
­
1
Revision
3
August
2002
METHOD
9010C
TOTAL
AND
AMENABLE
CYANIDE:
DISTILLATION
1.0
SCOPE
AND
APPLICATION
1.1
Method
9010
is
reflux­
distillation
procedure
used
to
extract
soluble
cyanide
salts
and
many
insoluble
cyanide
complexes
from
wastes
and
leachates.
It
is
based
on
the
decomposition
of
nearly
all
cyanides
by
a
reflux
distillation
procedure
using
a
strong
acid
and
a
magnesium
catalyst.
Cyanide,
in
the
form
of
hydrocyanic
acid
(
HCN)
is
purged
from
the
sample
and
captured
into
an
alkaline
scrubber
solution.
The
concentration
of
cyanide
in
the
scrubber
solution
is
then
determined
by
Method
9014
or
Method
9213.
Method
9010
may
be
used
as
a
reflux­
distillation
procedure
for
both
total
cyanide
and
cyanide
amenable
to
chlorination.
The
"
reactive"
cyanide
content
of
a
waste
is
not
determined
by
this
method.
Refer
to
40
CFR
261.23
for
information
on
the
characteristic
of
reactivity.

1.2
This
method
was
designed
to
address
the
problem
of
"
trace"
analyses
(<
1000
ppm).
The
method
may
also
be
used
for
"
minor"
(
1000
ppm
­
10,000
ppm)
and
"
major"
(>
10,000
ppm)
analyses
by
adapting
the
appropriate
sample
dilution.
However,
the
amount
of
sodium
hydroxide
in
the
standards
and
the
sample
analyzed
must
be
the
same.

2.0
SUMMARY
OF
METHOD
2.1
The
cyanide,
as
hydrocyanic
acid
(
HCN),
is
released
from
samples
containing
cyanide
by
means
of
a
reflux­
distillation
operation
under
acidic
conditions
and
absorbed
in
a
scrubber
containing
sodium
hydroxide
solution.
The
cyanide
concentration
in
the
absorbing
solution
is
then
determined
colorimetrically
or
titrametrically
by
Method
9014
or
by
ion­
selective
electrode
by
Method
9213.

3.0
INTERFERENCES
3.1
Interferences
are
eliminated
or
reduced
by
using
the
distillation
procedure.
Chlorine
and
sulfide
are
interferences
in
Method
9010.

3.2
Oxidizing
agents
such
as
chlorine
decompose
most
cyanides.
Chlorine
interferences
can
be
removed
by
adding
an
excess
of
sodium
arsenite
to
the
waste
prior
to
preservation
and
storage
of
the
sample
to
reduce
the
chlorine
to
chloride
which
does
not
interfere.

3.3
Sulfide
interference
can
be
removed
by
adding
an
excess
of
bismuth
nitrate
to
the
waste
(
to
precipitate
the
sulfide)
before
distillation.
Samples
that
contain
hydrogen
sulfide,
metal
sulfides,
or
other
compounds
that
may
produce
hydrogen
sulfide
during
the
distillation
should
be
treated
by
the
addition
of
bismuth
nitrate.

3.4
High
results
may
be
obtained
for
samples
that
contain
nitrate
and/
or
nitrite.
During
the
distillation,
nitrate
and
nitrite
will
form
nitrous
acid,
which
will
react
with
some
organic
compounds
to
form
oximes.
These
compounds
once
formed
will
decompose
under
test
conditions
to
generate
HCN.
The
possibility
of
interference
of
nitrate
and
nitrite
is
eliminated
by
pretreatment
with
sulfamic
acid
just
before
distillation.
Nitrate
and
nitrite
are
interferences
when
present
at
levels
higher
than
10
mg/
L
and
in
conjunction
with
certain
organic
compounds.
9010C
­
2
Revision
3
August
2002
3.5
Thiocyanate
is
reported
to
be
an
interference
when
present
at
very
high
levels.
Levels
of
10
mg/
L
were
not
found
to
interfere.

3.6
Fatty
acids,
detergents,
surfactants,
and
other
compounds
may
cause
foaming
during
the
distillation
when
they
are
present
in
high
concentrations
and
may
make
the
endpoint
for
the
titrimetric
determination
difficult
to
detect.
Refer
to
Sec.
6.8
for
an
extraction
procedure
to
eliminate
this
interference.

4.0
APPARATUS
AND
MATERIALS
4.1
Reflux
distillation
apparatus
such
as
shown
in
Figure
1
or
Figure
2.
The
boiling
flask
should
be
of
one
liter
size
with
inlet
tube
and
provision
for
condenser.
The
gas
scrubber
may
be
a
270­
mL
Fisher­
Milligan
scrubber
(
Fisher,
Part
No.
07­
513)
or
equivalent.
The
reflux
apparatus
may
be
a
Wheaton
377160
distillation
unit
or
equivalent.

4.2
Hot
plate
stirrer/
heating
mantle.

4.3
pH
meter.

4.4
Amber
light.

4.5
Vacuum
source.

4.6
Refrigerator.

4.7
Erlenmeyer
flask
­
500
mL.

4.8
KI
starch
paper.

4.9
Class
A
volumetric
flasks
­
1000,250,
and
100
mL.

5.0
REAGENTS
5.1
Reagent
grade
chemicals
shall
be
used
in
all
tests.
Unless
otherwise
indicated,
it
is
intended
that
all
reagents
shall
conform
to
the
specifications
of
the
Committee
on
Analytical
Reagents
of
the
American
Chemical
Society,
where
such
specifications
are
available.
Other
grades
may
be
used,
provided
it
is
first
ascertained
that
the
reagent
is
of
sufficiently
high
purity
to
permit
its
use
without
lessening
the
accuracy
of
the
determination.

5.2
Reagent
water.
All
references
to
water
in
this
method
refer
to
reagent
water,
as
defined
in
Chapter
One.

5.3
Reagents
for
sample
collection,
preservation,
and
handling
5.3.1
Sodium
arsenite
(
0.1N),
NaAsO
2.
Dissolve
3.2
g
NaAsO
2
in
250
mL
water.

5.3.2
Ascorbic
acid,
C
6
H
8
O
6.

5.3.3
Sodium
hydroxide
solution
(
50%),
NaOH.
Commercially
available.
9010C
­
3
Revision
3
August
2002
5.3.4
Acetic
acid
(
1.6M)
CH
3
COOH.
Dilute
one
part
of
concentrated
acetic
acid
with
9
parts
of
water.

5.3.5
2,2,4­
Trimethylpentane,
C
8
H
18.

5.3.6
Hexane,
C
6
H
14.

5.3.7
Chloroform,
CHCl
3.

5.4
Reagents
for
cyanides
amenable
to
chlorination
5.4.1
Calcium
hypochlorite
solution
(
0.35M),
Ca(
OCl)
2.
Combine
5
g
of
calcium
hypochlorite
and
100
mL
of
water.
Shake
before
using.

5.4.2
Sodium
hydroxide
solution
(
1.25N),
NaOH.
Dissolve
50
g
of
NaOH
in
1
liter
of
water.

5.4.3
Sodium
arsenite
(
O.
1N).
See
Sec.
5.3.1.

5.4.4
Potassium
iodide
starch
paper.

5.5
Reagents
for
distillation
5.5.1
Sodium
hydroxide
(
1.25N).
See
Sec.
5.4.2.

5.5.2
Bismuth
nitrate
(
0.062M),
Bi(
NO)
3
C
5H
2
O.
Dissolve
30
g
Bi(
NO)
3
C
5H
2
O
in
100
mL
of
water.
While
stirring,
add
250
mL
of
glacial
acetic
acid,
CH
3
COOH.
Stir
until
dissolved
and
dilute
to
1
liter
with
water.

5.5.3
Sulfamic
acid
(
0.4N),
H
2
NSO
3
H.
Dissolve
40
g
H
2
NSO
3
H
in
1
liter
of
water.

5.5.4
Sulfuric
acid
(
18N),
H
2
SO
4.
Slowly
and
carefully
add
500
mL
of
concentrated
H
2
SO
4
to
500
mL
of
water.

5.5.5
Magnesium
chloride
solution
(
2.5M),
MgCl
2
C
6H
2
O.
Dissolve
510
g
of
MgCl
2
C
6H
2
O
in
1
liter
of
water.

5.5.6
Lead
acetate
paper.

5.5.7
Stock
potassium
cyanide
solutions
­
Refer
to
Method
9014
for
the
preparation
of
stock
cyanide
solutions
and
calibration
standards.

6.0
SAMPLE
COLLECTION,
PRESERVATION
AND
HANDLING
6.1
Samples
should
be
collected
in
plastic
or
glass
containers.
All
containers
must
be
thoroughly
cleaned
and
rinsed.

6.2
Oxidizing
agents
such
as
chlorine
decompose
most
cyanides.
To
determine
whether
oxidizing
agents
are
present,
test
a
drop
of
the
sample
with
potassium
iodide­
starch
test
paper.
A
blue
color
indicates
the
need
for
treatment.
Add
0.1N
sodium
arsenite
solution
a
few
mL
at
a
time
until
a
drop
of
sample
produces
no
color
on
the
indicator
paper.
Add
an
additional
5
mL
of
sodium
arsenite
solution
for
each
liter
of
sample.
Ascorbic
acid
can
be
used
as
an
alternative
although
it
9010C
­
4
Revision
3
August
2002
is
not
as
effective
as
arsenite.
Add
a
few
crystals
of
ascorbic
acid
at
a
time
until
a
drop
of
sample
produces
no
color
on
the
indicator
paper.
Then
add
an
additional
0.6
g
of
ascorbic
acid
for
each
liter
of
sample
volume.

6.3
Aqueous
samples
must
be
preserved
by
adding
50%
sodium
hydroxide
until
the
pH
is
greater
than
or
equal
to
12
at
the
time
of
collection.

6.4
Samples
should
be
chilled
to
4
E
C.

6.5
When
properly
preserved,
cyanide
samples
can
be
stored
for
up
to
14
days
prior
to
sample
preparation
steps.

6.6
Solid
and
oily
wastes
may
be
extracted
prior
to
analysis
by
method
9013.
It
uses
a
dilute
NaOH
solution
(
pH
=
12)
as
the
extractant.
This
yields
extractable
cyanide.

6.7
If
fatty
acids,
detergents,
and
surfactants
are
a
problem,
they
may
be
extracted
using
the
following
procedure.
Acidify
the
sample
with
acetic
acid
(
1.6M)
to
pH
6.0
to
7.0.

CAUTION:
This
procedure
can
produce
lethal
HCN
gas.

Extract
with
isooctane,
hexane,
or
chloroform
(
preference
in
order
named)
with
solvent
volume
equal
to
20%
of
the
sample
volume.
One
extraction
is
usually
adequate
to
reduce
the
compounds
below
the
interference
level.
Avoid
multiple
extractions
or
a
long
contact
time
at
low
pH
in
order
to
keep
the
loss
of
HCN
at
a
minimum.
When
the
extraction
is
completed,
immediately
raise
the
pH
of
the
sample
to
above
12
with
50%
NaOH
solution.

7.0
PROCEDURE
7.1
Pretreatment
for
cyanides
amenable
to
chlorination
7.1.1
This
test
must
be
performed
under
amber
light.
K
3[
Fe­(
CN)
6]
may
decompose
under
UV
light
and
hence
will
test
positive
for
cyanide
amenable
to
chlorination
if
exposed
to
fluorescent
lighting
or
sunlight.
Two
identical
sample
aliquots
are
required
to
determine
cyanides
amenable
to
chlorination.

7.1.2
To
one
500
mL
sample
or
to
a
sample
diluted
to
500
mL,
add
calcium
hypochlorite
solution
dropwise
while
agitating
and
maintaining
the
pH
between
11
and
12
with
1.25N
sodium
hydroxide
until
an
excess
of
chlorine
is
present
as
indicated
by
KI­
starch
paper
turning
blue.
The
sample
will
be
subjected
to
alkaline
chlorination
by
this
step.

CAUTION:
The
initial
reaction
product
of
alkaline
chlorination
is
the
very
toxic
gas
cyanogen
chloride;
therefore,
it
is
necessary
that
this
reaction
be
performed
in
a
hood.

7.1.3
Test
for
excess
chlorine
with
KI­
starch
paper
and
maintain
this
excess
for
one
hour
with
continuous
agitation.
A
distinct
blue
color
on
the
test
paper
indicates
a
sufficient
chlorine
level.
If
necessary,
add
additional
calcium
hypochlorite
solution.

7.1.4
After
one
hour,
add
1
mL
portions
of
0.1N
sodium
arsenite
until
KI­
starch
paper
shows
no
residual
chlorine.
Add
5
mL
of
excess
sodium
arsenite
to
ensure
the
presence
of
excess
reducing
agent.
9010C
­
5
Revision
3
August
2002
7.1.5
Analyze
the
total
cyanide
concentration
of
both
the
chlorinated
and
the
unchlorinated
samples
by
Method
9014
or
9213.
The
difference
between
the
total
cyanide
concentration
in
the
chlorinated
and
unchlorinated
samples
is
equal
to
the
cyanide
amenable
to
chlorination.

7.2
Distillation
procedure
7.2.1
Place
500
mL
of
sample,
or
sample
diluted
to
500
mL
in
the
one
liter
boiling
flask.
Pipet
50
mL
of
1.25N
sodium
hydroxide
into
the
gas
scrubber.
If
the
apparatus
in
Figure
1
is
used,
add
water
until
the
spiral
is
covered.
Connect
the
boiling
flask,
condenser,
gas
scrubber
and
vacuum
trap.

7.2.2
Start
a
slow
stream
of
air
entering
the
boiling
flask
by
adjusting
the
vacuum
source.
Adjust
the
vacuum
so
that
approximately
two
bubbles
of
air
per
second
enter
the
boiling
flask
through
the
air
inlet
tube.

7.2.3
If
samples
are
known
or
suspected
to
contain
sulfide,
add
50
mL
of
0.062M
bismuth
nitrate
solution
through
the
air
inlet
tube.
Mix
for
three
minutes.
Use
lead
acetate
paper
to
check
the
sample
for
the
presence
of
sulfide.
A
positive
test
is
indicated
by
a
black
color
on
the
paper.

7.2.4
If
samples
are
known
or
suspected
to
contain
nitrate
or
nitrite,
or
if
bismuth
nitrate
was
added
to
the
sample,
add
50
mL
of
0.4N
sulfamic
acid
solution
through
the
air
inlet
tube.
Mix
for
three
minutes.

NOTE:
Excessive
use
of
sulfamic
acid
could
create
method
bias.

7.2.5
Slowly
add
50
mL
of
18N
sulfuric
acid
through
the
air
inlet
tube.
Rinse
the
tube
with
water
and
allow
the
airflow
to
mix
the
flask
contents
for
three
minutes.
Add
20
mL
of
2.5M
magnesium
chloride
through
the
air
inlet
and
wash
the
inlet
tube
with
a
stream
of
water.

7.2.6
Heat
the
solution
to
boiling.
Reflux
for
one
hour.
Turn
off
heat
and
continue
the
airflow
for
at
least
15
minutes.
After
cooling
the
boiling
flask,
and
closing
the
vacuum
source,
disconnect
the
gas
scrubber.

7.2.7
Transfer
the
solution
from
the
scrubber
into
a
250­
mL
volumetric
flask.
Rinse
the
scrubber
into
the
volumetric
flask.
Dilute
to
volume
with
water.

7.2.8
Proceed
to
the
cyanide
determinative
methods
given
in
Methods
9014
or
9213.
If
the
distillates
are
not
analyzed
immediately,
they
should
be
stored
at
4
E
C
in
tightly
sealed
flasks.

8.0
QUALITY
CONTROL
8.1
All
quality
control
data
should
be
maintained
and
available
for
easy
reference
or
inspection.

8.2
Employ
a
minimum
of
one
reagent
blank
per
analytical
batch
or
one
in
every
20
samples
to
determine
if
contamination
or
any
memory
effects
are
occurring.

8.3
Analyze
check
standards
with
every
analytical
batch
of
samples.
If
the
standards
are
not
within
15%
of
the
expected
value,
then
the
samples
must
be
reanalyzed.
9010C
­
6
Revision
3
August
2002
8.4
Run
one
replicate
sample
for
every
20
samples.
A
replicate
sample
is
a
sample
brought
through
the
entire
sample
preparation
and
analytical
process.
The
CV
of
the
replicates
should
be
20%
or
less.
If
this
criterion
is
not
met,
the
samples
should
be
reanalyzed.

8.5
Run
one
matrix
spiked
sample
every
20
samples
to
check
the
efficiency
of
sample
distillation
by
adding
cyanide
from
the
working
standard
or
intermediate
standard
to
500
mL
of
sample
to
ensure
a
concentration
of
approximately
40
µ
g/
L.
The
matrix
spiked
sample
is
brought
through
the
entire
sample
preparation
and
analytical
process.

8.6
It
is
recommended
that
at
least
two
standards
(
a
high
and
a
low)
be
distilled
and
compared
to
similar
values
on
the
curve
to
ensure
that
the
distillation
technique
is
reliable.
If
distilled
standards
do
not
agree
within
+
10%
of
the
undistilled
standards,
the
analyst
should
find
the
cause
of
the
apparent
error
before
proceeding.

8.7
The
method
of
standard
additions
shall
be
used
for
the
analysis
of
all
samples
that
suffer
from
matrix
interferences
such
as
samples
which
contain
sulfides.

9.0
METHOD
PERFORMANCE
9.1
The
titration
procedure
using
silver
nitrate
is
used
for
measuring
concentrations
of
cyanide
exceeding
0.1
mg/
L.
The
colorimetric
procedure
is
used
for
concentrations
below
1
mg/
L
of
cyanide
and
is
sensitive
to
about
0.02
mg/
L.

9.2
EPA
Method
335.2
(
sample
distillation
with
titration)
reports
that
in
a
single
laboratory
using
mixed
industrial
and
domestic
waste
samples
at
concentrations
of
0.06
to
0.62
mg/
L
CN­,
the
standard
deviations
for
precision
were
+
0.005
to
+
0.094,
respectively.
In
a
single
laboratory
using
mixed
industrial
and
domestic
waste
samples
at
concentrations
of
0.28
and
0.62
mg/
L
CN­,
recoveries
(
accuracy)
were
85%
and
102%,
respectively.

9.3
In
two
additional
studies
using
surface
water,
ground
water,
and
landfill
leachate
samples,
the
titration
procedure
was
further
evaluated.
The
concentration
range
used
in
these
studies
was
0.5
to
10
mg/
L
cyanide.
The
detection
limit
was
found
to
be
0.2
mg/
L
for
both
total
and
amenable
cyanide
determinations.
The
precision
(
CV)
was
6.9
and
2.6
for
total
cyanide
determinations
and
18.6
and
9.1
for
amenable
cyanide
determinations.
The
mean
recoveries
were
94%
and
98.9%
for
total
cyanide,
and
86.7%
and
97.4%
for
amenable
cyanide.

10.0
REFERENCES
1.
1985
Annual
Book
of
ASTM
Standards,
Vol.
11.01;
"
Standard
Specification
for
Reagent
Water";
ATSM:
Philadelphia,
PA,
1985,;
D1193­
77.

2.
1982
Annual
Book
ASTM
Standards,
Part
19;
"
Standard
Test
Methods
for
Cyanide
in
Water";
ASTM:
Philadelphia,
PA,
1982;
2036­
82.

3.
Bark,
L.
S.;
Higson,
H.
G.
Talanta
1964,
2,
471­
479.

4.
Britton,
P.;
Winter,
J.;
Kroner,
R.
C.
"
EPA
Method
Study
12,
Cyanide
in
Water";
final
report
to
the
U.
S.
Environmental
Protection
Agency.
National
Technical
Information
Service:
Springfield,
VA,
1984;
PB80­
196674.
9010C
­
7
Revision
3
August
2002
5.
Casey,
J.
P.;
Bright,
J.
W.;
Helms,
B.
D.
"
Nitrosation
Interference
in
Distillation
Tests
for
Cyanide";
Gulf
Coast
Waste
Disposal
Authority:
Houston,
Texas.

6.
Egekeze,
J.
O.;
Oehne,
F.
W.
J.
Anal.
Toxicology
1979,
3,
119.

7.
Elly,
C.
T.
J.
Water
Pollution
Control
Federation
1968,
40,
848­
856.

8.
Fuller,
W.
Cyanide
in
the
Environment;
Van
Zyl,
D.,
Ed.;
Proceedings
of
Symposium;
December,
1984.

9.
Gottfried,
G.
J.
"
Precision,
Accuracy,
and
MDL
Statements
for
EPA
Methods
9010,
9030,
9060,
7520,
7521,7550,
7551,
7910,
and
7911";
final
report
to
the
U.
S.
Environmental
Protection
Agency.
Environmental
Monitoring
and
Support
Laboratory.
Biospheric:
Cincinnati,
OH,
1984.

10.
Methods
for
Chemical
Analysis
of
Water
and
Wastes;
U.
S.
Environmental
Protection
Agency.
Office
of
Research
and
Development.
Environmental
Monitoring
and
Support
Laboratory.
ORD
Publication
Offices
of
Center
for
Environmental
Research
Information:
Cincinnati,
OH,
1983;
EPA­
600/
4­
79­
020.

11.
Rohrbough,
W.
G.;
et
al.
Reagent
Chemicals,
American
Chemical
Society
Specifications,
7th
ed.;
American
Chemical
Society:
Washington,
DC,
1986.

12.
Standard
Methods
for
the
Examination
of
Water
and
Wastewater,
18th
ed.;
Greenberg,
A.
E.;
Clesceri,
L.
S.;
Eaton,
A.
D.;
Eds.;
American
Water
Works
Association,
Water
Pollution
Control
Federation,
American
Public
Health
Association:
Washington,
DC,
1992.

13.
Umaña,
M.;
Beach,
J.;
Sheldon,
L.
"
Revisions
to
Method
9010";
final
report
to
the
U.
S.
Environmental
Protection
Agency.
Office
of
Solid
Waste.
Research
Triangle
Institute:
Research
Triangle
Park,
NC,
1986.

14.
Umaña,
M.;
Sheldon,
L.
"
Interim
Report:
Literature
Review";
interim
report
to
the
U.
S.
Environmental
Protection
Agency.
Office
of
Solid
Waste.
Research
Triangle
Institute:
Research
Triangle
Park,
NC,
1986.
9010C
­
8
Revision
3
August
2002
FIGURE
1.
APPARATUS
FOR
CYANIDE
DISTILLATION
9010C
­
9
Revision
3
August
2002
FIGURE
2.
APPARATUS
FOR
CYANIDE
DISTILLATION
9010C
­
10
Revision
3
August
2002
METHOD
9010C
TOTAL
AND
AMENABLE
CYANIDE:
DISTILLATION
