Appendix
A.
Quality
Assurance
Project
Plan,
Technical
Background
Document:
Mercury
Wastes,
Evaluation
of
Treatment
of
Bulk
Elemental
Mercury,
Final
Report
February
8,
2002
Submitted
to:

U.
S.
Environmental
Protection
Agency
Ariel
Rios
Building
Office
of
Solid
Waste
1200
Pennsylvania
Avenue,
N.
W.
Washington,
D.
C.
20460
Submitted
by:

Science
Applications
International
Corporation
Engineering
and
Environmental
Management
Group
11251
Roger
Bacon
Drive
Reston,
Virginia
20190
EPA
Contract
No.
68­
W­
98­
025
Work
Assignment
No.
3­
8
SAIC
Project
No.
06­
0758­
08­
1373­
000
QUALITY
ASSURANCE
PROJECT
PLAN
TECHNICAL
SUPPORT
FOR
AMENDMENT
OF
LAND
DISPOSAL
RESTRICTIONS
FOR
MERCURY
WASTES
SAIC/
EPA
Prime
Contract
No.
68­
W­
98­
025
Work
Assignment
WA#
2­
15
Submitted
to:
Mary
Cunningham,
EPA
Task
Order
Manager
Office
of
Solid
Waste
U.
S.
Environmental
Protection
Agency
Submitted
by:

ALTER
Corporation
December
2000
TABLE
OF
CONTENTS
Section
Name
Page
Revision
Date
1.0
Project
Description
1
0
12/
20/
00
2.0
Project
Organization
and
Responsibility
3
0
12/
20/
00
3.0
Experimental
Approach
7
0
12/
20/
00
4.0
Sampling
Procedures
13
0
12/
20/
00
5.0
Testing
and
Measurement
Protocols
17
0
12/
20/
00
6.0
QA/
QC
Checks
25
0
12/
20/
00
7.0
Data
Reduction,
Validation
and
Reporting
33
0
12/
20/
00
8.0
Assessments
36
0
12/
20/
00
Appendices
A
Acidity/
Alkalinity
B
University
of
Cincinnati's
Constant
pH
Leaching
Procedure
Project
Specific
 
Untreated
Surrogate
C
University
of
Cincinnati's
Constant
pH
Leaching
Procedure
Project
Specific
 
Treated
Surrogate
D
Chain
of
Custody
E
Standard
Operating
Procedures
for
Agvise
Laboratories
F
Project
Schedule
List
of
Illustrations
Figures
Page
2­
1
Project
Organization
6
3­
1
Experimental
Design
10
Tables
Page
3­
1
Surrogate
Sludge
Composition
7
5­
1
Test
Procedures
Used
by
Agvise
Laboratories
18
5­
2
Test
Procedures
Used
by
Environmental
Enterprises
18
5­
3
Test
Procedures
Used
by
ALTER
19
5­
4
Sample
Handling
and
Storage
Conditions
20
6­
1
Quality
Assurance
Objectives
for
MDL
Precision
and
27
Accuracy
of
Chemical
Analyses
6­
2
Quality
Control
Checks
32
6­
3
QC
Standards
32
Distribution
List
Mary
Cunningham
and
Josh
Lewis,
OSW
Linda
Rieser,
Project
Manager,
ALTER
Corporation
Rich
Abitz,
SAIC,
Quality
Assurance
Officer
for
ALTER
Jian
Zhang,
ALTER
Corporation
(
Staff
Laboratory
Copy)
Debbie
Jones,
Environmental
Enterprises
Mary
Thingelstad,
Agvise
Laboratories
Mike
Morris,
Oak
Ridge
National
Laboratory
/
UT
Battelle
Sara
Hartwell,
SAIC
EPA
QA
Section
No.
1.0
Revision
No.
0
Date:
December
20,
2000
Page
1
of
38
1.0
Project
Description
1.1
Purpose
There
are
concerns
about
incineration
of
mercury­
containing
wastes
since
incineration
does
not
destroy,
extract,
or
immobilize
mercury.
It
may
actually
increase
rather
than
minimize
mercury
movement
into
the
environment
by
releasing
mercury
vapor
and
mercury
salts
into
the
atmosphere.
The
Environmental
Protection
Agency
Office
of
Solid
Waste
(
EPA­
OSW)
in
collaboration
with
the
Accelerated
Life
Testing
and
Environmental
Research
Corporation
(
ALTER)
is
investigating
alternative
non­
combustion
technologies
for
the
disposal
of
mercurycontaining
wastes.

The
purpose
of
this
project
is
to
create
a
surrogate
mercury
sludge
and
to
investigate
a
range
of
commercial
remediation
technologies
using
a
surrogate
mercury
sludge.

1.2
Process
Description
A
laboratory
scale
surrogate
mercury
sludge
will
be
assembled
by
ALTER.
The
sludge
will
be
characterized
and
subjected
to
leaching
tests
to
provide
baseline
information.

Following
analysis
of
the
baseline
data
,
the
surrogate
mercury
sludge
components
will
be
shipped
to
commercial
treatment
vendors
selected
by
Oak
Ridge
National
Laboratory
(
ORNL)

and
EPA.
The
commercial
vendors
will
mix
and
treat
the
surrogate
sludge
and
return
the
treated
material
to
ALTER
for
testing.

The
vendor
treated
materials
will
be
characterized
and
subjected
to
leaching
tests
to
determine
the
applicability
of
the
treatment
processes.
EPA
QA
Section
No.
1.0
Revision
No.
0
Date
December
20,
2000
Page
2
of
38
1.3
Objectives
The
objective
of
this
investigation
is
to
provide
reliable
information
on
the
applicability
of
non­
thermal
alternative
treatment
technologies
to
treat
mercury­
containing
wastes.

Primary
objectives:

·
Prepare
a
surrogate
mercury
sludge
·
Characterize
and
determine
the
leachability
of
a
surrogate
mercury
sludge
under
controlled
laboratory
conditions.

·
Characterize
and
determine
leachability
of
the
treated
surrogate
mercury
sludge.
EPA
QA
Section
No.
2.0
Revision
No.
0
Date:
December
20,
2000
Page
3
of
38
2.0
Project
Organization
and
Responsibility
2.1
Organizations
Involved
in
the
Project
1.
Office
of
Solid
Waste
U.
S.
Environmental
Protection
Agency
Washington
D.
C.

Mary
Cunningham
Telephone
(
703)
308­
8453
Fax
(
703)
308­
8433
email
cunningham.
mary@
epa.
gov
Josh
Lewis
Telephone
(
703)
308­
7877
Fax
(
703)
308­
8433
email
lewis.
josh@
epa.
gov
2.
ALTER
Corporation
7852
State
Rd
62,
Dillsbord,
IN
47018
Linda
Rieser
Telephone
(
513)
556­
2060
Fax
(
513)
556­
3148
email
lrieser@
uceng.
uc.
edu
Graduate
Students
Telephone
(
513)
556­
1029
Fax
(
513)
556­
3148
Jian
Zhang
email
zhanjn@
email.
uc.
edu
Haishan
Piao
email
piaoh@
email.
uc.
edu
Li
Meng
email
mengli@
email.
uc.
edu
3.
Oak
Ridge
National
Lab(
ORNL)
PO
Box
2008,
Oak
Ridge,
TN37831­
6180
Mike
Morris
Telephone
(
865)
574­
0559
Fax
(
865)
574­
5912
email
morrismi@
ornl.
gov
4.
Environmental
Enterprises
Inc.
10163
Cincinnati
 
Dayton
Rd.,
Cincinnati,
Ohio
45241
Debbe
Jones
and
Jyoti
Desai
Telephone
(
513)
772­
2818
Fax
(
513)
782­
8970
EPA
QA
Section
No.
2.0
Revision
No.
0
Date:
December
20,
2000
Page
4
of
38
5.
Agvise
Laboratories,
Northwood
P.
O.
Box
510,
Highway
15,
Northwood,
ND.
58267
Julie
M.
Johnson
and
Mary
L.
Thingelstad
Telephone
(
701)
587­
6010
Fax
(
701)
587­
6013
6.
Science
Applications
International
Corporation
(
SAIC)
1710
Goodridge
Dr.
Mclean,
VA22102
Sara
Hartwell
Telephone
(
703)
318­
4662
Fax
(
703)
318­
4682
Email
hartwell@
saic.
com
Richard
Abitz
Telephone
(
513)
226­
5329
Fax
(
513)
556­
3148
email
rabitz@
att.
net
2.2
Quality
Assurance
Managers
1.
Charles
Sellers,
Quality
Assurance
Officer,
OSW,
U.
S.
EPA
2.
Rich
Abitz,
SAIC,
Quality
Assurance
Officer
for
ALTER
Corporation
The
ALTER
Quality
Assurance
officer
will
be
responsible
for
data
validation,

investigation
of
"
out
of
control"
situations
and
the
assurance
that
data
quality
checks
are
being
made.
Charles
Sellers
(
EPA­
OSW)
will
be
responsible
for
reviewing
the
QAPP
and
providing
comments
to
the
project
manager.
The
ALTER
QA
officer
will
review
QA
data
from
all
contributing
organizations.
The
ALTER
QA
officer
is
an
essential
link
between
all
research
members
as
data
is
developed,
analyzed,
reviewed
and
checked
prior
to
reporting
said
work.

These
responsibilities
are
more
specifically
outlined
in
sections
6.0
and
8.0
of
this
document.

2.3
Responsibilities
of
Project
Participants
Project
organization
and
reporting
relationships
are
depicted
on
the
following
chart.
Josh
Lewis
(
OSW),
Mary
Cunningham
(
OSW
Task
Order
Manager),
Charles
Sellers
(
OSW
QA
Officer)
and
Sara
Hartwell
(
SAIC)
will
be
responsible
for
providing
technical
direction,
project
coordination
and
communication
along
with
reviewing
and
approving
the
QAPP.
Mike
Morris,
ORNL
will
be
responsible
for
the
statement
of
work
for
stabilization
vendors,
evaluation
of
vendor
test
plans
and
coordination
of
surrogate
and
vendor
treated
EPA
QA
Section
No.
2.0
Revision
No.
0
Date:
December
20,
2000
Page
5
of
38
surrogate
transfer
between
vendors
and
ALTER.
Linda
Rieser
(
ALTER,
Subcontractor
to
SAIC)

will
serve
as
Project
Manager
and
shall
have
responsibility
for
supervision
and
monitoring
of
all
aspects
of
this
project,
including
the
collection
of
samples,
sample
custody,
project
planning,

QAPP
development,
daily
operations
oversight,
data
analysis
and
will
assist
SAIC
with
final
reports.
Rich
Abitz
(
SAIC)
will
serve
as
ALTER
QA
officer.
Student
research
assistants
and
professional
technicians
will
participate
in
the
research
under
the
guidance
of
the
project
manager.
Student
research
assistants
will
primarily
be
involved
in
the
laboratory
work
associated
with
leaching
tests
and
will
be
responsible
for
monthly
reports.
Sara
Hartwell,
SAIC
will
be
responsible
for
the
final
report.

Agvise
Laboratory
will
provide
support
for
characterization
(
Table
5.1).
Environmental
Enterprises
will
provide
mercury
analysis
of
surrogate,
treated
surrogate
and
leachates.
The
QA/
QC
control
functions
have
been
organized
to
allow
independent
review
of
project
activities.

The
objective
of
the
QA/
QC
efforts
is
to
assess
and
document
the
precision,
accuracy,
and
adequacy
of
the
data
derived
from
the
investigation.
Figure
2.1
shows
project
authority
lines.
EPA
QA
Section
No.
2.0
Revision
No.
0
Date:
December
20,
2000
Page
6
of
38
Figure
2.1
Project
Organization
Linda
Rieser
Project
Manager
ALTER
Corporation
Subcontractor
to
SAIC
Responsibitlites
 
Project
Planning,
QAPP
development,
daily
operations
oversight,
data
reduction
and
analysis,
final
report
preparation,
sample
collection,
and
sample
custody
ALTER
Graduate
Students
Jian
Zhang
Haishan
Piao
Li
Meng
Responsibilities
 
Execution
of
experiments
and
monthly
progress
report
generation
Agvise
Laboratories
Julie
M.
Johnson
 
Analytical
Manager
Mary
L.
Thingelstad
 
QA
Manager
Responsibilities
 
characterization
testing
Environmental
Enterprises
Debbe
Jones
 
Lab
Manager
Jyoti
Desai
 
QA
Manager
Responsibilities
 
Mercury
analysis
of
waste
and
leachates
Rich
Abitz
SAIC
Quality
Assurance
Officer
for
ALTER
Mary
Cunningham
Josh
Lewis
EPA­
OSW
Work
Assignment
Mgr.

Mike
Morris
ORNL
Charles
Sellers
EPA
Quality
Assurance
Officer
(
OSW)
Sara
Hartwell
SAIC
Contractor
to
OSW
Final
Report
EPA
QA
Section
No.
3.0
Revision
No.
0
Date:
December
20,
2000
Page
7
of
38
3.0
Experimental
Approach
A
surrogate
mercury
sludge
will
be
constructed
by
ALTER
for
use
in
this
evaluation.
The
surrogate
will
be
subjected
to
physical
and
chemical
characterization
and
leaching
tests
to
determine
leachability
of
the
surrogate
after
treatment.
The
surrogate
will
be
treated
by
vendors
selected
by
ORNL
and
EPA's
Office
of
Solid
Waste.
ALTER
will
ship
two
one­
hundred
pound
samples
to
selected
vendors
for
treatment
and
residuals
return
to
ALTER.
The
surrogate
will
be
shipped
as
pre­
measured
components
to
be
blended
by
the
vendors.
Additional
surrogate
will
be
made
available
to
the
vendors
upon
request
for
pre­
treatment
treatability
testing.
ALTER
will
observe
the
mixing
and
treatment.
Following
successful
treatment
of
the
two
one­
hundred
pound
surrogate
batches
by
the
selected
vendors,
the
entire
200
pounds
of
treated
surrogate
will
be
shipped
to
ALTER
for
sampling
and
evaluation.
Physical
and
chemical
characterization
and
leaching
tests
identical
to
those
performed
on
the
baseline
surrogate
will
be
performed
on
the
vendor­
stabilized
materials.
Figure
3.1
details
the
experimental
design
for
this
project.
Appendix
F
provides
the
project
schedule.

3.1
Construction
of
Surrogate
Sludge
A
surrogate
sludge
will
be
constructed
for
use
in
this
study.
The
sludge
composition
is
outlined
in
Table
3.1.

Table
3.1
Surrogate
Sludge
Composition
Sludge
Constituent
Weight
Percentage
%
Mercury
Concentration
ppm
Phenyl
Mercury
0.08
500
Mercury
Nitrate
0.17
1000
Elemental
Mercury
0.15
1500
Mercury
Oxide
0.11
1000
Mercury
Chloride
0.14
1000
Diatomaceous
Earth
20
Aluminum
Hydroxide
10
Ferric
Chloride
10
Sodium
Chloride
10
Motor
Oil
(
new)
1
Water
48.35
Total
100
5000
EPA
QA
Section
No.
3.0
Revision
No.
0
Date:
December
20,
2000
Page
8
of
38
Sludge
will
be
mixed
in
3
liter
batches
in
a
5
quart
Hobart
mixer.
Mercury
species
as
listed
in
Table
3.1
will
be
added
only
after
the
major
constituents
have
been
well
blended.
Three
random
samples
will
be
analyzed
to
assess
total
mercury
variability
and
three
TCLP
tests
will
be
performed
to
assess
leachability.
The
laboratory
scale
surrogate
will
be
characterized
and
leached
as
described
in
sections
3.2
and
3.3.

3.2
Characterization
Samples
of
the
baseline
surrogate,
the
vendor
mixed
surrogate
before
treatment
and
the
treated
surrogate
will
be
analyzed
for
total
mercury
and
subjected
to
the
Toxicity
Characteristics
Leaching
Procedure
(
TCLP).
Samples
of
the
sludge
and
leachate
will
be
submitted
to
Environmental
Enterprises
Inc.
for
mercury
analysis.
Samples
of
the
baseline
surrogate
and
treated
surrogate
will
also
be
sent
to
Agvise
for
physical
and
chemical
measurements,
including
bulk
density,
moisture
content,
percent
organic
matter,
cation
exchange
capacity,
and
particle
size
distribution.
The
Agvise
testing
uses
standard
methods
for
soils,
established
by
the
USDA
and
the
Soil
Society
of
America.

Additional
characterization
of
the
baseline
surrogate
and
vendor
stabilized
materials
by
ALTER
will
include
alkalinity
and
acidity
testing,
and
pH
analysis
on
all
samples.
All
characterization
testing
will
be
performed
in
duplicate.

3.3
Leaching
In
order
to
assess
the
stability
of
the
wastes,
several
leaching
procedures
will
be
performed
on
the
baseline
surrogate
and
vendor
treated
surrogate.
Leaching
tests
to
be
performed
by
ALTER
include
TCLP,
and
UC
constant
pH.
Upon
completion
of
each
leaching
test,
the
pH
values
will
be
taken
by
ALTER
and
the
leachate
mercury
concentration
will
be
determined
by
Environmental
Enterprises
Inc.
All
leaching
tests
will
be
performed
with
a
minimum
of
50%

duplicates
and
will
include
an
experimental
blank.
The
following
paragraphs
discuss
the
leaching
tests.
EPA
QA
Section
No.
3.0
Revision
No.
0
Date:
December
20,
2000
Page
9
of
38
Toxicity
Characteristic
Leaching
Procedure1
This
is
a
standard
regulatory
test
intended
to
determine
the
potential
mobility
of
contaminants
in
a
liquid
or
solid
under
simulated
landfill
conditions.
Tests
are
run
in
duplicate
and
analyzed
for
mercury
content.

UC
Constant
pH
Based
Leaching
Constant
pH
leaching
tests
are
a
means
to
determine
the
effect
pH
has
on
the
stability
of
a
waste.
The
constant
pH
procedure
was
developed
at
the
University
of
Cincinnati
and
is
attached
as
Appendix
B.
Separate
project
specific
pH
leaching
procedures
are
provided
for
untreated
and
treated
surrogate
to
accommodate
QC
specific
to
the
number
of
samples
leached.
Samples
are
leached
in
a
constant
pH
solution
that
is
adjusted
to
the
desired
pH
end
point.
The
constant
pH
leaching
test
will
be
run
on
the
6
pH
values
of
2,
4,
6,
8,
10
and
12.
The
pH
will
be
maintained
by
automated
systems
for
a
10
day
period
prior
to
leachate
sampling.
Three
pH
values
2,
8
and
12
experiments
will
be
duplicated.
The
test
shall
include
an
experimental
blank.
All
extracted
samples
are
filtered
and
analyzed
for
mercury
content.

1
Federal
Register­
Volume
51
EPA
QA
Section
No.
3.0
Revision
No.
0
Date:
December
20,
2000
Page
10
of
38
Agvise
Characterization
Table
5.1
ALTER
Characterization
Table
5.3
Data
Collection
and
Interpretation
at
ALTER
TCLP
Performed
by
ALTER
on
Baseline
Surrogate
Conduct
Leaching
Experiments
Table
5.3
Leachate
Sent
to
Environmental
Enterprises
for
Mercury
Analysis
Table
5.2
Results
to
ALTER
for
Data
Analysis
ALTER
Analysis
for
Acidity
and
Alkalinity
Construct
Baseline
Surrogate
pH
Measurements
Taken
on
All
Leachates
by
ALTER
Vendor
Test
Plans
evaluated
to
meet
Statement
of
Work
by
Mike
Morris,
ORNL
Leachate
and
Surrogate
Sent
to
Environmental
Enterprises
for
Mercury
Analysis
EPA
QA
Section
No.
3.0
Revision
No.
0
Date:
December
20,
2000
Page
11
of
38
Vendor
Mixes
and
Treats
Surrogate,
TCLP
to
Outside
Lab,
Ships
Stabilized
Materials
Passing
LDR
Treatment
ALTER
Ships
Surrogate
Components
to
Vendors
TCLP
and
Total
Mercury
Performed
on
Vendor
Mixed
Surrogate
and
Stabilized
Materials
Agvise
Characterization
Table
5.1
Data
Collection
and
Interpretation
at
ALTER
Conduct
Leaching
Experiments
Table
5.3
ALTER
Analysis
for
Acidity
and
Alkalinity
pH
Measurements
Taken
on
All
Leachates
by
ALTER
ALTER
Characterization
Table
5.3
EPA
QA
Section
No.
3.0
Revision
No.
0
Date:
December
20,
2000
Page
12
of
38
Figure
3.1
Experimental
Design
Leachate
Sent
to
Environmental
Enterprises
for
Mercury
Analysis
Table
5.2
Reporting
SAIC/
ALTER
Results
to
ALTER
for
Data
Analysis
EPA
QA
Section
No.
4.0
Revision
No.
0
Date:
December
20,
2000
Page
13
of
38
4.0
Sampling
Procedures
4.1
Laboratory
Scale
Surrogate
Sludge
Preparation
and
sampling
of
the
laboratory
scale
surrogate
sludge
will
be
performed
by
ALTER.
The
sludge
will
be
mixed
using
a
Hobart
5
quart
mixer.
The
sub­
samples
will
then
be
transferred
to
the
appropriate
sample
containers
for
each
test.
Observations
and
judgements
about
sample
homogeneity
(
e.
g.
color,
texture,
etc.)
will
be
recorded
in
the
lab
notebook.

4.2
Vendor
Sampling
Vendors
selected
by
ORNL
and
EPA
(
OSW)
will
receive
two
surrogate
pre­
measured
100
lb.
samples.
Vendors
will
be
responsible
for
mixing
the
surrogate
from
the
components
shipped
by
ALTER.
When
mixing
is
complete,
a
composite
sample
of
approximately
1
kg
will
be
removed
from
the
mixed
surrogate
as
10
approximately
100
g
random
grab
samples
to
be
shipped
with
the
treated
surrogate.
After
treatment
of
the
two
100
lb.
surrogate
batches,
vendors
will
submit
a
sample
of
each
batch
to
an
outside
lab
for
TCLP
testing,
then
will
return
the
successfully
treated
surrogate
to
ALTER
for
evaluation.

Each
vendor
will
submit,
for
review
by
Mike
Morris
ORNL,
a
plan
for
treatment
of
the
surrogate
batches.
The
plan
will
include
the
following:

·
Mixing
method
·
Sample
containerization
and
preservation
·
Process
design
and
operating
data
collection.

·
Total
mass
of
treatment
additives.

4.3
Sampling
for
Treatment
Tests
All
treated
surrogate
will
be
returned
to
ALTER
for
testing.
The
treated
surrogate
will
be
crushed
if
necessary
to
pass
a
9.5
mm
sieve.
Crushed
treated
material,
or
material
passing
the
9.5
mm
sieve
will
then
be
blended
and
sub­
sampled,
using
a
sample
splitter,
for
each
test
to
be
performed.
EPA
QA
Section
No.
4.0
Revision
No.
0
Date:
December
20,
2000
Page
14
of
38
4.4
Field
Sample
Custody
Sample
custody
will
begin,
in
all
cases,
at
the
time
of
sample
collection
by
placing
the
sample
in
a
sealed
container,
or
other
appropriate
container,
in
the
possession
of
the
designated
laboratory
or
field
sample
custodian.
A
line
item
on
the
chain­
of­
custody
record
form
(
Appendix
D)
will
be
immediately
filled
out
and
signed
by
the
field
or
laboratory
sample
custodian.
The
following
information
will
be
included
when
the
chain­
of­
custody
record
is
filled
out:

Project
Number
Enter
the
complete
project
number.

Project
Name
Enter
the
project
name
Samplers
Enter
signature
and
print
name
of
person
or
persons
who
participated
in
the
collection
of
the
samples
listed
and
who
should
be
contacted
if
questions
arise
during
sample
log­
in.

If
the
field
sample
custodian
is
not
listed
as
a
sampler,

receipt
of
documentation
is
to
be
indicated.

Field
Sample
No.
Enter
the
sample
numbers
for
each
of
the
two
100
lb
samples
collected.

Date
Enter
date
of
sample
collection.

Time
Enter
time
of
actual
sample
collection.

Sample
Location
Enter
the
number
of
containers
to
be
shipped
for
the
two
samples.

Remarks
Indicate
special
considerations
for
a
sample
(
i.
e.,

preservatives
used
and
mass
of
additives).

Upon
completion
of
all
line
items,
or
upon
sample
pickup,
the
custodian
will
sign,
date,

enter
the
time,
and
confirm
completeness
of
all
information
written
on
the
chain­
of­
custody
record.
Each
individual
who
subsequently
assumes
responsibility
for
the
sample
will
sign
the
chain­
of­
custody
record
and
indicate
the
reason
for
assuming
custody.

4.5
Sample
Transport
Samples
prepared
for
shipment
will
be
packaged
and
labeled
in
compliance
with
current
U.
S.
Department
of
Transportation
(
DOT)
and
International
Air
Transport
Association
(
IATA)

dangerous
goods
regulations.
Any
additional
requirements
stipulated
by
the
overnight
carrier
will
be
followed.
EPA
QA
Section
No.
4.0
Revision
No.
0
Date:
December
20,
2000
Page
15
of
38
Only
a
metal
or
plastic
ice
chest
will
be
used
as
the
outside
shipping
container
for
samples,
unless
otherwise
specified
by
the
shipping
regulations.
The
outside
container
must
be
able
to
withstand
a
4­
foot
drop
on
solid
concrete
in
the
position
most
likely
to
cause
damage.

Each
ice
chest
will
be
lined
with
a
6­
mil­
thick
plastic
bag.
Styrofoam
or
bubble
wrap
will
be
used
to
absorb
shock.
When
more
than
one
set
can
fit
into
an
ice
chest,
each
of
the
sets
will
be
placed
in
separate
plastic
bags
to
prevent
cross­
contamination
if
breakage
occurs.

After
sample
containers
are
sufficiently
packaged,
the
6­
mil­
thick
plastic
bag
will
be
sealed
around
the
samples
by
twisting
the
top
and
securely
taping
the
bag
closed
to
prevent
leakage.

Chain­
of­
custody
records
and
any
other
shipping/
sample
documentation
accompanying
the
shipment
will
be
enclosed
in
a
waterproof
plastic
bag
and
taped
to
the
underside
of
the
ice
chest
lid.

Each
ice
chest
prepared
for
shipment
will
be
securely
taped
shut.
This
can
be
accomplished
with
reinforced
or
other
suitable
tape
(
i.
e.,
strapping
tape)
wrapped
at
least
twice
around
the
ice
chest
near
each
end
where
the
hinges
are
located.
A
label,
or
a
business
card,

identifying
the
name
and
address
of
the
responsible
party
will
be
affixed
on
the
top
of
each
ice
chest
prepared
for
shipment.

Sample
shipping
containers
will
be
marked
in
accordance
with
DOT
Regulations
for
Shipping
Hazardous
Materials
(
49
CFR
172)
and/
or
IATA
Dangerous
Goods
Regulations,
28th
Edition,
January
1,
1987.
In
addition
to
the
complete
mailing
address,
each
ice
chest
must
be
clearly
marked
with
"
this
end
up"
arrows
on
all
four
sides.

At
the
time
of
shipment,
the
sampling
crew
chief
is
to
supply
the
following
information
to
the
ALTER
Project
Manager:
the
date
on
which
the
samples
were
shipped,
the
name
of
the
commercial
carrier,
the
carrier
invoice
number,
the
number
of
shipping
containers
shipped,
and
the
expected
time
of
arrival
at
the
laboratory.

4.6
Laboratory
Sample
Custody
After
the
ice
chests
are
checked
for
damage,
the
samples
will
be
unpacked
and
the
information
on
the
accompanying
chain­
of­
custody
records
will
be
examined.
If
the
samples
shipped
match
those
described
on
the
chain­
of­
custody
record,
the
ALTER
Project
Manager
will
sign
the
form
and
assume
responsibility
for
the
samples.
If
problems
are
noted
with
the
EPA
QA
Section
No.
4.0
Revision
No.
0
Date:
December
20,
2000
Page
16
of
38
sample
shipment,
the
Project
Manager
will
sign
the
form
and
record
the
problems
in
the
"
Remarks"
box,
and
notify
the
ALTER
QA
officer.

All
samples
will
then
be
logged
into
a
sample
logbook.
The
following
information
will
be
documented
in
the
logbook:

·
Date
and
time
of
sample
receipt
·
Project
number
·
Field
sample
number
·
Laboratory
sample
number
(
assigned
during
log­
in
procedure)

·
Sample
matrix
·
Sample
parameters
·
Storage
location
·
Log
in
person's
initials
All
information
relevant
to
the
samples
will
be
secured
at
the
end
of
each
business
day.

All
samples
will
be
stored
in
a
designated
sample
storage
area,
access
to
which
will
be
limited
to
laboratory
employees.

Samples
(
baseline
surrogate,
vendor
mixed
surrogate,
vendor
treated
surrogate
and
leachates)
will
be
delivered
to
Environmental
Enterprises
by
the
Project
Manager
for
mercury
analysis.
Chain
of
custody
records
will
be
generated
and
maintained
by
ALTER
for
these
samples.
EPA
QA
Section
No.
5.0
Revision
No.
0
Date:
December
20,
2000
Page
17of
38
5.0
Testing
and
Measurement
Protocols
Tables
5.1
thru
5.3
list
all
of
the
methods
that
may
be
used
by
Agvise
Laboratories,

Environmental
Enterprises,
and
the
Accelerated
Life
Testing
and
Environmental
Research
(
ALTER)
Corporation
in
this
research.
Most
of
these
are
standard
EPA
or
ASTM
procedures
and
are
referenced.
Non
 
standard
procedures
are
provided
as
appendices.
Standard
operating
procedures
for
Agvise
laboratories
are
located
in
Appendix
E.

Samples
are
immediately
placed
in
a
refrigerator
for
storage
after
sampling
unless
a
refrigerator
is
not
required.
The
parameters
for
sample
preparation
and
storage
are
listed
in
Table
5.4
for
various
matrices
and
analyses.
EPA
QA
Section
No.
5.0
Revision
No.
0
Date:
December
20,
2000
Page
18
of
38
Table
5.1
Test
Procedures
Used
by
Agvise
Laboratories
PROCEDURE
PRIMARY
REFERENCE1
PHYSICAL(
2)

Density
Water
Content
Particle
size
Cation
Ion
Exchange
Capacity
Percent
Organic
Matter
Cations
(
Magnesium,
Potassium,
Calcium,
Sodium)
NUT.
02.10
NUT.
02.36
NUT.
02.32
NUT.
02.03
NUT.
02.04
NUT.
02.12
Notes:
(
1)
These
procedures
are
based
on
Standard
Methods
for
Soils
established
by
the
USDA
and
the
Soil
Society
of
America.
NUT
refers
to
Agvise's
nutrient
laboratory
where
the
testing
is
conducted
and
the
numerical
reference
refers
to
their
standard
operating
procedures.

(
2)
A
total
of
250
g
of
raw
waste
is
submitted
for
the
6
analyses.
A
duplicate
(
250g)
is
also
submitted.

Table
5.2
Test
Procedures
Used
By
Environmental
Enterprises
PROCEDURE
PRIMARY
REFERENCE
Mercury
(
aqueous)(
1)
SW
846
Method
7470A
Mercury
(
solid)(
2)
SW
846
Method
7470A
Notes:
(
1)
Volume
of
sample
available
varies
with
test
performed.
Where
possible,
250
ml
is
submitted
for
analysis.
Test
duplicates
for
50%
of
the
data
points
are
also
submitted.
(
2)
A
total
of
100
g
is
submitted
for
analysis.
A
duplicate
is
also
submitted.
EPA
QA
Section
No.
5.0
Revision
No.
0
Date:
December
20,
2000
Page
19
of
38
Table
5.3
Test
Procedures
Used
by
ALTER
PROCEDURE
PRIMARY
REFERENCE
SAMPLE
VOLUME/
TEST
Characterization
Leachates
and
Wastes
Alkalinity
2320(
1)
200g(
2)
/
40
ml(
3)

Acidity(
Variable
Mass
Only)
2330(
1)
200g(
2)
/
40
ml(
3)

pH
(
All
Leachates)
4500(
1)
5g(
2)
/
Performed
on
gross
leachate
before
filtration
Wastes
Moisture
Content
ASTM
D
2216­
80
100g(
4)(
5)

Particle
Size
ASTM
D
422­
63
150g(
2)

Leaching
Experiments
TCLP
Federal
Register
Volume
51
200g(
2)

UC
Constant
pH
Leaching
Appendix
B
250g(
2)

Notes:

(
1)
Standard
Methods
for
the
Examination
of
Water
and
Wastewater,
18th
ed.
1992
(
2)
Minimum
Dry
Solids
Required.

(
3)
Minimum
Leachate
Required
(
4)
Minimum
Raw
Waste
Required
(
5)
Procedure
Modified
 
for
all
wastes
dry
in
hood
at
room
temperature,
72
°
F.
EPA
QA
Section
No.
5.0
Revision
No.
0
Date:
December
20,
2000
Page
20
of
38
Table
5.4
Sample
Handling
and
Storage
Conditions
ANALYTE
SAMPLE
CONTAINER
SAMPLE
CONTAINER
PREPARATION
SAMPLE
CONTAINER
PRESERVATION
SAMPLE
HOLDING
TIME
Acidity
400
ml
polyethylene
beakers
One
Time
Use
N/
A(
1)
N/
A(
1)

Alkalinity
400
ml
polyethylene
beakers
One
Time
Use
N/
A(
1)
N/
A(
1)

Mercury
Waste
for
Analysis
250
ml
or
larger
polyethylene
with
screw
cap
One
Time
Use
N/
A(
1)
Indefinite
Mercury
Waste
Stored
2­
liter
HDPE
Jars
with
Teflon
lids
One
Time
Use
None
Indefinite
Mercury
Leachates
250
ml
or
larger
polyethylene
with
screw
cap
One
Time
Use
Acidify
filtered
aqueous
samples
with
HNO3
to
obtain
a
pH
<
2.
Keep
cool
(
4
°
C)
28
days
pH
100
ml
polyethylene
with
screw
cap
One
Time
Use
N/
A(
1)
N/
A(
1)

Notes:

(
1)
N/
A
 
Samples
consist
of
leachates
generated
or
wastes
with
DI
water
added
which
are
measured
immediately.
EPA
QA
Section
No.
5.0
Revision
No.
0
Date:
December
20,
2000
Page
21
of
38
5.1
Calibration
Procedures
and
Frequency
Equipment
that
will
require
periodic
calibration
or
servicing
falls
into
two
general
categories:

1.
Facility
support
equipment
2.
Laboratory
testing
equipment
The
following
paragraphs
describe
the
types
of
equipment
in
each
category
and
the
proposed
method
and
frequency
of
calibration.

Facility
Support
Equipment
in
this
category
includes
the
Department's
water
deionization
system,

compressed
air
system,
constant
humidity
moisture
room
(
for
sample
storage
and
curing),
and
fume
hood.
All
of
these
systems
are
operational
and
are
maintained/
serviced
under
ALTER
service
contracts.

Laboratory
Testing
Equipment
Calibration
Calibration
will
be
performed
by
trained
personnel,
or
approved
vendors,
using
the
approved
procedures.
Identification
records
will
be
assigned
and
affixed
to
the
devices
and
entered
into
supporting
calibration
records.
The
calibration
frequency
of
each
instrument
will
be
defined
within
the
calibration
procedure.
When
the
integrity
of
a
product,
process
or
sample
is
in
question
because
of
an
out­
of­
calibration
device,
the
Project
Manager
will
be
notified.
Based
on
the
evaluation
performed,
the
extent
of
any
non­
conforming
situation
will
be
reported
to
the
Co­

PI
who
may
specify
the
disposition,
including
re­
measurement
or
re­
test.
Section
8.2
of
this
document
discusses
the
corrective
action
scheme.
EPA
QA
Section
No.
5.0
Revision
No.
0
Date:
December
20,
2000
Page
22
of
38
Analytical
Balances
Instrument
 
Mettler
PM
4600
Mettler
B303
Calibration
The
balances
are
calibrated
daily
when
in
use,
or
when
moved.

Standards
Standard
metric
weights
are
used
for
calibration.
Weights
used
for
calibration
should
bracket
the
expected
range
of
the
sample.
Calibration
must
be
within
+/­
0.01g.
If
variation
from
standard
exceeds
+/­
0.01
g,
balance
will
be
tagged
"
out
of
service"
and
will
not
be
used.
It
will
then
be
reported
to
Project
Manager.

Cold
Vapor
Mercury
Analysis
 
Environmental
Enterprises,
Inc.

Instrument
 
Varian
SpectrAA20
Atomic
Absorption
Spectrophotometer
with
VGA­
76
Vapor
Generation
Accessory
Calibration
Prior
to
daily
calibration
and
analysis,
the
instrument
is
turned
on
and
allowed
to
thermally
stabilize.
After
the
lamps
and
optical
pathway
is
optimized,
five
standards
(
0.5,
2,
5,

10,
40
ug/
L)
and
a
blank
are
analyzed
in
order
to
generate
a
calibration
curve.
The
correlation
coefficient
("
r")
is
calculated
and
must
be
greater
than
or
equal
to
0.995.
Immediately
after
calibration,
the
Initial
Calibration
Verification
(
ICV)
secondary
source
check
standard
is
analyzed.
ICV
acceptance
criteria
is
+/­
10%
of
the
true
value
(
5
ug/
L).
The
Initial
Calibration
Blank
(
ICB)
check
standard
is
then
analyzed.
ICB
value
must
be
less
than
the
reporting
limit
(
0.5
ug/
L).
The
Low
Detection
Limit
(
LDL)
secondary
source
check
standard
is
then
analyzed.

LDL
acceptance
criteria
is
+/­
30%
of
the
true
value
(
0.5
ug/
L).
Method
Blanks
(
MB)
and
Laboratory
Control
Samples
(
LCS)
are
then
analyzed.
MB
value
must
be
less
than
the
reporting
limit
(
0.5
ug/
L).
LCS
acceptance
criteria
is
+/­
15%
of
the
true
value
or
within
the
suppliers
certified
acceptance
limits
for
purchased
soil/
solid
reference
standards.
Continuing
Calibration
Verification
(
CCV)
secondary
source
check
standards
are
analyzed
after
every
10th
analysis.

CCV
acceptance
criteria
is
+/­
20%
of
the
true
value
(
5
ug/
L).
All
analytical
runs
must
end
with
a
CCV
and
CCB.
EPA
QA
Section
No.
5.0
Revision
No.
0
Date:
December
20,
2000
Page
23
of
38
Standards
Atomic
absorption
standards
and
reference
solution
are
ACS
grade.
Mercury
calibration
standards
are
purchased
from
Fisher
Scientific.
Secondary
check
standards
are
purchased
from
EM
Science.
To
ensure
optimum
stability,
each
solution
has
a
concentration
of
1000
ppm.
All
dilutions
are
prepared
volumetrically.
EPA
QA
Section
No.
5.0
Revision
No.
0
Date:
December
20,
2000
Page
24
of
38
pH
Meter
Instrument
 
Fisher
Scientific
Accumet
pH
meter
915
Fisher
Scientific
Accumet
research
AR50
Calibration
Calibration
procedures
for
the
pH
meter
are
described
in
Standard
Methods,
4500
 
H+
B1.

The
meter
will
be
calibrated
using
a
two­
point
calibration
with
certified
calibration
standards.

Standards
for
calibration
are
pH
4
and
pH
10.
A
pH
7
standard
will
be
used
as
the
check
standard.
The
meter
will
be
calibrated
not
less
than
twice
daily,
at
the
beginning
and
end
of
experiments,
using
a
two
point
calibration
protocol.
Based
upon
comparison
of
pH
standards
with
actual
pH,
a
range
of
+/­
0.05
pH
units
is
acceptable.
If
accuracy
is
not
in
this
range,
the
unit
will
be
tagged
"
out
of
service"
and
will
not
be
used.
It
will
then
be
reported
to
the
Project
Manger.

Standards
All
calibration
standards
certified
and
are
purchased
from
Fisher
Scientific.
Fresh
standards
are
used
for
each
calibration.

1
Standard
Methods
for
the
Examination
of
Water
and
Wastewater,
19th
ed.
1995.
EPA
QA
Section
No.
6.0
Revision
No.
0
Date:
December
20,
2000
Page
25
of
38
6.0
QA/
QC
Checks
The
parameters
routinely
used
to
gauge
data
quality
are
precision
and
accuracy.
Precision
is
defined
as
the
reproducibility
of
data
upon
repeated
analysis.
Precision
is
monitored
by
comparing
the
results
of
duplicate
samples.
Precision
objectives
for
all
the
measurements
listed
in
Table
6.1
are
presented
as
relative
percent
difference
(
RPD)
for
duplicate
samples.
In
addition
to
duplicate
extract
and
test
samples,
Environmental
Enterprises
performs
a
batch
duplicate
sample
digestion
and
analysis
at
a
rate
of
1
for
every
20
(
or
less)
mercury
samples
submitted.

Accuracy
is
defined
as
the
agreement
of
a
measurement
with
the
true
value
of
a
known
traceable
standard.
The
goal
is
to
maintain
results
within
the
specified
limits.
In
the
study
of
earth
or
sludge
materials,
where
numerous
physical
measurements
are
required,
there
are
no
standards
of
known
true
value
against
which
accuracy
can
be
estimated.
Furthermore,
it
is
clearly
not
feasible
to
"
spike"
a
physical
measurement.
Therefore,
accuracy
for
physical
measurements
related
to
percent
moisture
and
particle
size
will
be
determined
by
checking
the
analytical
balance
with
standard
weights
and
bracketing
the
anticipated
weights
of
the
samples.

Upon
the
development
of
a
new
method,
spiked
samples
are
analyzed
and
the
percent
recovery
calculated
for
the
analyses.
This
will
then
be
an
estimate
of
the
recoveries
that
can
be
expected
for
the
specific
test
system.
Environmental
Enterprises
performs
a
batch
spiked
sample
digestion
and
analysis
at
a
rate
of
1
for
every
20
(
or
less)
mercury
samples
submitted.
Accuracy
is
further
shown
by
the
evaluation
of
a
laboratory
control
sample
of
known
value
that
is
digested
and
analyzed
in
the
same
manner
as
the
samples
submitted.

This
project
incorporates
the
use
of
two
non­
standard
tests
for
leaching
of
mercurycontaining
wastes.
Procedures
for
these
tests
are
provided
as
Appendices
B
&
C.
EPA
QA
Section
No.
6.0
Revision
No.
0
Date:
December
20,
2000
Page
26
of
38
Quality
control
with
these
techniques
is
addressed
in
the
individual
procedures.

Wherever
possible,
reference
to
standards
promulgated
by
EPA,
ASTM
(
American
Society
for
Testing
and
Materials),
or
COE
(
Corps
of
Engineers)
will
be
followed.
Limits
of
accuracy
are
yet
to
be
determined
and
will
be
addressed
in
addenda
to
the
Quality
Assurance
Project
Plan
as
the
techniques
are
developed.

A
summary
of
the
estimated
QA
objectives
for
precision
and
accuracy
are
presented
in
Table
6.1.
EPA
QA
Section
No.
6.0
Revision
No.
0
Date:
December
20,
2000
Page
27
of
38
Table
6.1
Quality
Assurance
Objectives
for
MDL
Precision
and
Accuracy
of
Chemical
Analyses
Performed
at
ALTER
Chemical
/
Process
Method
MDL(
1)
Precision(
2
)
Accuracy(
3)

Alkalinity
2320(
4)
5
mg/
l
20
75­
125%
Acidity
2330(
4)
5
mg/
l
20
75­
125%
pH
4500H+
B
(
4)
­­
0.02(
6)
0.05(
5)

Quality
Assurance
Objectives
for
MDL
Precision
and
Accuracy
of
Chemical
Analyses
and
Performed
at
Environmental
Enterprises
Chemical
/
Process
Method
Reporting
Limit
Precision(
2)
Accuracy(
3)

Mercury
(
aqueous)
7470A(
7)
0.0005
mg/
l
25
75­
125%

Mercury
(
solids)
7470A(
7)
0.05
mg/
kg
25
75­
125%

Notes:

(
1)
Method
detection
limit
(
2)
As
relative
percent
difference
(
RPD)
of
analytical
duplicates
(
3)
As
percent
recovery
range
(
4)
Standard
Methods
for
the
Examination
of
Water
and
Wastewater,
18th
ed.
1992
(
5)
As
bias
limits
(
6)
Expressed
in
pH
units
as
limits
for
deviation
of
check
standards
from
true
value
(
7)
Test
methods
for
evaluating
solid
waste
use
SW­
846
EPA
QA
Section
No.
6.0
Revision
No.
0
Date:
December
20,
2000
Page
28
of
38
6.1
Calculations
of
Data
Quality
Indicators
Precision
Precision
is
measured
by
running
two
or
three
replicate
analyses.
When
duplicates
are
analyzed
the
precision
will
be
expressed
in
terms
of
the
Relative
Percent
Difference
(
RPD).

(
)
100
x
2
/
2
1
2
1
D
D
D
D
RPD
+
-
=
where:
RPD
=
Relative
Percent
Difference
D1
=
Duplicate
result
1
D2
=
Duplicate
result
2
When
three
samples
are
analyzed,
precision
will
be
reported
in
terms
of
the
standard
deviation
and/
or
the
coefficient
of
variation
(
relative
standard
deviation).

where:
s
=
Standard
deviation
n
=
Number
of
replicates
X1=
Replicate
result
X
=
Mean
of
the
replicate
measurements
(
)
X
s
CV
100
x
=
where:
CV
=
Coefficient
of
variation
s
=
Standard
deviation
X
=
Mean
of
replicate
results
(
)
(
)
2
1
1
-
-
=
å
=
n
X
X
s
n
i
i
EPA
QA
Section
No.
6.0
Revision
No.
0
Date:
December
20,
2000
Page
29
of
38
Accuracy
Accuracy
is
the
defined
as
the
degree
of
agreement
between
a
measurement
and
an
accepted
reference
value.
For
some
parameters,
accuracy
will
be
gauged
through
analysis
of
reference
standards.
This
of
course
depends
on
whether
or
not
a
reference
standard
exists
for
a
given
analysis.
Wet
chemical
waste
analyses
have
reference
standards
for
most
common
parameters.
Reference
standards
have
a
known
true
value
and
an
acceptable
range
of
values
(
usually
three
standard
deviations
established
from
interlaboratory
testing
of
the
standards).
When
accuracy
is
based
on
reference
standards,
it
is
the
accuracy
objective
to
be
within
this
acceptable
range
of
values.
Since
analysis
of
reference
standards
estimates
the
accuracy
of
the
measurement
process,
they
may
or
may
not
truly
evaluate
the
accuracy
of
the
unknown
sample
data.
When
applicable,
spiked
samples
will
be
analyzed
to
estimate
unknown
accuracy.
In
these
cases,
the
accuracy
objective
is
expressed
in
terms
of
maximum
acceptable
deviation
from
100
%
recovery.

Percent
recovery
is
defined
as
follows:

%
R
Sp
s
C
=
-
x100
where:
%
R
=
Percent
recovery
Sp
=
Spiked
sample
concentration
S
=
Unspiked
sample
concentration
C
=
Concentration
of
spike
added
EPA
QA
Section
No.
6.0
Revision
No.
0
Date:
December
20,
2000
Page
30
of
38
6.2
Internal
Quality
Control
Checks,
Performance,
and
System
Audits
The
internal
quality
control
checks
(
Table
6.2)
routinely
implemented
with
analytical
testing
are
method
blanks,
replicate
samples,
and
QC
standards.
The
following
discussions
describe
each
type
of
QC
that
is
applied
to
the
testing.

Experimental
test
blanks
pertain
only
to
the
leaching
or
chemical
characterization
tests.

These
blanks
are
deionized
water
or
a
standard
leachant,
as
outlined
in
a
specific
test
protocol,

taken
through
the
entire
equipment
cleaning/
sample
leaching
procedure
or
sample
preparation
and
analysis
routine.
When
steps
in
the
leaching
procedure
call
for
re­
use
of
a
piece
of
equipment
during
the
procedure
cleaning
between
samples
is
required
and
blanks
are
collected
to
determine
if
any
cross
contamination
has
occurred.
Should
test
blank
results
indicate
any
amount
of
detectable
contamination,
samples
will
be
re­
analyzed
if
possible.
If
this
is
not
possible,

results
of
the
blank
will
be
reported
along
with
the
results
from
the
samples.
Test
blanks
are
run
at
a
frequency
of
1
for
every
10
samples
analyzed.
If
a
set
of
tests
is
run
on
less
than
10
samples,

then
at
least
1
blank
is
run
for
each
test.
Each
Environmental
Enterprises,
Inc.
analytical
batch
consists
of
1
test
blank,
1
laboratory
control
sample
and
up
to
20
samples.
One
of
these
samples
in
each
batch
is
duplicated
and
spiked.

A
minimum
of
50%
duplicate
samples
are
run
on
all
leaching
tests.
These
are
individual
samples
that
are
tested
in
parallel.
The
replicate
analyses
provide
a
measure
of
the
variability
(
precision)
of
the
entire
testing
and
measurement
process.
Table
6.2
indicates
the
type
and
frequency
of
QC
checks.
EPA
QA
Section
No.
6.0
Revision
No.
0
Date:
December
20,
2000
Page
31
of
38
QC
standards
are
samples
of
a
known
concentration
which
have
been
prepared
from
an
independent
source.
This
type
of
analysis
is
useful
for
verifying
calibration
of
a
particular
system.
QC
Standards
are
analyzed
on
several
of
the
chemical
characterization
tests.
Table
6.3
indicates
those
tests
where
QC
Standards
are
applicable
and
the
frequency
required.

Other
internal
quality
control
considerations
include
the
following:

(
1)
All
chemicals
used
in
leaching
procedures
are
reagent
grade
or
higher
purity
(
e.
g.

samples
for
metals
analyses
from
leachate
are
acidified
with
re­
distilled
nitric
acid).

These
chemicals
are
dated
when
received.

(
2)
Water
used
in
all
leaching
tests
is
ASTM
Type
I
or
II
as
appropriate
to
the
specific
test.

The
QA
officer
will
participate
throughout
the
testing
and
analysis
cycles
as
was
noted
in
Section
2.
Performance
and
system
audits
will
be
handled
by
external
means.
ALTER
will
participate
as
required
by
EPA.
As
of
now,
no
audits
are
scheduled.
EPA
QA
Section
No.
6.0
Revision
No.
0
Date:
December
20,
2000
Page
32
of
38
Table
6.2
Quality
Control
Checks
QUALITY
CONTROL
CHECKS
FREQUENCY
Analytical
Method
Blanks
1
for
every
10
samples(
1)

Experimental
Test
Blanks
Leachant
used
in
Specific
Test
Calibration
Standards
Daily
Analytical
Duplicate
1
duplicate
for
every
10
samples(
1)

Test
Duplicate
(
pH
Based
Leaching)
Required
for
50%
of
data
points
Test
Duplicate
(
TCLP)
Each
sample
duplicated
Spiked
Samples
1
for
every
10
samples(
1)

(
1)
Note:
If
less
than
10
samples
are
analyzed
in
any
grouping,
1
blank,
1
duplicate,
and
1
spike
are
required.

Table
6.3
QC
Standards
TEST
STANDARD
USED
FREQUENCY
Alkalinity
Na2CO3
1
time/
test
day
prior
to
analysis
Acidity
NaOH
1
time/
test
day
prior
to
analysis
pH
pH
10.0
Calibration
Standard
pH
7.0
Check
Standard
pH
4.0
Calibration
Standard
Beginning
and
end
of
each
operating
day
Mercury
HgNO3
After
every
10
samples
EPA
QA
Section
No.
7.0
Revision
No.
0
Date:
December
20,
2000
Page
33
of
38
7.0
Data
Reduction,
Validation
and
Reporting
All
results
will
be
reduced
to
the
appropriate
reporting
units
(
designated
in
the
Standard
Procedures)
by
the
analyst
performing
the
test.
Calculations
are
prepared
by
computer
and
are
checked
by
the
analyst
for
gross
error
and
miscalculation.
Results
are
averaged
and
the
mean
and
the
standard
deviation
or
range
are
calculated.
All
data
is
reviewed
by
the
Project
Manager
prior
to
reporting.
All
data
points
are
reported
along
with
the
mean
and
appropriate
estimations
of
variability.
All
data
generated
by
ALTER
will
be
retained
for
five
years.

Raw
data
is
collected
from
the
instruments
and
entered
into
spreadsheets
for
final
data
calculations.
The
ALTER
QA
officer
determines
whether
or
not
data
have
met
QA
objectives.

Spot
recalculation
will
be
made
by
the
QA
officer
to
check
for
incorrect
calculations.

Approximately
10
%
of
the
data
will
be
checked
for
calculation
error
by
the
QA
officer.
Any
data
not
meeting
stated
objectives
are
brought
to
the
attention
of
the
appropriate
Project
Manager.
The
Project
Manager
determines
whether
results
are
indicative
of
a
problem
or
if
it
is
simply
a
statistical
outlier.
Suspect
data
will
be
excluded
from
the
mean
and
reported
individually
as
a
suspect
data
point.
At
no
time
will
data
be
discarded.
A
data
report
will
be
reviewed
by
the
Project
Manager
for
overall
technical
review.
Other
validation
procedures
executed
by
the
QA
officer
and/
or
Project
Manager
include
making
sure
proper
testing
procedures
are
followed,
adequate
documentation
is
maintained
and
spot
checks
of
calculations.

The
Project
Manager
and
the
QA
officer
review
QA/
QC
data
generated
to
determine
whether
objectives
are
being
met
and
if
trends
in
the
data
are
indicating
potential
problems.
If
necessary,

they
will
specify
new
tests
based
on
available
data
­
should
this
need
be
indicated
from
the
data
collected.
EPA
QA
Section
No.
7.0
Revision
No.
0
Date:
December
20,
2000
Page
34
of
38
ALTER
uses
the
EPA
definition
of
Method
Detection
Limit
(
MDL)
as
stated
in
40CFR
pt136,
App.
B.
pg.
554
(
7­
1­
91Ed):
"
The
method
detection
limit
is
defined
as
the
minimum
concentration
of
a
substance
that
can
be
measured
and
reported
with
99%
confidence
that
the
analyte
concentration
is
greater
than
zero.

7.1
Project
Output
Environmental
Enterprises
will
maintain
all
analytical
data
for
ten
years.
The
following
QA/
QC
data
will
be
provided
by
Environmental
Enterprises
Inc.
as
an
appendix
for
all
project
analytical
data:

Sample
Description
of
ID
Number
Laboratory
sample
ID
Number
Analyses
Performed
Method
Reference
Analyst
report
Chain
of
Custody
Date
Prepared
and
Analyzed
Blank
Report
Laboratory
Control
Sample
Report
Initial
Calibration
Curve
Copies
of
Analyst
Bench
Sheets
Case
Narrative
Monthly
reports
will
be
prepared
by
graduate
students,
reviewed
by
the
project
manager
and
submitted
to
the
EPA
on
the
15th
of
every
month.
Distribution
of
the
monthly
report
to
other
agencies
will
be
at
the
discretion
of
the
EPA
project
manager.
A
final
report
will
be
prepared
by
SAIC
with
input
from
the
ALTER
project
manager.
The
final
report
format
will
be
structured
as
follows:

1.0
Introduction
2.0
Background
Data
from
waste
generators
Vendor
process
descriptions
3.0
Characterization
Data
Generated
by
ALTER,
Agvise
and
Environmental
Enterprises
as
outlined
in
Section
3.0
of
the
QAPP.
Characterization
data
will
be
presented
in
tables
which
will
provide
the
parameter
measured,
the
result
and
the
organization
responsible
for
the
data.
4.0
Leaching
Detailed
methods
and
results
for
each
test
will
be
provided
as
follows:
EPA
QA
Section
No.
7.0
Revision
No.
0
Date:
December
20,
2000
Page
35
of
38
·
TCLP
 
will
be
presented
in
a
table
providing
mercury
analysis
results.
·
UC
Constant
pH
Leaching
 
will
be
presented
in
a
table
providing
pH
results
with
the
corresponding
mercury
analysis
of
the
leachate.
The
data
will
also
be
presented
graphically,
plotting
leachate
mercury
concentration
against
pH.
5.0
Data
Quality
Discussion
6.0
Conclusions
·
Data
Interpretation
·
Data
based
assessment
of
the
applicability
of
vendor
processes
to
treat
the
mercury­
containing
surrogate.

Modifications
or
deviations
to
standard
procedures
will
be
documented
and
presented
in
the
final
project
report.
EPA
QA
Section
No.
8.0
Revision
No.
0
Date:
December
20,
2000
Page
36
of
38
8.0
Assessments
8.1
Quality
Assurance
Reports
to
Management
Quality
Assurance
reports
will
be
compiled
by
the
analyst
computing
data,
then
reviewed
by
the
Project
Manager
and
the
QA
officer.
Review
of
data
quality
is
a
continuous
process.
All
key
project
personnel
will
meet
on
a
weekly
basis
while
experimental
work
is
in
progress
to
assure
that
all
QA/
QC
practices
are
being
followed.

Any
problems
and/
or
recommended
solutions
will
be
reported
as
they
are
encountered.
It
is
important
that
all
data
anomalies
be
examined
in
a
timely
fashion
in
order
to
minimize
unusable
data.
All
QA
activities
will
be
documented
in
appropriate
logbooks
at
the
time
of
any
action
for
later
review
at
the
routine
QA
meetings.

Requests
for
amendments
of
the
QA
Project
Plan
will
occur
only
after
agreement
by
the
Project
Manager
and
the
QA
officer.
The
Project
Manager
will
notify
EPA
when
a
change
is
required
and
the
change
will
be
documented
in
writing
and
a
copy
included
in
the
monthly
report
of
the
project.
This
documentation
will
describe
the
necessary
changes
and
present
the
reason
for
the
amendment
request.

All
principal
project
participants
on
the
distribution
list
will
receive
a
copy
of
the
approved
QA
Project
Plan.
Any
subsequent
revisions
will
be
distributed
to
these
individuals
as
the
revisions
are
documented.
The
document
control
format
in
the
upper
right
hand
corner
of
the
page
will
reflect
the
new
date
and
revision
number.
EPA
QA
Section
No.
8.0
Revision
No.
0
Date:
December
20,
2000
Page
37
of
38
8.2
Corrective
Action
Scheme
A
corrective
action
implies
the
identification
of
a
problem
and
subsequent
elimination
of
the
problem.
Occasionally,
a
problem
can
be
immediately
identified
by
the
research
assistants
and
eliminated
prior
to
any
data
collection.
More
often,
the
problem
has
been
in
existence
for
some
time
and,
therefore,
the
need
for
corrective
action
is
indicated
by
an
out­
of­
control
situation
or
unacceptable
levels
of
completeness.
In
these
situations,
it
is
the
responsibility
of
the
project
manager
to
document
and
oversee
the
corrective
action
process.
Appropriate
authorities
in
the
problem
area
are
contacted
for
assistance
in
the
identification
and
elimination
steps
when
necessary.

The
corrective
process
is
basically
divided
into
four
units:

1.
Identification
of
the
problem
2.
Elimination
of
the
problem
3.
Documentation
of
the
problem
4.
Verification
of
the
correction
In
all
cases,
problems
encountered
will
be
dealt
with
immediately
and
eliminated
as
quickly
as
possible.
No
data
will
be
generated
after
a
problem
is
identified
until
the
problem
has
been
eliminated.
If
possible,
suspect
results
generated
during
the
existence
of
problem
will
be
discarded
and
reanalyzed.
When
this
is
not
possible
or
practical,
suspect
results
will
be
flagged.

Final
disposition
of
such
flagged,
suspect
results
will
be
decided
by
the
Project
Manager
in
conjunction
with
the
Co­
PI
or
the
QA
officer.

Potential
problems
that
occur
and
corrective
action
taken
is
outlined
below:
EPA
QA
Section
No.
8.0
Revision
No.
0
Date:
November
15,
1999
Page
38
of
38
Problem
Area
Action(
s)*

·
Analytical
Methods
1)
If
the
operator
disagrees
with
any
b
procedure
or
part
of
the
analytical
method
·
Instrumental
Analysis
1)
If
blanks
produce
an
erratic
baseline
b,
c
and/
or
noise
2)
If
multiple
analyses
of
standard(
s)
b,
c
yield
inconsistent
results
3)
If
the
calibration
curve
is
nonlinear
b,
c
4)
Loss
of
greater
than
10
%
of
instrument
b,
c
sensitivity
during
any
given
test
day
5)
Instruments
out
of
calibration
a,
c
·
Data
Review
1)
If
the
data
is
contrary
to
that
expected
a,
b
2)
If
the
data
review
has
not
been
performed
a,
b
within
one
day
of
analytical
measurement
3)
If
precision
and
accuracy
calculations
are
a,
b
discovered
to
be
incorrect
after
data
has
been
reported
*
Action
Codes:

a
=
Notify
the
Project
Manager;
discuss
with
the
Co­
PI
over
that
area
b
=
Notify
the
QA
officer;
discuss
with
the
Co­
PI
c
=
Adjust,
repair
or
return
the
instrument
to
the
manufacturer
for
repair
APPENDIX
A
Acidity/
Alkalinity
ALTER
LABORATORY
Standard
Methods
for
the
Examination
of
Water
and
Wastewater,
1992
­
2310
ACIDITY
Acidity
of
a
water
is
its
quantitative
capacity
to
react
with
a
strong
base
to
a
designated
pH.
The
measured
value
may
vary
significantly
with
the
end­
point
pH
used
in
the
determination.
Acidity
is
a
measure
of
an
aggregate
property
of
water
and
can
be
interpreted
in
terms
of
specific
substances
only
when
the
chemical
composition
of
the
sample
is
known.
Strong
mineral
acids,
weak
acids
such
as
carbonic
and
acetic,
and
hydrolyzing
salts
such
as
ferrous
or
aluminum
sulfates
may
contribute
to
the
measured
acidity
according
to
the
method
of
determination.

Acids
contribute
to
corrosiveness
and
influence
chemical
reaction
rates,
chemical
speciation,
and
biological
processes.
The
measurement
also
reflects
a
change
in
the
quality
of
the
source
water.

1.
General
Discussion
a.
Principle:
Hydrogen
ions
present
in
a
sample
as
a
result
of
dissociation
or
hydrolysis
of
solutes
react
with
additions
of
standard
alkali.
Acidity
thus
depends
on
the
end­
point
pH
or
indicator
used.
The
construction
of
a
titration
curve
by
recording
sample
pH
after
successive
small
measured
additions
of
titrant
permits
identification
of
inflection
points
and
buffering
capacity,
if
any,
and
allows
the
acidity
to
be
determined
with
respect
to
any
pH
of
interest.

In
the
titration
of
a
single
acidic
species,
as
in
the
standardization
of
reagents,
the
most
accurate
end
point
is
obtained
from
the
inflection
point
of
a
titration
curve.
The
inflection
point
is
the
pH
at
which
curvature
changes
from
convex
to
concave
or
vice
versa.
Because
accurate
identification
of
inflection
points
may
be
difficult
or
impossible
in
buffered
or
complex
mixtures,
the
titration
in
such
cases
is
carried
to
an
arbitrary
end­
point
pH
based
on
practical
considerations.
For
routine
control
titrations
or
rapid
preliminary
estimates
of
acidity,
the
color
change
of
an
indicator
may
be
used
for
an
end
point.
Samples
of
industrial
wastes,
acid
mine
drainage,
or
other
solutions
that
contain
appreciable
amounts
of
hydrolyzable
metal
ions
such
as
iron,
aluminum,
or
manganese
are
treated
with
hydrogen
peroxide
to
ensure
oxidation
of
any
reduced
forms
of
polyvalent
cations,
and
boiled
to
hasten
hydrolysis.
Acidity
results
may
be
highly
variable
if
this
procedure
is
not
followed
exactly.
b.
End
points:
Ideally
the
end
point
of
the
acidity
titration
should
correspond
to
the
stoichiometric
equivalence
point
for
neutralization
of
acids
present.
The
pH
at
the
equivalence
point
will
depend
on
the
sample,
the
choice
among
multiple
inflection
points,
and
the
intended
use
of
the
data.
Dissolved
carbon
dioxide
(
CO2)
usually
is
the
major
component
of
unpolluted
surface
waters;
handle
samples
from
such
sources
carefully
to
minimize
the
loss
of
dissolved
gasses.
In
a
sample
containing
only
carbon
dioxide­
bicarbonates­
carbonates,
titration
to
pH
8.3
at
25

C
corresponds
to
stoichiometric
neutralization
of
carbonic
acid
to
bicarbonate.
Because
the
color
change
of
phenolphthalein
indicator
is
close
to
pH
8.3,
this
value
generally
is
accepted
as
a
standard
end
point
for
titration
of
total
acidity,
including
CO2
and
most
weak
acids.
Metacresol
purple
also
has
an
end
point
at
pH
8.3
and
gives
a
sharper
color
change.
For
more
complex
mixtures
or
buffered
solutions
selection
of
an
inflection
point
may
be
subjective.
Consequently,
use
fixed
points
of
pH
3.7
and
pH
8.3
for
standard
acidity
determinations
in
waste­
waters
and
neutral
waters
where
the
simple
carbonate
equilibria
discussed
above
cannot
be
assumed.
Bromphenol
blue
has
a
sharp
color
change
at
its
end
point
of
3.7.
The
resulting
titrations
are
identified,
traditionally,
as
"
methyl
orange
acidity"
(
pH
3.7)
and
"
phenolphthalein"
or
total
acidity
(
pH
8.3)
regardless
of
the
actual
method
of
measurement.
c.
Interferences:
Dissolved
gasses
contributing
to
acidity
or
alkalinity,
such
as
CO2,
hydrogen
sulfide,
or
ammonia,
may
be
lost
or
gained
during
sampling,
storage,
or
titration.
Minimize
such
effects
by
titrating
to
the
end
point
promptly
after
opening
sample
container,
avoiding
vigorous
shaking
or
mixing,
and
protecting
sample
form
the
atmosphere
during
titration,
and
letting
sample
become
no
warmer
than
it
was
at
collection.
In
the
potentiometric
titration,
oily
matter,
suspended
solids,
precipitates,
or
other
waste
matter
may
coat
the
glass
electrode
and
cause
sluggish
response.
Difficulty
from
this
source
is
likely
to
be
revealed
in
an
erratic
titration
curve.
Do
not
remove
interferences
from
sample
because
they
may
contribute
to
its
acidity.
Briefly
pause
between
titrant
additions
to
let
electrode
come
to
equilibrium
or
clean
the
electrodes
occasionally.
In
samples
containing
oxidizable
or
hydrolyzable
ions
such
as
ferrous
or
ferric
iron,
aluminum,
and
manganese,
the
rates
of
these
reactions
may
be
slow
enough
at
room
temperature
to
cause
drifting
end
points.
Do
not
use
indicator
titrations
with
colored
or
turbid
samples
that
may
obscure
the
color
change
at
the
end
point.
Residual
free
available
chlorine
in
the
sample
may
bleach
the
indicator.
Eliminate
this
source
of
interference
by
adding
1
drop
of
0.1N
sodium
thiosulfate
(
Na2S2O3).
d.
Selection
of
method:
Determine
sample
acidity
from
the
volume
of
standard
alkali
required
to
titrate
a
portion
to
a
pH
of
8.3
(
phenolphthalein
acidity)
or
pH
3.7
(
methyl
orange
acidity
of
waste­
waters
and
grossly
polluted
waters).
Titrate
at
room
temperature
using
a
properly
calibrated
pH
meter,
electrically
operated
titrator,
or
color
indicators.
Construct
a
titration
curve
for
a
standardization
of
reagents.
Use
the
hot
peroxide
procedure
to
pretreat
samples
known
or
suspected
to
contain
hydrolyzable
metal
ions
or
reduced
forms
of
polyvalent
cation,
such
as
iron
pickle
liquors,
acid
mine
drainage,
and
other
industrial
wastes.
Cool
to
room
temperature
before
titration.
Color
indicators
may
be
used
for
routine
and
control
titrations
in
the
absence
of
interfering
color
and
turbidity
and
for
preliminary
titrations
to
select
sample
size
and
strength
of
titrant
(

4b).
e.
Sample
size:
The
range
of
acidities
found
in
waste­
waters
is
so
large
that
a
single
sample
size
and
normality
of
base
used
as
titrant
cannot
be
specified.
Use
a
sufficiently
large
volume
of
titrant
(
20
mL
or
more
from
a
50­
mL
buret)
to
obtain
relatively
good
volumetric
precision
while
keeping
sample
volume
sufficiently
small
to
permit
sharp
end
points.
For
samples
having
acidities
less
than
about
1,000
mg
as
calcium
carbonate
(
CaCO3)/
L,
select
a
volume
with
less
than
50
mg
CaCO3
equivalent
acidity
and
titrate
with
0.02N
sodium
hydroxide
(
NaOH).
For
acidities
greater
than
about
1,000
mg
as
CaCO3/
L,
use
a
portion
containing
acidity
equivalent
to
less
than
250
mg
CaCO3
and
titrate
with
0.1N
NaOH.
If
necessary,
make
a
preliminary
titration
to
determine
optimum
sample
size
and/
or
normality
of
titrant.
f.
Sampling
and
storage:
Collect
samples
in
polyethylene
or
borosilicate
glass
bottles
and
store
at
low
temperature.
Fill
bottles
completely
and
cap
tightly.
Because
waste
samples
may
be
subject
to
microbial
action
and
to
loss
or
gain
of
carbon
dioxide
(
CO2)
or
other
gasses
when
exposed
to
air,
analyze
samples
without
delay,
preferably
within
1
day.
If
biological
activity
is
evident
analyze
within
6
hr.
Avoid
sample
agitation
and
prolonged
exposure
to
air.

2.
Apparatus
a.
Electrometric
titrator:
Use
any
commercial
pH
meter
or
electrometrically
operated
titrator
that
uses
a
glass
electrode
and
can
be
read
to
0.05
pH
unit.
Standardize
and
calibrate
according
to
the
manufacturer's
instructions.
Pay
special
attention
to
temperature
compensation
and
electrode
care.
If
automatic
temperature
compensation
is
not
provided,
titrate
at
25

C,

2

C.
b.
Titration
vessel:
The
size
and
form
will
depend
on
the
electrodes
and
the
sample
size.
Keep
the
free
space
above
the
sample
as
small
as
practicable,
but
allow
room
for
titrant
and
full
immersion
of
the
indicating
portions
of
electrodes.
For
conventional­
sized
electrodes,
use
a
200­
mL,
tall­
form
Berzelius
beaker
without
a
spout.
Fit
beaker
with
a
stopper
having
three
holes,
to
accommodate
the
two
electrodes
and
the
buret.
With
a
miniature
combination
glass­
reference
electrode
use
a
125­
mL
or
250­
mL
erlenmeyer
flask
with
a
two­
hole
stopper.
c.
Magnetic
stirrer.
d.
Pipets,
volumetric.
e.
Flasks,
volumetric,
1,000­,
200­,
100­
mL.
f.
Burets,
borosilicate
glass,
50­,
25­,
10­
mL.
g.
Polyolefin
bottle.

3.
Reagents
a.
Carbon
dioxide­
free
water:
Prepare
all
stock
and
standard
solutions
and
dilution
water
for
the
standardization
procedure
with
distilled
or
deionized
water
that
has
been
freshly
boiled
for
15
min
and
cooled
to
room
temperature.
The
final
pH
of
the
water
should
be

6.0
and
its
conductivity
should
be
<
2
m
mhos/
cm.
b.
Potassium
hydrogen
phthalate
solution,
approximately
0.05N:
Crush
15
to
20
g
primary
standard
KHC8H4O4
to
about
100
mesh
and
dry
at
120

C
for
2
hrs.
Cools
in
a
desiccator.
Weigh
10.0

0.5
g
(
to
the
nearest
mg),
transfer
to
a
1­
L
volumetric
flask,
and
dilute
to
1,000
mL.
c.
Standard
sodium
hydroxide
titrant,
0.1N:
Prepare
solution
approximately
0.1N
as
indicated
under
Preparation
of
Desk
Reagents
as
indicated
in
Table
B.

TABLE
B:
PREPARATION
OF
UNIFORM
SODIUM
HYDROXIDE
SOLUTIONS
Required
Required
Weight
of
Volume
of
Normality
NaOH
to
Prepare
15N
NaOH
to
of
1,000
mL
of
Prepare
1,000
NaOH
Solution
mL
of
Solution
Solution
g
mL
6
240
400
1
40
67
0.1
4
6.7
Standardize
by
titrating
40.00
mL
KHC8H4O4
solution
(
3b),
using
a
25­
mL
buret.
Titrate
to
the
inflection
point
(

1a),
which
should
be
close
to
pH
8.7.
Calculate
normality
of
NaOH:

where:
A
=
g
KHC8H4O4
weighed
into
1­
L
flask,
B
=
mL
KHC8H4O4
solution
taken
for
titration,
and
C
=
mL
NaOH
solution
used.

Use
the
measured
normality
in
further
calculations
or
adjust
to
0.1000N;
1
mL
=
5.00
mg
CaCO3.
d.
Standard
sodium
hydroxide
titrant,
0.02N:
Dilute
200
mL
0.1N
NaOH
to
1,000
mL
and
store
in
a
polyolefin
bottle
protected
from
atmospheric
C)
2
by
a
soda
lime
tube
or
tight
cap.
Standardize
against
KHC8H4O4
as
directed
in

3c,
using
15.00
mL
KHC8H4O4
solution
and
a
50­
mL
buret.
Calculate
normality
as
above
(

3c);
1
mL
=
1.00
mg
CaCO3.
e.
Hydrogen
peroxide,
H2O2,
30%.
f.
Bromphenol
blue
indicator
solution,
pH
3.7
indicator:
Dissolve
100mg
bromphenol
blue,
sodium
salt,
in
100
mL
water.
g.
Metacresol
purple
indicator
solution,
pH
8.3
indicator:
Dissolve
100
mg
metacresol
purple
in
100
mL
water.
h.
Phenolphthalein
indicator
solution,
alcoholic,
pH
8.3
indicator.
i.
Sodium
thiosulfate,
0.1M:
Dissolve
25
g
Na2S2O3

5H2O
and
dilute
to
1,000
mL
with
distilled
water.

4.
Procedure
If
sample
is
free
from
hydrolyzable
metal
ions
and
reduced
forms
of
polyvalent
cations,
proceed
with
analysis
according
to
b,
c,
or
d.
If
sample
is
known
or
suspected
to
contain
such
substances,
pretreat
according
to
a.
a.
Hot
peroxide
treatment:
Pipet
a
suitable
sample
(
see

1e)
into
titration
flasks.
Measure
pH.
If
pH
is
above
4.0
add
5­
mL
increments
of
0.02N
sulfuric
acid
(
H2SO4)(
Section
2320B.
3c)
to
reduce
pH
to
4
or
less.
Remove
electrodes.
Add
5
drops
30%
H2O2
and
boil
for
2
to
5
min.
Cool
to
room
temperature
and
titrate
with
standard
alkali
to
pH
8.3
according
to
the
procedure
of
4d.
b.
Color
change:
Select
a
sample
size
and
normality
of
titrant
according
to
criteria
of

1e.
Adjust
sample
to
room
temperature,
if
necessary,
and
with
a
pipet
discharge
sample
into
an
erlenmeyer
flask,
while
keeping
pipet
tip
near
flask
bottom.
If
free
residual
chlorine
is
present
add
0.05
mL
(
1
drop)
0.1N
Na2S2O3
solution,
or
destroy
with
ultraviolet
radiation.
Add
0.2
mL
(
5
drops)
indicator
solution
and
titrate
over
a
white
surface
to
a
persistent
color
change
characteristic
of
the
equivalence
point.
Commercial
indicator
solutions
or
solids
designated
for
the
appropriate
pH
range
(
3.7
or
8.3)
may
be
used.
Check
color
at
end
point
by
adding
the
same
concentration
of
indicator
used
with
sample
to
a
buffer
solution
at
the
designated
pH.
c.
Potentiometric
titration
curve:
C
x
204.2
B
x
A
=
Normality
1)
Rinse
electrodes
and
titration
vessel
with
distilled
water
and
drain.
Select
sample
size
and
normality
of
titrant
according
to
the
criteria
of

1e.
Adjust
sample
to
room
temperature,
if
necessary,
and
with
a
pipet
discharge
sample
while
keeping
pipet
tip
near
the
vessel
bottom.
2)
Measure
sample
pH.
Add
standard
alkali
in
increments
of
0.5
mL
or
less,
such
that
a
change
of
less
than
0.2
pH
units
occurs
per
increment.
After
each
addition,
mix
thoroughly
but
gently
with
a
magnetic
stirrer.
Avoid
splashing.
Record
pH
when
a
constant
reading
is
obtained.
Continue
adding
titrant
and
measure
pH
until
pH
9
is
reached.
Construct
the
titration
curve
by
plotting
observed
pH
values
versus
cumulative
milliliters
titrant
added.
A
smooth
curve
showing
one
or
more
inflections
should
be
obtained.
A
ragged
or
erratic
curve
may
indicate
that
equilibrium
was
not
reached
between
successive
alkali
additions.
Determine
acidity
relative
to
a
particular
pH
from
the
curve.
d.
Potentiometric
titration
to
pH
3.7
or
8.3:
Prepare
sample
and
titration
assembly
as
specified
in

4c1.
Titrate
to
preselected
end
point
pH
(

1d)
without
recording
intermediate
pH
values.
As
the
end
point
is
approached
make
smaller
additions
of
alkali
and
be
sure
that
pH
equilibrium
is
reached
before
making
the
next
addition.

5.
Calculation
Acidity,
as
mg
CaCO3/
L
where:
A
=
mL
NaOH
titrant
used,
B
=
normality
of
NaOH,
C
=
mL
H2SO4
used
(

4d),
and
D
=
normality
of
H2SO4.

Report
pH
of
the
end
point
used,
as
follows:
"
The
acidity
to
pH
=
mg
CaCO3/
L."
A
negative
value
signifies
alkalinity.

6.
Precision
No
general
statement
can
be
made
about
precision
because
of
the
great
variation
in
sample
characteristics.
The
precision
of
the
titration
is
likely
to
be
much
greater
than
the
uncertainties
involved
in
sampling
and
sample
handling
before
analysis.
Forty
analysts
in
17
laboratories
analyzed
synthetic
water
samples
containing
increments
of
bicarbonate
equivalent
to
20
mg
CaCO3/
L.
Titration
according
to
the
procedure
of

4d
gave
a
standard
deviation
of
1.8
mg
CaCO3/
L,
with
negligible
bias.
Five
laboratories
analyzed
two
samples
containing
sulfuric,
acetic,
and
formic
acids
and
aluminum
chloride
by
the
procedures
of

s
4b
and
4d.
The
mean
acidity
of
one
sample
(
to
pH
3.7)
was
487
mg
CaCO3/
L,
with
a
standard
deviation
of
11
mg/
L.
The
bromphenol
blue
titration
of
the
same
sample
was
90
mg/
L
greater,
with
a
standard
deviation
of
110
mg/
L.
The
other
sample
had
a
potentiometric
titration
of
547
mg/
L
with
a
standard
deviation
of
54
mg/
L,
while
the
corresponding
indicator
result
was
85
mg/
L
greater
sample
mL
50,000
x
D)]
x
(
C
­
B)
x
[(
A
=
with
a
standard
deviation
of
56
mg/
L.
The
major
difference
between
the
samples
was
the
substitution
of
ferric
ammonium
citrate,
in
the
second
sample,
for
part
of
the
aluminum
chloride.
ALTER
LABORATORY
Standard
Methods
for
the
Examination
of
Water
and
Wastewater,
1992
­
2320
ALKALINITY
Alkalinity
of
a
water
is
its
quantitative
capacity
to
react
with
a
strong
acid
to
a
designated
pH.
The
measured
value
may
vary
significantly
with
the
end­
point
pH
used.
Alkalinity
is
a
measure
of
an
aggregate
property
of
water
and
can
be
interpreted
in
terms
of
specific
substances
only
when
the
chemical
composition
of
the
sample
is
known.

Alkalinity
is
significant
in
many
uses
and
treatments
of
natural
and
waste­
waters.
Because
the
alkalinity
of
many
surface
waters
is
primarily
a
function
of
carbonate,
bicarbonate,
and
hydroxide
content,
it
is
taken
as
an
indication
of
the
concentration
of
these
constituents.
The
measured
values
may
include
contributions
from
borates,
phosphates,
or
silicates
if
these
are
present.
Alkalinity
in
excess
of
alkaline
earth
metal
concentrations
is
significant
in
determining
the
suitability
of
a
water
for
irrigation.
Alkalinity
measurements
are
used
in
the
interpretation
and
control
of
water
and
waste­
water
treatment
process.
Raw
domestic
waste­
water
has
an
alkalinity
less
than
or
only
slightly
greater
than
that
of
the
water
supply.
Properly
operating
anaerobic
digesters
typically
have
supernatant
alkalinities
in
the
range
of
2,000
to
4,000
mg
calcium
carbonate
(
CaCO3)/
L.

1.
General
Discussion
a.
Principle:
Hydroxyl
ions
present
in
a
sample
as
a
result
of
dissociation
or
hydrolysis
of
solutes
react
with
additions
of
standard
acid.
Alkalinity
thus
depends
on
the
end­
point
pH
used.
For
methods
of
determining
inflection
points
from
titration
curves
and
the
rationale
for
titrating
to
fixed
pH
end
points,
see
Section
LPC#
301.1a.
For
samples
of
low
alkalinity
(
less
than
20
mg
CaCO3/
L)
use
an
extrapolation
technic
based
on
the
near
proportionality
of
concentration
of
hydrogen
ions
to
excess
of
titrant
beyond
the
equivalence
point.
The
amount
of
standard
acid
required
to
reduce
pH
exactly
0.30
pH
unit
is
measured
carefully.
Because
this
change
in
pH
corresponds
to
an
exact
doubling
of
the
hydrogen
ion
concentration,
a
simple
extrapolation
can
be
made
to
the
equivalence
point.
b.
End
points:
When
alkalinity
is
due
entirely
to
hydroxide,
carbonate,
or
bicarbonate
content,
the
pH
at
the
equivalence
point
of
the
titration
is
determined
by
the
concentration
of
carbon
dioxide
(
CO2)
at
that
stage.
CO2
concentration
depends,
in
turn,
on
the
total
carbonate
species
originally
present
and
any
losses
that
may
have
occurred
during
titration.
The
following
pH
values
are
suggested
as
the
equivalence
points
for
the
corresponding
alkalinity
concentrations
as
milligrams
CaCO3
per
liter:
Table
1.
End
Point
pH
Values
End
Point
pH
Total
Alkalinity
Phenolphthalein
Alkalinity
Alkalinity,
mg
CaC03/
L:

30
4.9
8.3
150
4.6
8.3
500
4.3
8.3
Silicates,
phosphates
known
or
suspected
4.5
8.3
Routine
or
automated
analyses
4.5
8.3
Industrial
waste
or
complex
system
4.5
8.3
c.
Interferences:
Soaps,
oily
matter,
suspended
solids,
or
particulates
may
coat
the
glass
electrode
and
cause
a
sluggish
response.
Allow
additional
time
between
titrant
additions
to
let
electrode
come
to
equilibrium.
Do
not
filter,
dilute,
concentrate,
or
alter
sample.
d.
Selection
of
method:
Determine
sample
alkalinity
from
volume
of
standard
acid
required
to
titrate
a
portion
to
a
designated
pH
taken
from

1b.
Titrate
at
room
temperature
with
a
properly
calibrated
pH
meter
or
electrically
operated
titrator,
or
use
color
indicators.
Report
alkalinity
less
than
20
mg
CaCO3/
L
only
if
it
has
been
determined
by
the
lowalkalinity
method
of

4d.
Construct
a
titration
curve
for
standardization
of
reagents.
Color
indicators
may
be
used
for
routine
and
control
titrations
in
the
absence
of
interfering
color
and
turbidity
and
for
preliminary
titrations
to
select
sample
size
and
strength
of
titrant
(
see
below).
e.
Sample
size:
See
Section
LPC#
301.1e
for
selection
of
size
sample
to
be
titrated
and
normality
of
titrant,
substituting
0.02N
or
0.1N
sulfuric
(
H2SO4)
or
hydrochloric
(
HCl)
acid
for
the
standard
alkali
of
that
method.
For
the
low­
alkalinity
method,
titrate
a
200­
mL
sample
with
0.02N
H2SO4
from
a
10­
mL
buret.
f.
Sampling
and
storage:
See
Section
LPC#
301.1f.

2.
Apparatus
See
Section
LPC#
301.2.

3.
Reagents
a.
Sodium
carbonate
solution,
approximately
0.05N:
Dry
3
to
5
g
primary
standard
Na2CO3
at
250

C
for
4
hrs
and
cool
in
a
desiccator.
Weigh
2.5g,

0.2
g
(
to
the
nearest
mg),
transfer
to
a
1­
L
volumetric
flask,
fill
flask
to
the
mark
with
distilled
water,
and
dissolve
and
mix
reagent.
Do
not
keep
longer
than
1
week.
b.
Standard
sulfuric
acid
or
hydrochloric
acid,
0.1N:
Dilute
3.0
mL
conc
H2SO4
or
8.3
mL
conc
HCl
to
1
L
with
distilled
or
deionized
water.
Standardize
against
40.00
mL
0.05N
Na2CO3
solution,
with
about
60
mL
water,
in
a
beaker
by
titrating
potentiometrically
to
pH
of
about
5.
Lift
out
electrodes,
rinse
into
the
same
beaker,
and
boil
gently
for
3
to
5
min
under
a
watchglass
cover.
Cool
to
room
temperature,
rinse
cover
glass
into
beaker,
and
finish
titrating
to
the
pH
inflection
point.
Calculate
normality:

where:
A
=
g
Na2CO3
weighed
into
1
L
flask,
B
=
mL
Na2CO3
solution
taken
for
titration,
and
C
=
mL
acid
used.

Use
measured
normality
in
calculations
or
adjust
to
0.1000N;
1
mL
0.1000N
solution
=
5.00
mg
CaCO3.
c.
Standard
sulfuric
acid
or
hydrochloric
acid,
0.02N:
Dilute
200.00
mL
0.1000N
standard
acid
to
1,000
mL
with
distilled
or
deionized
water.
Standardize
by
potentiometric
titration
of
15.00
mL
0.05N
Na2CO3
according
to
the
procedure
of

3b;
1
mL
=
1.00
mg
CaCO3.
d.
Bromcresol
green
indicator
solution,
pH
4.5
indicator:
Dissolve
100
mg
bromcresol
green,
sodium
salt,
in
100
mL
distilled
water.
e.
Mixed
bromcresol
green­
methyl
red
indicator
solution:
Use
either
the
aqueous
or
the
alcoholic
solution:
1)
Dissolve
100
mg
bromcresol
green
sodium
salt
and
20
mg
methyl
red
sodium
salt
in
100
mL
distilled
water.
2)
Dissolve
100
mg
bromcresol
green
and
20
mg
methyl
red
in
100
mL
95%
ethyl
alcohol
or
isopropyl
alcohol.
f.
Methyl
orange
solution.
g.
Phenolphthalein
solution,
alcoholic.
h.
Sodium
thiosulfate,
0.1M:
See
Section
LPC#
301.3i.

4.
Procedure
a.
Color
change:
See
Section
LPC#
301.4a.
The
color
response
of
the
mixed
bromcresol
green­
methyl
red
indicator
is
approximately
as
follows:
above
pH
5.2,
greenish
blue;
pH
5.0,
light
blue
with
lavender
gray;
pH
4.8,
light
pink­
gray
with
bluish
cast;
and
pH
4.6,
light
pink.
Check
color
changes
against
reading
of
a
pH
meter
under
the
conditions
of
the
titration.
Because
colors
are
difficult
to
distinguish,
the
method
is
subject
to
relatively
large
operator
error.
b.
Potentiometric
titration
curve:
Follow
the
procedure
for
determining
acidity
(
LPC#
301.4b),
substituting
the
appropriate
normality
of
standard
acid
solution
for
standard
NaOH,
and
continue
titration
to
pH
4.5
or
lower.
Do
not
filter,
dilute,
concentrate,
or
alter
the
sample.
C
x
53.00
B
x
A
=
N
Normality,
c.
Potentiometric
titration
to
pre­
selected
pH:
Determine
the
appropriate
end­
point
pH
according
to

1b.
Prepare
sample
and
titration
assembly
(
LPC#
301.4b).
Titrate
to
the
end­
point
pH
without
recording
intermediate
pH
values
and
without
undue
delay.
As
the
end
point
is
approached
make
smaller
additions
of
acid
and
be
sure
that
pH
equilibrium
is
reached
before
adding
more
titrant.
d.
Potentiometric
titration
of
low
alkalinity:
For
alkalinities
less
than
20
mg/
L
titrate
100
to
200
mL
according
to
the
procedure
of

4c
above,
using
a
10­
mL
microburet
and
0.2N
standard
acid
solution.
Stop
the
titration
at
a
pH
in
the
range
4.3
to
4.7
and
record
volume
and
exact
pH.
Carefully
add
additional
titrant
to
reduce
the
pH
exactly
0.30
pH
unit
and
again
record
volume.

5.
Calculations
a.
Potentiometric
titration
to
end­
point
pH:

where:
A
=
mL
standard
acid
used
and,
N
=
normality
of
standard
acid.

or
where:
t
=
titer
of
standard
acid,
mg
CaCO3/
mL.

Report
pH
end
point
used
as
follows:
"
The
alkalinity
to
pH
=
mg
CaCO3/
L"
and
indicate
clearly
if
this
pH
corresponds
to
an
inflection
point
of
the
titration
curve.
b.
Potentiometric
titration
of
low
alkalinity:
Total
alkalinity,
mg
CaCO3/
L
where:
B
=
mL
titrant
to
first
recorded
pH,
C
=
total
mL
titrant
to
reach
pH
0.3
unit
lower,
and
N
=
normality
of
acid.

c.
Calculation
of
alkalinity
relationships:
The
results
obtained
from
the
phenolphthalein
and
total
alkalinity
determinations
offer
a
means
for
stoichiometric
classification
of
the
three
principle
forms
of
alkalinity
present
in
many
waters.
The
classification
ascribes
the
entire
alkalinity
to
bicarbonate,
carbonate,
and
hydroxide,
and
assumes
the
absence
of
other
(
weak)
inorganic
or
sample
mL
50,000
x
N
x
A
=
/
L
CaCO
mg
,
Alkalinity
3
sample
mL
1,000
x
t
x
A
=
/
L
CaCO
mg
,
Alkalinity
3
sample
mL
50,000
x
N
x
C)
­
B
(
2
=
organic
acids,
such
as
silicic,
phosphoric,
and
boric
acids.
It
further
presupposes
the
incompatibility
of
hydroxide
and
bicarbonate
alkalinities.
Because
the
calculations
are
made
on
a
stoichiometric
basis,
ion
concentrations
in
the
strictest
sense
are
not
represented
in
the
results,
which
may
differ
significantly
from
actual
concentrations
especially
at
pH
>
10.
According
to
this
scheme:
1)
Carbonate
(
CO3
2­)
alkalinity
is
present
when
phenolphthalein
alkalinity
is
not
zero
but
is
less
than
total
alkalinity.
2)
Hydroxide
(
OH­)
alkalinity
is
present
if
phenolphthalein
alkalinity
is
more
than
half
the
total
alkalinity.
3)
Bicarbonate
(
HCO3
­)
ions
are
present
if
phenolphthalein
alkalinity
is
less
than
half
the
total
alkalinity.
These
relationships
may
be
calculated
by
the
following
scheme,
where
P
is
phenolphthalein
alkalinity
and
T
is
total
alkalinity
(

1b):
Select
the
smaller
alkalinity
value
of
P
or
(
T­
P).
Then,
carbonate
alkalinity
equals
twice
the
smaller
value.
When
the
smaller
value
is
P,
the
balance
(
T­
2P)
is
bicarbonate.
When
the
smaller
value
is
(
T­
P),
the
balance
(
2P­
T)
is
hydroxide.
All
results
are
expressed
as
CaCO3.
The
mathematical
conversion
of
the
results
is
shown
in
the
following
table:

Result
of
Titration
Hydroxide
Alkalinity
Carbonate
Alkalinity
Bicarbonate
Concentration
P
=
0
0
0
T
P
<

T
0
2P
T
­
2P
P
=

T
0
2P
0
P
>

T
2P
­
T
2(
T
­
P)
0
P
=
T
T
0
0
Key:
P
­
phenolphthalein
alkalinity;
T
­
total
alkalinity.

Alkalinity
relationships
also
may
be
computed
nomographically
(
see
Carbon
Dioxide,
LPC#
316).
Accurately
measure
pH,
calculate
OH­
concentration
as
milligrams
CaCO3
per
liter,
and
calculate
concentrations
of
CO3
2­
and
HCO3
­
as
mg
CaCO3/
L
from
the
OH­
concentration,
and
the
phenolphthalein
and
total
alkalinities
by
the
following
equations:

Similarly,
if
difficultly
is
experienced
with
the
phenolphthalein
end
point,
or
if
a
check
on
the
phenolphthalein
titration
is
desired,
calculate
phenolphthalein
alkalinity
as
CaCO3
from
the
results
of
the
nomographic
determinations
of
carbonate
and
hydroxide
ion
concentrations:
]
OH
2[
­
2P
=
CO
­
­
2
3
]
OH
[
+
2P
­
T
=
HCO
­
­
3
6.
Precision
and
Bias
No
general
statement
can
be
made
about
precision
because
of
the
great
variation
in
sample
characteristics.
The
precision
of
the
titration
is
likely
to
be
much
greater
than
the
uncertainties
involved
in
sampling
and
sample
handling
before
the
analysis.
In
the
range
of
10
to
500
mg/
L,
when
the
alkalinity
is
due
entirely
to
carbonates
or
bicarbonates,
a
standard
deviation
of
1
mg
CaCO3/
L
can
be
achieved.
Forty
analysts
in
17
laboratories
analyzed
samples
containing
increments
of
bicarbonate
equivalent
to
120
mg
CaCO3/
L.
The
titration
procedure
of

4b
was
used,
with
an
end
point
pH
of
4.5
The
standard
deviation
was
5
mg/
L
and
the
average
bias
(
lower
than
the
true
value)
was
9
mg/
L.
Sodium
carbonate
solutions
equivalent
to
80
and
65
mg
CaCO3/
L
were
analyzed
by
12
laboratories
according
to
the
procedure
of

4c.
The
standard
deviations
were
8
and
5
mg/
L,
respectively,
with
negligible
bias.
Four
laboratories
analyzed
six
samples
having
total
alkalinities
of
about
1000
mg
CaCO3/
L
and
containing
various
ratios
of
carbonate/
bicarbonate
by
the
procedures
of
both

4a
and

4c.
The
pooled
standard
deviation
was
40
mg/
L,
with
negligible
difference
between
the
procedures.
]
OH
[
+
]
CO
1/
2[
=
P
­
­
2
3
APPENDIX
B
University
of
Cincinnati's
Constant
pH
Leaching
Procedure
Project
Specific
 
Untreated
Surrogate
University
of
Cincinnati
ALTER
Facility
Constant
pH
Leaching
Procedure
Project
Specific
 
Untreated
Surrogate
Summary
The
constant
pH
test
is
a
static
leach
test
that
is
conducted
to
assess
the
chemical
integrity
of
a
waste
form
at
the
pH,
temperature,
and
pressure
of
interest.
A
series
of
tests
is
commonly
run
to
provide
data
on
contaminant
concentration
as
a
function
of
pH
(
e.
g.,
six
tests
at
pH
values
of
2,
4,
6,
8,
10,
and
12).
This
information
is
used
to
determine
the
optimum
pH
condition
for
immobilizing
the
contaminant.

For
the
mercury
LDR
project,
two
sets
of
pH
profiles
(
pH
2,
4,
6,
8,
10,
and
12)
will
be
performed
on
untreated
surrogate
made
at
ALTER.
The
tests
will
be
conducted
using
automated
pH
controllers.
The
specified
pH
will
be
held
constant
for
ten
days
±
one
hour.
The
leachant
will
be
continuously
stirred
during
the
contact
period
with
the
waste
form.
Automated
adjustments
will
be
made
with
0.1N
nitric
acid
or
0.1N
sodium
hydroxide
to
maintain
the
specified
pH.
Prior
to
collection
of
the
analytical
sample
at
ten
days,
the
leachate
will
be
filtered.

Materials
Waste
form
Beakers
for
leach
tests
(
teflon,
HDPE,
or
glass;
800
mL)
Magnetic
stir
bars
Stir
plates
Constant
pH
controllers
Parafilm
Reagent
grade
nitric
acid
(
ACS
or
equivalent)
Reagent
grade
sodium
hydroxide
(
ACS
or
equivalent)
Deionized
water
(
ASTM
Type
2)
3­
liter
vessels
for
preparing
leachant
(
HDPE
or
glass)
pH
meter
(
accurate
to
within
±
0.1
pH
units)
Filters
(
borosilicate
glass
fiber;
pore
size
of
0.7
m
m)
Filter
holders
(
teflon,
HDPE,
or
glass;
Nuclepore
Corp.
425910
or
410400,
or
equivalent)
Polyethylene
sample
bottles
Laboratory
balance
(
accurate
to
within
±
0.01
g)
Laboratory
hood
or
oven
Sieves
(
if
needed)

Procedure
Prepare
the
waste
sample:
If
needed,
reduce
the
particle
size
of
the
waste
sample
to
less
than
9.5
mm
in
diameter.
Determine
the
moisture
content
of
the
sample
using
modified
ASTM
D
2216
(
Drying
temperature
is
modified
to
60
°
C).
The
moisture
content
will
be
used
to
calculate
the
weight
of
waste
sample
for
each
pH
test.
25
g
of
waste
sample
on
dry
basis
is
needed
for
each
data
point.

Prepare
the
leachant:
Using
reagent
grade
nitric
acid
and
sodium
hydroxide,
prepare
stock
solutions
of
0.1
N
nitric
acid
and
0.1
N
sodium
hydroxide.
Prepare
2
liters
of
leachant
for
each
pH
test
by
adjusting
the
pH
of
deionized
water
using
the
0.1
N
nitric
acid
or
0.1
N
sodium
hydroxide.
Leachant
pH
values
are
2,
4,
6,
8,
10,
and
12.

Prepare
the
leach­
test
beakers,
filter
holders,
and
filters:
Prepare
a
stock
solution
of
1.0
N
nitric
acid.
Place
the
test
beakers
and
filter
holders
in
a
bath
of
1.0
N
nitric
acid
for
one
hour.
Remove
each
beaker
and
filter
holder
and
rinse
with
1.0
N
nitric
acid
followed
by
three
consecutive
rinses
with
deionized
water
(
minimum
of
500
mL
per
rinse).
Place
the
beakers
and
filter
holders
upside
down
on
a
clean,
absorbent
material
(
e.
g.,
kimwipes)
until
needed.
Rinse
the
borosilicate
glass
fibers
with
1.0
N
nitric
acid
followed
by
three
consecutive
rinses
with
deionized
water
(
minimum
of
500
mL
per
rinse).
Assemble
the
filter
apparatus
using
the
filter
holders
and
glass
filters.

Prepare
leach
tests:
Set
up
11
acid
washed
800
ml
beakers
under
a
hood
and
label
them
as
follows:
pH­
2­
1
-
pH
2
sample
1
pH­
4­
1
-
pH
4
sample
1
pH­
6­
1
-
pH
6
sample
1
pH­
8­
1
-
pH
8
sample
1
pH­
10­
1
-
pH
10
sample
1
pH­
12­
1
-
pH
12
sample
1
Duplicates:
pH­
2­
D
-
pH
2
sample
2
pH­
8­
D
-
pH
8
sample
2
pH­
12­
D
-
pH
12
sample
2
Blanks:
pH­
2­
B
-
pH
2
method
blank
pH­
12­
B
-
pH
12
method
blank
Record
the
information
in
the
log
book.

Weigh
out
25
±
0.01g
of
dry
waste
sample
(
as
calculated
using
the
waste
moisture
content)
for
each
of
the
3
test
beakers
for
each
pH.
Add
500mL
of
the
appropriate
pH
leachant
to
each
of
the
3
test
beakers
for
each
pH
and
the
blank
beaker.
Measure
the
leachant
pH
in
each
beaker
to
the
nearest
0.1
pH
unit
and
record
the
initial
value
in
the
log
book.
Place
a
stir
bar
in
each
beaker,
cover
each
with
parafilm
and
place
the
beakers
on
a
stir
plate.
Connect
constant
pH
controllers
to
each
beaker
and
adjust
for
hourly
pH
correction.
Begin
stirring
all
beakers
simultaneously,
and
maintain
rapid
stirring
throughout
the
experiment.
Monitor
and
maintain
pH
value:
The
pH
shall
be
checked
manually
using
a
pH
meter
on
days
1,
2,
7
and
10.
Record
this
information
in
the
log
book.

Filtration:
At
the
conclusion
of
each
test,
the
sample
will
be
filtered
prior
to
placing
the
leachate
in
the
sample
container.
The
leachate
from
each
500
mL
test
will
be
filtered
through
a
separate
0.7
m
m
glass
filter
and
collected
in
a
polyethylene
bottle.
A
minimum
of
200
mL
of
filtrate
must
be
collected
for
each
sample.
The
filtrate
will
be
acidified
with
nitric
acid
to
a
pH
of
less
than
2
and
stored
at
4o
C
until
analyzed.

Analysis:
The
leachate
will
be
analyzed
for
mercury
content
using
the
cold
vapor
atomic
absorption
method
(
SW­
846
Method
7470
or
Standard
Method
3112B).
The
maximum
allowable
detection
limit
is
0.001
mg/
L.

Quality
Assurance
Requirements:
All
data,
including
log
books
and
analytical
results,
should
be
maintained
and
available
for
reference
and
inspection.
Duplicates
and
blank
sample
will
be
analyzed
for
each
pH
value
tested.
Analytical
work
will
follow
all
quality
control
measures
listed
in
the
method
ant
the
QAPP.
APPENDIX
C
University
of
Cincinnati's
Constant
pH
Leaching
Procedure
Project
Specific
 
Treated
Surrogate
University
of
Cincinnati
ALTER
Facility
Constant
pH
Leaching
Procedure
Project
Specific
 
Treated
Surrogate
Summary
The
constant
pH
test
is
a
static
leach
test
that
is
conducted
to
assess
the
chemical
integrity
of
a
waste
form
at
the
pH,
temperature,
and
pressure
of
interest.
A
series
of
tests
is
commonly
run
to
provide
data
on
contaminant
concentration
as
a
function
of
pH
(
e.
g.,
six
tests
at
pH
values
of
2,
4,
6,
8,
10,
and
12).
This
information
is
used
to
determine
the
optimum
pH
condition
for
immobilizing
the
contaminant.

For
the
mercury
LDR
project,
two
sets
of
pH
profiles
will
be
performed
on
the
two
100
lb
samples
of
treated
surrogate
returned
to
ALTER
from
the
vendors.
Two
pH
profiles
(
pH
2,
4,
6,
8,
10,
and
12)
will
be
generated
from
batch
1
and
one
pH
profile
will
be
generated
from
batch
2.
The
tests
will
be
conducted
using
automated
pH
controllers.
The
specified
pH
will
be
held
constant
for
ten
days
±
one
hour.
The
leachant
will
be
continuously
stirred
during
the
contact
period
with
the
waste
form.
Automated
adjustments
will
be
made
with
0.1N
nitric
acid
or
0.1N
sodium
hydroxide
to
maintain
the
specified
pH.
Prior
to
collection
of
the
analytical
sample
at
ten
days,
the
leachate
will
be
filtered.

Materials
Waste
form
Beakers
for
leach
tests
(
teflon,
HDPE,
or
glass;
800
mL)
Magnetic
stir
bars
Stir
plates
Constant
pH
controllers
Parafilm
Reagent
grade
nitric
acid
(
ACS
or
equivalent)
Reagent
grade
sodium
hydroxide
(
ACS
or
equivalent)
Deionized
water
(
ASTM
Type
2)
3­
liter
vessels
for
preparing
leachant
(
HDPE
or
glass)
pH
meter
(
accurate
to
within
±
0.1
pH
units)
Filters
(
borosilicate
glass
fiber;
pore
size
of
0.7
m
m)
Filter
holders
(
teflon,
HDPE,
or
glass;
Nuclepore
Corp.
425910
or
410400,
or
equivalent)
Polyethylene
sample
bottles
Laboratory
balance
(
accurate
to
within
±
0.01
g)
Laboratory
hood
or
oven
Sieves
(
if
needed)
Procedure
Prepare
the
waste
sample:
If
needed,
reduce
the
particle
size
of
the
waste
sample
to
less
than
9.5
mm
in
diameter.
Determine
the
moisture
content
of
the
sample
using
modified
ASTM
D
2216
(
Drying
temperature
is
modified
to
60
°
C).
The
moisture
content
will
be
used
to
calculate
the
weight
of
waste
sample
for
each
pH
test.
25
g
of
waste
sample
on
dry
basis
is
needed
for
each
data
point.

Prepare
the
leachant:
Using
reagent
grade
nitric
acid
and
sodium
hydroxide,
prepare
stock
solutions
of
0.1
N
nitric
acid
and
0.1
N
sodium
hydroxide.
Prepare
2
liters
of
leachant
for
each
pH
test
by
adjusting
the
pH
of
deionized
water
using
the
0.1
N
nitric
acid
or
0.1
N
sodium
hydroxide.
Leachant
pH
values
are
2,
4,
6,
8
10,
and
12.

Prepare
the
leach­
test
beakers,
filter
holders,
and
filters:
Prepare
a
stock
solution
of
1.0
N
nitric
acid.
Place
the
test
beakers
and
filter
holders
in
a
bath
of
1.0
N
nitric
acid
for
one
hour.
Remove
each
beaker
and
filter
holder
and
rinse
with
1.0
N
nitric
acid
followed
by
three
consecutive
rinses
with
deionized
water
(
minimum
of
500
mL
per
rinse).
Place
the
beakers
and
filter
holders
upside
down
on
a
clean,
absorbent
material
(
e.
g.,
kimwipes)
until
needed.
Rinse
the
borosilicate
glass
fibers
with
1.0
N
nitric
acid
followed
by
three
consecutive
rinses
with
deionized
water
(
minimum
of
500
mL
per
rinse).
Assemble
the
filter
apparatus
using
the
filter
holders
and
glass
filters.

Prepare
leach
tests:
Set
up
20
acid
washed
800
ml
beakers
under
a
hood
and
label
them
as
follows:

pH­
2­
1
-
pH
2
sample
1
Batch
1
pH­
2­
2
-
pH
2
sample
1
Batch
2
pH­
4­
1
-
pH
4
sample
1
Batch
1
pH­
4­
2
-
pH
4
sample
1
Batch
2
pH­
6­
1
-
pH
6
sample
1
Batch
1
pH­
6­
2
-
pH
6
sample
1
Batch
2
pH­
8­
1
-
pH
8
sample
1
Batch
1
pH­
8­
2
-
pH
8
sample
1
Batch
2
pH­
10­
1
-
pH
10
sample
1
Batch
1
pH­
10­
2
-
pH
10
sample
1
Batch
2
pH­
12­
1
-
pH
12
sample
1
Batch
1
pH­
12­
2
-
pH
12
sample
1
Batch
2
Duplicates:
pH­
2­
D1
-
pH
2
sample
2
Batch
1
pH­
2­
D2
-
pH
2
sample
2
Batch
2
pH­
8­
D1
-
pH
8
sample
2
Batch
1
pH­
8­
D2
-
pH
8
sample
2
Batch
2
pH­
12­
D1
-
pH
12
sample
2
Batch
1
pH­
12­
D2
-
pH
12
sample
2
Batch
2
Blanks:
pH­
2­
B
-
pH
2
method
blank
pH­
12­
B
-
pH
12
method
blank
Record
the
information
in
the
log
book.

Weigh
out
25
±
0.01g
of
dry
waste
sample
(
as
calculated
using
the
waste
moisture
content)
for
each
of
the
3
test
beakers
for
each
pH.
Add
500mL
of
the
appropriate
pH
leachant
to
each
of
the
3
test
beakers
for
each
pH
and
the
blank
beaker.
Measure
the
leachant
pH
in
each
beaker
to
the
nearest
0.1
pH
unit
and
record
the
initial
value
in
the
log
book.
Place
a
stir
bar
in
each
beaker,
cover
each
with
parafilm
and
place
the
beakers
on
a
stir
plate.
Connect
constant
pH
controllers
to
each
beaker
and
adjust
for
hourly
pH
correction.
Begin
stirring
all
beakers
simultaneously,
and
maintain
rapid
stirring
throughout
the
experiment.

Monitor
and
maintain
pH
value:
The
pH
shall
be
checked
manually
using
a
pH
meter
on
days
1,
2,
7
and
10.
Record
this
information
in
the
log
book.

Filtration:
At
the
conclusion
of
each
test,
the
sample
will
be
filtered
prior
to
placing
the
leachate
in
the
sample
container.
The
leachate
from
each
500
mL
test
will
be
filtered
through
a
separate
0.7
m
m
glass
filter
and
collected
in
a
polyethylene
bottle.
A
minimum
of
200
mL
of
filtrate
must
be
collected
for
each
sample.
The
filtrate
will
be
acidified
with
nitric
acid
to
a
pH
of
less
than
2
and
stored
at
4o
C
until
analyzed.

Analysis:
The
leachate
will
be
analyzed
for
mercury
content
using
the
cold
vapor
atomic
absorption
method
(
SW­
846
Method
7470
or
Standard
Method
3112B).
The
maximum
allowable
detection
limit
is
0.001
mg/
L.

Quality
Assurance
Requirements:
All
data,
including
log
books
and
analytical
results,
should
be
maintained
and
available
for
reference
and
inspection.
Duplicates
and
blank
sample
will
be
analyzed
for
each
pH
value
tested.
Analytical
work
will
follow
all
quality
control
measures
listed
in
the
method
and
the
QAPP.
APPENDIX
D
Chain
of
Custody
APPENDIX
E
Standard
Operating
Procedures
for
Agvise
Laboratories
METHOD
SUMMARY
FOR
SOIL
ANALYSIS
TESTING
LABORATORY:
AGVISE
LABORATORIES,
INC.
P.
O.
BOX
510;
Highway
15
Northwood,
ND
58267
(
701)­
587­
6010
The
following
is
a
summary
of
analytical
methods
used
by
AGVISE
Laboratories
in
the
determination
of
soil
characteristics
and
nutrient
content.
Analytical
data
of
some
or
all
of
these
analytical
methods
are
presented
based
upon
the
testing
requested
by
the
firm
submitting
the
soil
specimens.

Chemical
Properties
Carbonates
­
Determined
by
gravimetric
loss
of
carbon
dioxide
(
NUT.
02.14).

Cation
Exchange
Capacity
 
Determined
by
summing
the
cations
with
hydrogen
(
NUT.
02.03).
The
cations
of
Magnesium,
Potassium,
Calcium,
and
Sodium
are
determined
by
extraction
with
1.0
N
ammonium
acetate
(
NUT.
02.12).
Hydrogen
is
determined
by
measuring
the
pH
of
the
soil
in
Adams­
Evans
Buffer
Solution
(
NUT.
02.11).

Nitrogen,
%
Total
 
Determined
by
the
Kjeldahl
method
(
NUT.
02.15).

Organic
Carbon
%
­
Determined
by
the
Walkley­
Black
Procedure
(
NUT.
02.20).

Organic
Matter
%
­
Determined
by
the
Walkley­
Black
Procedure
(
NUT.
02.09)
in
soils
with
less
than
10%
organic
matter.
Determined
by
the
loss
of
weight
on
ignition
procedure
(
NUT.
02.04)
in
soils
with
a
10%
or
more
organic
matter.

pH
 
Determined
with
a
pH
electrode
in
a
1:
1
soil:
water
suspension
(
NUT.
02.05)
except
when
specified
by
state
regulations
to
use
a
saturated
paste
(
NUT.
02.39).

Phosphorus
 
Determined
by
the
Olsen
method
(
NUT.
02.07).

Soluble
Salts
 
Determined
using
a
conductivity
meter
in
a
1:
1
soil:
water
suspension
(
NUT.
02.19).

Physical
Properties
%
Gravel
 
Determined
by
dry
sieving
and
weighing
the
fraction
over
2
mm
(
NUT.
02.16).

%
Sand,
Silt,
and
Clay
 
Determined
by
hydrometer
method
(
NUT.
02.06)
or
by
pipette
method
(
NUT.
02.56).
Sand
Particle
Size
 
Determined
by
weighing
fractions
obtained
by
wet
sieving
(
NUT.
02.32).
Bulk
Density
 
Disturbed
bulk
density
is
determined
by
weighing
a
known
volume
of
dried
and
ground
soil
(
NUT.
02.10).
Core
or
non­
disturbed
bulk
density
is
determined
by
weighing
a
known
volume
of
an
intact,
dried
soil
core
(
NUT.
02.02).

Water
Holding
Capacity
and
Water
Relations
Moisture
%
­
Determined
by
gravimetric
loss
upon
drying
(
NUT.
02.36).

Saturated
Hydraulic
Conductivity
 
Determined
by
using
the
constant
head
method
and
measuring
the
rate
of
flow
of
water
through
a
saturated
soil
column
(
NUT.
02.34).

Water
Infiltration
Rate
 
Determined
by
using
the
constant
head
method
and
measuring
the
length
of
time
from
water
application
to
production
of
a
leachate
from
a
soil
column
(
NUT.
02.35).

Water
Holding
Capacity
 
Determined
by
measuring
the
moisture
remaining
when
saturated
soil
is
placed
under
1/
3
or
0.10
bar
pressure
(
NUT.
02.08).

Water
Holding
Capacity
 
Determined
by
measuring
the
moisture
remaining
when
saturated
soil
is
placed
under
15
bar
pressure
(
NUT.
02.13).

All
of
the
above
methods
are
detailed
in
the
current
analytical
SOPs
used
by
AGVISE
Laboratories'
Characterization
testing
laboratory.

NUT.
05.01.
Long
Term
Storage
of
Soil
and
Water
Characterization
Specimens:
According
to
this
Sop,
soil
characterization
samples
will
be
retained
by
AGVISE
Laboratories
for
at
least
two
years
before
disposal
and
water
characterization
samples
will
be
retained
for
a
period
of
60
days
before
disposal.

Adm.
05.01.
Archivist
Duties
and
Archiving
Procedures:
This
SOP
states
that
copies
of
soil
and
water
characterization
reports,
original
COC's
and
original
raw
data
will
be
archived
within
60days
after
the
signature
by
the
analytical
investigator.
Hard
copies
generated
by
computer
will
be
archived
weekly,
and
supplemental
data
will
be
archived
annually.

QAU.
08.01.
Quality
Assurance
Inspections
of
Facilities,
Studies,
and
Processes
for
GLP
Compliance:
Method
inspections
will
be
performed
on
a
regular
basis
at
AGVISE
Laboratories,
Inc.
For
soil
characterization,
two
methods
will
be
inspected
per
month
and
one
water
characterization
inspection
will
be
conducted
per
month.
An
annual
facility
audit
will
be
performed
by
AGVISE
Laboratories,
Inc.
Quality
Assurance
Unit.

All
of
the
above
methods
are
detailed
in
the
current
analytical
SOP's
used
in
AGVISE
Laboratories'
characterization
laboratory.
APPROVED
BY
ANALYTICAL
INVESTIGATOR:
___________________________________________
Robert
L.
Deutsch,
Soil
Scientist
Date
APPENDIX
F
Project
Schedule
Mercury
>
260
ppm
Surrogate
Sludge
Testing
Program
Schedule
Date:
10/
18/
00,
Revision
0,
Page
1
of
2
ID
Task
Name
Duration
Start
Finish
Responsible
1
Start
0
days
Mon
10/
2/
00
Mon
10/
2/
00
2
Kick­
Off
Meeting
2
days
Tue
10/
10/
00
Wed
10/
11/
00
3
QA
Task
55
days
Thu
10/
12/
00
Wed
1/
3/
01
LR
4
Revise
Draft
QA
plan
5
days
Thu
10/
12/
00
Wed
10/
18/
00
LR
5
Review
Draft
QA
plan
5
days
Thu
10/
19/
00
Wed
10/
25/
00
All
6
Phone
Call
Meeting
1
day
Thu
10/
26/
00
Thu
10/
26/
00
LR,
Vega,
MC
7
Revise
Draft
QA
plan
5
days
Fri
10/
27/
00
Thu
11/
2/
00
LR
8
Submit
Draft
plan
to
EPA
0
days
Thu
11/
2/
00
Thu
11/
2/
00
LR
9
EPA
Revise
&
Comment
plan
19
days
Fri
11/
3/
00
Fri
12/
1/
00
EPA,
LR
10
Revise/
Settle
Comments
to
plan
10
days
Mon
12/
4/
00
Fri
12/
15/
00
LR
11
Submit
Plan
for
Final
Approval
to
EPA
0
days
Fri
12/
15/
00
Fri
12/
15/
00
LR
12
Plan
Reviewed/
Approved
by
EPA
10
days
Mon
12/
18/
00
Wed
1/
3/
01
EPA,
LR
13
QA
Plan
Approved
0
days
Wed
1/
3/
01
Wed
1/
3/
01
LR
14
Surrogate
Testing
113
days
Mon
11/
6/
00
Thu
4/
19/
01
LR
15
Purchase
bench
scale
testing
materials
30
days
Mon
11/
6/
00
Tue
12/
19/
00
LR
16
Go/
No­
Go
Surrogate
test
10
days
Thu
1/
4/
01
Thu
1/
18/
01
LR
17
Reformulate
surrogate
(
if
necessary)
10
days
Fri
1/
19/
01
Thu
2/
1/
01
LR
18
Extended
surrogate
testing
50
days
Fri
2/
2/
01
Thu
4/
12/
01
LR
19
Complete
Extended
Surrogate
Testing
0
days
Thu
4/
12/
01
Thu
4/
12/
01
LR
20
Purchase
raw
materials
for
vendor
kits
20
days
Fri
3/
16/
01
Thu
4/
12/
01
LR
21
Make
up
vendor
surrogate
waste
kits
5
days
Fri
4/
13/
01
Thu
4/
19/
01
LR
22
Ship
Surrogate
Waste
Kits
to
Vendors
0
days
Thu
4/
19/
01
Thu
4/
19/
01
LR
23
Procurement
Process
107
days
Thu
10/
12/
00
Mon
3/
19/
01
MM
24
Prepare
CBD
announcement
15
days
Thu
10/
12/
00
Wed
11/
1/
00
MM
25
Review
&
Comment
CBD
announcement
10
days
Thu
11/
2/
00
Wed
11/
15/
00
All
26
Revise
CBD
announcement
5
days
Thu
11/
16/
00
Wed
11/
22/
00
MM
27
Issue
CBD
Announcement
1
day
Mon
11/
27/
00
Mon
11/
27/
00
MM
28
Vendor
responses
to
CBD
30
days
Tue
11/
28/
00
Thu
1/
11/
01
Vendors
29
Prepare
draft
SOW
&
RFP
10
days
Thu
11/
2/
00
Wed
11/
15/
00
MM
30
Review
&
Comment
SOW
&
RFP
15
days
Thu
11/
16/
00
Fri
12/
8/
00
All
31
Revise
SOW
&
RFP
10
days
Mon
12/
11/
00
Tue
12/
26/
00
MM
32
Issue
SOW
&
RFP
to
Vendors
0
days
Wed
1/
3/
01
Wed
1/
3/
01
MM
33
Vendor
Response
22
days
Thu
1/
4/
01
Mon
2/
5/
01
Vendor
34
Review
Proposals
15
days
Tue
2/
6/
01
Mon
2/
26/
01
All
35
Vendor
best
&
final
proposal
5
days
Tue
2/
27/
01
Mon
3/
5/
01
Vendor
36
Contract
awards
to
vendors
10
days
Tue
3/
6/
01
Mon
3/
19/
01
MM
37
Contracts
Awarded
to
Vendors
0
days
Mon
3/
19/
01
Mon
3/
19/
01
MM
10/
2
11/
2
12/
15
1/
3
4/
12
4/
19
1/
3
3/
19
Q1
Q2
Q3
Q4
Q5
2001
Mercury
>
260
ppm
Surrogate
Sludge
Testing
Program
Schedule
Date:
10/
18/
00,
Revision
0,
Page
2
of
2
ID
Task
Name
Duration
Start
Finish
Responsible
38
Vendor
Testing
105
days
Tue
3/
20/
01
Fri
8/
17/
01
MM
39
Prepare
test
plans
20
days
Tue
3/
20/
01
Mon
4/
16/
01
Vendor
40
Review
&
comment
test
plans
5
days
Tue
4/
17/
01
Tue
4/
24/
01
all
41
Test
Plans
Approved
0
days
Tue
4/
24/
01
Tue
4/
24/
01
MM
42
Receive
surrogate
waste
kits
5
days
Wed
4/
25/
01
Tue
5/
1/
01
LR
43
Begin
Vendor
Testing
0
days
Tue
5/
1/
01
Tue
5/
1/
01
Vendor
44
Bench
scale
testing
20
days
Wed
5/
2/
01
Wed
5/
30/
01
Vendor
45
Two­
100
lb
batch
scale
testing
10
days
Thu
5/
31/
01
Wed
6/
13/
01
Vendor
46
Complete
Vendor
Testing
0
days
Wed
6/
13/
01
Wed
6/
13/
01
Vendor
47
Waste
form
(
WF)
analysis
10
days
Thu
6/
14/
01
Wed
6/
27/
01
Outside
lab
48
Package
&
ship
WF
to
U
of
C
5
days
Thu
6/
28/
01
Fri
7/
6/
01
Vendor
49
Prepare
draft
report
30
days
Mon
7/
9/
01
Fri
8/
17/
01
Vendor
50
Vendor
Report
to
DOE
0
days
Fri
8/
17/
01
Fri
8/
17/
01
Vendor
51
Waste
Form
(
WF)
Evaluation
75
days
Fri
7/
6/
01
Mon
10/
22/
01
LR
52
Receive
Waste
Forms
From
Vendors
0
days
Fri
7/
6/
01
Fri
7/
6/
01
LR
53
Sample
preparation
5
days
Mon
7/
9/
01
Fri
7/
13/
01
LR
54
WF
TCLP
testing
3
vendors
15
days
Mon
7/
16/
01
Fri
8/
3/
01
LR
55
WF
pH
testing
for
3
vendors
70
days
Mon
7/
16/
01
Mon
10/
22/
01
LR
56
WF
variable
mass
testing
for
3
vendors
15
days
Mon
7/
16/
01
Fri
8/
3/
01
LR
57
Complete
WF
Testing
0
days
Mon
10/
22/
01
Mon
10/
22/
01
LR
58
Final
Report
40
days
Tue
10/
23/
01
Wed
12/
19/
01
SAIC
59
Prepare
Final
Draft
Report
20
days
Tue
10/
23/
01
Mon
11/
19/
01
SAIC
60
Review
&
Comment
Draft
Report
10
days
Tue
11/
20/
01
Wed
12/
5/
01
All
61
Revise
&
issue
final
report
10
days
Thu
12/
6/
01
Wed
12/
19/
01
62
Issue
Final
Report
0
days
Wed
12/
19/
01
Wed
12/
19/
01
4/
24
5/
1
6/
13
8/
17
7/
6
10/
22
12/
19
Q2
Q3
Q4
Q5
Q6
2001
2002
