United
States
Office
Of
Water
EPA
823­
B­
96­
007
Environmental
Protection
(
4305)
June
1996
Agency
The
Metals
Translator:
Guidance
For
Calculating
A
Total
Recoverable
Permit
Limit
From
A
Dissolved
Criterion
i
FORWARD
This
document
is
the
result
of
a
successful
collaborative
effort
between
the
United
States
Environmental
Protection
Agency
(
USEPA),
Electric
Power
Research
Institute
(
EPRI),
and
Utility
Water
Act
Group
(
UWAG).
Methods
and
procedures
suggested
in
this
guidance
are
for
the
specific
purpose
of
developing
the
metals
translator
in
support
of
the
dissolved
metals
criteria
and
should
not
be
interpreted
to
constitute
a
change
in
EPA
regulatory
policy
as
to
how
metals
should
be
measured
for
such
regulatory
purposes
as
compliance
monitoring.

This
document
provides
guidance
to
EPA,
States,
and
Tribes
on
how
best
to
implement
the
Clean
Water
Act
and
EPA's
regulations
to
use
dissolved
metal
concentrations
for
the
application
of
metals
aquatic
life
criteria
and
to
calculate
a
total
recoverable
permit
limit
from
a
dissolved
criterion.
It
also
provides
guidance
to
the
public
and
to
the
regulated
community
on
appropriate
protocols
that
may
be
used
in
implementing
EPA's
regulations.
The
document
does
not,
however,
substitute
for
EPA's
regulations,
nor
is
it
a
regulation
itself.
Thus,
it
cannot
impose
legally­
binding
requirements
on
EPA,
States,
or
the
regulated
community,
and
may
not
apply
to
a
particular
situation
based
upon
the
circumstances.
EPA
may
change
this
guidance
in
the
future,
as
appropriate.

This
document
will
be
revised
to
reflect
ongoing
peer
reviews
and
technical
advances
and
to
reflect
the
results
of
planned
as
well
as
ongoing
studies
in
this
technically
challenging
area.
Comments
from
users
will
be
welcomed.
Send
comments
to
USEPA,
Office
of
Science
and
Technology,
Standards
and
Applied
Science
Division
(
4305),
401
M
Street
SW,
Washington,
DC
20460.

Tudor
Davies,
Director
Office
of
Science
and
Technology
ii
ABSTRACT
On
October
1,
1993,
in
recognition
that
the
dissolved
fraction
is
a
better
representation
of
the
biologically
active
portion
of
the
metal
than
is
the
total
or
total
recoverable
fraction,
the
Office
of
Water
recommended
that
dissolved
metal
concentrations
be
used
for
the
application
of
metals
aquatic
life
criteria
and
that
State
water
quality
standards
for
the
protection
of
aquatic
life
(
with
the
exception
of
chronic
mercury
criterion)
be
based
on
dissolved
metals.
Consequently,
with
few
exceptions,
each
metal's
total
recoverable­
based
criterion
must
be
multiplied
by
a
conversion
factor
to
obtain
a
dissolved
criterion
that
should
not
be
exceeded
in
the
water
column.
The
Wasteload
Allocations
(
WLA)
or
Total
Maximum
Daily
Loads
(
TMDLs)
must
then
be
translated
into
a
total
recoverable
metals
permit
limit.

By
regulation
(
40
CFR
122.45(
c)),
the
permit
limit,
in
most
instances,
must
be
expressed
as
total
recoverable
metal.
This
regulation
exists
because
chemical
differences
between
the
effluent
discharge
and
the
receiving
water
body
are
expected
to
result
in
changes
in
the
partitioning
between
dissolved
and
adsorbed
forms
of
metal.
As
we
go
from
total
recoverable
to
dissolved
criteria,
an
additional
calculation
called
a
translator
is
required
to
answer
the
question
"
What
fraction
of
metal
in
the
effluent
will
be
dissolved
in
the
receiving
water?"
Translators
are
not
designed
to
consider
bioaccumulation
of
metals.

This
technical
guidance
examines
what
is
needed
in
order
to
develop
a
metals
translator.
The
translator
is
the
fraction
of
total
recoverable
metal
in
the
downstream
water
that
is
dissolved;
that
is,
the
dissolved
metal
concentration
divided
by
the
total
recoverable
metal
concentration.
The
translator
may
take
one
of
three
forms.
(
1)
It
may
be
assumed
to
be
equivalent
to
the
criteria
conversion
factors.
(
2)
It
may
be
developed
directly
as
the
ratio
of
dissolved
to
total
recoverable
metal.
(
3)
Or
it
may
be
developed
through
the
use
of
a
partition
coefficient
that
is
functionally
related
to
the
number
of
metal
binding
sites
on
the
adsorbent
in
the
water
column
(
i.
e.,
concentrations
of
TSS,
TOC,
or
humic
substances).

Appendix
A
illustrates
how
the
translator
is
applied
in
deriving
permit
limits
for
metals
for
single
sites
and
as
part
of
a
TMDL
for
multiple
sources.
Appendix
B
presents
some
indications
of
site
specificity
in
translator
values.
Appendix
C
illustrates
the
process
of
calculating
the
translator.
Appendix
D
provides
some
detail
of
a
statistical
procedure
to
estimate
sample
size.
Appendices
E
and
F
present
information
on
clean
sampling
and
analytical
techniques
which
the
reader
may
elect
to
follow.
This
material
(
E
and
F)
is
presented
only
to
assist
the
reader
by
providing
more
detailed
discussion
rather
than
only
providing
literature
citations;
these
procedures
are
not
prescriptive.
iii
ACKNOWLEDGMENT
Many
people
have
contributed
long
hours
reviewing
and
editing
the
many
drafts
of
this
document.
The
success
of
technical
guidance
documents,
such
as
this
one,
depends
directly
on
the
quality
of
such
reviews
and
the
quality
of
the
reviewers
suggestions.
As
such,
we
thank
the
many
reviewers
for
their
contributions.
We
wish
to
express
our
gratitude
to
the
Coors
Brewing
Company
for
making
available
a
large
and
very
complete
data
set
for
our
use
in
developing
this
technical
guidance
document;
and
to
the
City
of
Palo
Alto,
Dept.
of
Public
Works
for
permitting
us
to
use
the
data
they
are
collecting
as
part
of
a
NPDES
Permit
Application.
The
Cadmus
Group,
Inc.
and
EA
Engineering,
Science
and
Technology,
Inc
also
contributed
to
the
success
of
this
document.

Development
of
this
document
has
been
a
collaborative
effort
between
industry
and
the
USEPA;
it
has
been
authored
by
Russell
S.
Kinerson,
Ph.
D.
(
USEPA),
Jack
S.
Mattice,
Ph.
D.
(
EPRI),
and
James
F.
Stine
(
UWAG).
iv
TABLE
OF
CONTENTS
1.
INTRODUCTION
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1
1.1
Considerations
of
Reasonable
Potential
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2
1.2.
Margin
of
Safety
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2
1.3.
Converting
from
Total
Recoverable
to
Dissolved
Criteria
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2
1.4.
Translating
from
a
Dissolved
Metal
Ambient
Water
Quality
Criterion
to
a
Total
Recoverable
Concentration
in
the
Effluent
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5
1.5.
Developing
Translators
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5
1.5.1.
Direct
Measurement
of
the
Translator
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6
1.5.2.
Calculating
the
Translator
Using
the
Partition
Coefficient
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6
1.5.3.
The
Translator
as
a
Rebuttable
Presumption
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7
1.6.
Applying
Metals
Translators
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7
2.
UNDERSTANDING
THE
METALS
TRANSLATOR
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9
2.1.
Sorption­
Desorption
Theory
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9
2.2.
The
Partition
Coefficient
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9
2.2.1.
Developing
Site
Specific
Partition
Coefficients
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10
3.
FIELD
STUDY
DESIGN
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11
3.1.
Sampling
Schedule
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11
3.1.1.
Considerations
of
Appropriate
Design
Flow
Conditions
for
Metals
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12
3.1.2.
Frequency
and
Duration
of
Sampling
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12
3.2.
Sampling
Locations
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13
3.2.1.
Collect
Samples
at
or
Beyond
the
Edge
of
the
Mixing
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13
3.2.3.
Collect
Samples
from
Effluent
and
Ambient
Water
and
Combine
in
the
Laboratory
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14
3.3.
Number
of
Samples
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15
3.4
Parameters
to
Measure
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16
3.5.
The
Need
for
Caution
in
Sampling
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16
4.
DATA
GENERATION
AND
ANALYSIS
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17
4.1.
Analytical
Data
Verification
and
Validation
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17
4.2.
Evaluation
of
Censored
Data
Sets
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17
4.3
Calculating
the
Translator
Value
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18
5.
SITE­
SPECIFIC
STUDY
PLAN
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20
5.1.
Objective
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20
5.2.
Approach
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20
5.3.
Parameters
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21
5.4.
Sampling
Stations
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21
5.5.
Sampling
Schedule
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22
5.6.
Preparation
.
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23
5.7
Sampling
Procedure
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24
5.8.
Field
Protocol
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25
5.9.
Data
Analysis
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26
v
5.10.
Schedule
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26
5.11.
State
Approval
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26
6.
BUILDING
A
SPREADSHEET
MODEL
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27
7.
REFERENCES
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29
APPENDIX
A
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31
APPENDIX
B
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40
APPENDIX
C
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42
APPENDIX
D
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51
APPENDIX
E
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52
APPENDIX
F
.
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58
vi
Executive
Summary
his
guidance
presents
show
a
functional
relationship
to
environmental
Tprocedures
that
may
be
used
to
properties
such
as
TSS,
pH,
and
salinity,
determine
translator
values
that
samples
should
be
collected
under
an
more
accurately
reflect
site
specific
conditions.
appropriate
range
of
conditions
in
order
to
In
this
Executive
Summary,
steps
to
implement
develop
a
statistically
robust
translator.
If
the
the
dissolved
metals
policy
through
translator
is
not
to
be
functionally
related
to
development
and
use
of
the
translator
are
adsorbent
concentrations,
or
other
presented.
environmental
parameters,
the
study
would
Before
beginning
a
translator
study
one
low
flow
conditions
where
TSS
concentrations
should
make
a
determination
of
reasonable
are
relatively
constant.
Either
the
directly
potential
with
a
translator
of
1
(
all
the
metal
in
determined
translator
(
the
ratio
of
C
/
C
)
or
a
the
effluent
becomes
dissolved
in
the
receiving
translator
calculated
by
using
a
partition
water).
If
the
releases
of
metal
from
a
coefficient
(
K
)
may
be
used.
discharge
do
not
pose
a
reasonable
potential
of
exceeding
water
quality
criteria
levels
with
the
The
most
direct
procedure
for
largest
possible
translator,
then
a
permit
limit
determining
a
site­
specific
metal
translator
is
does
not
have
to
be
written
for
their
release.
simply
to
determine
f
by
measuring
C
and
C
However,
if
a
discharge
has
a
water
quality
and
to
develop
the
dissolved
fraction
as
the
based
permit
limit
for
a
metal,
and
the
State
is
ratio
C
/
C
.
The
translator
is
calculated
as
the
adopting
standards
based
on
dissolved
metals,
geometric
mean
of
the
dissolved
fractions.
then
a
translator
study
is
needed.

In
the
toxicity
tests
to
derive
metal
as
a
function
of
TSS
and
other
factors
such
as
criteria,
some
fraction
of
the
metal
was
pH,
salinity,
etc.
The
partition
coefficient
is
dissolved
and
some
fraction
was
bound
to
the
ratio
of
the
particulate­
sorbed
and
dissolved
particulate
matter.
Assuming
that
the
dissolved
metal
species
multiplied
by
the
adsorbent
fraction
more
closely
approximates
the
concentration.
Use
of
the
partition
coefficient
biologically
available
fraction
than
does
total
may
provide
advantages
over
the
dissolved
recoverable,
conversion
factors
have
been
fraction
when
using
dynamic
simulation
for
calculated.
The
conversion
factors
are
Waste
Load
Allocation
(
WLA)
or
the
Total
predictions
of
how
different
the
criteria
would
Maximum
Daily
Load
(
TMDL)
calculations
be
if
they
had
been
based
on
measurements
of
and
permit
limit
determinations
because
K
the
dissolved
concentrations.
allows
for
greater
mechanistic
representation
of
The
translator
is
the
fraction
of
total
variables
have
on
f
.
recoverable
metal
in
the
downstream
water
that
is
dissolved;
f
=
C
/
C
.
It
may
be
determined
D
D
T
directly
by
measurements
of
dissolved
and
total
recoverable
metal
concentrations
in
water
samples
taken
from
the
well
mixed
effluent
and
receiving
water
(
i.
e.,
at
or
below
the
edge
of
the
mixing
zone).
EPA
encourages
that
site
specific
data
be
generated
to
develop
site
specific
translators.

If
the
translator
is
being
developed
to
normally
be
designed
to
collect
samples
under
D
T
P
D
T
D
D
T
A
partition
coefficient
may
be
derived
P
the
effects
that
changing
environmental
D
1
1.
INTRODUCTION
he
U.
S.
Environmental
dissolved
metal.
EPA
will
also
approve
a
State
TProtection
Agency
(
EPA)
risk
management
decision
to
adopt
standards
issued
a
policy
memorandum
based
on
total
recoverable
metal,
if
those
on
October
1,
1993,
entitled
Office
of
Water
standards
are
otherwise
approvable
as
a
matter
Policy
and
Technical
Guidance
on
of
law.
Interpretation
and
Implementation
of
Aquatic
Life
Metals
Criteria
("
Metals
Policy").
The
The
adoption
of
the
Metals
Policy
did
1
Metals
Policy
states:
not
change
the
Agency's
position
that
the
It
is
now
the
policy
of
the
Office
of
Water
that
under
Section
304(
a)
of
the
Clean
Water
Act
the
use
of
dissolved
metal
to
set
and
measure
continue
to
be
scientifically
defensible.
When
compliance
with
water
quality
standards
is
the
developing
and
adopting
its
own
standards,
a
recommended
approach,
because
dissolved
State,
in
making
its
risk
management
decision,
metal
more
closely
approximates
the
may
wish
to
consider
sediment,
food
chain
bioavailable
fraction
of
metal
in
the
water
effects
and
other
fate­
related
issues
and
decide
column
than
does
total
recoverable
metal.
to
adopt
total
recoverable
or
dissolved
metals
The
primary
mechanism
for
toxicity
to
organisms
that
live
in
the
water
column
is
by
Because
EPA's
Section
304(
a)
criteria
adsorption
to
or
uptake
across
the
gills;
this
are
expressed
as
total
recoverable
metal,
to
physiological
process
requires
metal
to
be
in
a
express
the
criteria
as
dissolved,
application
of
dissolved
form.
This
is
not
to
say
that
a
conversion
factor
is
necessary
to
account
for
particulate
metal
is
nontoxic,
only
that
the
particulate
metal
present
in
the
laboratory
particulate
metal
appears
to
exhibit
toxicity
tests
used
to
develop
the
total
substantially
less
toxicity
than
does
dissolved
recoverable
criteria.
metal.
Dissolved
metal
is
operationally
defined
as
that
which
passes
through
a
0.45
µ
m
or
a
By
regulation
(
40
CFR
122.45(
c)),
the
0.40
µ
m
filter
and
particulate
metal
is
permit
limit,
in
most
instances,
must
be
operationally
defined
as
total
recoverable
metal
expressed
as
total
recoverable
metal.
Because
minus
dissolved
metal.
Even
at
that,
a
part
of
chemical
differences
between
the
discharged
what
is
measured
as
dissolved
is
particulate
effluent
and
the
receiving
water
are
expected
to
metal
that
is
small
enough
to
pass
through
the
result
in
changes
in
the
partitioning
between
filter,
or
that
is
adsorbed
to
or
complexed
with
organic
colloids
and
ligands.
Some
or
all
of
this
may
be
unavailable
biologically.

The
Metals
Policy
further
states:

Until
the
scientific
uncertainties
are
better
resolved,
a
range
of
different
risk
management
decisions
can
be
justified.
EPA
recommends
that
State
water
quality
standards
be
based
on
2
existing
total
recoverable
criteria
published
criteria.

3
The
complete
October
1,
1993
memorandum
1
can
be
obtained
from
EPA's
Office
of
Water
Resource
metals
in
the
effluent,
in
this
case,
would
underestimate
Center
(
202)
260­
7786
or
the
Office
of
Water
Docket.
the
impact
on
the
receiving
water.
See
Section
510,
Federal
Water
Pollution
2
Control
Act,
Public
Law
100­
4,
33
U.
S.
C.
466
et
seq.

For
example,
metals
in
the
effluent
of
an
3
electroplating
facility
that
adds
lime
and
uses
clarifiers
will
be
a
combination
of
solids
not
removed
by
the
clarifiers
and
residual
dissolved
metals.
When
the
effluent
from
the
clarifiers,
usually
with
a
high
pH
level,
mixes
with
receiving
water
with
a
significantly
lower
pH
level,
these
solids
instantly
dissolve.
Measuring
dissolved
2
dissolved
and
adsorbed
forms
of
metal,
an
uncertainties
in
establishing
the
TMDL
and
additional
calculation
using
what
is
called
a
shall
describe
the
manner
in
which
the
MOS
is
translator
is
required.
This
translator
determined
and
incorporated
into
the
TMDL.
calculation
answers
the
question
"
What
fraction
The
MOS
may
be
provided
by
leaving
a
portion
of
metal
in
the
effluent
will
be
dissolved
in
the
of
the
loading
capacity
unallocated
or
by
using
receiving
water
body?"
Translators
are
not
conservative
modeling
assumptions
to
establish
designed
to
consider
bioaccumulation
of
WLAs
and
LAs.
If
a
portion
of
the
loading
metals.
capacity
is
left
unallocated
to
provide
a
MOS,

1.1
Considerations
of
Reasonable
Potential
Water
quality­
based
permit
limitations
percentile
translator
value
to
address
MOS
are
imposed
when
a
discharge
presents
a
needs
and
account
for
variabliity
of
data
and
to
reasonable
potential
to
cause
or
contribute
to
a
use
the
critical
10
and
90
percentiles
for
violation
of
the
applicable
water
quality
other
variables
such
as
hardness
and
TSS
when
standard.
.
If
the
releases
of
metal
from
a
conducting
steady­
state
modeling.
facility
are
sufficiently
low
so
as
to
pose
no
reasonable
potential
of
exceeding
water
quality
criteria
levels,
then
a
permit
limit
does
not
have
to
be
written
for
their
release.
If
a
facility
has
a
water
quality
based
permit
limit
for
a
metal,
and
the
State
is
adopting
standards
based
on
In
the
toxicity
tests
used
to
develop
dissolved
metals,
then
a
translator
is
needed
to
metals
criteria
for
aquatic
life,
some
fraction
of
produce
a
permit
limit
expressed
as
total
the
metal
is
dissolved
and
some
fraction
is
recoverable
metal.
Of
course,
if
the
facility
has
bound
to
particulate
matter.
When
the
toxicity
a
technology
based
permit
limit
for
the
metal
tests
were
originally
conducted,
metal
and
the
limit
is
more
stringent
than
a
limitation
concentrations
were
expressed
as
total.
Some
necessary
to
meet
water
quality
standards,
then
of
the
tests
were
repeated
and
some
test
no
translator
is
required
or
appropriate.
conditions
were
simulated,
for
the
purpose
of
1.2.
Margin
of
Safety
TMDLs
must
ensure
attainment
of
than
does
total
recoverable,
these
conversion
applicable
water
quality
standards,
including
all
factors
have
the
effect
of
reducing
the
water
numeric
and
narrative
criteria.
TMDLs
include
quality
criteria
concentrations.
The
conversion
waste
load
allocations
(
WLAs)
for
point
factors
are
predictions
of
how
different
the
sources
and
load
allocations
(
LAs)
for
nonpoint
criteria
would
be
if
they
had
been
based
on
sources,
including
natural
background,
such
measurements
of
the
dissolved
concentrations
that
the
sum
of
these
allocations
is
not
greater
in
all
of
the
toxicity
tests
that
were
most
than
the
loading
capacity
of
the
water
for
the
important
in
the
derivation
of
the
criteria.
pollutant(
s)
addressed
by
the
TMDL,
minus
the
sum
of
a
specified
margin
of
safety
(
MOS)
and
Consequently
each
metal's
total
any
capacity
reserved
for
future
growth.
The
recoverable
criterion
must
be
multiplied
by
a
MOS
shall
be
sufficient
to
account
for
technical
conversion
factor
to
obtain
a
dissolved
criterion
the
amount
left
unallocated
shall
be
described.
If
conservative
modeling
assumptions
are
relied
on
to
provide
a
MOS,
the
specific
assumptions
providing
the
MOS
shall
be
identified.
For
example,
a
State
may
recommend
using
the
90
th
th
th
1.3.
Converting
from
Total
Recoverable
to
Dissolved
Criteria
determining
the
percent
of
total
recoverable
metal
that
is
dissolved.
Working
from
the
premise
that
the
dissolved
fraction
more
closely
approximates
the
biologically
available
fraction
3
that
should
not
be
exceeded
in
the
water
column.
For
example,
the
silver
acute
For
additional
details
on
aquatic
life
conversion
factor
of
0.85
is
a
weighted
average
criteria
for
metals,
the
reader
is
referred
to
FR
and
is
used
as
a
prediction
of
how
much
the
60(
86):
22229­
22237.
final
acute
value
would
change
if
dissolved
had
been
measured.
At
a
hardness
of
100
mg/
L
as
calcium
carbonate
(
CaCO
)
,
the
acute
total
3
recoverable
criterion
is
4.06
µ
g/
L
while
the
dissolved
silver
criterion
is
3.45
µ
g/
L.

Both
freshwater
(
acute
and
chronic)
and
saltwater
(
acute)
conversion
factors
are
4
presented
(
Tables
1
and
2);
conversion
factors
for
saltwater
chronic
criteria
are
not
currently
available.
Where
possible,
these
conversion
factors
are
given
to
three
decimal
places
as
they
are
intermediate
values
in
the
calculation
of
dissolved
criteria.
Most
freshwater
aquatic
life
criteria
are
hardness­
dependent
as
are
the
5
conversion
factors
for
Cd
and
Pb.
The
values
shown
in
these
tables
are
with
a
hardness
of
100
mg/
L.
Conversion
factors
(
CF)
for
any
hardness
can
be
calculated
using
the
following
equations:

Cadmium
Acute:
CF
=
1.136672
­
[
ln
(
hardness)
(
0.041838)]

Chronic:
CF
=
1.101672
­
[
ln
(
hardness)
(
0.041838)]

Lead
Acute
and
Chronic:
CF
=
1.46203
­
[
ln(
hardness)
(
0.145712)]

Federal
Register
/
Vol.
60,
No.
86
/
22229­
4
22237
/
Thursday,
May
4,
1995
/
Rules
and
Regulations.
Water
Quality
Standards;
Establishment
of
Numeric
Criteria
for
Priority
Toxic
Pollutants;
States'
Compliance­­
Revision
of
Metals
Criteria.

Although
most
of
the
freshwater
aquatic
life
5
criteria
for
metals
are
hardness
dependent,
those
for
trivalent
arsenic,
trivalent
chromium,
mercury,
aluminum,
iron,
and
selenium
are
not.
4
Table
1.
Freshwater
Criteria
Conversion
Factors
for
Dissolved
Metals
Metal
Conversion
Factors
Acute
Chronic
Arsenic
1.000
1.000
Cadmium
0.944
0.909
*

Chromium
(
III)
0.316
0.860
Chromium
(
VI)
0.982
0.962
Copper
0.960
0.960
Lead
0.791
0.791
*

Mercury
0.85
N/
A
Nickel
0.998
0.997
Silver
0.85
N/
A
Zinc
0.978
0.986
Conversion
factors
fro
Cd
and
Pb
are
hardness
dependent.
The
valuse
show
*

are
with
a
hardness
of
100
mg/
L
as
calcium
carbonate
(
CaCO
).
3
Table
2.
Saltwater
Criteria
Conversion
Factors
for
Dissolved
Metals
Metal
Conversion
Factors
(
Acute)

Arsenic
1.000
Cadmium
0.994
Chromium
(
III)
N/
A
Chromium
(
IV)
0.993
Copper
0.83
Lead
0.951
Mercury
0.85
Nickel
0.990
Selenium
0.998
Silver
0.85
Zinc
0.946
The
fractions
of
metals
in
dissolved
and
particulate
phases
are
very
dependent
on
water
5
chemistry.
Because
of
the
(
typically)
great
most
straightforward
approach
is
to
analyze
the
differences
between
chemical
properties
of
mixture
to
determine
the
dissolved
and
total
effluents,
the
chemical
properties
of
receiving
recoverable
metal
fractions.
This
ratio
of
waters,
and
the
chemical
properties
of
the
dissolved
to
total
recoverable
metal
waters
used
in
the
toxicity
tests,
there
is
no
concentrations
can
then
be
used
to
translate
reason
to
expect
that
the
conversion
factors
can
from
a
dissolved
concentration
in
the
water
be
used
to
estimate
either
the
fraction
of
metal
column
downstream
of
the
effluent
discharge
that
would
be
in
the
dissolved
phase
in
the
(
the
criterion
concentration)
to
the
total
receiving
waters
or
the
total
recoverable
metal
recoverable
metal
concentration
in
the
effluent
concentration
in
the
effluent
that
would
result
that
will
not
exceed
that
dissolved
in
a
receiving
water
concentration
not
concentration
in
the
water
column.
exceeding
a
criterion
concentration.
Thus,
a
translator
is
required
to
derive
a
total
Appendix
A
presents
an
example
that
recoverable
permit
limit
from
a
dissolved
summarizes
the
steps
involved
in
applying
the
criterion
.
dissolved
metals
policy,
using
the
translator,
to
6
1.4.
Translating
from
a
Dissolved
Metal
Ambient
Water
Quality
Criterion
to
1.5.
Developing
Translators
a
Total
Recoverable
Concentration
in
the
Effluent
As
the
effluent
mixes
with
the
regarding
development
and
application
of
the
receiving
water,
the
chemical
properties
of
the
metals
translator
to
go
from
a
dissolved
metal
mixture
will
determine
the
fraction
of
the
metal
criterion
to
a
total
recoverable
permit
limit.
that
is
dissolved
and
the
fraction
of
the
metal
This
chapter
identifies
different
approaches
that
that
is
in
particulate
form
(
typically
adsorbed
to
may
be
used
in
developing
site
specific
surfaces
of
other
compounds).
Many
different
translators.
In
the
following
chapters,
we
will
properties
influence
this
dissolved
to
total
focus
on
designing
and
conducting
field
studies,
recoverable
metal
ratio.
Important
factors
analytical
chemistry
procedures,
data
analysis,
include
water
temperature,
pH,
hardness,
and
application
of
the
metals
translator
to
meet
concentrations
of
metal
binding
sites
such
as
mass
balance
requirements.
concentrations
of
total
suspended
solids
(
TSS),
particulate
organic
carbon
(
POC),
and
There
is
always
a
translator
in
going
dissolved
organic
carbon
(
DOC),
as
well
as
from
a
dissolved
criterion
to
a
total
recoverable
concentrations
of
other
metals
and
organic
permit
limit.
The
rebuttable
presumption
is
compounds
that
compete
with
the
metal
ions
that
the
metal
is
dissolved
to
the
same
extent
as
for
the
binding
sites.
It
is
difficult
to
predict
it
was
during
criteria
development.
The
default
the
result
of
such
complex
chemistry.
The
translator
value
should
be
that
the
translator
develop
a
permit
limit.

The
purpose
of
this
technical
guidance
document
is
to
present
additional
details
equals
the
conversion
factor,
this
represents
a
reasonable
worst
case.

EPA
encourages
that
site
specific
data
be
generated
to
develop
site
specific
partition
coefficients
(
translators),
and
use
of
translators
based
on
EPA's
old
data
(
as
published
in
USEPA,
1984
and
presented
in
Table
3
below)
As
a
reasonable
worst
case,
however,
it
may
be
6
assumed
that
metal
in
the
receiving
environment
would
be
biologically
available
to
the
same
extent
as
during
toxicity
testing;
and
the
conversion
factors
may
be
used
as
translators
if
a
site­
specific
translator
is
not
developed.
In
that
case,
the
water
quality
criterion
that
already
has
been
multiplied
by
the
conversion
factor
would
be
divided
by
the
conversion
factor.
6
be
phased
out
unless
other
data
as
suggested
conservative
estimates
of
the
translator.
below,
have
been
generated
that
establish
their
Similar
conclusions
have
been
arrived
at
with
validity
for
the
sites
in
question.
The
guidance
data
from
rivers
and
streams
in
Washington.
released
on
October
1,
1993
identified
three
Therefore,
it
may
be
appropriate
to
develop
a
methods
of
estimating
the
metals
translator.
dissolved
to
total
recoverable
ratio
based
on
a
One
of
these
was
the
use
of
the
relationships
single
sample
to
confirm
that
the
partition
developed
from
the
STORET
data
(
USEPA,
coefficient
produces
an
estimate
of
the
1984).
In
the
years
between
1984
and
1993
translator
that
is
either
reasonably
accurate
or
there
was
general
recognition
that
the
conservative.
relationships
had
some
inaccuracies
due
to
contaminated
metals
data
and
other
factors.
This
guidance
document
presents
However,
limited
comparisons
of
predictions
procedures
that
may
be
used
to
determine
from
these
relationships
with
data
generated
translator
values
that
accurately
reflect
site
and
analyzed
with
good
QA/
QC
indicated
specific
conditions.
generally
good
agreement
and
some
tendency
to
be
conservative.
The
stream
data
for
lead
The
procedures
in
this
document
do
not
were
reanalyzed
and
a
better
relationship
was
cover
all
possible
approaches.
Greater
developed.
The
parameters
for
these
default
precision
can
be
achieved
by
means
of
more
partition
coefficient
estimation
equations
are
elaborate
procedures
which,
at
the
current
time,
presented
in
Table
3
where
K
has
units
of
L/
kg
are
generally
used
only
in
research
situations.
P
with
TSS
expressed
as
mg/
L.
Although,
the
use
of
such
procedures
is
Table
3.
Calculation
of
Default
Partition
document.
Coefficients
[
K
=
K
°
TSS
]
P
PO
Lakes
Streams
Metal
K
K
PO
PO
Cu
2.85E+
06
­
0.9000
1.04E+
06
­
0.7436
Zn
3.34E+
06
­
0.6788
1.25E+
06
­
0.7038
dissolved
water
quality
criterion
to
a
total
Pb
2.0E+
06
­
0.5337
2.80E+
06
­
0.8
Cr(
III
2.17E+
06
­
0.2662
3.36E+
06
­
0.9304
fractions.
The
translator
is
the
fraction
of
total
)

Cd
3.52E+
06
­
0.9246
4.00E+
06
­
1.1307
Ni
2.21E+
06
­
0.7578
4.90E+
05
­
0.5719
Site
specific
conditions
may
render
these
default
partition
coefficients,
overly
or
underly
protective.
Data
presented
in
Appendix
B
illustrate
the
variability
that
exists
between
different
sites
in
some
values
of
the
dissolved
metal
fractions.
Recent
work
by
Sung
(
1995)
demonstrates
that
reliance
on
the
relationships
in
Table
3
does
not
always
provide
for
7
acceptable,
they
will
not
be
discussed
in
this
1.5.1.
Direct
Measurement
of
the
Translator
As
mentioned
in
Section
1.4,
the
most
straightforward
approach
for
translating
from
a
recoverable
effluent
concentration
is
to
analyze
directly
the
dissolved
and
total
recoverable
recoverable
metal
that
is
dissolved
and
may
be
determined
directly
by
measurements
of
dissolved
and
total
recoverable
metal
concentrations
in
water
samples.

1.5.2.
Calculating
the
Translator
Using
the
Partition
Coefficient
Personal
communication
with
Gregory
7
Pelletier,
Department
of
Ecology,
Olympia,
WA
(
206)­
407­
6485.
7
The
partition
coefficient
(
K
)
may
be
options
are
unavailable.
There
are
some
P
derived
as
a
function
of
the
number
of
metal
advantages
to
its
use
including
the
fact
that
it
is
binding
sites
associated
with
the
adsorbent.
already
being
used
by
some
States,
it
is
easy
to
USEPA
(
1984)
and
the
technical
support
explain
and
implement,
and
it
effectively
accompanying
EPA's
Dissolved
Policy
implements
the
statutory
requirement
found
in
Memorandum
expressed
the
translator
§
303(
d)
of
the
Clean
Water
Act
calling
for
a
according
to
Eqn
2.7.
The
role
of
TSS
is
margin
of
safety
(
MOS)
in
developing
TMDLs.
evident
from
this
equation;
as
TSS
increases,
The
disadvantage
is
that,
as
demonstrated
by
the
dissolved
fraction
decreases
because
of
the
the
conversion
factors
used
to
convert
total
increased
number
of
binding
sites.
recoverable
water
quality
criteria
into
the
There
is
a
general
tendency
to
assume
will
remain
totally
in
the
dissolved
form,
even
that
the
partition
coefficient
will
increase
with
in
high
quality
water.
Furthermore,
when
the
increasing
TSS.
It
is
important
to
recognize
assumption
that
all
of
the
metal
is
dissolved
is
that
in
both
the
laboratory
and
in
the
field,
K
applied
in
combination
with
dissolved
criteria
P
has
been
observed
to
be
constant
or
to
decrease
conversion
factors,
the
resulting
permit
limit
is
with
increasing
particulate
concentrations
(
Di
more
restrictive
than
that
which
existed
when
Toro,
1985).
metal
criteria
were
expressed
as
total
The
fraction
of
the
total
metal
in
the
presumption,
conversion
factors
can
be
used
as
downstream
water
that
is
dissolved
(
the
the
translator
where
no
site­
specific
translator
translator)
may
be
determined
indirectly
by
is
developed;
this
is
the
reasonable
worst
case
.
means
of
a
partition
coefficient.
The
partition
coefficient,
in
turn,
may
be
either
a
function
of
varying
adsorbent
concentrations
or
be
related
to
a
constant
adsorbent
concentration
associated
with
critical
flow
conditions.
See
Section
3.1.1
for
considerations
of
factors
affecting
the
If
the
translator
is
to
be
a
function
of
appropriate
design
flow
for
metals.
adsorbent
concentrations
(
e.
g.,
TSS)
it
is
critical
1.5.3.
The
Translator
as
a
Rebuttable
Presumption
In
the
Technical
Support
Document
for
samples
under
low
flow
conditions
where
TSS
Water
Quality­
based
Toxics
Control
(
EPA,
concentrations
are
relatively
constant.
Either
1991a)
commonly
called
the
TSD,
as
well
as
in
the
directly
determined
ratio
(
C
/
C
)
or
a
other
documents,
EPA
has
discussed
the
translator
calculated
using
a
partition
options
one
has
for
translators.
These
options
coefficient
(
K
)
may
be
used.
include
using
a
translator
which
assumes
no
difference
between
dissolved
and
total
In
actuality,
metal
partitioning
in
recoverable
metal
concentrations.
The
TSD
receiving
water
bodies
is
more
complicated
identifies
this
as
the
most
stringent
approach
and
suggests
it
would
be
appropriate
in
waters
with
low
solids
concentrations,
situations
where
the
discharged
form
of
the
metal
was
mostly
in
the
dissolved
phase,
or
where
data
to
use
other
dissolved
form,
it
is
highly
unlikely
that
metals
recoverable.
Therefore,
as
a
rebuttable
8
1.6.
Applying
Metals
Translators
that
samples
be
collected
under
a
broad
range
of
TSS
conditions
to
develop
a
statistically
robust
translator.
If
the
translator
is
not
to
be
functionally
related
to
adsorbent
concentrations
the
study
would
normally
be
designed
to
collect
D
T
P
Using
the
conversion
factors
as
a
translator
will
8
produce
the
same
result
as
assuming
no
difference
between
dissolved
and
total
recoverable
metal
concentrations.
8
than
can
be
explained
by
TSS
alone.
Consequently,
it
is
possible
and
permissible
to
develop
the
translator
on
some
basis
other
than
TSS,
such
as
humic
substances
or
POC.
The
9
materials
presented
in
Appendix
C
guide
the
reader
through
a
possible
evaluation
of
other
factors
that
might
be
warranted
in
some
studies.

Basically,
the
translator
is
applied
by
dividing
a
dissolved
WLA
or
permit
limitation
by
the
translator
to
produce
a
total
recoverable
permit
limitation.
Appendix
A
contains
a
detailed
explanation
of
how
permit
limits
can
be
derived.

If
the
adsorbent
is
POC,
then
K
(
L/
mg)
=
C
9
P
P
(
µ
g/
L
)
/
(
C
(
µ
g/
L)
°
POC
(
mg/
L)
D
9
2.
UNDERSTANDING
THE
METALS
TRANSLATOR
he
translator
is
the
fraction
of
Tthe
total
recoverable
metal
in
The
metal
concentrations
are
typically
the
downstream
water
that
is
expressed
as
mass
per
volume
(
i.
e.,
C
dissolved.
The
reason
for
using
a
metal
(
mass/
vol
water),
C
(
mass/
vol
solids
plus
translator
is
to
allow
calculation
of
a
total
water,
the
bulk
volume)).
recoverable
permit
limit
from
a
dissolved
criterion.
For
a
given
adsorbent
concentration
A
translator
is
used
to
estimate
the
concentration
of
total
recoverable
metal
in
the
C
=
x
°
m
[
Eqn
2.2]
effluent
discharge
that
equates
to
(
or
results
in)
the
criterion
concentration
in
the
receiving
where
x
is
the
metal
concentration
of
the
water
body.
In
this
chapter
we
will
explore
particulate
phase
expressed
on
a
dry
weight
some
of
the
possible
approaches
to
developing
solids
basis
(
e.
g.,
µ
g/
mg)
and
m
is
the
site
specific
metals
translators.
The
purpose
of
adsorbent
concentration
(
mass
of
solids/
vol
of
this
document
is
to
help
implement
EPA's
solids
and
water;
e.
g.,
mg/
L).
With
these
dissolved
metals
policy;
therefore,
every
dimensions,
C
has
units
of
µ
g/
L.
attempt
has
been
made
to
keep
the
following
discussion
as
technically
simple
as
possible.
As
you
read
this
discussion,
keep
in
mind
that
the
metals
partition
between
dissolved
and
adsorbed
forms.
The
partition
coefficient
expresses
this
equilibrium
relationship
and
may
The
distribution
of
metal
at
equilibrium
be
used
to
calculate
the
dissolved
fraction.
The
between
the
particulate
and
dissolved
forms
is
following
discussion
presents
only
the
essential
the
partition
coefficient
K
(
L/
mg).
The
equations
needed
to
develop
the
translator.
For
partition
coefficient
is
the
slope
of
the
data
of
a
comprehensive
discussion
of
partition
particulate
metal
(
µ
g/
mg)
against
dissolved
coefficients,
see
Thomann
and
Mueller
(
1987).
metal
(
µ
g/
L)

2.1.
Sorption­
Desorption
Theory
In
effluents
and
receiving
waters,
provides
other
useful
relationships
between
metals
can
exist
in
either
of
two
basic
phases;
dissolved
and
particulate
metals
concentrations
adsorbed
to
particulates
or
dissolved
in
water.
More
precisely,
these
"
particulates"
are
C
=
C
°
K
°
m
[
Eqn
2.4]
sorbents
including
clays
and
related
minerals,
humic
substances,
organic
and
inorganic
ligands,
and
iron
and
sulfur
compounds.
The
Substituting
Eqn
2.4
into
Eqn.
2.1
gives
total
concentration
of
a
metal
in
the
water
column
can
be
expressed
as
C
=
C
+
C
[
Eqn
2.1]
C
=
(
C
°
K
°
m)
+
C
T
P
D
where
C
=
total
metal,
T
C
=
particulate
sorbed
metal,
and
P
C
=
dissolved
metal.
D
D
P
(
e.
g.,
TSS)
C
can
be
expressed
as
P
P
P
2.2.
The
Partition
Coefficient
and
the
Dissolved
Fraction
P
K
=
x
/
C
[
Eqn.
2.3]
P
D
Combining
Eqn.
2.3
with
Eqn
2.2
P
D
P
C
=
C
+
C
T
P
D
T
D
P
D
10
C
=
C
(
K
°
m
+
1)
[
Eqn
2.5]
dissolved
metal
(
C
).
T
D
P
The
translator,
or
dissolved
metal
fraction,
f
,
K
=
x
/
C
D
is
defined
as
f
=
C
/
C
[
Eqn.
2.6]
let
m
=
TSS,
then
x
=
C
/
TSS.
D
D
T
Substituting
Eqn
2.6
into
Eqn
2.5
and
solving
for
f
gives
D
f
=
(
1
+
K
°
m)
[
Eqn.
2.7]
D
P
­
1
The
distribution
of
metal
between
dissolved
and
adsorbed
phases
therefore
depends
on
the
K
=
C
/
(
C
°
TSS
)
[
Eqn.
2.9]
partition
coefficient
and
the
adsorbent
concentration.
This
is
the
basis
of
the
metals
translator.

2.2.1.
Developing
Site
Specific
Partition
Coefficients
As
we
saw
in
Eqn.
2.3,
the
partition
coefficient
is
not
measured
directly,
rather
it
is
calculated
from
measured
values
(
at
equilibrium)
of
adsorbed
metal
per
unit
adsorbent
(
x)
divided
by
the
concentration
of
10
D
P
D
We
also
saw
in
Eqn.
2.2
that
C
=
x
°
m.
If
we
P
P
Substituting
into
Eqn
2.3
gives
K
=
(
C
/
TSS
)
/
C
[
Eqn.
2.8]
P
P
D
which
rearranges
to
11
P
P
D
TSS
is
used
throughout
this
document
as
the
10
measure
of
metal
binding
sites.
It
is
possible
to
use
other
measures
of
the
binding
sites
such
as
total
organic
carbon
(
TOC),
particulate
organic
carbon
(
POC),
dissolved
modified
by
the
conversion
factor
of
10
kg/
mg:
organic
carbon
(
DOC),
or
some
combination
of
TSS,
TOC,
K
(
L/
kg)
=
C
(
µ
g/
L
)
/
(
C
(
µ
g/
L)
°
TSS
(
mg/
L)
DOC,
etc.
°
10
(
kg/
mg))
If
K
is
desired
with
units
of
L/
kg,
Eqn
2.9
is
11
P
­
6
P
P
D
­
6
11
3.
FIELD
STUDY
DESIGN
onsideration
should
be
given
to
in
the
watershed,
photosynthetic
activity
in
the
Cuse
of
clean
sampling
and
water
body
(
lowest
pH
at
dawn
and
highest
pH
analytical
techniques.
These
in
early
afternoon
coincident
with
peak
are
recommended
but
not
necessarily
required;
photosynthetic
activity
of
phytoplankton
and
however,
it
is
essential
that
appropriate
other
aquatic
vegetation),
or
effluent
discharge
procedures
be
used
to
detect
metals
at
the
to
the
water
body.
Changes
in
pH
over
a
concentrations
present
in
the
effluent
and
specific
range
may
have
a
marked
effect
on
receiving
waters.
Clean
sampling
and
metal
solubility.
Consequently,
it
may
be
analytical
methods
are
useful
ways
of
obtaining
important
to
consider
the
normal
range
of
pH
good
data
when
traditional
methods
may
when
designing
the
study
and
to
collect
provide
data
with
significantly
high
or
low
bias.
samples
under
pH
conditions
that
would
render
Sufficient
quality
control
data
must
accompany
the
metal
or
metals
of
interest
most
soluble,
or
environmental
data
to
allow
its
validation.
over
a
narrow
range
of
pH
conditions
to
reduce
12
A
statistically
valid
field
study
design,
is
of
concern
in
geographic
areas
that
have
little
with
attendant
QA/
QC,
(
e.
g.,
adequate
number
buffering
capacity
and
on
"
acid
sensitive"
of
samples,
field
blanks,
spiked
samples,
etc.)
streams.
is
essential
for
the
successful
development
of
a
metals
translator.
Recognizing
that
a
key
factor
Industrial
and
municipal
waste
waters
in
metals
availability
to
biota
in
the
water
and
receiving
waters
vary
greatly
in
chemical
column
is
the
partitioning
of
metals
between
constituents
and
characteristics.
This
chapter
the
solid
phase
material
and
water,
TSS
(
which
presents
general
guidelines
and
considerations
contains
humic
materials,
clay
minerals,
other
to
assist
in
establishing
effective
sampling
organic
matter
both
living
and
dead)
emerges
programs
for
varied
situations.
as
the
obvious
environmental
variable
of
interest.
However,
the
composition
of
TSS
is
highly
variable
both
in
terms
of
the
constituents
(
e.
g.,
sand,
silt,
clay,
planktonic
organisms,
and
decomposing
organic
materials)
and
their
size
The
sampling
design
should
be
distributions.
Highly
variable
relationships
adequate
to
evaluate
spatial
and/
or
temporal
between
TSS
and
metals
partitioning
must
be
variability
and
to
properly
characterize
the
anticipated
because
of
the
temporal
(
e.
g.,
environmental
condition.
The
choice
of
when
season
of
year,
type
and
magnitude
of
storm)
and
where
to
conduct
the
study,
how
long
to
and
the
spatial
variability
(
e.
g.,
such
as
may
be
study,
and
how
frequently
to
sample
may
be
associated
with
changes
in
hydrology,
influenced
by
the
type
of
translator
being
geochemistry,
or
presence,
number,
and
type
of
developed.
effluent
dischargers)
of
the
receiving
water
bodies.
For
example,
pH
may
vary
over
several
units
as
a
result
of
acidic
precipitation
scatter
in
the
resulting
data
set.
The
pH
effect
3.1.
Sampling
Schedule
For
instance,
the
translator
may
be
developed
specifically
for
use
under
conditions
that
are
most
likely
to
be
representative
of
"
critical
flow"
or
"
design"
conditions.
(
The
critical
flow
may
or
may
not
be
the
same
as
the
7Q10
or
4B3
design
low
flow;
this
is
discussed
in
Section
3.1.1
below.)
To
meet
this
application,
samples
should
be
collected
under
Measurements
made
below
the
quantitation
12
levels
(
QL)
will
suffer
from
significant
analytical
variability,
which
may
directly
affect
the
ratio
(
especially
if
the
ratio
in
near
1.0).
Test
measurements
capable
of
achieving
extremely
low
detection
levels
and
QLs
should
be
sought
to
avoid
the
excessive
analytical
variability.
The
choice
of
laboratories
and
analytical
methods
can
be
critical
to
the
success
of
a
translator
study.
12
conditions
that
approximate
the
critical
flow.
For
instance,
consider
a
facility
that
has
On
the
other
hand,
the
translator
may
fraction
of
the
receiving
water
flow.
It
may
be
be
developed
for
use
over
a
broad
range
of
flow
that
TSS
concentrations
in
the
mixing
zone
and
associated
TSS
concentrations.
If
this
is
show
a
bimodal
distribution
with
stream
flow
desired,
then
the
samples
should
be
collected
to
(
high
under
low
flow
conditions
because
of
the
produce
a
data
set
representative
of
a
broad
effluent
dominance,
low
under
higher
stream
range
of
conditions.
flow
conditions
because
of
greater
dilution,
and
3.1.1.
Considerations
of
Appropriate
Design
Flow
Conditions
for
Metals
In
the
absence
of
data
to
the
contrary,
Additionally,
pH
may
vary
throughout
the
day,
the
normal
assumption
will
be
that
low
flow
may
vary
seasonally,
or
may
be
somehow
(
limited
dilution
capacity)
is
the
critical
flow
correlated
with
flow.
Information
of
this
nature
for
metals.
However,
determining
the
period
should
also
be
used
in
selecting
the
most
13
of
critical
flow
is
more
complicated
for
metals
appropriate
conditions
and
most
appropriate
than
for
many
other
pollutants
because
one
time
to
conduct
the
study.
To
reduce
cannot
necessarily
ascertain
the
appropriate
variability
in
the
data
caused
by
factors
other
design
conditions
without
a
field
study
to
than
adsorbent
concentration,
it
will
be
helpful
generate
data
on
flow,
pH,
and
adsorbent
to
measure
pH
and,
to
the
extent
possible,
concentrations.
If
one
were
to
collect
samples
collect
samples
under
similar
pH
conditions.
of
TSS,
POC,
water
flow,
hardness
pH,
As
suggested
above,
samples
should
be
ambient
metals,
etc.
over
a
prolonged
period
collected
under
pH
conditions
that
would
(
i.
e.,
several
years)
then
one
could
examine
the
render
the
metal(
s)
of
interest
most
soluble.
data
set
to
determine
which
combination
of
conditions
would
result
in
the
highest
dissolved
metal
concentration
for
a
"
unit
load"
of
metal
in
the
effluent
stream.
The
flow
regime
associated
with
this
critical
condition
would
A
field
study
to
develop
a
metals
constitute
the
design
flow.
Because
the
translator
is
expected
to
extend
over
several
dissolved
metals
concentration
in
the
receiving
months.
A
long
sampling
schedule
has
many
water
depends
on
metals
partitioning
to
solids
advantages,
chief
among
them
is
the
ability
to
as
well
as
dilution
of
dissolved
metals
in
the
generate
data
that
are
representative
of
the
water,
and
because
the
lowest
TSS
(
or
other
many
conditions
that
characterize
receiving
adsorbent)
concentrations
do
not
always
water
bodies.
Ideally,
prior
to
collecting
data
correspond
with
low
stream
flow
conditions,
to
develop
a
metals
translator,
the
receiving
there
will
be
some
combination
of
TSS,
flow,
water
body
would
have
been
studied
hardness
and
pH
that
will
result
in
the
greatest
sufficiently
to
characterize
temporally,
if
not
dissolved
concentration.
spatially,
distributions
of
flow,
TSS,
hardness,
high
solids
releases
and
contributes
a
sizeable
high
under
high
flow
conditions
because
of
upstream
nonpoint
source
solids
loadings).
It
is
conceivable
that
the
low
TSS
may
be
more
important
than
low
flow
in
achieving
water
quality
standards
in
this
stream
segment.

3.1.2.
Frequency
and
Duration
of
Sampling
and
pH.
To
the
extent
that
such
data
exist,
the
sampling
can
be
stratified
to
reduce
variability.
If
such
data
are
available
to
characterize
the
system,
statistical
methods
may
be
used
to
determine
the
frequency
of
sampling.
In
the
absence
of
such
data,
EPA
suggests
weekly
or
It
is
important
to
recognize
that
worse­
case
13
acute
dilution
(
highest
concentration
of
effluent)
may
not
occur
during
periods
of
low
flow
and
TSS,
especially
in
estuarine
waters.
Under
such
circumstances,
the
data
to
develop
the
translator
should
be
collected
to
represent
the
critical
conditions.
13
biweekly
sampling
during
specified
receiving
zone,
the
CMC
applies
at
the
end
of
the
pipe.
water
flow
conditions
when
developing
the
The
criteria
chronic
concentration
(
CCC)
translator
for
use
under
"
design
flow"
applies
at
all
points
outside
the
CCC
mixing
conditions
and
biweekly
or
monthly
sampling
zone.
when
developing
the
translator
for
use
over
a
range
of
flow
conditions.
There
are
some
practical
difficulties
In
addition
to
receiving
water
the
receiving
environment.
In
the
absence
of
a
conditions,
it
is
equally
important
to
consider
mixing
zone
study
it
is
very
difficult
to
define
variable
plant
operations
when
determining
with
any
certainty
the
shape
and
extent
of
a
sampling
frequency.
In
addition
to
continuous
mixing
zone,
or
the
dilution
and
dispersion
that
and
uniform
releases,
the
range
of
conditions
occur
within
the
mixing
zone.
Many
states
may
include:
have
separate
boundaries
for
compliance
with
(
1)
Seasonal
operation,
dispersion
processes
are
influenced
not
only
by
(
2)
Less
than
24
hour
per
day
volume,
velocity,
and
other
characteristics
of
operation,
the
discharge,
but
also
by
convection,
currents,
(
3)
Special
times
during
the
day,
week
and
wind
effects
in
the
receiving
water.
As
a
or
month,
or
result,
extensive
sampling
and
computer
(
4)
Any
combination
of
the
above.
modeling
are
typically
required
to
estimate
the
When
monitoring
these
types
of
operations,
it
is
necessary
to
sample
during
The
following
approaches
are
normal
working
shifts
in
the
season
of
acceptable
for
the
purpose
of
developing
the
productive
operations.
translator.
When
deciding
where
to
locate
3.2.
Sampling
Locations
Depending
on
state
guidance
or
constitute
a
basis
for
concern
that
downstream
regulatory
negotiations,
samples
may
be
conditions
may
result
in
nontoxic
metal
collected
from
the
effluent,
the
receiving
water
becoming
toxic.
before
mixing
with
the
effluent,
the
receiving
water
at
the
edge
of
the
mixing
zone,
and/
or
the
receiving
water
in
the
far
field
(
beyond
the
mixing
zone).
Results
obtained
from
these
different
locations
may
differ
substantially.

The
magnitude
of
the
translator
may
collected
at
or
beyond
the
edge
of
the
mixing
depend
on
the
concentration
of
effluent
in
the
zone.
Appropriate
field
sampling
techniques
downstream
water.
The
concentration
of
and
appropriate
QA/
QC
are
discussed
in
effluent
in
the
downstream
water
will
depend
Appendix
E.
It
is
important
to
recognize
that
if
on
where
the
sample
is
taken,
which
will
not
be
samples
are
not
also
collected
from
the
ambient
the
same
for
acute
and
chronic
mixing
zones.
water
(
background),
then
the
subsequent
The
criteria
maximum
concentration
(
CMC)
analysis
(
for
permit
limit
determination)
applies
at
all
points
except
those
inside
a
CMC
implicitly
assumes
that
all
of
the
metal
in
the
mixing
zone;
thus
if
there
is
no
CMC
mixing
receiving
water
comes
from
the
discharger.
involved
in
selecting
the
sampling
location
in
acute
and
chronic
criteria.
Dilution
and
nature
and
extent
of
mixing.

sampling
stations,
consideration
should
be
given
to
sampling
at
the
point
of
complete
mixing
(
rather
than
at
the
edge
of
the
mixing
zone)
if
existing
environmental
factors
3.2.1.
Collect
Samples
at
or
Beyond
the
Edge
of
the
Mixing
Zone
It
is
recommended
that
samples
be
14
The
translator
should
result
in
a
permit
concentrations
and
increased
analytical
limit
that
is
protective
of
the
receiving
water.
difficulties
must
also
be
considered
when
In
order
to
ensure
this,
under
some
conditions,
contemplating
these
studies.
If,
however,
the
it
may
be
important
that
samples
be
collected
samples
are
collected
within
the
same
reach,
from
a
point
where
complete
mixing
has
there
should
not
be
any
appreciable
increase
in
occurred.
It
may
be
advisable
within
a
given
dilution.
river
segment
to
take
the
samples
well
below
the
edge
of
the
mixing
zone
in
order
to
ensure
If
samples
for
translators
are
collected
good
mixing
and
to
reduce
variability
in
the
from
far­
field
locations
a
translator
will
result
data
set.
Environmental
processes
that
might
whose
value
is
established
based
on
the
cause
nontoxic
metal
to
become
toxic
include
characteristics
of
the
receiving
water,
not
on
fate
processes
such
as
oxidation
of
organic
the
characteristics
at
the
edge
of
the
mixing
matter
or
sulfides
or
an
effluent
or
tributary
that
zone
or
on
the
characteristics
of
the
effluent
lowers
the
pH
of
the
downstream
water.
The
before
it
is
fully
mixed.
Recent
investigations
approach
of
collecting
samples
beyond
the
edge
of
discharges
from
a
Waste
Water
Treatment
of
the
mixing
zone
may
be
especially
valuable
Plant
(
WWTP)
to
a
lowflow
stream
in
Florida
in
estuarine
and
coastal
ocean
locations
where
have
demonstrated
an
apparent
increase
in
the
the
ebb
and
flow
of
tidal
cycles
complicate
the
dissolved
fraction
of
silver
at
a
distance
(
travel
hydrodynamics.
In
areas
where
cumulative
time)
of
four
hours
downstream
of
the
14
discharge
effects
can
be
anticipated,
the
discharge.
individual
contributions
and
combined
effects
of
the
multiple
discharges
must
be
considered
in
developing
the
translator,
as
well
as
in
the
TMDL
allocation
and
development
of
the
permit
limit.

3.2.2.
Collect
Samples
from
the
Far
Field
There
are
times
when
concerns
for
far
water
(
i.
e.,
upstream
of
the
outfall
in
rivers
and
field
effects
will
require
evaluation
of
the
ratios
streams;
outside
of
the
influence
of
the
of
dissolved
and
total
recoverable
metals
and
discharge
in
lakes,
reservoirs,
estuaries,
and
metal
partitioning
beyond
the
mixing
zone.
Far
oceans).
Appropriate
QA/
QC
and
field
field
sampling
is
appropriate
in
circumstances
sampling
techniques
are
discussed
in
Appendix
where
changes
in
geology,
land
use/
land
cover,
E.
Mixing
and
filtration
must
be
done
as
soon
or
low
pH
effluent
discharges
from
other
as
possible
to
minimize
risk
of
changes
to
the
facilities
may
alter
the
water
body
chemistry.
dissolved/
total
metals
ratio
due
to
adsorption
Far
field
studies
also
may
be
required
where
onto
the
container
and
partitioning
effects.
The
spatial
changes
in
water
chemistry
and
Agency
is
soliciting
data
that
will
allow
hydrology
affect
sorption­
desorption
rates
and
recommendations
to
be
developed
regarding
settling
rates
respectively
with
the
potential
maximum
delays
in
combining
the
samples
and
adverse
effects
on
the
biological
integrity
of
how
long
the
combined
sample
should
be
benthic
communities.
The
potential
for
allowed
to
equilibrate
before
filtering
an
aliquot
increased
dilution
resulting
in
lower
metal
for
the
dissolved
portion.
15
3.2.3.
Collect
Samples
from
Effluent
and
Ambient
Water
and
Combine
in
the
Laboratory
Samples
are
collected
from
the
effluent
(
i.
e.,
end
of
pipe)
and
the
ambient
receiving
This
document
does
not
discuss
hydrologic
Personal
communication
with
Tim
Fitzpatrick,
14
differences
that
are
specific
to
marine
and
estuarine
Florida
Department
of
Environmental
Protection,
discharges.
Tallahassee,
FL.
15
15
Samples
are
collected
from
the
effluent
a
theoretical
minimum
number
of
samples.
and
the
receiving
water
before
it
mixes
with
the
Beyond
this
consideration,
it
is
necessary
to
be
discharge
and
are
mixed
in
accordance
with
the
cognizant
of
such
factors
as
spatial
and
dilution
factor
to
create
a
simulated
temporal
variability
in
physical
and
chemical
downstream
water
in
proportion
to
the
dilution
conditions
that
may
affect
the
value
of
the
that
the
mixing
zone
is
designed
to
achieve.
translator
and
to
design
the
study
to
The
mixed
waters
are
analyzed
for
dissolved
appropriately
account
for
these
differences.
and
total
recoverable
metal.
The
translator
is
Seasonality
of
receiving
water
flow
and
calculated
from
the
dissolved
fractions.
associated
chemical
properties
need
to
be
For
rivers
and
streams,
the
receiving
appropriate
to
provide
protection
to
the
water
water
samples
would
be
collected
upstream
of
body
during
the
low
flow
or
otherwise
critical
the
discharge.
For
lakes,
reservoirs,
estuaries,
condition
associated
with
a
particular
critical
and
oceans,
the
samples
would
be
collected
at
a
time
of
the
year.
point
beyond
the
influence
of
the
discharge,
yet
representative
of
water
that
will
mix
with
the
In
the
metals
guidance
memorandum
discharge.
In
tidal
situations,
where
the
(
Prothro,
1993),
EPA
recommended
the
effluent
plume
may
move
in
different
development
of
site­
specific
chemical
directions
over
the
tidal
cycle,
some
knowledge
translators
based
on
the
determination
of
of
the
hydrodynamics
of
the
receiving
water
dissolved­
to­
total
ratios:
EPA's
initial
will
be
necessary
to
select
the
appropriate
point
recommendation
was
that
at
least
four
pairs
of
as
well
as
the
appropriate
sampling
time
within
total
recoverable
and
dissolved
ambient
metal
the
tidal
cycle.
In
estuaries
that
are
dominated
measurements
be
made
during
low
flow
by
either
river
flow
or
tidal
flushing,
the
conditions
or
20
pairs
over
all
flow
conditions.
sampling
location
should
reflect
the
dominant
EPA
suggested
that
the
average
of
data
source
of
dilution
water.
collected
during
low
flow
or
the
95th
percentile
In
cases
of
multiple
discharges
to
the
The
low
flow
average
provides
a
representative
same
river
segment,
for
example,
the
translator
picture
of
conditions
during
the
rare
low
flow
should
be
developed
as
f
at
the
downstream
events.
The
95th
percentile
highest
dissolved
D
end
of
the
river
segment
and
applied
to
all
fraction
for
all
flows
provides
a
critical
dischargers
to
that
segment
condition
approach
roughly
analogous
to
the
3.3.
Number
of
Samples
The
collection
of
dissolved
and
total
Most
statistics
textbooks
(
e.
g.,
concentrations
at
low
flows
is
still
the
Snedecor,
1956;
Steel
and
Torrie,
1980;
Zar,
recommended
approach,
but
the
collection
of
at
1984;
Gilbert,
1987))
present
discussions
of
least
10
samples,
rather
than
4,
is
sample
size
(
i.
e.,
number
of
samples).
recommended
to
achieve
higher
confidence
in
Generally,
sample
size
is
affected
by
the
the
data.
The
95
percentile
or
other
extreme
variance
of
the
data,
the
allowable
error
in
the
percentile
of
f
(
e.
g.,
90
percentile)
may
be
estimation
of
the
mean,
and
the
desired
used
as
an
alternative
method
of
including
a
confidence
level.
If
data
have
been
collected
MOS
in
TMLDs
or
WLAs.
Additional
details
previously,
they
can
be
used
to
provide
a
good
of
determining
the
required
sample
size
are
estimate
of
the
expected
variance.
presented
in
Appendix
D.
From
a
statistical
basis
we
can
specify
considered.
The
value
of
the
translator
must
be
highest
dissolved
fraction
for
all
flows
be
used.

approach
used
to
identify
low
flows
and
other
critical
environmental
conditions.

th
D
th
16
3.4
Parameters
to
Measure
Ideally
the
field
study
is
designed
to
and
(
2)
that
new
guidance
is
needed
for
generate
data
on
total
recoverable
(
C
),
sampling
and
analysis
that
will
produce
reliable
T
dissolved
(
C
),
and
particulate
metal
fractions
results
for
trace
metals
determinations.
D
(
C
)
as
well
as
TSS,
POC,
pH,
hardness,
and
P
stream
(
volume)
flow.
A
complete
data
set
EPA
has
released
guidance
for
allows
for
more
complete
understanding
of
the
sampling
in
the
form
of
Method
1669
environmental
fate
and
transport
processes
and
"
Sampling
Ambient
Water
for
Determination
may
result
in
a
more
accurate
permit
limit
of
Trace
Metals
at
EPA
Water
Quality
Criteria
because
of
reduced
variability
and
Levels"
(
USEPA,
1995a).
This
sampling
uncertainties.
method
describes
the
apparatus,
techniques,
and
Depending
on
the
means
by
which
the
quality
control
necessary
to
assure
reliable
translator
is
being
developed,
some
of
these
sampling.
Method
1669
was
developed
based
data
elements
may
not
need
to
be
generated.
on
information
from
the
U.
S.
Geological
For
instance,
it
may
be
desirable
to
estimate
Survey
and
researchers
in
academia,
marine
C
=
C
­
C
rather
than
to
measure
C
.
Of
laboratories,
and
the
commercial
laboratory
P
T
D
P
course,
if
C
is
the
parameter
of
greatest
community.
A
summary
of
salient
points
are
P
interest,
calculating
C
from
the
dissolved
and
presented
in
Appendix
E.
Interested
readers
P
total
recoverable
concentrations
incorporates
may
also
wish
to
refer
to
the
1600
series
of
the
uncertainty
associated
with
the
latter
two
methods,
CFR
40,
Part
136,
July
1,
1995.
measurements.
A
direct
measurement
of
the
particulate
fraction
may
reduce
this
uncertainty.
Note
that
recent
studies
conducted
by
Of
course,
the
measurement
of
the
particulate
the
USGS
(
Horowitz,
1996)
indicate
that
great
fraction
then
increases
the
total
uncertainty
bias
can
be
introduced
into
dissolved
metals
because
of
the
uncertainty
associated
with
its
determinations
by
filtration
artifacts.
The
use
measurement.
It
is
likely
that
if
the
three
of
the
Gelman
#
12175
capsule
filter,
which
has
fractions
(
total,
dissolved,
and
particulate)
are
an
effective
filtration
area
of
600
cm
,
and
the
measured,
the
sum
of
these
three
fractions
will
practice
of
limiting
the
volume
of
sample
not
equal
C
.
It
is
possible
to
develop
the
passed
through
the
filter
to
1000
ml
are
T
translator
from
a
study
that
only
generates
data
necessary
to
ensure
unbiased
collection
of
on
total
recoverable
and
dissolved
dissolved
metals.
Variations
from
these
concentrations
in
the
downstream
water.
recommendations
must
be
demonstrated
to
3.5.
The
Need
for
Caution
in
Sampling
The
sampling
procedures
for
metals
that
have
been
used
routinely
over
the
years
have
recently
come
into
question
in
the
academic
and
regulatory
communities
because
the
concentrations
of
metals
that
have
been
entered
in
some
databases
have
been
shown
to
be
the
result
of
contamination.
At
EPA's
Annapolis
Metals
Conference
in
January
of
1993,
the
consensus
of
opinion
was
(
1)
that
many
of
the
historical
low­
concentration
ambient
metals
data
are
unreliable
because
of
contamination
during
sampling
and/
or
analysis,

2
produce
equivalent
quality
data.
17
4.
DATA
GENERATION
AND
ANALYSIS
etermination
of
metals'
reported
by
laboratories
and
permittees
Dconcentrations
at
ambient
so
that
Agency
reviewers
can
validate
criteria
levels
is
not
presently
the
data.
routine
in
many
commercial
and
industrial
laboratories.
To
familiarize
laboratories
with
The
review
of
data
collected
and
the
equipment
and
techniques
that
will
allow
reported
in
accordance
with
data
determination
of
metals
at
trace
levels,
the
elements
reported.
Agency
has
supplemented
existing
analytical
methods
for
determination
of
metals
at
these
A
Data
Inspection
Checklist
that
can
be
levels,
and
published
this
information
in
the
used
to
standardize
procedures
for
"
Quality
Control
Supplement
for
Determination
documenting
the
findings
of
each
data
of
Trace
Metals
at
EPA
Water
Quality
Criteria
inspection.
Levels
Using
EPA
Metals
Methods"
(
QC
Supplement;
USEPA,
1994a).
The
QC
Supplement
is
based
on
the
procedures
and
techniques
used
by
researchers
in
marine
research
laboratories
who
have
been
at
the
Frequently
data
sets
are
generated
that
forefront
of
trace
metals
determinations.
contain
values
that
are
lower
than
limits
An
overview
of
the
QC
Supplement
is
values
(
i.
e.,
quantitation
levels
[
QL]).
These
presented
in
Appendix
E
for
the
reader's
data
points
are
often
reported
as
nondetected
convenience.
Persons
actually
developing
a
and
are
referred
to
as
censored.
The
level
of
metal
translator
should
read
the
QC
censoring
is
based
on
the
confidence
with
Supplement
which
the
analytical
signal
can
be
discerned
4.1.
Analytical
Data
Verification
and
Validation
In
addition
to
Method
1669
for
Measurements
made
below
the
sampling
(
USEPA,
1995a)
and
analytical
quantitation
levels
will
suffer
from
analytical
methods
for
determination
of
trace
metals
variability,
which
may
directly
effect
the
ratio,
(
USEPA,
1994b),
the
Agency
has
produced
especially
if
C
/
C
is
near
1.0.
Extremely
low
guidance
for
verification
and
validation
of
detection
levels
and
quantitation
levels
should
analytical
data
received
(
USEPA,
1995b).
This
be
sought
to
avoid
excessive
analytical
guidance
was
produced
in
response
to
the
variability.
Agency's
need
to
prevent
unreliable
trace
metals
data
from
entering
Agency
databases
This
guidance
does
not
address
whether
and
other
databases
in
the
environmental
or
not
it
is
appropriate
to
use
test
measurements
community
and
relies
on
established
techniques
below
quantitation
or
detection
levels
in
any
from
the
Agency's
data
gathering
in
its
Water
context
other
than
chemical
translator
studies
and
Superfund
analytical
programs
to
conducted
by
the
discharger.
For
translator
rigorously
assess
and
document
the
quality
of
studies,
measurements
at
or
above
a
detection
analytical
data.
General
issues
covered
in
the
level
that
is
reliably
achievable
by
the
guidance
include:

The
data
elements
that
must
be
4.2.
Evaluation
of
Censored
Data
Sets
deemed
reliable
enough
to
report
as
numerical
from
the
noise.
While
the
concentration
may
be
highly
uncertain
for
substances
below
the
reporting
limit,
it
does
not
necessarily
mean
that
the
concentration
is
zero
(
USEPA,
1992).

D
T
18
Box
1.
The
Translator
is
the
Dissolved
Fraction:
f
=
C
/
C
D
D
T
Step
1
­
For
each
field
sample
determine
f
=
C
/
C
D
D
T
Step
2
­
If
the
translator
is
not
dependent
on
TSS,
determine
the
geometric
mean
GM_
f
=
exp(
ln(
f
)/
n)
D
1
D
n
and
upper
percentile
values
of
the
dissolved
fraction.
If
the
data
are
found
not
to
be
log­
normal,
then
alternative
transformations
should
be
considered
to
normalize
the
data
and
determine
the
transformed
mean
and
percentiles.
Also,
alternative
upper
percentiles
may
be
adopted
as
a
state's
policy
to
address
MOS
(
e.
g.,
90
or
95
th
th
percentiles
may
be
appropriate.)

Step
3
­
If
the
translator
is
found
to
be
dependent
on
TSS,
regression
equations
relating
f
to
TSS
should
D
be
developed.
Appropriate
transformations
should
be
used
to
meet
the
normality
assumptions
for
regression
analysis
(
for
example
log­
transformation
of
f
D
and
TSS
may
be
appropriate).
The
regression
equation
or
an
upper
prediction
interval
may
be
considered
for
estimation
of
f
D
from
TSS
depending
on
the
strategy
for
addressing
MOS.
particular
laboratory
performing
the
analyses
can
be
used.
If
concentrations
are
near
the
detection
level,
some
of
the
samples
may
be
reported
as
below
the
detection
level
(
i.
e.,
nondetects).
If
both
total
recoverable
and
dissolved
concentrations
are
nondetects,
the
data
pair
should
be
discarded.
If
only
the
dissolved
concentration
is
nondetect,
it
could
be
assumed
to
equal
one­
half
the
detection
level.
Some
studies
have
collected
enough
data
so
that
incomplete
records,
including
records
where
dissolved
concentrations
were
nondetects,
were
discarded
prior
to
analysis.
If,
for
example,
the
translator
is
a
function
of
TSS,
the
TSS
concentration
that
accompanies
each
total
recoverable
and
dissolved
data
pair
must
also
be
at
or
above
the
detection
level.
Alternatively,
assuming
that
an
adequate
number
of
samples
have
been
collected,
incomplete
records
may
be
eliminated
from
analysis.

4.3
Calculating
the
Translator
Value
The
most
direct
procedure
for
determining
a
site­
specific
metal
translator
is
simply
to
determine
f
by
measuring
C
and
C
D
T
D
and
to
develop
the
dissolved
fraction
as
the
ratio
C
/
C
.
The
first
step
(
Box
1)
is
to
D
T
calculate
the
dissolved
fraction
in
the
receiving
water.
The
translator
is
calculated
as
the
geometric
mean
of
the
dissolved
fractions.

As
a
general
comment
on
the
proposed
use
of
the
geometric
mean,
the
geometric
mean
is
only
an
appropriate
estimate
of
the
central
tendency
if
the
data
are
log­
normal.
Alternative
measures
of
central
tendency
or
transformations
should
be
considered
if
the
distribution
of
f
is
found
not
to
be
log­
normal.
D
For
example,
the
arcsine
square
root
transformation
is
often
used
to
normalize
populations
of
percentages
or
proportions
19
Box
2.
The
Translator
is
the
Dissolved
Fraction
(
f
)
D
Calculated
via
Site
Specific
Partition
Coefficients
Step
1
­
For
each
field
sample
determine
C
=
C
­
C
,
P
T
D
K
=
C
/(
C
°
TSS)
P
P
D
Step
2
­
Fit
least
squares
regressions
to
data
(
transformed,
stratified
by
pH,
etc.)
as
appropriate
to
solve
for
K
.
P
Step
3
­
Substitute
the
regression
derived
value
of
K
in
Eqn
2.7,
P
f
=
(
1
+
K
°
TSS)
D
P
­
1
Step
4
Determine
f
for
a
TSS
value
D
representative
of
critical
conditions.
(
square
root
of
each
value
is
transformed
to
its
have
on
f
.
arcsine).

A
partition
coefficient
may
be
derived
determine
appropriate
translator
values
are
as
a
function
of
TSS
and
other
factors
such
as
presented
in
Appendix
C.
pH,
salinity,
etc.
(
Box
2).
The
partition
coefficient
is
the
ratio
of
the
particulate­
sorbed
and
dissolved
metal
species
multiplied
by
the
adsorbent
concentration.
The
dissolved
fraction
and
the
partition
coefficient
are
related
as
shown
in
step
3.

The
partition
coefficient
may
provide
advantages
over
the
dissolved
fraction
when
using
dynamic
simulation
for
Waste
Load
Allocation
(
WLA)
or
the
Total
Maximum
Daily
Load
(
TMDL)
calculations
and
permit
limit
determinations
because
K
allows
for
P
greater
mechanistic
representation
of
the
effects
that
changing
environmental
variables
D
Examples
of
these
analyses
to
20
5.
SITE­
SPECIFIC
STUDY
PLAN
hapter
3
discusses
the
to
any
type
of
receiving
water.
Where
Cconsiderations
involved
in
differences
in
the
study
plan
would
occur
for
designing
a
field
study
for
a
different
receiving
waters,
the
considerations
site­
specific
chemical
translator
for
metals.
are
highlighted
with
a
.
Dischargers
on
run­
Chapter
4
and
Appendix
D
discuss
analytical
of­
river
reservoirs,
or
on
lakes
or
reservoirs
chemistry
considerations.
This
Chapter
dominated
by
riverain
discharges
during
runoff
provides
guidance
on
preparing
a
basic
study
events,
should
generally
follow
the
plan
for
implementing
a
translator
study,
with
considerations
listed
for
rivers/
streams.
specific
considerations
for
each
of
four
types
of
receiving
waters:
rivers
or
streams,
lakes
or
reservoirs,
estuaries,
and
oceans.
It
can
be
used
for
all
of
the
options
discussed
in
this
guidance.
This
generic
plan
is
based
on
the
determination
State
the
objective
of
the
project.
For
of
dissolved­
to­
total
ratios
in
a
series
of
10
or
example,
more
samples.
With
this
guidance,
the
discharger
should
be
able
to
prepare
a
study
"
To
determine
the
acute
[
or
plan
that
its
environmental
staff
could
chronic
or
acute
and
chronic]
implement
or
one
that
could
be
used
to
solicit
metals
translator
for
[
list
bids
from
outside
consultants
to
conduct
the
metals]
in
the
discharge
from
studies.
In
most
cases,
the
study
plan
should
be
Outfall
00X."
submitted
to
the
state
for
review
and
approval
before
implementation.

The
format
of
this
chapter
is
to
present
sequentially
the
essential
sections
of
a
study
Describe
briefly
the
approach
adopted
plan:
objective,
approach,
parameters,
in
the
study
plan
to
achieve
the
objective.
For
sampling
stations,
sampling
schedule,
example,
preparation,
sampling
procedure,
field
protocol,
and
data
analysis.
Within
each
section
a
three­
"
Samples
of
effluent
and
tiered
format
is
used
to
provide
instructions
for
upstream
receiving
water
will
the
study
plan
preparer.
The
basic
directions
be
collected
and
mixed
in
for
preparing
the
section
are
presented
left­
proportions
appropriate
to
the
justified
on
the
page.
Under
each
direction
is
a
dilution
at
the
edge
of
the
checklist
of
decisions
or
selections,
designated
[
acute/
chronic]
mixing
zone[
s].
with
the
symbol
,
that
the
preparer
must
make
These
mixed
samples
will
be
to
complete
that
direction.
Under
each
of
these
analyzed
for
total
recoverable
decision
points
is
a
list
of
important
and
dissolved
[
list
metals].
The
considerations,
noted
by
the
symbol
.
translator
will
be
calculated
as
References
to
more
detailed
discussions
are
the
geometric
mean
of
the
provided
where
appropriate.
If
any
state
ratios
of
dissolved
metal
to
guidance
for
translator
studies
exists,
it
would
total
recoverable
metal
for
all
supersede
any
of
the
considerations
discussed
sample
pairs."
below
unless
the
state
and
the
discharger
agree
to
an
alternative
plan.
Equipment
blanks
and
field
blanks
are
Much
of
the
basic
study
plan
is
presented
in
a
generic
context
that
is
applicable
5.1.
Objective
5.2.
Approach
critical
to
document
sample
quality,
21
especially
at
low
concentrations
which
can
be
be
necessary
to
achieve
detection
levels
significantly
biased
by
even
small
amounts
of
low
enough
to
produce
a
valid
contaminants.
Field
duplicate
samples
are
also
translator.
Such
alternatives
include
very
important
to
establish
precision
in
matrix
modifiers,
backgroundsampling
and
final
sample
preparation.
correction
instrumentation,
and
5.3.
Parameters
analyses.
Preliminary
testing
and
Prepare
a
table
listing
parameters,
detection
level
studies
may
be
analytical
methods,
and
required
detection
necessary
to
determine
if
a
problem
levels.
exists.

Select
parameters
 
see
Section
3.4.
As
an
option
for
justifying
the
selected
Select
analytical
methods
and
detection
agency,
prepare
a
narrative
of
the
rationale
for
levels
 
see
Section
4.
the
selections
made.

Detection
level
will
be
the
primary
Identify
the
laboratory
that
will
be
determinant
of
the
analytical
methods
analyzing
the
samples
and
provide
evidence
of
to
be
used.
Metals
potentially
requiring
state
certification,
if
required.
GFAA
and
perhaps
ultralow
analyses
are
those
with
very
low
aquatic
life
Describe
laboratory
protocols
and
QA
criteria
and
concentrations
below
10
requirements.
g/
L.
Prime
candidates
are
cadmium
(
fresh
water),
copper
(
salt
water),
Select
standard
or
clean
(
class­
100)
mercury,
and
silver.
practices
 
see
Section
3.1,
4.3.

Ideally,
the
detection
level
should
be
5­
Select
QA
requirements
10
times
lower
than
the
concentration
of
dissolved
metal.
An
ultralow
Trip
blank
detection
level
should
be
considered
if
Duplicate
analysis
of
all
samples
and
dissolved
concentrations
are
less
than
blanks
1­
2
times
higher
than
the
standard
Laboratory
method
blank
for
each
detection
level.
batch
of
samples
Detection
levels
and
methods
should
be
reviewed
with
the
analytical
laboratory
expected
to
perform
the
analyses
before
finalizing
the
study
plan.
One
or
more
test
samples
may
be
advisable
if
Prepare
a
map
and/
or
a
narrative
detection
levels
or
concentrations
are
description
of
the
sampling
stations.
unknown
in
any
particular
matrix.

Estuary/
Ocean
Chloride
interference
may
affect
detection
levels,
particularly
for
GFAA
methods.
Special
steps
may
extraction
or
preconcentration.
If
uncertain,
check
with
a
local
laboratory
experienced
in
saltwater
matrix
methods
and
detection
levels
to
the
regulatory
MS/
MSD
on
each
batch
of
samples
5.4.
Sampling
Stations
Select
a
sample
location
option
 
see
Sections
3.2,
3.2.1,
3.2.2,
3.2.3.

Conceptually,
collecting
samples
at
the
22
edge
of
the
mixing
zone
is
the
Determine
whether
grab
or
composite
most
direct
way
to
determine
samples
will
be
used
 
see
Appendix
the
translator.
However,
the
E.
edge
of
the
mixing
zone
may
be
difficult
to
define,
especially
Wastewater
treatment
plant
if
stream
flow
and
discharge
effluent
 
24­
hour
composite
rate
(
e.
g.,
number
of
units
Noncontact
cooling
water
 
same
as
operating)
will
be
variable
over
receiving
water
the
course
of
the
study.
Even
if
the
mixing
zone's
dimensions
are
prescribed
exactly,
the
samples
may
have
to
be
collected
at
some
critical
hydrologic
condition
to
represent
the
critical
toxicological
conditions.
An
alternative
option
may
be
to
collect
effluent
and
upstream
receiving
water
samples,
and
mix
them
in
the
appropriate
proportions
before
analysis.
In
addition,
far­
field
sampling
may
be
required
to
establish
that
dissolved
metal
concentrations
do
not
increase
after
the
effluent
is
well­
mixed
with
the
receiving
water.

Definition
of
the
"
upstream"
sampling
point
will
vary
with
the
receiving
water
type:

River/
Stream
Immediately
upstream
of
the
influence
of
the
discharge,
or
any
point
further
upstream
with
no
contributing
source
between
it
and
the
outfall
Lake/
Reservoir
Beyond
the
influence
of
the
discharge
(
dilution
>
100:
1),
generally
in
a
direction
toward
the
headwaters
of
the
lake/
reservoir
if
possible
Estuary/
Ocean
Beyond
the
influence
of
the
discharge
(
dilution
>
100:
1),
generally
in
a
direction
away
from
the
movement
of
the
discharge
plume
at
the
time
of
sampling
River/
Stream
 
Grab,
under
low­
flow
conditions
Lake/
reservoir
 
Grab
Estuary/
Ocean
 
Grab
(
slack
tide)
for
acute;
tidal
composite
for
chronic
5.5.
Sampling
Schedule
Specify
the
number
of
samples,
frequency
of
sampling,
study
period,
and
any
other
conditions
(
e.
g.,
season,
stream
flow)
affecting
the
sampling
schedule.

Select
the
number
of
samples
 
see
Section
3.3.

The
recommended
minimum
number
of
samples
for
a
low­
flow
sampling
program
is
10;
12
would
be
appropriate
if
monthly
sampling
for
a
year
is
desired
to
incorporate
seasonality.
If
sampling
occurs
over
a
wide
range
of
flows
or
the
translator
is
developed
through
regression
analyses,
20
or
more
samples
may
be
appropriate.

Select
the
frequency
of
sampling
 
see
Section
3.1.2.

Weekly
sampling
is
recommended;
monthly
sampling
may
be
appropriate
if
seasonality
is
expected
to
be
an
issue.
River/
Stream
The
interval
between
samples
will
have
to
be
somewhat
flexible
because
samples
should
be
collected
under
low­
flow
conditions;
e.
g.,
if
a
sample
is
to
be
collected
on
Wednesday
and
the
river
flow
is
high
23
on
that
day,
sampling
should
be
collected
during
periods
of
typical
postponed
until
the
first
day
operation,
particularly
with
respect
to
when
flow
returns
to
base­
flow
operations
that
affect
the
TSS
levels,
or
it
will
have
to
be
concentration
or
the
concentration
or
postponed
until
the
next
the
total:
dissolved
ratio
of
the
metal(
s)
planned
weekly
event.
being
studied.
Estuary/
Ocean
Monthly
or
biweekly
sampling
may
be
required
if
state
regulations
reference
critical
monthly
tidal
periods,
such
as
biweekly
neap
tides.

Determine
the
study
period
 
see
conducted
under
base­
flow
conditions,
Section
3.1.
which
could
be
defined
in
terms
of
River/
Stream
Generally,
the
low­
flow
period
of
the
year
(
e.
g.,
July
through
October
in
the
East
and
Midwest)
is
preferred,
unless
the
time
constraints
of
the
permitting
process
or
the
local
hydrologic
regimen
dictate
otherwise.
Lake/
Reservoir
Unless
there
are
seasonal
discharges
or
reservoir
operating
procedures
that
significantly
affect
water
quality,
study
period
generally
is
not
critical
to
study
plan.
Algal
bloom
conditions
should
be
avoided.
Estuary
May
need
to
split
sampling
between
low­
and
high­
salinity
seasons,
because
large
changes
in
salinity
between
seasons
indicates
the
dominance
of
different
water
sources
(
fresh
water
at
low
salinity
and
salt
water
at
high
salinity)
with
potentially
different
particulate
matter
concentrations
or
binding
capacities.
Ocean
Unless
seasonal
currents
significantly
affect
water
quality,
study
period
generally
is
not
critical
to
study
plan.

Determine
other
important
considerations
Plant
operating
conditions
should
be
considered.
Samples
should
be
If
copper
is
being
studied
by
an
electric
utility,
and
the
plant
has
copper
and
non­
copper
condenser
tubes,
sampling
should
occur
when
the
units
with
copper
tubing
are
operating.
River/
stream
Sampling
should
be
measured
stream
flow
(
e.
g.,
less
than
the
25th
percentile
low
flow),
stream
stage
(
e.
g.,
stream
height
less
than
1.5
feet
at
gaging
station
XYZ),
turbidity
(
e.
g.,
less
than
5
NTU),
TSS
concentration
(
e.
g.,
less
than
10
mg/
L),
visual
appearance
(
e.
g.,
no
visible
turbidity),
or
days
since
last
significant
rainfall
(
e.
g.,
more
than
3
days
since
rainfall
of
0.2
inches
or
more).
Lake/
Reservoir
As
long
as
the
sampling
location
is
unaffected
by
runoff,
hydrologic
considerations
are
not
significant.
Estuary/
Ocean
Since
acute
criteria
are
generally
considered
to
have
an
exposure
duration
of
1
hour,
samples
for
acute
translators
should
be
collected
under
worst­
case
tidal
conditions
 
generally
low
slack
when
dilution
is
typically
at
its
lowest.
Chronic
criteria
are
usually
expressed
with
a
4­
day
average
exposure
duration,
so
sampling
over
a
tidal
cycle
is
appropriate
for
chronic
translators.
If
the
discharger
is
willing
to
accept
the
conservatism
of
sampling
for
a
chronic
translator
under
worst­
case
conditions
 
slack
tide
 
then
sampling
costs
could
be
reduced
substantially.

5.6.
Preparation
24
Prepare
a
list
of
equipment
and
supplies
Prepare
a
list
of
contacts
and
phone
that
need
to
be
assembled
before
each
sampling
numbers.
event;
for
example,

Sample
bottles,
labeled,
with
preservative
(
for
total
recoverable)

Samples
bottles,
labeled,
without
correct
procedure
for
collecting
a
sample
at
any
preservative
(
for
dissolved
station.

Sample
bottle
carrier,
e.
g.,
clean
plastic
Start
with
guidance
on
the
careful
cooler
sampling
techniques
necessary
to
avoid
sample
Waterproof
marker
for
filling
in
bottle
labels
1.
Given
the
low
metals
concentrations
Chain­
of­
custody
form
taken
to
ensure
that
samples
are
not
Sampling
gear
 
e.
g.,
sampling
bottle,
Smoking
or
eating
is
not
permitted
sampling
pole
(
plastic
or
aluminum
if
while
on
station,
at
any
time
when
aluminum
is
not
being
studied),
high­
sample
bottles
are
being
handled,
or
speed
peristaltic
pump
and
teflon
during
filtration.
tubing
Field
portable
glove
box
(
for
on­
site
wear
clean
clothing,
i.
e.,
free
of
dirt,
filtering
and
compositing)
grease,
etc.
that
could
contaminate
Plastic
gloves
(
non­
talc)
sampling
apparatus
or
sample
bottles.

Filtering
apparatus,
if
required
for
field
3.
An
equipment
blank
should
be
done
crew
with
the
actual
equipment
used
for
the
Field
notebook
or
log
sheet
blank
described
in
this
section
should
Safety
equipment
equipment
BEFORE
the
environmental
Describe
cleaning
requirements
for
serve
to
verify
equipment
and
sampling
sample
bottles
and
sampling
equipment
that
protocol
cleanliness.
will
come
in
contact
with
samples.

Select
standard
or
clean
apparatus
or
sample
bottles
should
wear
sampling/
analysis.
the
sampling
gloves
provided.
One
Prepare
a
list
of
actions
to
be
bottles,
and
that
person
should
touch
completed
before
the
sampling
event,
such
as
nothing
else
while
collecting
or
contacts
to
be
made
(
discharger,
consultant,
transferring
samples.
laboratory,
regulatory
agency).
5.7
Sampling
Procedure
Prepare
detailed
instructions
on
the
contamination.
For
example,

expected,
extreme
care
needs
to
be
contaminated
during
sample
collection.

2.
Each
person
on
the
field
crew
should
environmental
samples.
The
field
be
performed
with
the
sampling
samples
are
collected.
This
blank
will
4.
Each
person
handling
sampling
person
only
should
handle
sample
Then
provide
step­
by­
step
instructions
25
for
the
sampling
crew
to
follow.
The
specific
Are
hydrologic
conditions
(
e.
g.,
base
steps
will
vary
depending
on
what
type
of
flow,
slack
tide)
acceptable?
water/
wastewater
is
being
sampled
and
what
type
of
sampling
device
is
being
used.
For
grab
Describe
in
clear,
simple
instructions
samples
collected
by
hand
using
a
sampling
the
sequence
of
actions
that
the
field
crew
will
pole
to
which
the
sample
bottles
are
attached,
follow
from
the
beginning
to
end
of
a
sampling
the
guidance
might
continue:
event.
This
sequence
will
vary
from
project
to
5.
Attach
unpreserved
bottle
to
sample
collecting
pole.
Plunge
pole
2
to
3
feet
1.
Before
embarking,
confirm
number
and
under
water
surface
quickly.
Pull
type
(
preserved/
unpreserved)
of
sample
sample
bottle
up
and
fill
preserved
bottles,
and
read
off
checklist
of
bottle
from
unpreserved
sample
bottle,
equipment/
supplies.
leaving
½
to
1
inch
of
air
space
at
the
top.
Swirl
to
mix
acid,
close
cap
2.
Before
beginning
sampling,
fill
in
tightly,
and
return
bottle
to
carrier.
chain­
of­
custody
forms
and
bottle
6.
Collect
duplicate
sample
by
plunging
of
sampling.
unpreserved
sample
bottle
back
under
water,
retrieving,
and
capping
bottle
Each
bottle
should
have
a
unique
tightly
for
dissolved
sample,
again
sample
number,
and
it
should
be
leaving
½
to
1
inch
of
air
space
in
the
labeled
"
Total"
or
"
Dissolved."
If
bottle.
Return
bottle
to
carrier.
preservative
has
been
added
to
the
Other
sampling
procedures
may
be
should
note
that
fact.
chosen
to
produce
acceptable
quality
data,
e.
g.
Chain­
of­
custody
forms
pre­
prepared
a
closed
sampling
system
with
immediate
with
everything
but
the
sampling
date
sample
processing.
Equipment
for
in­
line
and
time
are
recommended.
sample
collection
used
for
filtering
with
the
Provide
sample
chain­
of­
custody
form
(
essentially
mandatory)
Gelman
capsule
filter
and
bottle
label
as
attachments
to
study
can
be
used
for
sample
collection.
See
Method
plan.
1669
§
8.2.8
for
a
description
of
sampling
steps
and
Method
1669
§
8.3
for
on­
site
composting
3.
At
Station
1,
fill
in
sampling
time
on
and
filtration
in
a
glove
box.
See
also
label
of
two
samples
bottles,
one
Appendix
E.
2.
preserved
and
one
unpreserved.

5.8.
Field
Protocol
Provide
a
list
of
criteria
which
the
field
form
 
weather,
hydrologic
conditions,
crew
leader
should
review
before
starting
plant
operating
status
(
if
known),
sampling
to
ensure
that
proper
conditions
exist.
sample
bottle
numbers
and
collection
Is
there
a
discharge?
Are
operating
observations
or
circumstances.
conditions
at
the
facility
appropriate
for
measuring
the
metals
of
concern
in
the
4.
At
Station
2,
fill
in
sampling
time
on
effluent?
labels
of
two
sample
bottles,
one
project.
Typical
steps
might
include:

labels
with
all
information
except
time
bottles
before
sampling,
the
label
Collect
samples
following
the
procedure
outline
above.
Return
bottles
to
carrier
immediately
after
collection.
Fill
in
field
notebook
or
log
time
(
total
and
dissolved),
and
unusual
26
preserved
and
one
unpreserved.
automatic
samplers,
field
filtering,
and
Collect
samples
following
the
overnight
shipping
of
samples.
Because
data
procedure
outline
above.
quality
is
directly
dependent
on
quality
control,
Return
bottles
to
carrier
the
Quality
Control
Supplement(
EPA,
1994a)
immediately
after
collection.
should
be
reviewed.
Fill
in
field
notebook
or
log
form
 
weather,
hydrologic
conditions,
plant
operating
status
(
if
known),
sample
bottle
numbers
and
collection
time
Describe
the
method
for
calculating
the
(
total
and
dissolved),
and
chemical
translator.
unusual
observations
or
circumstances.
Select
a
calculation
procedure
 
see
5.
After
finishing
at
Station
2,
collect
the
Specify
the
treatment
for
values
below
field
blanks
 
one
preserved
and
one
the
detection
level
 
see
Section
4.2.
unpreserved.
Fill
in
sampling
time
on
label,
open
sample
bottle,
and
pour
in
laboratory
water.
Cap
bottles
tightly
and
place
in
carrier.
Note
bottle
numbers
and
collection
time
in
field
Provide
a
schedule
for
the
entire
study,
notebook
or
log
sheet.
from
selection
of
consultant
or
mobilization
of
If
additional
sampling
gear
is
used
in
report.
collecting
the
samples,
the
field
blanks
should
be
collected
by
rinsing
that
gear
Link
schedule
to
receipt
of
approval
three
times
with
the
laboratory
water,
from
state,
if
required
and
then
filling
the
gear
with
enough
Emphasize
impact
of
delays
on
study
if
water
to
transfer
to
the
2
field
blank
sampling
must
occur
within
a
certain
bottles.
If
a
pump
or
an
automatic
calendar
timeframe
sampler
is
used,
several
sample
bottle
Incorporate
contingencies
for
sampling
volumes
of
laboratory
water
should
be
events
postponed
because
of
pumped
through
the
sampler
tubing
unacceptable
conditions
before
the
field
blank
bottles
are
filled.

6.
Complete
chain­
of­
custody.
Check
bottle
carrier
to
ensure
bottles
are
upright
and
well
packed.
Provide
a
signoff
line
for
state
7.
Deliver
samples
to
laboratory.
Have
not
mandatory.
sample
custodian
sign
chain­
of­
custody
for
receipt
of
samples,
and
obtain
a
copy
of
the
chain­
of­
custody.

Depending
on
the
project,
additional
instructions
may
be
needed
for
setting
up
5.9.
Data
Analysis
Sections
1.5.

5.10.
Schedule
field
effort
through
completion
of
final
study
5.11.
State
Approval
regulatory
agency.
This
is
recommended,
but
27
6.
BUILDING
A
SPREADSHEET
MODEL
s
discussed
in
earlier
chapters,
For
example,
with
Eqn
6.1,
the
Aa
series
of
steps
must
be
taken
downstream
TSS
concentration
is
estimated
to
implement
the
dissolved
from
mass
balance
calculations
of
upstream
metals
policy,
including
converting
the
water
and
effluent
loadings:
quality
criteria
from
the
total
recoverable
to
the
dissolved
form,
translation
from
the
dissolved
CCC
or
CMC
to
the
total
recoverable
metal
concentration
in
the
discharger's
waste
stream,
calculating
the
WLA
or
TMDL,
and
developing
the
permit
limit.
These
steps
or
calculations
are
easily
handled
using
a
simple
spreadsheet
model.
Use
of
these
equations,
whether
in
a
spreadsheet
or
not,
can
avoid
many
common
mistakes.

The
following
equations
may
be
used
to
translate
dissolved
criteria
to
total
recoverable
permit
limits
with
translators
developed
through
studies
such
as
those
described
in
Chapter
5.
This
model
may
be
used
as
a
static
model
with
design
flow
conditions,
it
may
be
used
in
a
continuous
mode
(
i.
e..,
using
daily
flow
and
other
data),
or
it
may
be
used
(
with
programs
such
as
@
RISK
or
Crystal
Ball
)
to
perform
Monte
Carlo
analyses.
These
calculations
do
not
provide
concentration
estimates
between
the
point
of
discharge
and
the
point
of
complete
mixing.

The
in­
stream
total
recoverable
concentration
is
estimated
by
solving
the
following
equation:

C
=
(
Q
C
+
Q
C
)
/
(
Q
+
Q
)
t
u
u
e
e
u
e
[
Eqn
6.1]

where
C
=
pollutant
concentration
at
the
t
edge
of
the
mixing
zone,
Q
=
upstream
flow,
u
C
=
upstream
pollutant
u
concentration
(
background),
Q
=
effluent
flow,
e
C
=
effluent
pollutant
e
concentration,
and
=
fraction
of
flow
available
for
mixing.

TSS
=
(
Q
TSS
+
Q
TSS
)
/
(
Q
+
Q
)
u
u
e
e
u
e
[
Eqn
6.2]

For
translators
developed
from
partitioning
equations
,
(
Eqn
2.7),
the
16
dissolved
in­
stream
concentration
can
be
expressed
as:

C
=
C
/
(
1+
K
TSS)
[
Eqn
6.3]
d
t
p
By
setting
the
dissolved
in­
stream
concentration
(
C
)
equal
to
the
dissolved
d
criterion
concentration
(
C
=
CC
)
and
d
d
rearranging
the
equation,
we
can
solve
for
the
in­
stream
total
recoverable
concentration
(
C
')
t
that
equates
to
a
dissolved
in­
stream
concentration
equal
to
the
dissolved
criterion.
Note
that
this
corresponds
to
Eqn
2.5.

C
'
=
CC
(
1+
K
TSS)
[
Eqn
6.4]
t
d
p
The
total
recoverable
concentration
in
the
effluent
(
C
')
that
equates
to
a
dissolved
in­
e
stream
concentration
which
equals
the
dissolved
criterion
in
the
mixed
receiving
waters
is
calculated
by
Eqn
6.5.
This
represents
the
maximum
release
that
will
still
allow
attainment
of
water
quality
standards,

If
the
translator
has
been
determined
directly
16
from
measurements
of
dissolved
and
total
recoverable
metal
in
the
downstream
water,
Eqns
6.3
and
6.4
are
not
be
used.
Instead,
the
dissolved
criterion
concentration
is
divided
by
f
to
calculate
C
'
which
in
turn
is
used
in
Eqn
D
t
6.5.
If
the
partition
coefficient
has
units
of
L/
kg,
then
both
Eqns
6.3
and
6.4
contain
the
term
1E­
6.
28
that
is
the
maximum
WLA
or
the
maximum
Streamix,
an
EPA
developed
TMDL.
spreadsheet
application
for
mixing
zone
C
'
=
(
C
'
(
Q
+
Q
)
­
Q
C
)
/
Q
e
t
u
e
u
u
e
[
Eqn
6.5]

Table
4
presents
a
simple
spreadsheet
that
utilizes
these
relationships.
Note
that
the
second
equation
in
the
spreadsheet
calculates
K
and
the
third
equation
calculates
the
P
associated
f
.
In
studies
where
the
translator
is
D
developed
directly
as
f
,
the
K
equation
in
the
D
P
spreadsheet
is
deleted
and
f
is
changed
from
D
an
equation
to
an
input
parameter.
analyses,
has
been
enhanced
to
consider
metal
partitioning
between
dissolved
and
particulatesorbed
forms.
This
version,
developed
for
EXCEL,
is
called
METALMIX
and
provides
details
of
mixing
between
the
point
of
discharge
and
the
point
of
complete
mix.

Beyond
these
approaches,
EPA's
DYNTOX
model
(
USEPA,
1995c)
has
been
modified
to
properly
account
for
the
distribution
of
metals
between
dissolved
and
particulate­
sorbed
forms.
DYNTOX
supports
Continuous
Simulation,
Monte
Carlo,
and
Lognormal
Probabilistic
Analyses
Table
4.
Spreadsheet
to
Calculate
Total
Recoverable
Waste
Load
Allocation
based
on
Dissolved
Criterion
Variables:
Input
Values:
Q_
u
104
TSS_
u
325
C_
u
19
Q_
e
8.75
TSS_
e
1845
Hardness_
u
100
Hardness_
e
50
mixing
fraction
(
theta)
0.25
Equations:
CC_
d
=
EXP(
a*
LN(
Hardness_
mix)+
b)*
conv_
fact
<
dissolved
criterion
concentration>
Kp
=
2.8*
TSS_
mix^­
0.8
<
example
only>
fD
=
1/(
1
+
Kp*
TSS_
mix)
Hardness_
mix
=(
theta
*
Q_
u
*
Hardness_
u
+
Q_
e
*
Hardness_
e)
/
(
theta
*
Q_
u
+
Q_
e)
TSS_
mix
=(
theta
*
Q_
u
*
TSS_
u
+
Q_
e
*
TSS_
e)
/
(
theta
*
Q_
u
+
Q_
e)
C_
t_
prime
=
CC_
d*(
1
/
fD)
<
instream
total
recov
conc
that
equates
to
dissolved
criterion>
C_
e_
prime
=(
C_
t_
prime
*
(
theta
*
Q_
u
+
Q_
e)
­
theta
*
Q_
u
*
C_
u)/
Q_
e
<
effluent
total
recov
conc
resulting
in
the
dissolved
criterion
in
receiving
water>
29
7.
REFERENCES
Benedetti,
M.
F.,
Milne,
C.
J.,
Kinniburgh,
D.
G.,
Van
Riemskijk,
W.
H.,
and
Koopal,
L.
K.
1995.
U.
S.
Environmental
Protection
Agency
Metal
Ion
Binding
to
Humic
Substances:
(
USEPA).
1983.
Methods
for
Chemical
Application
of
the
Non­
Ideal
Competitive
Analysis
of
Water
and
Wastes.
EPA
600­
4­
79­
Adsorption
Model.
Environ.
Sci.
Technol.
020.
29,446­
457.

Di
Toro,
D.
M.
1985.
A
Particle
Interaction
(
USEPA).
1984.
Technical
Guidance
Manual
Model
of
Reversible
Organic
Chemical
for
Performing
Waste
Load
Allocations
­
Book
Sorption.
Chemosphere
14(
10):
1503­
1538.
II
Streams
and
Rivers
­
Chapter
3
Toxic
Gilbert,
R.
O.
1987.
Statistical
Methods
for
Environmental
Pollution
Monitoring.
Van
U.
S.
Environmental
Protection
Agency
Nostrand
Reinhold,
NY.
(
USEPA).
1991a.
Technical
Support
Horowitz,
A.
J.,
Lum,
K.
R.,
Lemieux,
C.,
Control.
EPA
505­
2­
90­
001.
Garbarino,
J.
R.,
Hall,
G.
E.
M.,
Demas,
C.
R.
1996.
Problems
Associated
with
Using
U.
S.
Environmental
Protection
Agency
Filtration
to
Define
Dissolved
Trace
Element
(
USEPA).
1991b.
Methods
for
the
Concentrations
in
Natural
Water
Samples.
Determination
of
Metals
in
Environmental
Environmental
Science
&
Technology,
Vol
30,
Samples.
EPA
600­
4­
91­
010.
No
3.

Shi,
B.,
Grassi,
M.
T.,
Allen,
H.
E.,
Fikslin,
T.
J.,
(
USEPA).
1992.
Guidelines
for
Exposure
and
Kinerson,
R.
S.
1996.
Development
of
a
Assessment;
Notice.
Federal
Register
Chemical
Translator
for
Heavy
Metals
in
57(
104):
22888­
22938.
Receiving
Water.
Paper
Presented
at
Water
Environment
Federation
69th
Annual
U.
S.
Environmental
Protection
Agency
Conference
&
Exposition,
Dallas,
TX
(
USEPA).
1994a.
Quality
Control
Supplement
Snedecor,
G.
W.
1956.
Statistical
Methods.
Water
Quality
Criteria
Levels
Using
EPA
The
Iowa
State
University
Press,
Ames,
Iowa,
Metals
Methods.
Engineering
and
Analysis
534pp.
Division
(
4303),
USEPA,
Washington,
DC
Steel,
R.
G.
D.
and
Torrie,
J.
H.
1980.
Principles
and
Procedures
of
Statistics,
A
U.
S.
Environmental
Protection
Agency
Biometrical
Approach.
Second
Edition.
(
USEPA).
1994b.
Methods
for
the
McGraw­
Hill.
Determination
of
Metals
in
Environmental
Sung,
W.
1995.
Some
observations
on
surface
partitioning
of
Cd,
Cu,
and
Zn
in
estuaries.
U.
S.
Environmental
Protection
Agency
Environ.
Sci.
Technol.
29:
1303­
1312.
(
USEPA).
1995a.
Method
1669,
Sampling
Thomann,
R.
V.
and
Mueller,
J.
A.
(
1987)
Metals
at
EPA
Water
Quality
Criteria
Levels.
Principles
of
Surface
Water
Quality
Modeling
and
Control.
HarperCollins
Publishers
Inc,
New
York,
NY,
644pp.

U.
S.
Environmental
Protection
Agency
Substances.
EPA
440­
4­
84­
022.

Document
for
Water
Quality­
based
Toxics
U.
S.
Environmental
Protection
Agency
for
Determination
of
Trace
Metals
at
EPA
20460,
December
1994.

Samples.
EPA
600­
R­
94­
111.

Ambient
Water
for
Determination
of
Trace
30
EPA
821­
R­
95034.

U.
S.
Environmental
Protection
Agency
(
USEPA).
1995b.
Guidance
on
the
Documentation
and
Evaluation
of
Trace
Metals
Data
Collected
for
Clean
Water
Act
Compliance
Monitoring.
Engineering
and
Analysis
Division
(
4303),
Washington,
DC
20460,
December
1994.

U.
S.
Environmental
Protection
Agency
(
USEPA).
1995c.
Dynamic
Toxics
Wasteload
Allocation
Model
(
DYNTOX).
EPA
823­
C­
95­
005.

Zar,
J.
H.
1984.
Biostatistical
Analysis.
Second
Edition.
Prentice
Hall,,
NJ.
WQC
Metal
exp
a
ln(
H)
b
31
(
1)
APPENDIX
A
Deriving
Permit
Limits
for
Metals
his
Appendix
summarizes
the
Tsteps
involved
in
applying
the
dissolved
metals
policy
and
illustrates
how
the
translator
is
used
in
developing
a
permit
limit.
Water
quality
standards
consist
of
degradation
statement.
The
river,
in
this
A.
1
The
Setting
for
the
Example
Our
example
site
is
a
river
which
has
recreation
(
i.
e.,
"
fishable,
swimmable"),
and
been
identified
as
being
water
quality­
limited
the
State
has
adopted
the
federal
water
quality
because
of
high
copper
concentrations
with
criteria
into
its
water
quality
standards
to
potential
adverse
impacts
on
aquatic
life.
protect
aquatic
life
and
human
health.
The
Copper
loading
to
the
impaired
reach
comes
numeric
water
quality
criteria
for
acute
toxicity
from
naturally
occurring
and
anthropogenic
(
criterion
maximum
concentration,
or
CMC)
sources
in
the
watershed
(
background)
and
and
chronic
toxicity
(
criterion
continuous
permitted
point
source
discharges,
including
concentration,
or
CCC)
to
aquatic
life
are
part
two
metal
plating
facilities
and
a
publicly
of
the
water
quality
standards
and
are
based
on
owned
treatment
works
(
POTW).
For
the
sake
the
dissolved
fraction
of
metals.
The
CMC
and
of
simplicity,
steady­
state
modeling
is
used.
CCC
depend
on
ambient
hardness
Episodic,
precipitation­
driven
runoff
loadings
concentrations
as
expressed
by
the
following
from
urban
and
industrial
areas
adjacent
to
the
equation
form
(
as
total
recoverable
metal):
river
could
be
accounted
for
using
continuous
simulation.

Design
low
flows
are
typically
used
for
calculating
steady­
state
wasteload
allocations
(
WLAs),
including
the
1­
day
average
low
flow
with
a
ten
year
recurrence
period
(
1Q10)
for
where
a
and
b
are
metal­
specific
constants
acute
criteria
and
the
7­
day
average
low
flow
defined
as
part
of
the
water
quality
criterion.
with
a
ten­
year
recurrence
period
(
7Q10)
for
For
copper
in
freshwater
systems,
these
chronic
criteria.
Analysis
of
30
years
of
constants
are:
records
from
the
USGS
gage
above
the
sources
indicates
a
1Q10
flow
of
111.77
cfs
and
a
7Q10
flow
of
140.09
cfs.

The
two
metal
plating
facilities
in
our
example
have
multiport
diffusers,
which
have
been
shown
to
quickly
achieve
complete
mixing
across
the
width
of
the
river.
The
POTW
effluent
enters
the
same
reach
as
the
facility
discharges
and
is
released
to
a
bend
in
the
river
where
mixing
also
occurs
rapidly.
The
State's
water
quality
regulations
require
that
water
quality
criteria
are
met
at
the
edge
of
the
mixing
zone.

A.
2
Water
Quality
Standards
and
Criteria
criteria,
designated
uses,
and
an
antiexample
is
classified
as
having
designated
uses
for
aquatic
habitat
and
primary
contact
Copper
a
b
Chronic
Criteria
0.8545
­
1.465
(
µ
g/
L)

Acute
Criteria
0.9422
­
1.464
(
µ
g/
L)
32
Box
A­
1.
Calculation
of
Acute
(
CMC)
and
Chronic
(
CCC)
WQC
for
Copper
Hardness
(
mg/
L)
100
Conversion
Factor
0.96
CMC
(
µ
g/
L)
=
(
total
recoverable)

exp[.
9422
x
ln(
100)
­
1.464]
=
17.7
CMC
(
µ
g/
L)
=
17.7
x
.96
=
17.0
(
dissolved)

CCC
(
µ
g/
L)
=
(
total
recoverable)

exp[.
8545
x
ln(
100)
­
1.465]
=
11.8
CCC
(
µ
g/
L)
=
11.8
x
.96
=
11.4
(
dissolved)
At
100
mg/
L
hardness,
these
lead
to
a
CCC
of
11.8
µ
g/
L
and
a
CMC
of
17.7
µ
g/
L.
These
criteria
concentrations
are
expressed
on
the
basis
of
total
recoverable
metal
(
Box
A­
1).

A.
3
Change
from
Total
Recoverable
to
Dissolved
Criteria
As
illustrated
in
Box
A­
1,
each
metal's
total
recoverable
criterion
must
be
multiplied
by
a
conversion
factor
to
obtain
a
dissolved
criterion
that
should
not
be
exceeded
in
the
water
column.
The
criteria
are
based
on
a
total
recoverable
concentration.
For
example,
the
copper
acute
(
and
chronic)
conversion
factor
of
0.960
is
a
weighted
average
and
is
used
as
a
prediction
of
how
much
the
final
value
would
change
if
dissolved
had
been
measured.
Where
can
then
be
used
to
translate
from
a
dissolved
possible,
these
conversion
factors
are
given
to
concentration
in
the
water
column
(
the
criterion
three
decimal
places
as
they
are
intermediate
concentration
or
some
fraction
thereof
)
to
the
values
in
the
calculation
of
dissolved
criteria.
total
recoverable
metal
concentration
in
the
At
a
hardness
of
100
mg/
L,
the
acute
dissolved
effluent
that
will
equate
to
that
dissolved
criterion
is
17.0
µ
g/
L.
Most
of
the
freshwater
concentration
in
the
water
column.
aquatic
life
criteria
and
their
conversion
factors
are
hardness­
dependent.
Box
A­
1
shows
an
example
calculation
of
dissolved
and
total
recoverable
copper
criteria
concentrations.

A.
4
Translating
from
a
Dissolved
Metal
Ambient
Criterion
to
a
Total
Recoverable
Concentration
in
the
Effluent
As
the
effluent
mixes
with
the
recoverable
copper
in
the
river
at
low
flow
receiving
water,
the
chemical
properties
of
the
(
upstream
of
the
effluent
discharge)
is
4
µ
g/
L
mixture
will
determine
the
fraction
of
the
metal
and
varies
within
a
relatively
small
range,
from
that
is
dissolved
and
the
fraction
of
the
metal
less
than
2
to
9.5
µ
g/
L,
with
the
average
that
is
in
particulate
form
(
typically
adsorbed
to
declining
to
about
3
µ
g/
L
above
median
flows.
surfaces
of
other
compounds).
The
most
direct
For
this
analysis
the
mean
background
approach
to
determining
the
fraction
of
the
total
concentration
is
used.
recoverable
metal
in
the
downstream
water
that
is
dissolved
(
f
)
is
to
analyze
the
downstream
The
(
instream)
total
recoverable
D
water
(
the
mixing
zone
of
effluent
and
concentration
[
C
]
that
equates
to
the
receiving
water)
to
determine
the
dissolved
and
dissolved
criterion
concentration
is
expressed
total
recoverable
metal
fractions.
This
ratio
as:
A.
5
Calculation
of
WLAs
for
a
Point
Source
For
this
example,
it
is
assumed
that
the
site­
specific
data
have
been
collected
and
analyzed
to
determine
that
f
=
0.4.
D
From
analysis
of
existing
data,
the
average
background
concentration
of
total
instream
[
C
instream]
WQC(
dissolved)
1
f
D
WLA(
total
metal)
[
C
instream]
(
Q
e
Q
s)
Q
s
C
s
Q
e
WLA
a
42.5
(
50
111.77)
111.77
4
50
128.6
µ
g/
L
total
recoverable
Cu
33
(
2)

(
3)

(
4)
Box
A­
2.
Data
for
Calculation
of
WLAs
and
Existing
Permit
Limits
for
the
POTW
Effluent
Flow
(
cfs)
50
Average
Effluent
Concentration,
as
Total
Recoverable
Copper
(
µ
g/
L)
81
Coefficient
of
Variation
of
Load
0.12
Given
the
information
on
the
design
other
words,
the
full
assimilative
capacity
of
flows
and
background
concentrations
(
Box
A­
the
water
body
is
not
available
to
each
source;
2),
WLAs,
expressed
as
total
recoverable
instead,
this
capacity
must
be
apportioned
metal,
are
calculated
to
meet
the
dissolved
between
all
three
sources
via
the
TMDL
CCC
and
dissolved
CMC
at
the
edge
of
the
procedure.
mixing
zone
assuming
that
the
effluent
is
mixed
rapidly
and
that
a
simple,
mass­
balance
The
three
permitted
point
sources
in
equation
is
appropriate.
our
example
all
operate
within
the
effluent
Chronic
and
acute
WLAs
(
for
any
permits.
They
do
not,
however,
address
single
source,
without
consideration
of
other
cumulative
impacts
of
all
three
sources.
sources)
can
be
calculated
at
the
7Q10
and
Permits
for
the
two
metal
finishing
facilities
1Q10
flows,
respectively,
for
total
recoverable
specify
a
maximum
daily
limit
(
MDL)
of
copper
concentration,
using
Equation
3.
3380
µ
g/
L
and
an
average
monthly
limit
where
[
C
]
is
calculated
from
Equation
2,
effluent
concentrations.
At
an
average
instream
Q
is
the
effluent
flow,
concentration
of
81
µ
g/
L
of
total
recoverable
e
Q
is
the
receiving
water
flow,
and
copper
and
an
increased
effluent
flow
of
80
s
C
is
the
background
(
upstream
)
cfs,
the
load
from
the
POTW
(
see
Box
A­
3)
s
concentration.
would
be
35
lbs/
day.
The
increased
flow
A.
6
Calculating
the
TMDL
for
Multiple
Point
Sources
The
previous
section
shows
the
calculation
of
wasteload
allocations
for
a
single
point
source.
Concentrations
in
the
receiving
water,
however,
are
influenced
by
all
three
point
sources
simultaneously.
In
limits
specified
in
their
current
NPDES
(
AML)
of
2070
µ
g/
L.

In
addition
to
potential
impairment
under
current
permit
limits,
the
POTW
is
undergoing
a
significant
(
60%)
capacity
expansion,
and
its
increased
effluent
flow
will
also
increase
copper
loading
at
current
from
the
plant
also
has
a
significant
impact
on
low
flow
volumes
in
the
receiving
water,
requiring
recalculation
of
the
WLAs.

The
TMDL
analysis
is
straightforward
when
multiple,
steady­
state
sources
are
considered
using
hydrologically
based
design
conditions.
The
strategy
is
to:
TMDL
WQC
(
Q
e
Q
s)

TMDL
[
C
instream]
(
Q
e
Q
s)

34
Box
A­
3.
Conversion
Factors
for
Concentration
and
Load
Concentration
to
load
rate:
(
µ
g/
L)
x
(
cfs)
x
0.005394
=
(
lbs/
day)

Load
rate
to
concentration:
(
lbs/
day)
/
(
cfs)
x
185.4
=
(
µ
g/
L)
(
5)

(
6)
(
1)
calculate
the
acute
and
chronic
dissolved
(
for
metals)
criteria
concentrations
[
Eqn
1],

(
2)
calculate
the
instream
concentration
[
C
]
(
in
terms
of
total
recoverable
metal)
instream
that
equates
to
the
dissolved
criterion
concentration
[
Eqn
2],

(
3)
calculate
the
total
loading
capacity
(
TMDL)
of
the
waterbody
(
in
terms
of
total
recoverable
metal)
[
Eqn
6],

(
4)
calculate
the
background
load,

(
5)
calculate
the
allocatable
portion
of
the
loading
capacity
(
i.
e.,
the
difference
between
the
loading
capacity
and
background)
[
Eqn
7],

(
6)
calculate
the
current
loadings
from
the
sources
and
their
fractional
contributions
to
the
total
current
load,

(
7)
compare
the
current
total
loadings
to
the
waterbody
with
the
required
TMDL
(
if
either
the
acute
or
chronic
total
loadings
exceed
the
TMDL
then
the
loads
must
be
reduced),
and
(
8)
reduce
loadings
from
the
point
sources,
equitably
allocating
waste
loads
to
the
discharging
facilities.
The
steady­
state
TMDL
for
a
given
location
or
reach
of
the
river
is
calculated
(
in
units
of
cfs
­
µ
g/
L)
as:

where
Q
is
the
total
flow
of
effluents
e
discharging
to
the
reach
(
cfs),
Qs
is
the
appropriate
flow
(
e.
g.,
7Q10)
of
the
river
upstream
of
all
the
discharges
(
cfs),
and
WQC
is
the
water
quality
criterion
expressed
in
µ
g/
L.

TMDLs
for
metals
are
developed
on
the
basis
of
the
instream
total
recoverable
metal
concentrations
that
equate
to
the
dissolved
criteria
concentrations.
Consequently,
the
term
WQC
in
Equation
5
is
replaced
with
the
term
[
C
]
as
calculated
instream
by
Equation
2.

The
calculated
TMDL
is
then
divided
among
WLAs
for
point
sources;
LAs,
for
nonpoint
sources
and
background
loads;
and
a
margin
of
safety
(
MOS).
The
TMDL
and
the
portion
of
the
TMDL
taken
up
by
background
load
(
at
4
µ
g/
L)
can
be
calculated
in
terms
of
total
copper
mass,
as
shown
in
Table
A­
1.

Because
the
current
loading
for
the
chronic
TMDL
exceeds
the
allocatable
portion,
loadings
from
all
of
the
NPDES
permitted
sources
must
be
reduced.
Many
different
mechanisms
or
schemes
for
apportioning
the
necessary
reductions
in
allocations
are
possible.
Assume
for
the
purpose
of
this
example
that
the
State
has
determined
that
necessary
reductions
will
be
applied
equally
to
all
point
sources.
Reduced
TMDL­
based
WLAs
can
then
be
calculated
based
on
the
current
proportion
of
load
attributable
to
a
given
source:
WLA
i
TMDL
Background
x
f
i
35
(
7)

where
WLA
is
the
WLA
for
source
I,
and
f
i
i
is
the
proportion
of
the
existing
load
attributable
to
a
given
source.

The
allocation
fraction,
f
,
is
simply
a
i
proportionality
constant
that
is
arrived
at
by
dividing
the
current
load
from
source
by
the
i
sum
of
all
the
loads
(
e.
g.,
f
=
PS1
/
(
PS1
+
1
PS2
+
POTW
+
MOS)).
The
allocation
fraction
is
then
multiplied
by
the
Allocatable
Portion
to
yield
the
Allowed
Load
as
in
Table
A­
2.
In
the
calculations
summarized
in
Table
A­
2
and
A­
3,
a
MOS
of
10
percent
of
the
allowable
TMDL
has
been
applied.
36
Table
A­
1.
Calculation
of
TMDL
(
Total
Recoverable
Copper)

Acute
TMDL
Chronic
TMDL
TMDL
(
lbs/
day)
44.11
33.76
(
total
recoverable
copper)

[
Eqn
6]

Background
at
design
flow
(
lbs/
day)
2.41
3.02
(
total
recoverable
copper)

[
Background
=
Q
*
C
]
s
s
Allocatable
Portion
(
lbs/
day)
41.69
30.73
[
Allocatable
Portion
=
TMDL
­
Background]

Current
Loading
(
lbs/
day)
42.38
42.99
[
Loading
=
PS1
+
PS2
+
POTW
+
Background]

.

Table
A­
2.
Allocation
of
Loads
to
Achieve
the
(
Chronic)
TMDL
Source
Current
Load
Allocation
Allocatable
Allowed
Load
(
lbs/
day)
Fraction
Portion
(
lbs/
day)
(
f
)
i
(
TMDL
­
Background)

PS1
1.67
0.04
30.73
1.16
PS2
3.35
0.08
30.73
2.32
POTW
34.95
0.79
30.73
24.18
MOS
4.44
0.10
30.73
3.07
SUM
44.41
1
30.73
37
Table
A­
3.
Allocation
of
Loads
to
Achieve
the
(
Acute)
TMDL
Source
Current
Load
Allocation
Allocatable
Allowed
Load
(
lbs/
day)
Fraction
Portion
(
lbs/
day)
(
f
)
i
(
TMDL
­
Background)

PS1
1.67
0.04
41.69
1.57
PS2
3.35
0.08
41.69
3.14
POTW
34.95
0.79
41.69
32.81
MOS
4.44
0.10
41.69
4.17
SUM
44.41
1
41.69
LTA
c
WLA
exp
[
0.5
24
z
99
4]

24.18
lbs/
day
0.87
21.0
lbs/
day
LTA
a
32.81
lbs/
day
0.76
24.9
lbs/
day
38
Box
A­
4.
Calculation
of
LTA
Multipliers
LTAc
CV
=
0.12
z
=
2.326
99
²
=
ln
[
CV
²
/
4+
1]
=
0.00359
4
exp
[
0.5
²
 
z
]
=
0.87
4
99
4
LTAa
CV
=
0.12
z
=
2.326
99
²
=
ln
[
CV
²
+
1]
=
0.014297
exp
[
0.5
²
­
z
]
=
0.76
99
(
9)

(
10)
A.
7
Calculating
the
Permit
Limits
for
a
Point
Source
Permit
limits
for
the
POTW
are
developed
in
accordance
with
USEPA
(
1991a)
guidance
on
establishing
WLAs
and
permit
limits
for
single
sources.
In
accordance
with
NPDES
regulations,
effluent
limits
for
the
POTW
are
expressed
in
the
permit
as
mass
units
(
pounds
per
day
total
recoverable
copper),
using
the
conversion
factors
shown
in
Box
A­
3.
The
WLA
for
c
total
recoverable
copper
(
Table
A­
2)
is
equivalent
to
24.18
lbs/
day
and
is
more
restrictive
than
the
WLA
32.81
lbs/
day
a
(
Table
A­
3).
Converting
the
WLA
to
a
permit
limit
involves
two
additional
considerations:
(
1)
there
is
variability
in
the
effluent
concentration,
and
concentrations
on
any
given
day
may
be
greater
or
less
than
the
average
value
used
to
calculate
the
WLA;
and
(
2)
permit
compliance
will
be
assessed
from
limited
sampling
(
e.
g.,
weekly),
which
means
there
will
be
uncertainty
in
the
estimation
of
actual
load
from
the
facility.
These
issues
are
addressed
by
(
1)
calculating
a
long­
term
average
(
LTA)
which
accounts
for
the
variability
in
actual
load,
and
(
2)
using
the
LTA
to
calculate
a
maximum
daily
limit
(
MDL)
and
average
monthly
limit
(
AML)
which
serve
as
trigger
values
for
compliance
monitoring.

The
permit
limits
are
developed
using
a
steady­
state,
two­
value
WLA
model,
as
described
in
Chapter
5
of
USEPA
(
1991a).
First,
variability
in
effluent
load,
expressed
through
the
coefficient
of
variation
(
CV),
is
incorporated
into
the
calculation
of
appropriate
long­
term
averages
(
LTAs).
The
chronic
long­
term
average
(
LTA
)
for
copper
c
was
calculated
from
where
the
value
for
the
factor
exp
[
0.5
²
 
4
z
]
was
calculated
from
the
coefficient
of
99
4
variation
of
effluent
concentrations
(
CV,
defined
as
standard
deviation
divided
by
the
mean,
and
assumed
to
be
0.12)
by
the
methods
of
USEPA
(
1991a,
Table
5­
1),
using
the
99th
percentile
occurrence
probability
(
Box
A­
4).

The
acute
LTA
was
calculated
in
a
a
similar
manner,
again
using
a
99th
occurrence
probability
as
a
multiplier:
MDL
LTA
exp
[
z
99
0.5
2]

21.0
lbs/
day
1.37
28.8
lbs/
day
AML
LTA
exp
[
z
99
n
0.5
2
n]

21.0
lbs/
day
1.15
24.2
lbs/
day
39
(
11)

(
12)
The
limiting
LTA
for
copper
discharges
from
the
facility
is
the
smaller
of
the
LTA
and
a
LTA
,
or
21.0
lbs/
day.
This
is
well
below
the
c
current
average
load
from
the
facility
of
43.95
lbs/
day.

The
permit
for
the
POTW
is
written
to
ensure
an
LTA
load
not
to
exceed
21.0
lbs/
day
total
recoverable
copper
through
the
specification
of
an
MDL
and
AML
for
compliance
monitoring.
The
MDL
for
copper
is
calculated
using
the
expression
where
the
value
for
exp
[
z
 
0.5
²
]
is
99
taken
from
Table
5­
2
in
USEPA
(
1991a),
using
a
CV
value
of
0.12
and
the
column
for
the
99th
percentile
basis.
The
AML
for
copper
is
calculated
from
where
the
value
for
exp
[
z
 
0.5
²
]
is
99
n
n
taken
from
Table
5­
2
in
USEPA
(
1991a),
in
which
n
equals
4
samples
per
month
for
total
recoverable
copper,
using
the
99th
percentile
basis.
40
APPENDIX
B
Table
B­
1.
Comparison
of
average
f
data
from
three
locations
in
the
U.
S.
Three
different
D
calculation
methods
are
used
with
the
Pima
County
data.

NY/
NJ
Boulder,
Pima
County,
AZ
Harbor
CO
Cd/
Ct
Cd/(
Cd+
Cp)
by
regression
from
logKp
Copper
0.56
0.23
0.37
0.43
0.42
Cadmium
1.00
0.51
0.71
0.51
0.69
Lead
0.18
0.29
0.20
0.28
0.26
Nickel
0.86
~
1.0
­­­
­­­
­­­

Zinc
0.90
0.44
0.61
0.63
0.65
These
data
illustrate
two
points.
First,
notice
the
similarity
in
the
values
of
the
translators
for
each
of
the
metals
in
the
Pima
County
study.
The
differences
between
column
1
and
column
2
of
the
Pima
County
data
arise
from
limits
in
the
analytical
precision
of
measurements
of
dissolved
and
particulate
sorbed
fractions.
Second,
notice
the
differences
in
the
values
of
the
translators
between
the
three
sites
represented
in
this
table.
These
differences
reflect
the
site
specificity
of
the
translator,
further
strengthing
the
case
for
development
of
site
specific
translator
values
in
contrast
to
the
use
of
nation
wide
values.

Preliminary
data
collected
for
the
City
of
Palo
Alto
Regional
Water
Quality
Control
Plant
permit
renewal
process
(
Table
B­
2)
suggest
a
translator
value
of
0.62
for
copper
(
62%
of
the
copper
in
the
downstream
water
is
dissolved).
This
differs
from
all
of
the
translator
values
in
Table
B­
1.
Station#
Date
Cd
Ct
Cp
TSS
fD
Station
1
9/
7/
89
2.6
3.4
0.8
89
0.76
Station
1
10/
2/
89
3.3
4.5
1.2
290
0.73
Station
1
10/
25/
89
3
4
1
52
0.75
Station
1
1/
10/
90
2.9
4.1
1.2
49
0.71
Station
1
2/
7/
90
1.4
8
6.6
228
0.18
Station
1
3/
7/
90
3
5
2
77
0.60
Station
1
7/
9/
90
4.2
9.6
5.4
180
0.44
Station
1
8/
7/
90
6.3
7
0.7
83
0.90
Station
1
9/
19/
90
3.6
5.7
2.1
125
0.63
Station
1
12/
12/
90
2.9
5.9
3
57
0.49
Station
1
1/
10/
91
3.5
4.3
0.8
46
0.81
Station
1
2/
13/
91
4
4.7
0.7
55
0.85
Station
1
10/
10/
91
4.3
4.6
0.3
78
0.93
Station
1
2/
19/
92
2
9.9
7.9
250
0.20
Station
2
9/
7/
89
3
5
2
110
0.60
Station
2
10/
2/
89
2.2
4.5
2.3
160
0.49
Station
2
10/
25/
89
6
11
5
132
0.55
Station
2
1/
10/
90
2.9
4.1
1.2
46
0.71
Station
2
2/
7/
90
1.7
6.1
4.4
110
0.28
Station
2
3/
7/
90
4.3
5
0.7
60
0.86
Station
2
7/
9/
90
6.8
7.2
0.4
100
0.94
Station
2
8/
7/
90
6.5
8.2
1.7
48
0.79
Station
2
9/
19/
90
3.9
5.6
1.7
65
0.70
Station
2
12/
12/
90
2.8
4.6
1.8
51
0.61
Station
2
1/
10/
91
4.2
4.8
0.6
61
0.88
Station
2
2/
13/
91
4.5
4.8
0.3
47
0.94
Station
2
10/
10/
91
4.5
4.7
0.2
77
0.96
Station
2
2/
19/
92
2
4.9
2.9
120
0.41
Mean
3.7
5.8
2.1
101.6
0.67
Stdev
1.4
2.0
2.0
65.5
0.22
95%
6.4
9.8
6.2
243.4
0.94
25%
2.9
4.6
0.7
54.3
0.53
Geomean
3.4
5.5
1.4
86.6
0.62
41
Table
B­
2.
Data
Collected
in
Palo
Alto,
CA
for
Cu
Permit
Limit
from
a
Waste
Water
Treatment
Plant.
42
APPENDIX
C
C.
2.
The
Translator
is
the
Ratio
of
C.
Developing
the
Metals
Translator
s
may
be
concluded
from
the
calculated
from
data
collected
over
some
Adiscussion
in
Chapter
2,
period
of
time
and
some
range
of
flow
there
are
several
ways
of
conditions.
For
example,
samples
may
be
developing
the
metals
translator.
This
collected
weekly
for
three
months
under
Appendix
presents
two
suggested
possibilities
conditions
of
"
relatively
low
flow"
(
which
and
illustrates
their
application.
may
or
may
not
include
design
low
flow
C.
1.
Minimum
Data
Requirements
Samples
should
be
collected
to
expect
to
have
a
broad
range
of
TSS
characterize
completely
mixed
effluent
plus
conditions.
The
dissolved
fraction
may
be
receiving
water
downstream
of
the
discharge
determined
(
directly)
from
measurements
of
(
such
as
should
occur
at,
or
below,
the
edge
dissolved
and
total
recoverable
metal
of
the
mixing
zone).
These
represent
the
concentrations
collected
from
waters
absolute
minimum
in
data
requirements.
downstream
of
the
effluent
discharge.
The
Ideally,
samples
should
be
collected
from
the
dissolved
fraction
may
be
related
to
a
constant
effluent
and
the
upstream
receiving
water
adsorbent
concentration
associated
with
low
(
before
mixing
with
the
effluent
)
to
quantify
flow
conditions
or
a
function
of
varying
metal
loading
and
background
adsorbent
concentrations.
concentrations.
An
alternative
to
collecting
the
downstream
samples
on
site
is
to
combine
Note
that
this
ratio
(
C
/
C
),
as
upstream
and
effluent
waters
to
meet
the
exemplified
by
Eqn
2.6
and
2.7,
is
not
a
desired
dilution
fraction
in
the
mixing
zone.
partition
coefficient
but
it
does
embody
a
In
addition,
there
may
be
occasions
when
it
is
partition
coefficient.
As
shown
by
Eqn
2.3
desirable
to
collect
samples
to
characterize
and
Eqn
2.8,
the
partition
coefficient
is
the
the
far­
field
conditions,
particularly
when
ratio
of
the
particulate­
sorbed
and
the
encountering
deposits
containing
metals,
mine
dissolved
metal
species.
The
dissolved
tailings,
drainage
waters
of
high
acidity,
or
fraction
and
the
partition
coefficient
are
different
geologic
substrates.
related
according
to
f
=
(
1
+
K
°
m)
.
It
is
To
keep
this
simple
and
to
avoid
fraction
(
f
)
and
the
partition
coefficient
(
K
)
having
to
develop
data
on
the
kinetics
of
because
what
we're
interested
is
the
dissolved
metal
adsorption
and
desorption,
the
translator
fraction.
We're
only
using
the
partition
should
be
developed
to
describe
equilibrium
coefficient
because
it
is
one
way
of
getting
to
partitioning.
Equilibrium
partitioning
also
the
dissolved
fraction.
reduces
the
frequency
for
which
far
field
effects
need
to
be
investigated.
It
also
lets
us
This
guidance
uses
TSS
as
a
default
apply
the
same
translator
for
evaluation
of
parameter
to
represent
all
of
the
ion
both
acute
and
chronic
mixing
zones.
adsorption
sites.
It
is
generally
recognized,
C
/
C
D
T
The
translator
is
the
fraction
of
the
total
recoverable
metal
in
the
downstream
water
that
is
dissolved
(
f
=
C
/
C
).
It
is
D
D
T
conditions)
or
samples
may
be
collected
monthly
for
a
period
of
one
or
more
years
under
a
broad
range
of
flow
conditions.
Under
this
latter
sampling
scheme
we
may
D
T
D
P
­
1
important
to
distinguish
between
the
dissolved
D
P
however,
that
humic
substances
play
a
major
43
Box
C­
1.
The
Translator
is
the
Dissolved
Fraction:
f
=
C
/
C
D
D
T
Step
1
­
For
each
field
sample
determine
f
=
C
/
C
D
D
T
Step
2
­
If
the
translator
is
not
dependent
on
TSS,
determine
the
geometric
mean
GM_
f
=
exp(
ln(
f
)/
n)
D
1
D
n
and
upper
percentile
values
of
the
dissolved
fraction.
If
the
data
are
found
not
to
be
log­
normal,
then
alternative
transformations
should
be
considered
to
normalize
the
data
and
determine
the
transformed
mean
and
percentiles.
Also,
alternative
upper
percentiles
may
be
adopted
as
a
state's
policy
to
address
MOS
(
e.
ge.,
90
or
95
th
th
percentiles
may
be
appropriate.)

Step
3
­
If
the
translator
is
found
to
be
dependent
on
TSS,
regression
equations
relating
f
to
TSS
should
D
be
developed.
Appropriate
transformations
should
be
used
to
meet
the
normality
assumptions
for
regression
analysis
(
for
example
log­
transformation
of
f
D
and
TSS
may
be
appropriate).
The
regression
equation
or
an
upper
prediction
interval
may
be
considered
for
estimation
of
f
D
from
TSS
depending
on
the
strategy
for
addressing
MOS.
role
in
the
environmental
fate
and
availability
from
Table
1
and
following
the
sequence
as
of
metal
ions
in
the
environment.
The
humic
outlined
in
Box
C­
1.
The
metal
and
fulvic
acids
are
mixtures
of
naturally
concentrations
in
Table
1
are
for
lead.
The
occurring
polyelectrolytes
that
have
different
data
records,
numbers
1
through
27,
represent
types
of
functional
groups
to
which
ions
can
spatially
separate
sampling
stations
in
the
bind.
Benedetti,
et.
al.
(
1995)
write
that
metal
estuary.
The
first
step
(
Step
1
in
Box
C­
1)
is
binding
in
natural
systems
will
be
affected
by
to
calculate
the
dissolved
fraction
in
the
humic
acids
whose
chemical
heterogeneity
receiving
water.
The
result
of
this
calculation
and
polyelectric
properties
will
affect
metal
is
shown
in
Column
8
of
Table
1.
binding.
Multivalent
cations
will
compete
for
the
same
sites,
along
with
other
ions
and
protons
in
the
aquatic
systems,
and
hence
influence
the
binding
of
each
other.

The
following
step­
by­
step
examples
are
designed
to
guide
the
reader
through
possible
sequences
of
data
analyses
leading
to
the
development
of
the
metals
translator.
One
set
of
data
was
collected
during
the
New
York/
New
Jersey
Harbor
study.
The
data
presented
here
are
a
subset
of
the
total
and
do
not
include
samples
that
are
incomplete
(
i.
e.,
records
lacking
pH
or
POC
values)
to
simplify
this
presentation.
The
data
set
reflects
spatial
differences.
The
data
are
not
a
time
series
at
a
single
location.
However,
there
would
not
be
a
great
difference
in
the
following
analyses
if
the
data
did
represent
a
time
series.

The
second
data
set
was
provided
by
the
Coors
Brewing
Company.
Again,
the
data
presented
here
are
a
subset
of
the
total.
The
original
data
set
contains
time
series
data
for
several
variables
at
several
locations.
To
simplify
this
example,
however,
the
data
for
only
one
metal
and
one
site
are
presented.

C.
2.1.
Spatial
Example
Using
the
Ratio
of
C
/
C
D
T
The
most
direct
procedure
for
determining
a
site­
specific
metal
translator
is
simply
to
determine
f
by
measuring
C
and
D
T
C
and
to
develop
the
dissolved
fraction
as
D
the
ratio
C
/
C
.
This
is
illustrated,
using
data
D
T
Lead
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0
20
40
60
TSS
fD
Lead
­
0.10
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
­
1.00
0.00
1.00
2.00
3.00
4.00
ln
(
TSS)
fD
R­
Square
=
0.77
44
Step
2
indicates
that
there
is
a
lot
of
transformations
would
be
appropriate.
variation
in
the
values
of
f
;
the
mean
is
0.21
Examination
of
Figure
2
further
supports
the
D
with
a
standard
deviation
is
0.17.
The
logarithmic
transformation
of
values
and
the
variability
in
this
dataset
indicates
that
it
is
choice
of
the
geometric
mean.
Even
at
that,
unwise
to
attempt
to
spatially
average
f
the
geometric
mean
value
of
the
dissolved
D
values
in
this
situation.
To
do
so
would
be
to
fraction
(
0.16
does
not
provide
a
good
ignore
spatially
critical
conditions.
Because,
representation
of
the
waterbody
in
which
TSS
it
does
not
provide
a
good
representation
of
is
spatially
correlated.
The
translator
needs
to
the
waterbody,
one
cannot
accept
the
mean
f
account
for
the
spatial
and/
or
temporal
D
(
0.21)
as
the
translator.
variability
evidenced
in
the
waterbody.

The
translator
should
be
calculated
as
a
geometric
mean
or
other
estimate
of
central
tendency
(
see
Section
4.3).
Use
of
the
arithmetic
mean
is
appropriate
when
the
values
can
range
from
minus
infinity
to
plus
infinity.
The
geometric
mean
is
equivalent
to
using
the
arithmetic
mean
of
the
logarithms
of
the
values.
The
dissolved
fraction
cannot
be
negative,
but
the
logarithms
of
the
dissolved
fraction
can
be.
The
distribution
of
the
Figure
1.
Dissolved
fraction
(
lead)
vs
TSS.

logarithms
of
the
translator
is
therefore
more
likely
to
be
normally
distributed.
Figure
1
displays
the
arithmetic
distributions
of
the
dissolved
fractions
with
TSS.
Note
that
the
skewed
distributions
suggest
that
logarithmic
In
order
to
account
for
the
spatial
variability
of
this
waterbody,
we
need
a
translator
that
can
be
tied
functionally
to
important
physical
or
chemical
variables.
TSS
concentrations
vary
spatially
throughout
the
estuary.
Spatial
variability
in
TSS
concentrations
requires
the
use
of
a
translator
that
includes
the
relationship
between
TSS
and
f
.
This
empirically
derived
relationship
D
is
valid
for
this
estuary.

Figure
2.
Dissolved
fraction
(
lead)
vs
log
transformation
of
TSS.

The
regression
of
the
natural
logarithm
of
f
against
the
natural
logarithm
D
of
TSS
(
Figure
2)
provides
a
reasonably
good
fit
as
evidenced
by
the
R
Square
of
0.77.
The
45
dissolved
fraction
is
highly
correlated
with
TSS;
therefore
the
translator
(
Figure
2)
takes
the
form
of:

ln(
f
)
=
­
0.6017
­
0.6296
°
ln(
TSS).
D
The
translator
is
the
dissolved
fraction,
not
the
regression
equation.
The
way
to
use
the
regression
equation
is
to
select
TSS
concentrations
that
are
representative
of
specific
locations
in
the
estuary
and
calculate
f
values
that
serve
as
the
translators
for
the
D
discharges
in
these
respective
locations.

Sung,
et.
al.
(
1995)
have
demonstrated
a
relationship
between
K
and
salinity
for
Cd,
P
Cu,
and
Zn
in
the
Savannah
River
Estuary.
It
may
well
be
that
by
considering
salinity
as
well
as
TSS,
more
variability
could
have
been
accounted
for
in
the
relationship
portrayed
in
Figure
2.
No.
pH
POC
TSS
CT
CD
CP
fD
KP
(
CT/
CD)­
1
1
8.8
0.132
0.61
0.046
0.027
0.019
0.59
1.15
0.704
2
8.6
0.104
0.92
0.044
0.03
0.014
0.68
0.51
0.467
3
8.6
0.159
1.88
0.25
0.094
0.156
0.38
0.88
1.660
4
8.4
0.280
1.28
0.31
0.16
0.15
0.52
0.73
0.938
5
8.4
0.376
3.32
0.68
0.10
0.58
0.15
1.75
5.800
6
8.4
0.190
2.94
0.46
0.098
0.362
0.21
1.26
3.694
7
8.2
0.183
5.36
0.89
0.14
0.75
0.16
1.00
5.357
8
8.3
0.351
4.71
0.80
0.27
0.53
0.34
0.42
1.963
9
8.4
0.266
3.50
0.67
0.22
0.45
0.33
0.58
2.045
10
8.1
0.416
7.98
2.40
0.59
1.81
0.25
0.38
3.068
11
8.1
1.060
44.42
9.10
0.27
8.83
0.03
0.74
32.704
12
8.1
0.538
11.08
3.40
0.44
2.96
0.13
0.61
6.727
13
8.1
0.596
10.60
3.90
0.85
3.05
0.22
0.34
3.588
14
8.2
0.785
14.77
3.20
0.54
2.66
0.17
0.33
4.926
15
8.4
0.626
8.95
1.40
0.26
1.14
0.19
0.49
4.385
16
8.4
0.602
19.94
2.20
0.17
2.03
0.08
0.60
11.941
17
8.3
0.540
21.10
2.10
0.14
1.96
0.07
0.66
14.000
18
8.3
0.676
19.45
2.10
0.15
1.95
0.07
0.67
13.000
19
8.2
0.629
25.70
2.90
0.15
2.75
0.05
0.71
18.333
20
8.4
0.726
27.75
1.90
0.16
1.74
0.08
0.39
10.875
21
8.4
0.494
22.30
1.50
0.17
1.33
0.11
0.35
7.824
22
8.4
2.360
7.89
1.40
0.26
1.14
0.19
0.56
4.385
23
8.4
0.427
7.32
1.70
0.22
1.48
0.13
0.92
6.727
24
8.4
0.414
8.48
1.60
0.27
1.33
0.17
0.58
4.926
25
8.5
1.470
8.22
1.20
0.10
1.10
0.08
1.34
11.000
26
8.5
0.407
7.09
0.82
0.088
0.732
0.11
1.17
8.318
27
8.6
0.381
7.52
0.58
0.065
0.515
0.11
1.05
7.923
Mean
0.56
11.30
1.76
0.22
1.54
0.21
0.75
7.31
Stdev
0.46
10.23
1.80
0.19
1.72
0.17
0.36
6.77
95%
1.35
27.14
3.75
0.58
3.02
0.57
1.31
17.03
25%
0.32
4.11
0.68
0.10
0.52
0.10
0.50
3.33
Geomean
0.44
7.26
1.06
0.17
0.82
0.16
0.67
4.90
46
Table
C­
1.
Example
Data
Used
to
Calculate
Translator
for
Lead
(
Source:
NY/
NJ
Harbor
Study)
DATE
pH
TSS
CT
CD
(
CT/
CD)­
1
fD
10/
16/
91
7.5
3
0.47
0.24
0.96
0.51
11/
13/
91
7.3
32
0.72
0.27
1.67
0.38
12/
11/
91
8.1
5
0.47
0.20
1.35
0.43
01/
16/
92
8.2
8
0.43
0.38
0.13
0.88
02/
18/
92
8.2
7
0.55
0.19
1.86
0.35
03/
18/
92
8.1
7
0.49
0.24
1.07
0.48
04/
14/
92
7.2
14
0.84
0.44
0.92
0.52
05/
12/
92
7.7
15
0.34
0.18
0.87
0.54
06/
17/
92
7.5
8
0.25
0.15
0.64
0.61
07/
15/
92
7.5
5
0.18
0.13
0.43
0.70
08/
18/
92
7.2
23
0.26
0.08
2.12
0.32
09/
09/
92
7.2
4
0.22
0.03
5.72
0.15
10/
14/
92
8.0
7
0.25
0.11
1.27
0.44
11/
16/
92
8.2
13
0.44
0.22
1.00
0.50
12/
15/
92
7.9
1
0.47
0.24
0.97
0.51
01/
12/
93
8.8
6
0.67
0.32
1.08
0.48
02/
18/
93
7.9
12
0.71
0.38
0.87
0.54
03/
16/
93
8.1
10
0.57
0.22
1.58
0.39
04/
13/
93
8.0
18
0.48
0.16
2.04
0.33
05/
12/
93
7.5
20
0.42
0.08
4.10
0.20
06/
15/
93
8.1
64.6
0.54
0.10
4.67
0.18
07/
15/
93
7.5
10
0.14
0.06
1.25
0.44
08/
12/
93
7.8
6
0.17
0.09
0.94
0.52
09/
16/
93
8.1
4
0.24
0.12
1.09
0.48
10/
13/
93
8.1
5
0.26
0.12
1.11
0.47
11/
10/
93
8.4
1.7
0.30
0.15
1.03
0.49
12/
13/
93
7.9
4.6
0.45
0.23
1.00
0.50
01/
13/
94
7.5
1.8
0.33
0.17
0.97
0.51
02/
11/
94
7.9
5.5
0.49
0.24
1.01
0.50
03/
09/
94
8.4
5
0.34
0.09
2.57
0.28
04/
07/
94
8.3
16
0.48
0.14
2.54
0.28
05/
12/
94
7.6
47.7
0.72
0.09
7.35
0.12
07/
13/
94
7.8
6
0.13
0.05
1.43
0.41
08/
23/
94
8.0
13
0.14
0.05
2.20
0.31
09/
20/
94
8.1
6
0.15
0.06
1.30
0.44
10/
18/
94
8.0
5.5
0.28
0.14
1.06
0.49
Mean
11.68
0.40
0.17
1.73
0.43
Stdev
12.90
0.19
0.10
1.50
0.15
95%
0.71
0.71
0.33
0.71
0.71
25%
5.00
0.25
0.09
0.97
0.34
Geomean
7.90
0.35
0.14
1.33
0.40
47
Table
C­
2.
Time
Series
Example
Calculating
the
Translator
for
Zinc.
(
Source:
Coors
Brewing
Company
Study)
48
Box
C­
2.
The
Translator
is
the
Dissolved
Fraction
(
f
)
D
Calculated
via
Site
Specific
Partition
Coefficients
Step
1
­
For
each
field
sample
determine
C
=
C
­
C
,
P
T
D
K
=
C
/(
C
°
TSS)
P
P
D
Step
2
­
Fit
least
squares
regressions
to
data
(
transformed,
stratified
by
pH,
etc.)
as
appropriate
to
solve
for
K
.
P
Step
3
­
Substitute
the
regression
derived
value
of
K
in
Eqn
2.7,
P
f
=
(
1
+
K
°
TSS)
D
P
­
1
Step
4
Determine
f
for
a
TSS
value
D
representative
of
the
critical
conditions.
C.
2.2.
Time
Series
Example
Using
the
Ratio
of
C
/
C
D
T
Using
a
data
set
developed
over
a
partition
coefficient,
and
the
dissolved
metal
three
year
time
span
on
Clear
Creek
in
Colorado
and
the
same
analytical
procedure
as
described
in
Box
1,
f
is
calculated
as
the
D
ratio
of
C
/
C
.
A
subset
of
the
collected
D
T
data,
Table
C­
2,
illustrate
the
approach.

This
subset
includes
the
following
variables:
total
recoverable
Zn,
dissolved
Zn,
TSS,
and
pH
that
were
measured
at
one
sampling
location.
Additionally,
presented
in
Table
2
are
f
values
(
Box
C­
1
­
Step
1).
D
This
data
set
was
censored
in
the
following
manner.
When
calculating
f
,
if
the
dissolved
D
concentration
was
found
to
exceed
the
total
recoverable
concentration,
C
was
set
equal
D
to
C
and
f
calculated
as
1
(
100%
dissolved
T
D
metal).

At
the
pH
levels
encountered
in
Clear
Creek
during
the
three
year
sampling
period,
no
relationship
was
obtained
between
pH
and
f
.
This
is
not
an
unexpected
result
because
D
pH
is
in
the
7
to
9
range;
the
major
effect
of
pH
on
the
dissolved
fraction
is
normally
observed
at
low
pH
levels.
Relationships
based
on
POC
(
not
shown)
provide
no
improvement
over
the
TSS
based
relationships.

The
translator
value
selected
for
Zn
between
total
recoverable
and
dissolved
on
Clear
Creek
is
the
geometric
mean
of
the
metal
concentrations.
The
partition
f
values
(
0.40).
coefficient
the
ratio
of
the
particulate­
sorbed
D
C.
3.
The
Translator
Calculated
Using
Site
Specific
Partition
Coefficients
It
is
important
to
remember
with
this
method,
as
with
the
previous
method,
that
the
translator
is
the
dissolved
fraction
in
the
downstream
water.
Box
C­
2
provides
a
procedure
for
developing
the
translator
via
partition
coefficients.
In
Step
1
calculate
the
particulate
fraction,
the
fraction.
C
is
calculated
as
the
difference
P
17
and
the
dissolved
metal
species
times
the
adsorbent
concentration
(
Eqn
2.9).
The
The
particulate
fraction
can
also
be
17
measured
in
the
laboratory
by
filtering
the
solids,
scraping
the
solids
from
the
filter,
drying,
weighing,
and
subjecting
to
appropriate
chemical
analyses.
The
increased
number
of
steps
may
provide
opportunities
for
additional
sources
of
error,
accompanied
by
increased
uncertainty.
See
Eqn
2.2,
2.3,
and
2.4.
Lead
0.000
0.200
0.400
0.600
0.800
1.000
1.200
1.400
1.600
1.800
0
10
20
30
40
50
TSS
Kp
R­
Square
=
0.11
Lead
0.000
5.000
10.000
15.000
20.000
25.000
30.000
35.000
0
10
20
30
40
50
TSS
(
Ct/
Cd)­
1
(
Ct/
Cd)­
1
=
0.62402
*
TSS
R­
Square
=
0.81
49
dissolved
fraction
and
the
partition
coefficient
are
related
according
to
Eqn
2.7.

C.
3.1.
Spatial
Example
Using
Partition
Coefficients
Using
the
same
NY/
NJ
Harbor
data
as
used
above
(
Table
C­
1),
this
example
Figure
3.
K
as
a
function
of
TSS.
P
demonstrates
the
calculation
of
K
and
how
it
P
may
be
used
to
arrive
at
site­
specific
values
of
f
.
D
The
partition
coefficient
­
TSS
data
are
not
as
well
behaved
(
Figure
3)
as
are
the
f
­
TSS
data.
However,
Shi,
et.
al.
(
1996)
D
show
that
after
algebraic
rearrangement
of
Eqn
2.7
to
(
Ct/
Cd)­
1
=
K
°
TSS,
P
K
can
be
obtained
by
linear
regression.
The
P
slope
of
the
curve
is
the
partition
coefficient
(
Figure
4).
Figure
4.
The
fraction
[(
Ct/
Cd)­
1]
as
a
function
of
TSS.

By
regression
analysis,
K
=
0.624
P
L/
mg.
This
value
is
used
in
Eqn
2.7
along
with
an
appropriate
value
of
TSS
to
calculate
the
translator.

C.
3.2.
Time
Series
Example
Using
Partition
Coefficients
Continuing
the
analysis
of
data
collected
from
Clear
Creek,
this
section
demonstrates
estimating
the
dissolved
fraction
by
using
a
site­
specific
partition
coefficient.
The
particulate
sorbed
fraction
is
operationally
defined
as
C
­
C
and
the
T
D
partition
coefficient
is
calculated
as
a
function
of
TSS
according
to
Equation
2.8
following
the
procedure
given
in
Box
2
­
Step
1.
Table
C­
2
presents
the
data
generated
by
the
field
study
as
well
as
the
calculated
values.

Substitute
the
regression
derived
value
of
K
in
Eqn
2.7,
as
suggested
in
Box
2
P
­
Step
3.
As
in
the
previous
example,
the
way
to
use
this
equation
is
to
select
TSS
concentrations
that
are
representative
of
Zinc
0
1
2
3
4
5
6
7
8
0
20
40
60
80
TSS
(
Ct/
Cd)­
1
(
Ct/
Cd)­
1
=
0.107885
*
TSS
R­
Square
=
0.23
50
critical
conditions
in
the
receiving
waterbody
and
calculate
the
dissolved
fractions
(
translator
values)
.

Figure
5.
The
fraction
[(
Ct/
Cd)­
1]
as
a
function
of
TSS.
51
APPENDIX
D
D.
1.
Sample
Size
tatistically,
the
most
A
sample
size
of
4,
therefore,
would
Simportant
objective
for
a
determine
that
a
difference
exists
only
if
the
metal
translator
study
is
to
difference
between
the
means
is
4
or
more.
determine
the
mean
concentrations
of
total
At
very
low
concentrations
typical
of
many
and
dissolved
metal
within
an
acceptable
metals
 
for
example,
if
the
dissolved
copper
confidence
interval
of
the
true
mean
such
that
concentration
is
3
g/
L
and
the
total
the
estimated
dissolved
fraction
is
a
good
concentration
is
6
g/
L
and
is
1
g/
L
 
this
representation
of
the
true
dissolved
fraction.
sample
size
would
not
be
adequate
to
The
null
hypothesis
(
H
)
is:
mean
translator
would
be
rejected,
therefore,
even
0
total
concentration
(
)
=
mean
dissolved
though
it
is
actually
valid.
A
sample
size
of
t
concentration
(
).
8,
on
the
other
hand,
would
be
large
enough
d
To
determine
sample
size,
three
and
support
the
use
of
a
translator
other
than
factors
must
be
selected:
1.

1.
Type
I
error
(
)
is
the
probability
of
A
sample
size
of
10
(
or
greater)
is
rejecting
a
true
hypothesis.
recommended
because
it
would
allow
2.
Type
II
error
(
)
is
the
probability
of
demonstration
of
a
significant
difference
for
accepting
a
false
hypothesis.
somewhat
less
than
2.0,
while
still
keeping
3.
The
expected
difference
between
the
=
=
0.05.
Furthermore,
if
1
or
2
samples
means
(
),
expressed
as
a
multiple
of
have
to
be
discarded
because
of
undetectable
the
standard
deviation
(
),
which
is
concentrations,
outlier
concentrations,
or
assumed
to
be
equal
for
the
two
other
sampling
or
analytical
problems,
there
populations
(
=
=
):
would
still
be
an
adequate
number
of
samples
t
d
=
(
­
)
÷
only
really
reliable
method
of
estimating
how
t
d
For
a
translator
study,
the
null
collect
some
data,
examine
the
statistical
hypothesis
is
assumed
to
be
false,
i.
e.,
there
variability,
and
project
from
that
basis.
is
a
difference
between
total
and
dissolved
concentrations.
Therefore,
must
be
small
to
ensure
that
a
translator
is
not
rejected
(
no
difference
detected
between
the
means)
when
a
difference
does
exist.
For
and
levels
of
0.05,
the
following
shows
the
relationship
between
and
n,
assuming
a
t
distribution:

n
0.05
0.05
1.0
27
2.0
8
3.0
5
4.0
4
demonstrate
that
a
difference
exists.
The
to
show
a
difference
between
the
two
means
to
meet
the
assumed
statistical
criteria.
The
many
samples
are
going
to
be
needed
is
to
52
APPENDIX
E
E.
1.
Topics
covered
in
Method
1669
include:

ontamination
control,
Quality
assurance/
quality
control
Cincluding:
minimizing
procedures,
including:
collection
of
exposure
of
the
sample,
the
an
equipment
blank,
field
blank,
and
wearing
of
gloves,
use
of
metal­
free
field
duplicate.
apparatus,
and
avoiding
sources
of
contamination.
Re­
cleaning
procedures
for
cleaning
Safety,
including:
use
of
material
sites.
safety
data
sheets
and
descriptions
of
the
risks
of
sampling
in
and
around
Suggestions
for
pollution
prevention
water
and
in
hot
and
cold
weather.
and
waste
management.

Apparatus
and
materials
for
Twenty
references
to
the
technical
sampling,
including:
descriptions
and
literature
on
which
the
Method
is
part
numbers
for
sample
bottles,
based
and
a
glossary
of
unique
terms
surface
sampling
devices
such
as
used
in
the
Method.
poles
and
bottles,
a
subsurface
jar
sampling
device,
continuous
flow
samplers
including
peristaltic
and
Table
E­
1
details
some
of
the
submersible
pumps,
glove
bag
for
differences
between
standard
sampling
for
processing
samples,
gloves,
storage
metals
and
sampling
for
trace
metals
using
bags,
a
boat
for
collection
of
samples
the
procedures
outlined
below
and
detailed
in
on
open
waters,
filtration
apparatus
Method
1669.
consistent
with
the
apparatus
studied
and
used
by
USGS,
and
apparatus
for
field
preservation
of
samples.

Reagents
and
standards
for
sample
preservation,
blanks,
and
for
processing
samples
for
determination
of
trivalent
chromium.

Site
selection
Sample
collection
procedures,
including:
"
clean
hands/
dirty
hands"
techniques,
precautions
concerning
wind
direction
and
currents,
manual
collection
of
surface
and
sub­
surface
samples,
depth
sampling
using
a
jar
sampler,
and
continuous
flow
sampling
using
a
pump.
Field
filtration
and
preservation
procedures
using
an
inflatable
glove
bag,
and
instructions
for
packaging
and
shipment
to
the
laboratory.

the
equipment
and
apparatus
between
53
Table
E­
1.
Standard
vs.
Trace
Metals
Sampling
Component
Standard
Sampling
Technique
Trace
Metals
Sampling
(
USEPA,
1983,
1991b)
Technique
(
USEPA,
1995a)
Bottles
Borosilicate
glass,
Fluoropolymer,
polyethylene,
polyethylene,
polypropylene,
or
or
polycarbonate,
filled
and
Teflon
stored
with
0.1%
ultrapure
HCl
®
solution
Cleaning
Wash
with
detergent;
rinse
Detergent
wash,
DI
water
successively
with
tap
water,
1:
1
rinse,
soak
for
2
h
minimum
in
HNO
,
tap
water,
1:
1
HCl,
tap
hot,
concentrated
HNO
,
DI
3
water,
deionized
distilled
water
water
rinse,
soak
for
48
h
(
GFAA
methods;
EPA,
1983).
minimum
in
hot,
dilute
Soak
overnight;
wash
with
ultrapure
HCl
solution,
drain,
detergent;
rinse
with
water;
fill
with
0.1%
ultrapure
HCl
soak
in
HNO
:
HCl:
water
solution,
double
bag,
and
store
3
(
1:
2:
9);
rinse
with
water;
oven
until
use.
dry
(
ICP
Method
200.7;
USEPA,
1991b)
3
Gloves
No
specification.
Powder­
free
(
non­
talc,
class­
100)
latex,
polyethylene,
or
polyvinyl
chloride.
Filter
0.45
µ
m
membrane;
glass
or
Gelman
#
12175
capsule
filter
plastic
filter
holder
or
equivalent
capacity
0.45
µ
m
filter
with
a
minimum
600
cm
2
filtration
area.
Rinsing
the
#
12175
filter
with
1000
ml
ultrapure
water
is
adequate
cleaning
for
current
ambient
level
determinations.
Preservative
Conc.
redistilled
HNO
,
5
ml/
L
Ultrapure
HNO
to
pH
<
2
or
3
(
GFAA
methods;
USEPA,
lab
preserve
and
soak
for
2
1983).
1:
1
HNO
to
pH
<
2
days.
Lab
preserve
samples
3
(
3ml/
L)
(
ICP
Method
200.7;
for
mercury
to
preclude
USEPA,
1991b)
atmospheric
contamination.
3
54
E.
2.
Method
of
Sampling
Sampling
Method
1669
(
USEPA,
submerges
the
sampling
device
to
the
desired
1995a)
provides
detailed
guidance
on
steps
depth
and
pulls
the
cord
to
fill
the
sample
that
can
be
followed
to
collect
a
reliable
bottle.
After
filling,
rinsing,
and
retrieval,
sample
and
preclude
contamination.
Choose
"
clean
hands"
removes
the
sample
bottle
manual
or
continuous
sampling
depending
from
the
sampling
device,
caps
the
bottle,
upon
which
method
is
best
for
the
specific
and
places
it
in
the
sample
bag.
"
Dirty
sampling
program.
Only
trained
personnel
hands"
reseals
the
bag
for
further
processing
should
be
entrusted
the
task
of
sample
or
shipment.
collection.

E.
2.1.
Manual
Sampling
of
Surface
E.
2.3.
Grab
Sampling
of
Subsurface
Water
or
Effluent
Water
or
Effluent
Using
a
Jar
In
the
manual
sampling
procedure,
the
sampling
team
puts
on
gloves
and
orients
In
sampling
with
the
jar
sampling
themselves
with
respect
to
the
wind
and
device,
"
dirty
hands"
removes
the
device
current
to
minimize
contamination.
"
Dirty
from
its
storage
container
and
opens
the
outer
hands"
opens
the
sample
bag.
"
Clean
hands"
bag.
"
Clean
hands"
opens
the
inner
bag,
removes
the
sample
bottle
from
the
bag,
removes
the
jar
sampler,
and
attaches
the
removes
the
cap
from
the
bottle,
and
discards
pump
to
the
flush
line.
"
Dirty
hands"
lowers
the
dilute
acid
solution
in
the
bottle
into
a
the
weighted
sampler
to
the
desired
depth
and
carboy
for
wastes.
"
Clean
hands"
submerges
turns
on
the
pump,
allowing
a
large
volume
the
bottle,
collects
a
partial
sample,
replaces
of
water
to
pass
through
the
system.
After
the
cap,
rinses
the
bottle
and
cap
with
stopping
the
pump,
"
dirty
hands"
pulls
up
the
sample,
and
discards
the
sample
away
from
sampler
and
places
it
in
the
field­
portable
the
site.
After
two
more
rinses,
"
clean
glove
bag.
"
Clean
hands"
aliquots
the
sample
hands"
fills
the
bottle,
replaces
the
cap,
and
into
various
sample
bottles
contained
within
returns
the
sample
to
the
sample
bag.
"
Dirty
the
glove
bag.
If
field
filtration
and/
or
hands"
reseals
the
bag
for
further
processing
preservation
are
required,
these
operations
(
filtration
and/
or
preservation)
or
for
are
performed
at
this
point.
After
shipment
to
the
laboratory.
filtration/
preservation,
"
clean
hands"
caps
E.
2.2.
Grab
Sampling
of
Subsurface
Water
or
Effluent
Using
a
Pole
Sampler
In
sampling
with
the
pole
(
grab)
sampling
device,
"
dirty
hands"
removes
the
pole
and
sampling
device
from
storage
and
opens
the
bag.
"
Clean
hands"
removes
the
sampling
device
from
the
bag.
"
Dirty
hands"
In
the
continuous­
flow
sampling
opens
the
sample
bag.
"
Clean
hands"
technique
using
a
submersible
pump,
the
removes
the
sample
bottle,
empties
the
dilute
sampling
team
prepares
for
sampling
by
acid
shipping
solution
into
the
carboy
for
setup
of
the
pump,
tubing,
batteries,
and,
if
wastes,
and
installs
the
bottle
in
the
sampling
device.
Using
the
pole,
"
dirty
hands"

Sampler
each
bottle
and
returns
it
to
its
bag.
"
Dirty
hands"
seals
the
bag
for
shipment
to
the
laboratory.

E.
2.4.
Continuous
Sampling
of
Surface
Water,
Subsurface
Water,
or
Effluent
Using
a
Submersible
Pump
55
required,
the
filtration
apparatus.
"
Clean
To
preclude
contamination
from
hands"
removes
the
submersible
pump
from
atmospheric
sources,
mercury
samples
should
its
storage
bag
and
installs
the
lengths
of
be
shipped
unfiltered
and
unpreserved
via
tubing
required
to
achieve
the
desired
depth.
overnight
courier
and
filtered
and/
or
"
Dirty
hands"
connects
the
battery
leads
and
preserved
upon
receipt
at
the
laboratory.
cable
to
the
pump,
lowers
it
to
the
desired
depth,
and
turns
on
the
pump.
The
pump
is
allowed
to
run
for
5
­
10
minutes
to
pump
50
­
100
liters
through
the
system.
If
required,
"
clean
hands"
attaches
the
filter
to
the
outlet
Because
the
operational
definition
of
tube.
"
Dirty
hands"
unseals
the
bag
"
dissolved"
is
so
greatly
affected
by
filtration
containing
the
sample
bottle.
"
Clean
hands"
artifacts,
the
Gelman
#
12175
capsule
filter
or
removes
the
bottle,
discards
the
dilute
acid
equivalent
capacity
filter
must
be
used,
shipping
solution
into
the
waste
carboy,
regardless
of
how
the
samples
are
collected.
rinses
the
bottle
and
cap
three
times
with
(
The
next
largest
capacity
filter
is
sample,
collects
the
sample,
caps
the
bottle,
approximately
80
cm
surface
area.)
The
and
places
the
bottle
back
in
the
bag.
"
Dirty
minimization
of
filtration
artifacts
can
be
hands"
seals
the
bag
for
further
processing
or
assured
with
high
capacity
tortuous
path
shipment.
filters
and
limited
sample
volume
(
1000
E.
3.
Preservation
Samples
to
be
analyzed
for
total
Method
1669
is
used
for
samples
collected
recoverable
metals
are
preserved
with
using
the
manual,
grab,
or
jar
collection
concentrated
nitric
acid
(
HNO
)
to
a
pH
less
systems.
In­
line
filtration
using
the
3
than
2.
In
normal
natural
waters,
3­
5
ml
of
continuous­
flow
approach
was
described
acid
per
liter
of
sample
is
recommended
above.
The
filtration
procedure
used
in
(
EPA,
1983,
1991b)
to
achieve
the
required
Method
1669
is
based
on
procedures
used
by
pH.
The
nitric
acid
must
be
known
to
be
free
USGS,
and
the
capsule
filter
is
the
filter
of
the
metal(
s)
of
interest.
Method
1669
evaluated
and
used
by
USGS.
provides
specifications
for
the
acid.
Samples
for
total
recoverable
metals
should
be
The
filtration
system
is
set
up
inside
preserved
immediately
after
sample
a
glove
bag,
and
a
peristaltic
pump
is
placed
collection.
It
is
common
for
laboratories
to
immediately
outside
of
the
glove
bag.
recommend
sample
acidification
in
a
Tubing
from
the
pump
is
passed
through
controlled
uncontaminating
environment
for
small
holes
in
the
glove
bag
to
assure
that
all
both
total
recoverable
and
dissolved
metal
metallic
parts
of
the
pump
are
isolated
from
fractions.
the
sample.
The
capsule
filter
is
also
placed
Field
preservation
is
necessary
for
trivalent
and
hexavalent
chromium.
Field
Using
"
clean
hands/
dirty
hands"
preservation
is
advised
for
hexavalent
techniques,
blank
water
and
sample
are
chromium
in
order
to
provide
sample
pumped
through
the
system
and
collected.
stability
for
up
to
30
days.
The
sample
is
acidified,
placed
back
inside
E.
4.
Filtration
2
ml).
The
Gelman
#
12175
capsule
filter
has
equivalent
filtration
area
of
600
cm
.
2
The
filtration
procedure
given
in
inside
the
glove
bag.

the
sample
bag,
and
shipped
to
the
laboratory.
56
E.
5.
Field
Quality
Assurance
The
study
plan
should
describe
the
sampling
location(
s),
sampling
schedule,
and
Field
blank
­
In
order
to
demonstrate
collection
methodology,
including
explicit
that
sample
contamination
has
not
information
on
the
sampling
protocol.
occurred
during
field
sampling
and
Detailed
requirements
and
procedures
for
sample
processing,
at
least
one
(
1)
field
quality
control
and
quality
assurance
are
field
blank
must
be
generated
for
given
in
USEPA
Method
1669.
If
Method
every
ten
(
10)
samples
that
are
1669
is
not
used,
deviations
from
that
collected
at
a
given
site.
The
field
Method
should
be
described
and
the
Method
blank
is
collected
prior
to
sample
should
be
supplemented
by
standard
collection
and
should
be
collected
for
operating
procedures
(
SOPs)
where
each
trip
to
a
given
site
if
fewer
than
appropriate.
It
is
desirable
to
include
blind
10
samples
are
collected
per
QC
samples
as
part
of
the
project.
sampling
trip.

Equipment
blank
­
Prior
to
the
use
of
Field
blanks
are
generated
by
filling
a
any
sampling
equipment
at
a
given
large,
pre­
cleaned
carboy
or
other
site,
the
laboratory
or
equipment
appropriate
container
with
reagent
cleaning
contractor
is
required
to
water
(
water
shown
to
be
free
from
generate
equipment
blanks
to
metals
at
the
level
required)
in
the
demonstrate
that
the
equipment
is
laboratory,
transporting
the
filled
free
from
contamination.
Two
types
container
to
the
sampling
site,
of
equipment
blanks
are
required:
processing
the
water
through
each
of
bottle
blanks
and
sampling
equipment
the
sample
processing
steps
and
blanks.
equipment
(
e.
g.,
tubing,
sampling
Equipment
blanks
must
be
run
on
all
in
the
field,
collecting
the
field
blank
equipment
that
will
be
used
in
the
in
one
of
the
sample
bottles,
and
field.
If,
for
example,
samples
are
to
shipping
the
bottle
to
the
laboratory
be
collected
using
both
a
grab
for
analysis.
sampling
device
and
the
jar
sampling
device,
then
an
equipment
blank
must
If
it
is
necessary
to
clean
the
be
run
on
both
pieces
of
equipment.
sampling
equipment
between
The
equipment
blank
must
be
collected
after
the
cleaning
analyzed
using
the
same
analytical
procedures
but
before
the
next
procedures
used
for
analysis
of
sample
is
collected.
samples
so
that
contamination
at
the
same
level
is
detected.
If
any
Field
duplicate
­
A
field
duplicate
is
metal(
s)
of
interest
or
any
potentially
used
to
assess
the
precision
of
the
interfering
substance
is
detected
in
field
sampling
and
analytical
the
equipment
blank,
the
source
of
processes.
It
is
recommended
that
at
contamination/
interference
must
be
least
one
(
1)
field
duplicate
sample
identified
and
removed.
The
equipment
must
be
demonstrated
to
be
free
from
the
metal(
s)
of
interest
before
the
equipment
may
be
used
in
the
field.

devices,
filters,
etc.)
that
will
be
used
samples,
a
field
blank
should
be
57
be
collected
for
every
ten
(
10)
samples
that
are
collected
at
a
given
site
or
for
each
sampling
trip
if
fewer
than
10
samples
are
collected
per
sampling
trip.

The
field
duplicate
is
collected
either
by
splitting
a
larger
volume
into
two
aliquots
in
the
glove
bag,
by
using
a
sampler
with
dual
inlets
that
allows
simultaneous
collection
of
two
samples,
or
by
collecting
two
samples
in
rapid
succession.
58
APPENDIX
F
F.
1.
Laboratory
Facility,
Equipment,
and
Reagents
any
of
the
laboratories
analyzing
an
aliquot
from
the
lot
using
the
Mpresently
performing
techniques
and
instrumentation
to
be
used
for
metals
determinations
are
analysis
of
samples.
The
lot
will
be
incapable
of
making
measurements
at
or
near
acceptable
if
the
concentration
of
the
metal
ambient
criteria
levels
because
of
limitations
of
interest
is
below
the
detection
limit
of
the
in
facilities,
equipment,
or
reagents.
The
QC
method
being
used.
Ultrapure
acids
are
Supplement
suggests
the
facilities
available
and
should
be
used
to
preclude
modifications
necessary
to
assure
reliable
contamination
from
this
source,
although
determinations
at
these
levels.
The
technical
grades
of
acid
may
be
pure
enough
modifications
required
can
be
extensive
or
to
be
used
for
the
first
steps
in
the
cleaning
minimal,
depending
on
the
existing
processes.
capabilities
of
the
laboratory.
The
ideal
facility
is
a
class­
100
clean
room
with
walls
Reagent
water­­
water
demonstrated
constructed
of
plastic
sheeting
attached
to
be
free
from
the
metal(
s)
of
interest
and
without
metals
fasteners,
down­
flow
potentially
interfering
substances
at
the
ventilation,
air­
lock
entrances,
pass­
through
method
detection
limit
(
MDL)
for
that
metal
doors,
and
adhesive
mats
for
use
at
entry
in
the
analytical
method
being
used­­
is
points
to
control
dust
and
dirt
from
entering
critical
to
reliable
determination
of
metals
at
via
foot
traffic.
If
painted,
paints
that
do
not
trace
levels.
Reagent
water
may
be
prepared
contain
the
metal(
s)
of
interest
must
be
used.
by
distillation,
deionization,
reverse
osmosis,

Class­
100
clean
benches,
one
other
techniques
that
remove
the
metal(
s)
and
installed
in
the
clean
room;
the
other
adjacent
potential
interferant(
s).
to
the
analytical
instrument(
s)
for
preparation
of
samples
and
standards,
are
recommended
to
preclude
airborne
dirt
from
contaminating
the
labware
and
samples.

All
labware
must
be
metal
free.
Part
136
may
not
be
sufficiently
sensitive
for
Suitable
construction
materials
are
trace
metals
determinations.
The
Agency
fluoropolymer
(
FEP,
PTFE),
conventional
or
believes
dischargers
may
use
more
sensitive
linear
polyethylene,
polycarbonate,
or
methods,
such
as
stabilized
temperature
polypropylene.
Only
fluoropolymer
should
graphite
furnace
atomic
absorption
be
used
when
mercury
is
a
target
analyte.
spectroscopy
(
STGFAA)
and
inductively
The
QC
supplement
suggests
cleaning
coupled
plasma/
mass
spectrometry
procedures
for
labware.
Gloves,
plastic
(
ICP/
MS)
(
USEPA,
1994c)
even
though
wrap,
storage
bags,
and
filters
may
all
be
those
methods
have
not
yet
been
approved
in
used
new
without
additional
cleaning
unless
40
CFR
Part
136
for
general
use
in
Clean
results
of
the
equipment
blank
pinpoint
any
Water
Act
applications.
In
some
instances,
of
these
materials
as
a
source
of
STGFAA
and
ICP/
MS
may
be
preceded
by
contamination.
In
this
case,
either
an
hydride
generation
or
on­
line
or
off­
line
alternate
supplier
should
be
found
or
the
materials
will
need
to
be
cleaned.

Each
reagent
lot
should
be
tested
for
the
metals
of
interest
by
diluting
and
anodic/
cathodic
stripping
voltammetry,
or
F.
2.
Analytical
Methods
The
test
methods
currently
in
40
CFR
preconcentration
to
achieve
these
levels.
The
59
Agency
is
developing
methods
for
those
analysis
of
samples.
This
metals
that
cannot
as
yet
be
measured
at
demonstration
is
comprised
of
tests
ambient
criteria
levels.
The
methods
being
to
prove
that
the
laboratory
can
developed
use
the
apparatus
and
techniques
achieve
the
MDL
in
the
EPA
method
described
in
the
open
technical
literature.
and
the
precision
and
accuracy
This
guidance
does
not
address
the
use
on
specified
in
the
QC
Supplement.
non­
Part
136
methods
in
any
context
other
than
metal
translator
studies
performed
by
Analyses
of
blanks
are
required
the
discharger.
initially
and
with
each
batch
of
Although
analyses
by
STGFAA
are
process
at
the
same
time
to
generally
cheaper
than
those
by
ICP/
MS,
the
demonstrate
freedom
from
cost
differences
are
usually
not
a
limiting
contamination.
consideration
given
the
implications
of
obtaining
a
precise
and
accurate
translator
The
laboratory
must
spike
at
least
value.
Achieving
low
detection
levels
can
10%
of
the
samples
with
the
metal(
s)
add
appreciably
to
the
cost,
but
those
costs
of
interest
to
monitor
method
may
be
justified
if
a
translator
means
the
performance.
When
results
of
these
difference
between
permit
compliance
and
spikes
indicate
atypical
method
noncompliance.
performance
for
samples,
an
F.
3.
Laboratory
Quality
Control
The
QC
Supplement
provides
detailed
quality
control
procedures
that
The
laboratory
must,
on
an
ongoing
should
assure
reliable
results.
The
QC
basis,
demonstrate
through
Supplement
requires
each
laboratory
that
calibration
verification
and
through
performs
trace
metals
determinations
to
analysis
of
a
laboratory
control
operate
a
formal
quality
assurance
program.
sample
that
the
analytical
system
is
The
minimum
requirements
of
this
program
in
control.
consist
of
an
initial
demonstration
of
laboratory
capability,
analysis
of
samples
The
laboratory
must
maintain
records
spiked
with
metals
of
interest
to
evaluate
and
to
define
the
quality
of
data
that
are
document
data
quality,
and
analysis
of
generated.
standards
and
blanks
as
tests
of
continued
performance.
Laboratory
performance
is
In
recognition
of
advances
that
are
compared
to
established
performance
criteria
occurring
in
analytical
technology,
the
to
determine
if
the
results
of
analyses
meet
analyst
is
permitted
to
exercise
certain
the
performance
characteristics
of
the
options
to
eliminate
interferences
or
lower
method.
This
formal
QA
program
has
the
the
costs
of
measurements.
These
options
following
required
elements:
include
alternate
digestion,
concentration,

The
analyst
must
make
an
initial
instrumentation.
Alternate
determinative
demonstration
of
the
ability
to
techniques,
such
as
the
substitution
of
a
generate
acceptable
accuracy
and
colorimetric
technique
or
changes
that
precision
with
the
method
used
for
degrade
method
performance,
are
not
samples
started
through
the
analytical
alternative
extraction
or
cleanup
technique
must
be
used
to
bring
method
performance
within
acceptable
limits.

and
cleanup
procedures
and
changes
in
60
allowed.
If
an
analytical
technique
other
than
the
technique
specified
in
the
EPA
method
is
used,
then
that
technique
must
have
a
specificity
equal
to
or
better
than
the
specificity
of
the
techniques
in
EPA
method
for
the
analytes
of
interest.
