FINAL
REPORT
ESTIMATION
OF
WATER
CHEMISTRY
PARAMETERS
FOR
ACUTE
COPPER
TOXICITY
TESTS
For:

U.
S.
Environmental
Protection
Agency
Health
and
Ecological
Criteria
Division
Office
of
Science
and
Technology,
Office
of
Water
1200
Pennsylvania
Avenue,
NW
Washington,
DC
20460
Great
Lakes
Environmental
Center
Program
Manager
G.
M.
DeGraeve
Great
Lakes
Environmental
Center,
Inc.
739
Hastings
Street,
Traverse
City,
Michigan
49686
Phone:
(
231)
941­
2230
D­
1
CONTENTS
Foreword
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D­
3
1.0
Data
Acquisition
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D­
4
2.0
Technical
Issues
and
Corresponding
Recommendations
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D­
4
2.1
Estimating
Ion
Concentrations
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D­
4
2.2
pH
Adjustment
with
HCl
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D­
6
2.3
Estimation
of
DOC
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D­
7
2.4
DOC
in
Lake
Superior
Water
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D­
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2.5
Applying
Water
Chemistry
Data
to
Lake
Superior
Water
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D­
8
2.6
Predicting
Ionic
Composition
of
WFTS
Well
Water
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D­
8
2.7
Data
for
Measurement
of
Blacksburg/
New
River
Water
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D­
10
2.8
Cu
Concentrations
and
Alkalinity
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D­
11
2.9
Calculation
of
DOC
and
Humic
Acid
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D­
13
2.10
Alkalinity
of
Lake
Superior
Water
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D­
14
2.11
Availability
of
LC50s
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D­
14
2.12
Cl
and
Na
Concentrations
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D­
14
2.13
Calculating
DOC
in
Dilution
Water
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D­
15
2.14
Ionic
Composition
of
Chehalis
River
Water
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D­
15
2.15
Chemistry
of
Water
in
Howarth
and
Sprague
(
1978)
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D­
15
2.16
Default
Values
of
Analyte
Concentrations
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D­
16
2.17
Organic
Carbon
Content
of
Samples
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D­
17
2.18
Additional
Water
Chemistry
Data
Needed
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D­
18
2.19
Estimating
Data
for
Waters
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D­
18
References
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D­
30
Appendix
D­
1,
Calculations
for
Ionic
Composition
of
Standard
Laboratory
Reconstituted
Water
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D­
33
Appendix
D­
2,
Dissolved,
Particulate,
and
Estimated
Total
Organic
Carbon
for
Streams
and
Lakes
by
State
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D­
34
Appendix
D­
3,
Mean
TOC
and
DOC
in
Lake
Superior
Dilution
Water
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D­
36
Appendix
D­
4,
Measured
Hardness
and
Major
Ion
and
Cation
Concentrations
in
WFTS
Well
Water
from
April
1972
to
April
1978
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D­
37
Appendix
D­
5,
Analytical
Results
of
New
and
Clinch
Rivers
and
Sinking
Creek,
VA,
Water
Samples
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D­
39
Appendix
D­
6,
Water
Composition
of
St.
Louis
River,
MN,
from
USGS
NASQAN
and
Select
Relationships
to
Water
Hardness
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D­
40
Appendix
D­
7,
Supplementary
Data
for
Bennett
et
al.
(
1995)
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D­
46
Appendix
D­
8,
Supplementary
Data
for
Richards
and
Beitinger
(
1995)
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D­
49
Appendix
D­
9,
Water
Quality
Data
for
the
American
River,
CA
for
July
1978
Through
December
1980
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D­
50
Appendix
D­
10,
STORET
Data
for
Minnesota
Lakes
and
Rivers
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D­
51
D­
2
TABLES
Table
1.
Standard
Reconstituted
Water
Composition
and
Target
Water
Quality
Characteristics
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D­
5
Table
2.
Calculated
Ion
Concentrations
Based
on
the
Standard
Salts
Added
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D­
6
Table
3.
Adjusted
Ion
Concentrations
for
a
Standard
Reconstituted
Water
Mix
Based
on
Reported
Hardness
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D­
6
Table
4.
Recommended
Spreadsheet
Addition
for
Lake
Superior
Dilution
Water
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D­
8
Table
5.
Predicted
Ion
Concentrations
in
WFTS
Well
Water
Based
on
Measured
Hardness
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D­
10
Table
6.
Comparison
of
Values
for
Untreated
(
Natural)
and
Treated
(
Dechlorinated
City
of
Blacksburg,
VA)
New
River
Water
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D­
12
Table
7.
Estimated
Alkalinity
in
Natural
Surface
Water
Based
on
pH
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D­
13
Table
8.
Estimates
of
Dissolved
Organic
Carbon
and
Percent
Humic
Acid
for
the
Winner
(
1985)
Toxicity
Tests
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D­
13
Table
9.
Example
Calculations
to
Estimate
Water
Chemistry
of
Tests
Conducted
at
100
mg/
L
as
CaCo3
by
Howarth
and
Sprague
(
1978)
Using
a
Mixture
of
University
of
Guelph
Well
Water
and
De­
ionized
Water
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D­
17
FIGURES
Figure
1.
Relationship
Between
Ca
and
Hardness
in
WFTS
Well
Water
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D­
22
Figure
2.
Relationship
Between
Mg
and
Hardness
in
WFTS
Well
Water
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D­
23
Figure
3.
Relationship
Between
Na
and
Hardness
in
WFTS
Well
Water
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D­
24
Figure
4.
Relationship
Between
K
and
Hardness
in
WFTS
Well
Water
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D­
25
Figure
5.
Relationship
Between
Cl
and
Hardness
in
WFTS
Well
Water
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D­
26
Figure
6.
Relationship
Between
SO4
and
Hardness
in
WFTS
Well
Water
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D­
27
Figure
7.
Slopes
of
the
Regression
Equations
Derived
for
Na
Concentration
in
St.
Louis
River,
MN,
Water
Versus
Water
Hardness
from
1973
to
1993
.
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D­
28
Figure
8.
Intercepts
of
the
Regression
Equations
Derived
for
Na
Concentration
in
St.
Louis
River,
MN,
Water
Versus
Water
Hardness
from
1973
to
1993
.
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D­
29
D­
3
FOREWORD
This
report
was
developed
by
the
Great
Lakes
Environmental
Center.
Some
minor
revisions
were
made
by
the
U.
S.
Environmental
Protection
Agency
(
EPA).
These
revisions
were
primarily
editorial.
Additional
editorial
and
formatting
revisions
were
made
by
the
CDM
Group,
Inc.

The
purpose
of
this
report
is
to
provide
input
water
chemistry
information
for
a
Biotic
Ligand
Model
(
BLM)
analysis
of
the
acute
copper
toxicity
data
in
Table
1a
of
the
U.
S.
Environmental
Protection
Agency's
(
EPA)
draft
2003
Update
of
Ambient
Water
Quality
Criteria
for
Copper.
EPA
will
use
these
BLM
data
to
derive
adjusted
aquatic
life
criteria
for
copper.
Many
of
the
reported
Table
1a
acute
copper
toxicity
data
lack
sufficient
information
on
the
chemistry
of
the
dilution
water
to
generate
BLM­
derived
critical
accumulation
values.
This
compendium
contains
data
from
the
primary
authors
of
these
articles.
It
also
contains
recommendations
for
the
use
of
these
data,
additional
supporting
documentation
and/
or
computations,
and
recommendations
for
estimating
missing
parameters.
D­
4
Estimation
of
Water
Chemistry
Parameters
for
Acute
Copper
Toxicity
Tests
To
prepare
for
the
possibility
of
incorporating
the
Biotic
Ligand
Model
(
BLM)
(
Di
Toro
et
al.
2001)
into
an
updated
copper
aquatic
life
criteria
document,
the
U.
S.
Environmental
Protection
Agency
(
EPA)
sought
to
generate
a
data
table
summarizing
the
acute
toxicity
of
copper
to
freshwater
organisms
that
included
the
following
parameters:
alkalinity,
dissolved
organic
carbon
(
DOC),
pH,
and
the
major
anions
(
Cl
and
SO4)
and
cations
(
Ca,
Mg,
Na,
K)
of
the
test
water.
Published
literature
was
reviewed
and
appropriate
information
tabulated,
but
measurements
for
many
of
the
aforementioned
parameters
were
not
reported.
To
resolve
the
overwhelming
number
of
missing
test
water
chemistry
values
in
the
database,
certain
authors
were
contacted
for
additional
information
and
to
obtain
additional
measurements
in
waters
where
critical
information
was
either
not
measured
or
not
reported.
EPA
also
attempted
to
determine
appropriate
methods
for
estimating
test
water
chemistry
in
the
absence
of
reported
values.
The
information
received
from
the
authors
and
recommended
procedures
for
estimating
missing
parameters
are
the
subject
of
this
report.

1.0
Data
Acquisition
The
authors
of
several
studies
were
contacted
for
additional
information
on
the
chemistry
of
the
water
or
methods
used
in
their
studies.
If
the
primary
or
corresponding
authors
could
not
be
contacted,
an
attempt
was
made
to
contact
secondary
authors
or
personnel
from
the
laboratories
where
the
studies
had
been
conducted.
In
a
few
instances,
this
initial
effort
failed
to
produce
the
desired
information,
and
censored
databases
(
U.
S.
Geological
Survey's
[
USGS]
National
Stream
Quality
Accounting
Network
[
NASQAN]
and
EPA's
STOrage
and
RETrieval
[
STORET]
data
warehouse)
were
consulted
to
obtain
the
missing
data.
As
a
last
resort,
other
available
sources
of
water
compositional
data
(
e.
g.,
city
drinking
water
treatment
officials)
were
contacted.

The
acquired
data
were
scrutinized
for
representativeness
and
usefulness
in
estimating
surrogate
values
to
complete
the
water
quality
information
in
the
original
studies.
Summary
tables
and
figures
generated
from
these
data
are
included
in
the
following
pages,
which
serve
as
the
basis
for
the
addition
of
values
in
the
spreadsheets.
Information
used
for
the
tabular
and
graphical
summaries
of
these
data
is
included
in
separate
appendices.

2.0
Technical
Issues
and
Corresponding
Recommendations
2.1
Estimating
Ion
Concentrations
Develop
a
methodology
for
estimating
Ca,
Mg,
Na,
K,
Cl,
and
SO4
concentrations
in
laboratoryreconstituted
waters.

Recommendation:
The
best
approach
for
estimating
ion
concentrations
in
standard
laboratoryreconstituted
water
involves
scaling
default
ion
concentrations
based
on
measured
hardness.
The
default
ion
concentrations
can
be
computed
from
the
concentrations
of
the
salts
added.
The
use
of
calculated
ion
concentrations
as
input
for
the
BLM
applies
only
to
reconstituted
water
prepared
following
the
standard
recipes
reported
in
guidance
documents
for
conducting
acute
bioassays
with
aquatic
organisms
(
ASTM
2000;
U.
S.
EPA
1993)
(
see
Table
1).
If
similar
salts
are
added
in
different
amounts,
then
the
ion
concentrations
must
be
calculated
using
the
recipe
reported
in
the
article.
Otherwise,
specific
ion
ratios,
and
more
importantly
ion
concentrations,
cannot
be
calculated.
D­
5
Table
1.
Standard
Reconstituted
Water
Composition
and
Target
Water
Quality
Characteristics
Water
Type
Reagent
Added
(
mg/
L)
Final
Water
Quality
NaHCO3
CaSO4

2H2O
MgSO4
KCl
pHa
Hardnessa
Alkalinityb
Very
Soft
12.0
7.5
7.5
0.5
6.4­
6.8
10­
13
10­
13
Soft
48.0
30.0
30.0
2.0
7.2­
7.6
40­
48
30­
35
Mod.
Hard
96.0
60.0
60.0
4.0
7.4­
7.8
80­
100
60­
70
Hard
192.0
120.0
120.0
8.0
7.6­
8.0
160­
180
110­
120
Very
Hard
384.0
240.0
240.0
16.0
8.0­
8.4
280­
320
225­
245
a
Approximate
equilibrium
pH
after
24­
hour
aeration
b
Expressed
as
mg/
L
CaCO3
When
standard
laboratory­
reconstituted
water
is
cited
as
the
dilution
water,
and
no
additional
measurements
are
reported,
the
recommended
approach
for
estimating
ion
concentrations
is
to
use
the
ion
concentrations
calculated
from
the
amount
of
salts
added
for
the
type
of
reconstituted
water
reported
in
the
article.
For
example,
if
the
range
of
hardness
of
the
reconstituted
water
is
reported
as
80­
100
mg/
L
CaCO3,
then
the
specific
ion
concentrations
calculated
from
the
standard
recipe
for
moderately
hard
reconstituted
water
should
be
used
for
BLM
input
(
see
Table
2
and
example
calculation
in
Appendix
D­
2).
The
use
of
ion
concentrations
calculated
from
the
standard
recipes
assumes
that
salts
were
stored
in
a
manner
to
prevent
hydration
and
that
technician
errors
in
weighing
of
salts,
measurements
of
dilution
water,
and
measurement
of
solution
volumes
were
minimal.

Alternatively,
if
the
authors
state
that
moderately
hard
water
was
prepared
following
one
of
the
standard
recipes,
and
they
measured
the
hardness
of
the
water,
then
the
calculated
ion
concentrations
should
be
adjusted
to
account
for
any
difference
from
the
mean
of
the
expected
range.
For
example,
if
the
mean
measured
hardness
in
a
test
water
prepared
using
the
recipe
for
moderately
hard
reconstituted
water
was
78
mg/
L
CaCO3,
the
Ca:
Mg
ratio
would
be
0.700
for
all
reconstituted
water
types,
and
the
respective
Ca
and
Mg
concentrations
could
be
calculated
using
the
following
equations:

Ca
=
(
0.4008
×
measured
hardness)
÷
[
1+(
1
÷
Ca:
Mg
ratio)]
Equation
1
Mg
=
(
0.2431
×
measured
hardness)
÷
(
1+
Ca:
Mg
ratio)
Equation
2
The
remaining
ion
concentrations
are
each
multiplied
by
0.92
(
quotient
of
78
and
85
mg/
L
CaCO3,
the
latter
of
which
is
the
expected
hardness
for
moderately
hard
reconstituted
water),
as
in
Table
1.

Table
3
provides
ion
concentrations
predicted
for
a
standard
reconstituted
water
mix
using
the
hardness
adjustment
in
accordance
with
the
example
above.

Note
that
this
same
rationale
for
scaling
the
default
major
anions
and
cations
in
reconstituted
water
also
applies
to
a
variety
of
natural
surface
and
well
waters.
Analysis
of
St.
Louis
River,
MN,
water
and
Western
Fish
Toxicology
Station
(
WFTS)
well
water
indicated
that
a
strong
linear
relationship
also
exists
between
water
hardness
and
the
major
anion
(
Cl,
SO4)
and
cation
(
Ca,
Mg,
Na)
concentrations
in
these
water
types
(
see
Sections
2.6,
2.7,
and
2.19).
The
strong
relationships
are
consistent
with
findings
D­
6
Table
2.
Calculated
Ion
Concentrations
Based
on
the
Standard
Salts
Added
Water
Type
(
Nominal
Hardness
Range)
Specific
Ionsa
(
mg/
L)

Ca:
Mgb
Expected
Hardness
(
mg/
L
CaCO3)
c
Ca
Mg
Na
K
Cl
SO4
Very
Soft
(
10­
13
mg/
L
CaCO3)
1.75
1.51
3.28
0.262
0.238
10.2
0.700
11
Soft
(
40­
48
mg/
L
CaCO3)
6.99
6.06
13.1
1.05
0.951
40.7
0.700
42
Moderately
Hard
(
80­
100
mg/
L
CaCO3)
14.0
12.1
26.3
2.10
1.90
81.4
0.700
85
Hard
(
160­
180
mg/
L
CaCO3)
27.9
24.2
52.5
4.20
3.80
163
0.700
170
Very
Hard
(
280­
320
mg/
L
CaCO3)
55.9
48.5
105
8.39
7.61
325
0.700
339
a
Ion
concentrations
were
calculated
from
standard
salt
recipes
(
refer
to
Table
1
and
example
calculation
for
very
soft
water
in
Appendix
D­
1).
b
Ratio
equals
quotient
of
(
Ca
÷
40.08)
and
(
Mg
÷
24.31),
where
40.08
and
24.31
are
the
molecular
weights
of
Ca
and
Mg,
respectively,
in
units
of
mg/
mmol.
c
Hardness
calculated
according
to
the
concentrations
of
Ca
and
Mg
given
here
and
the
equation
given
in
Appendix
D­
1.

Table
3.
Adjusted
Ion
Concentrations
for
a
Standard
Reconstituted
Water
Mix
Based
on
Reported
Hardness
Moderately
Hard
Reconstituted
Water
Hardness
(
mg/
L
CaCO3)
Specific
Ions
(
mg/
L)

Ca
Mg
Na
K
Cl
SO4
Nominal
85a
14.0
12.1
26.3
2.10
1.90
81.4
Adjusted
78
12.9
11.2
24.2
2.10
1.75
74.9
a
Expected
hardness
based
on
the
amount
of
salts
added
(
from
Table
1).
Calcium
and
magnesium
are
calculated
using
Equations
1
and
2.
Other
adjusted
values
(
italic
and
bold)
are
a
result
of
the
product
of
the
ratio
of
measured
hardness
(
78
mg/
L)
to
expected
hardness
(
85
mg/
L)
and
nominal
ion
concentrations,
e.
g.,
the
adjusted
sodium
ion
concentration
for
a
standard
laboratory
reconstituted
water
mix
based
on
a
reported
total
hardness
of
78
mg/
L
CaCO3
is:
78
÷
85=
0.92;
0.92*
26.3=
24.2.

presented
in
an
earlier
comprehensive
report
by
Erickson
(
1985).
Note,
however,
that
because
there
is
generally
poor
correlation
between
K
and
water
hardness
in
the
various
ambient
surface
and
ground
water
types
(
see
Section
2.6),
the
value
calculated
for
K
should
not
be
scaled
according
to
hardness.

2.2
pH
Adjustment
with
HCl
Schubauer­
Berigan
et
al.
(
1993)
adjusted
pH
using
HCl
but
reported
only
nominal
hardness
and
alkalinity.
The
tests
were
conducted
at
the
EPA
Office
of
Research
and
Development,
Mid­
Continent
Ecology
Division,
Duluth,
MN,
using
a
standard
very
hard
reconstituted
water
mix.
The
authors
need
to
be
contacted
to
obtain
any
additional
water
chemistry
data
they
might
have.
D­
7
Recommendation:
Alkalinity
and
hardness
were
not
measured
in
the
tests
reported
in
Schubauer­
Berigan
et
al.
(
1993),
and
no
additional
water
chemistry
data
are
available
from
the
study
(
Phil
Monson,
U.
S.
EPA­
Duluth,
personal
communication).
The
HCl
required
to
adjust
the
pH
was
assumed
to
be
added
in
amounts
too
small
to
significantly
affect
any
of
the
other
water
quality
parameters
(
Gerald
Ankley,
U.
S.
EPA­
Duluth,
personal
communication).
Based
on
these
remarks,
we
believe
ion
concentrations
for
this
particular
study
should
be
estimated
using
methods
outlined
in
Section
2.1.

2.3
Estimation
of
DOC
How
should
DOC
be
estimated
if
only
total
organic
carbon
(
TOC)
was
measured
in
the
study?
Can
DOC
be
estimated
if
no
measurements
of
organic
carbon
were
reported
in
the
study?

Recommendation:
As
a
general
rule,
TOC
values
can
be
used
directly
in
place
of
DOC
for
dechlorinated
and
de­
ionized
city
tap
water,
well
water,
and
oligotrophic
lake
water
(
e.
g.,
Lake
Superior
water).
TOC
values
are
not
recommended
in
place
of
DOC
for
water
from
estuaries,
wetlands,
or
higher
order
streams
unless
data
are
included
that
indicate
otherwise.
Rather,
the
proportion
of
organic
carbon
expected
to
be
dissolved
in
surface
waters
should
be
estimated
and
used
to
scale
the
measured
TOC
value.
When
possible,
the
DOC:
TOC
ratio
for
a
surface
water
should
be
obtained
using
the
USGS
NASQAN
dataset.
The
NASQAN
dataset
can
be
reached
through
the
USGS
Web
site
(
water.
usgs.
gov/
nasqan/
data/
finaldata.
html).
If
a
representative
ratio
for
a
particular
body
of
water
cannot
be
determined,
the
ratio
for
the
particular
water
type
(
lake
or
stream)
should
be
obtained
from
the
final
draft
of
the
Ambient
Water
Quality
Criteria
Derivation
Methodology
Human
Health
Technical
Support
Document
(
U.
S.
EPA
1998a,
Table
2.4.11).
A
summary
of
these
data,
by
State,
is
provided
in
Appendix
D­
2.
In
this
appendix,
TOC
is
operationally
defined
as
the
sum
of
DOC
and
particulate
organic
carbon
(
POC).
The
national
mean
fraction
of
organic
carbon
is
86
percent
for
streams
and
88
percent
for
lakes.
The
DOC:
TOC
ratio
can
be
applied
to
lakes
or
streams
within
a
State
to
obtain
an
estimate
of
DOC
from
values
reported
for
TOC.

Example:

Reference
Water
Body
TOC
(
mg/
L)
DOC:
TOC
Estimated
DOC
(
mg/
L)

Lind
et
al.
manuscript
St.
Louis
R,
MN
32
0.87
28
For
tests
with
reconstituted,
city
tap,
or
well
water,
default
DOC
values
can
be
applied
if
the
author
does
not
report
a
measured
value.
The
recommended
default
TOC
(
DOC)
value
for
laboratory
prepared
reconstituted
water
is
0.5
mg
carbon/
L
(
note:
some
newer
laboratory
water
systems
can
achieve
a
TOC
of
less
than
0.5
mg/
L).
For
regular
city
tap
and
well
water,
a
value
of
1.6
mg
carbon/
L
can
be
assumed.
The
recommended
default
value
for
laboratory­
prepared
reconstituted
water
is
based
on
the
arithmetic
mean
of
recent
measurements
of
DOC
in
reconstituted
water
prepared
at
two
Federal
(
U.
S.
EPA
Cincinnati,
OH,
and
USGS
Yankton,
SD)
and
two
consulting
(
Commonwealth
Biomonitoring
and
GLEC)
laboratories
(
range
0.1
to
1
mg/
L).
The
recommended
default
value
for
dechlorinated
city
tap
and
well
water
is
based
on
the
arithmetic
mean
of
measurements
of
DOC
in
source
water
from
Lake
Ontario
(
Environment
Canada,
Burlington,
ON)
and
the
New
River,
VA
(
City
of
Blacksburg,
VA),
and
well
water
from
Oak
Ridge
National
Laboratory
(
Oak
Ridge,
TN)
and
EPA's
WFTS
(
Corvallis,
OR).
The
DOC
values
in
these
waters
ranged
from
1.1
to
2.5
mg/
L.

For
tests
conducted
in
surface
waters,
we
do
not
recommend
the
use
of
a
default
DOC
value
because
of
the
large
variability
of
DOC
observed.
Rather,
a
reliable
database
such
as
USGS
NASQAN
(
as
described
above)
should
be
searched
for
DOC
measurements.
If
a
database
such
as
NASQAN
is
consulted,
D­
8
only
those
DOC
measurements
closest
to
the
time
of
the
study
should
be
considered
as
surrogate
values.
In
general,
these
DOC
concentrations
should
not
differ
by
more
than
a
factor
of
1.25.
If
DOC
measurements
for
the
surface
water
cannot
be
obtained
from
a
reliable
source,
then
the
toxicity
test
should
not
be
included
in
Table
1
for
BLM
normalization.

2.4
DOC
in
Lake
Superior
Water
Lake
Superior
water
has
been
used
in
a
number
of
acute
and
chronic
toxicity
studies
included
in
the
Aquatic
Life
Criteria
for
Copper
(
U.
S.
EPA
1998b).
Dissolved
organic
matter
(
DOM)
in
Lake
Superior
is
assumed
to
be
anywhere
from
1
to
3
mg/
L
(
Russ
Erickson,
U.
S.
EPA­
Duluth,
personal
communication;
McGeer
et
al.
2000).
This
value
is
expected
to
be
at
least
90
percent
of
TOC
(
or
2
mg/
L)
(
see
Spehar
and
Fiandt
1986).
A
default
value
based
on
recent
measurements
is
needed
for
DOC
in
Lake
Superior
water.

Recommendation:
Recent
measurements
of
TOC
in
Lake
Superior
dilution
water
are
in
Appendix
D­
3
(
Greg
Lien,
U.
S.
EPA­
Duluth,
personal
communication).
The
geometric
mean
concentration
of
TOC
in
Lake
Superior
dilution
water
from
multiple
measurements
is
1.27
mg/
L.
Given
the
recommendation
in
Section
2.3,
the
recommended
DOC
for
Lake
Superior
dilution
water
is
1.1
mg/
L
(
1.27
mg/
L
×
0.88).

2.5
Applying
Water
Chemistry
Data
to
Lake
Superior
Water
The
ionic
composition
included
in
the
Table
1
spreadsheet
for
Lake
Superior
water
is
based
on
concentrations
converted
from
values
reported
in
Erickson
et
al.
(
1996b):
Ca
at
0.68
meq/
L
=
13.6
mg/
L;
Mg
at
0.24
meq/
L
=
2.9
mg/
L;
Na
at
0.065
meq/
L
=
1.5
mg/
L;
K
at
0.015
meq/
L
=
0.59
mg/
L;
SO4
at
0.070
meq/
L
=
3.4
mg/
L;
Cl
at
0.035
meq/
L
=
1.2
mg/
L;
and
alkalinity
at
0.85
meq/
L
=
43
mg/
L.
The
concentrations
for
most
of
these
parameters
were
also
reported
in
Biesinger
and
Christensen
(
1972)
and
approximate
those
listed
above.
Should
the
Erickson
et
al.
(
1996b)
data
be
applied
to
all
Lake
Superior
studies,
or
is
there
a
stronger
rationale
for
applying
the
Biesinger
and
Christensen
(
1972)
data
to
the
older
studies?

Recommendation:
We
recommend
applying
the
mean
of
the
Erickson
et
al.
(
1996b)
citation
and
Biesinger
and
Christensen
(
1972)
water
chemistry
data
to
all
Lake
Superior
studies
prior
to
1987,
when
the
results
were
initially
reported.
After
1987,
we
recommend
use
of
the
Erickson
et
al.
(
1996b)
water
chemistry
data
alone
(
Table
4).
For
each
test,
Ca
and
Mg
concentrations
should
be
estimated
using
Equations
1
and
2,
the
Ca:
Mg
ratios
given
below,
and
the
measured
hardness
of
the
test
water
(
Section
2.1).
Ions
other
than
K
should
be
scaled
according
to
the
measured
test
hardness,
also
discussed
in
Section
2.1.

Table
4.
Recommended
Spreadsheet
Addition
for
Lake
Superior
Dilution
Water
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Pre­
1987a
46
42
13.6
3.0
2.75
1.3
0.57
1.2
3.4
Post­
1987b
46
43
13.6
2.9
2.84
1.5
0.59
1.2
3.4
a
Mean
of
the
Erickson
et
al.
(
1996b)
and
Biesinger
and
Christensen
(
1972)
water
chemistry
data
b
Erickson
et
al.
(
1996b)
water
chemistry
data
alone
2.6
Predicting
Ionic
Composition
of
WFTS
Well
Water
D­
9
The
following
studies
seem
were
conducted
at
EPA's
WFTS
using
well
water:
Andros
and
Garton
(
1980),
Chapman
(
1975,
1978),
Chapman
and
Stevens
(
1978),
Lorz
and
McPherson
(
1976),
Nebeker
et
al.
(
1984a,
1986a,
b),
and
Seim
et
al.
(
1984).
Among
these
studies,
however,
there
is
a
wide
range
of
hardness
values
(
20­
100
mg/
L),
and
the
ionic
composition
of
the
water
was
not
always
reported.

The
large
variation
in
WFTS
well
water
hardness,
and
consequently,
ionic
composition,
is
due
to
seasonal
variability
(
Samuelson
1976).
The
TOC
content
of
this
water
has
been
reported
to
be
1.1
mg/
L
(
McCrady
and
Chapman
1979),
of
which
100
percent
is
expected
to
be
dissolved.
A
general
strategy
is
needed
to
predict
the
ionic
composition
of
WFTS
well
water
based
on
measured
water
hardness.

Recommendation:
The
well
feeding
the
WFTS
is
susceptible
to
influx
from
ground
water
during
rain
events
in
late
fall
and
winter
(
November
through
March
or
April).
During
this
period
the
water
hardness
can
reach
measured
levels
as
high
as
100
mg/
L
CaCO3.
Over
the
remaining
months
(
particularly
from
July
to
November),
hardness
stabilizes
at
around
25
to
40
mg/
L
CaCO3,
as
do
other
water
quality
parameters
(
Al
Nebeker,
U.
S.
EPA
Corvallis,
personal
communication;
Samuelson
1976).
It
is
important
to
note
that
the
high
hardness
reported
for
WFTS
well
water
is
sporadic,
even
in
the
winter.

The
recommended
strategy
for
filling
the
existing
gaps
in
data
reported
from
studies
using
this
well
water
is
to
estimate
the
ion
concentrations
on
the
basis
of
their
relationship
to
the
total
hardness
measured
during
a
particular
test.
The
acceptability
of
tests
conducted
using
WFTS
water
depends
on
the
range
of
hardness
values
reported,
i.
e.,
if
the
hardness
varies
widely
over
the
course
of
a
particular
test,
then
perhaps
the
test
should
not
be
used.
Regression
analyses
were
performed
using
measured
hardness
and
ion
data
for
the
WFTS
well
water
reported
in
Samuelson
(
1976),
April
1972
to
April
1974,
and
supplemented
with
additional
data
from
Gary
Chapman,
personal
communication
(
only
those
data
from
May
1974
to
April
1978;
see
Appendix
D­
4).
These
relationships
and
the
corresponding
regression
equations
are
presented
in
Figures
1
through
6
(
found
at
the
end
of
this
report).
Major
ion
concentrations
for
WFTS
well
water
were
predicted
using
the
regression
equations
over
a
wide
range
of
water
hardness
(
10
to
80
mg/
L
CaCO3)
to
determine
the
accuracy
of
the
procedure
(
Table
5).
The
error
between
predicted
and
measured
ion
concentrations
is
generally
within
10
percent
for
all
ions
except
K,
where
a
default
value
of
0.7
mg/
L
was
chosen
for
all
hardness
levels
(
actual
range
is
0.1
to
1.1
mg/
L,
with
the
majority
of
data
falling
between
0.5
and
0.9
mg/
L).
The
correlation
coefficient
(
R2)
for
the
relationship
between
K
and
water
hardness
in
WFTS
well
water
was
only
0.124.
Note:
BLM
predictions
of
copper
gill
accumulation
and
toxicity
are
relatively
insensitive
to
the
concentration
of
K,
so
errors
in
its
estimation
should
not
appreciably
affect
model
predictions.
The
following
regression
equations
were
used
to
generate
the
example
data
provided
in
Table
5:

[
Ca]
=
0.3085
+
(
measured
hardness
*
0.2738)
[
Mg]
=
0.5429
+
(
measured
hardness
*
0.0573)
[
Na]
=
3.3029
+
(
measured
hardness
*
0.0713)
[
Cl]
=
2.7842
+
(
measured
hardness
*
0.1278)
[
SO4]
=
­
3.043
+
(
measured
hardness
*
0.2816)

Lorz
and
McPherson
(
1976)
and
the
Seim
et
al.
(
1984)
tests
were
not
run
in
WFTS
well
water,
but
in
water
from
different
wells
along
the
Willamette
River.
Water
chemistry
appears
to
be
less
variable
for
these
wells
(
Harold
Lorz
and
Wayne
Seim,
personal
communication).
The
following
additional
water
chemistry
information
for
the
two
well
water
types
used
in
these
studies
was
provided
by
the
respective
authors
in
January
2001.
D­
10
Many
of
the
studies
conducted
by
Chapman
used
reverse
osmosis
treatment
to
maintain
a
blended
water
supply
that
was
of
essentially
constant
ion
content
throughout
the
tests.
All
the
test
data
from
Chapman
appear
to
be
acceptable;
the
only
test
complicated
by
fluctuating
hardness
was
the
22­
month
chronic
zinc
test
with
sockeye
salmon,
and
that
test
produced
only
a
NOEC.
Table
5.
Predicted
Ion
Concentrations
in
WFTS
Well
Water
Based
on
Measured
Hardness
Total
Hardness
(
Mean
Measured
value)
mg/
L
CaCO3
Predicted
Ion
Concentrations
(
mg/
L)

Ca
Mg
Na
Cl
SO4
Defaulta
K
15.00
4.42
1.40
4.10
4.70
1.18
0.70
20.00
5.78
1.69
4.46
5.34
2.59
0.70
25.00
7.15
1.98
4.82
5.98
4.00
0.70
30.00
8.52
2.26
5.17
6.62
5.41
0.70
35.00
9.89
2.55
5.53
7.26
6.81
0.70
40.00
11.26
2.83
5.88
7.90
8.22
0.70
45.00
12.63
3.12
6.24
8.54
9.63
0.70
50.00
14.00
3.41
6.60
9.17
11.04
0.70
55.00
15.37
3.69
6.95
9.81
12.45
0.70
60.00
16.74
3.98
7.31
10.45
13.85
0.70
65.00
18.11
4.27
7.67
11.09
15.26
0.70
70.00
19.47
4.55
8.02
11.73
16.67
0.70
75.00
20.84
4.84
8.38
12.37
18.08
0.70
80.00
22.21
5.13
8.74
13.01
19.49
0.70
a
Value
not
corrected.
Assume
default
value
of
0.70
mg/
L.

Recommended
Spreadsheet
Addition
for
Oregon
Well
Water.

Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ionsa
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Lorz
and
McPherson
1976
95
66
6.8­
7.9
1.6B
19
12
1.0
7.6
1.0
7.0
12
Seim
et
al.
1984
120
126
7.7
1.6B
34
8.6
2.4
15
0.7
5.0
2.3
a
Specific
ion
values
were
obtained
through
personal
communication
with
the
primary
authors;
hardness,
alkalinity,
and
pH
values
are
as
reported
in
the
article.
The
Ca:
Mg
ratios
were
calculated
on
the
basis
of
data
provided
by
authors,
then
Ca
and
Mg
values
used
were
back­
calculated
on
the
basis
of
these
ratios
and
the
measured
test
hardness
(
see
Equations
1
and
2).
b
Suggested
default
value
for
untreated
well
water
(
see
Section
2.3).

2.7
Data
for
Measurement
of
Blacksburg/
New
River
Water
A
substantial
amount
of
acute
copper
toxicity
data
to
various
freshwater
organisms
is
reported
using
dechlorinated
City
of
Blacksburg,
VA,
tap
water.
These
include
studies
by
Belanger
et
al.
(
1989),
Cairns
et
al.
(
1981),
Hartwell
et
al.
(
1989),
and
Thompson
et
al.
(
1980).
Hardness,
alkalinity,
and
pH
values
are
reported
for
City
of
Blacksburg
water
in
all
of
these
studies,
but
the
ionic
compositional
data
are
not.
This
information
is
required
to
obtain
BLM­
normalized
LC50s
for
these
data.
D­
11
Recommendation:
According
to
Don
Cherry
(
personal
communication),
tests
conducted
at
Virginia
Polytechnic
Institute
and
State
University
used
City
of
Blacksburg,
VA,
tap
water,
which
is
drawn
from
the
nearby
New
River.
Don
Cherry
collected
a
sample
of
New
River
water
for
analysis
under
Work
Assignment
1­
20.
The
results
of
the
analysis
are
provided
in
Appendix
D­
5.
The
sample
was
of
untreated
natural
water
prior
to
any
treatment
by
the
City
of
Blacksburg.
Values
for
treated
New
River
water
(
city)
were
provided
by
Jerry
Higgins,
Water
Superintendent,
City
of
Blacksburg.
Table
6
summarizes
the
measured
values
for
New
River
and
City
of
Blacksburg
dechlorinated
tap
water.

Historically,
hardness
and
alkalinity
vary
substantially
in
dechlorinated
City
of
Blacksburg
tap
water
and
in
raw
New
River
water
(
Table
6).
Some
of
this
difference
may
be
attributed
to
seasonal
effects.
For
example,
strong
seasonal
influence
was
observed
in
both
well
water
(
influenced
by
surface
water,
i.
e.,
WFTS
well
water;
see
Section
2.6)
and
a
natural
surface
water
(
St.
Louis
River,
MN;
refer
ahead
to
Section
2.19).
Previously,
we
plotted
ion
concentrations
against
hardness
for
each
of
these
two
water
types
(
Figures
1
through
6
and
Appendix
D­
6).
The
relationships
were
good
in
almost
all
cases
(
positive,
R2
=
0.5
to
0.9),
and
the
resultant
regression
equations
were
used
to
scale
ion
concentrations
according
to
reported
water
hardness.
Incomplete
datasets,
however,
preclude
the
use
of
the
same
approach
for
City
of
Blacksburg
tap
and
raw
New
River
water.
Instead,
we
recommend
using
the
ion
and
hardness
values
from
the
City
of
Blacksburg
water
sample
and
USGS
NASQAN
ion
data,
respectively
(
Table
6),
to
generate
surrogate
ion
values
for
the
respective
waters
that
were
not
reported
in
the
previous
studies
(
indicated
by
the
shaded
area
in
Table
6).
The
operation
is
simply
to
multiply
ion
concentrations
for
the
"
acquired
data"
by
the
ratio
of
hardness
values
in
City
of
Blacksburg
and
NASQAN
water
and
the
corresponding
test
waters
as
was
done
in
Section
2.1.
We
used
the
NASQAN
ion
data
as
the
basis
for
scaling
the
raw
New
River
water
ion
estimates
because
NASQAN
represents
data
collected
over
several
representative
years,
including
the
years
in
the
timeframe
in
which
the
studies
of
interest
were
initiated
and
completed.
The
exception
was
with
DOC.
We
felt
that
the
DOC
value
obtained
from
the
sample
of
New
River
water
collected
in
August
2000
would
be
more
representative
than
the
few
values
generated
from
NASQAN
(
all
pre­
1980).

2.8
Cu
Concentrations
and
Alkalinity
The
methods
sections
of
both
Belanger
and
Cherry
(
1990)
and
Belanger
et
al.
(
1989)
state
that
total
and
dissolved
Cu
were
measured,
but
it
is
not
clear
whether
the
reported
LC50s
are
based
on
total
or
dissolved
copper
concentration.
Also,
in
Belanger
and
Cherry
(
1990),
pH
was
adjusted
with
sodium
hydroxide
(
NaOH)
or
nitric
acid
(
HNO3),
but
only
nominal
pHs
were
reported.
Alkalinity
and
hardness
after
pH
adjustment
were
not
reported.
Can
alkalinity
be
adjusted
for
these
tests?

Recommendation:
The
concentration
Cu
in
algae
is
reported
on
a
total
metal
basis
in
Belanger
et
al.
(
1989)
and
Belanger
and
Cherry
(
1990).
The
Cu
in
water
is
reported
on
an
acid­
soluble
basis.
The
acidsoluble
concentration
of
Cu
in
water
was
used
to
derive
the
LC50.
For
all
intents
and
purposes,
acidsoluble
Cu
can
be
considered
as
dissolved
Cu
because
the
acidification
of
the
filtrate
after
filtration
is
probably
sufficient
to
obtain
most
of
the
Cu
associated
with
colloidal
material.
Normally
a
digestion
procedure
is
required
to
convert
all
Cu
to
the
dissolved
form.
If
the
sample
had
not
been
filtered,
it
would
not
have
been
acceptable
because
it
could
have
been
elevated
by
dissolution
of
particulate
copper.

The
pH
levels
achieved
in
the
batch
culture
pH
tests
in
Belanger
and
Cherry
(
1990)
were
reported
as
6.15,
8.02,
and
8.95.
Given
the
proximity
of
these
values
to
the
desired
target
pH
values
of
6,
8,
and
9,
respectively,
it
would
appear
that
the
researchers
were
able
to
closely
approximate
the
nominal
pH
levels,
including
those
selected
for
the
acute
heavy
metal
tests
(
also
pH
6,
8,
and
9,
respectively).
Assuming
that
the
target
pH
values
of
6,
8,
and
9
were
achieved
in
the
acute
tests,
adjustment
with
NaOH
and
HNO3
D­
12
would
have
affected
alkalinity,
but
probably
not
hardness
or
the
major
anion
and
cation
concentrations,
except
possibly
Na.
The
contribution
to
Na
by
the
addition
of
NaOH
was
probably
small,
so
no
further
adjustment
would
be
necessary.
D­
13
Table
6.
Comparison
of
Values
for
Untreated
(
Natural)
and
Treated
(
Dechlorinated
City
of
Blacksburg,
VA)
New
River
Water
Source
Water
Type
pH
Total
Hardness
(
mg/
L
CaCO3)
Total
Alkalinity
(
mg/
L
CaCO3)
Specific
Ions
(
mg/
L)
Ca:
Mg
ratio
DOC
(
mg/
L)

Ca
Mg
Na
K
Cl
SO4
NO3
Acquired
Data
City
of
Blacksburg,
VAa
City
8.5
44
39
­
­
9.3
­
33
45
­
­
1.5
Cherry
2000
(
08/
00)
b
New
R.
8.0
­
52
15
0.6
6.6
2.0
6.1
9.8
0.7
2
NASQANc
New
R.
­
61
­
15
5.8
3.4
1.6
4.0
13
0.8
1.6
5.4
Values
To
Be
Applied
to
Table
1
Toxicity
Testsd
Belanger
et
al.
1989
City
7.7
45
40
11
4.2
9.5
1.6
34
46
­
1.6
1.5
Hartwell
et
al.
1989
City
7.5
72
43
18
6.8
15
1.6
54
74
­
1.6
1.5
Cairns
et
al.
1981
City
7.0
26
27
6.4
2.4
5.5
1.6
19
26
­
1.6
1.5
Thompson
et
al.
1980
City
7.2
40
28
9.9
3.8
8.5
1.6
30
41
­
1.6
1.5
Belanger
et
al.
1989
New
R.
8.2
94
70
23
8.8
5.2
1.6
6.2
20
­
1.6
2
Belanger
and
Cherry
1990
New
R.
6,
8,
9
98
74
24
9.1
5.4
1.6
6.4
21
­
1.6
2
a
Data
provided
by
Gerard
(
Jerry)
Higgins
of
Blacksburg­
Christianburg
VPI
Water
Authority,
Blacksburg,
VA.
Values
presented
are
from
a
grab
sample
collected
January
31,
2000.
Organic
carbon
(
originally
measured
and
reported
as
TOC)
is
assumed
to
be
100
percent
dissolved.

b
Sample
provided
by
Don
Cherry,
Virginia
Polytechnic
Institute
and
State
University,
Blacksburg,
VA,
and
analyzed
by
Environmental
Health
Laboratories,

South
Bend,
IN.
Values
presented
are
from
a
grab
sample
collected
August
2000.
The
value
for
Mg
of
0.6
mg/
L
appears
to
be
a
reporting
error,
and
was
not
used
for
subsequent
calculations
of
total
hardness
or
scaling
of
ion
values.

c
Data
obtained
from
USGS
NASQAN
database.
Values
presented
are
means
of
213
samples,
except
for
DOC,
which
is
a
mean
of
seven
samples,
collected
and
analyzed
from
January
1973
to
August
1995.

d
Shaded
area
indicates
mean
values
estimated
from
previously
(
NASQAN)
or
recently
measured
(
Cherry
2000
or
City
of
Blacksburg;
nonadjusted)
ion
values.
All
values
have
been
rounded
to
two
significant
figures.
Shaded
values
were
derived
according
to
text
above
using
the
approach
outlined
in
Section
2.1.
D­
14
Using
a
nomograph
found
in
Faust
and
Aly
(
1981),
alkalinity
at
pH
6
should
be
approximately
33
percent
of
the
alkalinity
at
pH
8,
and
alkalinity
at
pH
9
should
be
5
percent
higher
than
the
alkalinity
at
pH
8
(
Table
7).
Therefore,
the
values
for
alkalinity
in
Table
7
should
be
used
for
the
acute
toxicity
tests
presented
in
Belanger
and
Cherry
(
1990)
in
this
case.
For
other
analyses,
different
adjustment
factors
may
be
appropriate,
based
on
other
interpretations
from
the
Faust
and
Aly
nomograph
or
other
methods
as
well.
Appropriate
consideration
should
also
be
given
to
the
test
system
equilibration
with
the
atmosphere.

Table
7.
Estimated
Alkalinity
in
Natural
Surface
Water
Based
on
pH
Source
Water
Nominal
pH
Alkalinity
(
mg/
L
CaCO3)

New
River
6
24.5
8.1
74.2a
9
77.9
Clinch
River
6
47.6
8.3
144a
9
152
Amy
Bayou
6
40.2
8.3
122a
9
128
a
Indicates
values
reported
in
text.

2.9
Calculation
of
DOC
and
Humic
Acid
What
was
the
technical
approach
used
to
calculate
DOC
and
percent
humic
acid
(
HA)
for
the
Winner
(
1985)
toxicity
tests?

Recommendation:
At
a
nominal
HA
concentration
of
0.0
mg/
L
in
soft
and
medium
hardness
test
waters,
the
DOC
is
assumed
to
be
that
of
the
ultrapure
laboratory
water,
which
is
estimated
to
be
0.3
mg/
L
(
approximately
one­
half
of
the
recommended
default
value
for
DOC
in
laboratory
water;
see
Section
2.3).
At
nominal
HA
concentrations
of
0.15,
0.75,
and
1.50
mg/
L,
the
DOC
is
calculated
by
dividing
by
a
value
of
2,
based
on
the
assumption
in
the
BLM
User's
Guide
(
Di
Toro
et
al.
2000)
that
the
percent
carbon
in
HA
is
0.50
(
see
example
below
and
Table
8).
Because
the
water
used
to
obtain
these
HA
concentrations
was
ultrapure
laboratory
water,
0.3
mg
carbon/
L
was
added;
final
rounded
values
of
0.38,
0.68,
and
1.1
are
recommended.

Table
8.
Estimates
of
Dissolved
Organic
Carbon
and
Percent
Humic
Acid
for
the
Winner
(
1985)
Toxicity
Tests
Humic
Acid
Added
(
mg/
L)
a
Calculated
DOC
(
mg/
L)
Calculated
Percent
Humic
Acid
0
0.3
10
0.15
0.38
28
0.75
0.68
60
1.5
1.1
74
a
As
indicated
in
Table
3
of
Winner
(
1985).
D­
15
2.10
Alkalinity
of
Lake
Superior
Water
For
the
Lind
et
al.
(
manuscript)
tests
conducted
in
Lake
Superior
water
(
adjusted
with
CaSO4
or
MgSO4),
is
there
any
way
to
estimate
alkalinity
values?

Recommendation:
For
tests
conducted
in
Lake
Superior
water,
assume
an
alkalinity
of
42
mg/
L
CaCO3
(
see
Section
2.5).

2.11
Availability
of
LC50s
The
LC50s
reported
by
Collyard
et
al.
(
1994)
are
shown
graphically
in
publication.
The
LC50s
provided
in
Table
1
are
interpolated
from
the
figure.
Are
the
actual
measured
LC50s
available
from
the
authors?

Recommendation:
The
actual
LC50s
generated
and
presented
graphically
in
Collyard
et
al.
(
1994)
have
been
archived
at
U.
S.
EPA­
Duluth,
as
reported
by
Gerald
Ankley
(
personal
communication,
3
November
2000).
These
values
are
not
readily
available
in
any
other
form.
The
data
are
acceptable
as
is
on
the
basis
of
recommendations
in
the
Guidelines
(
Stephan
et
al.
1985).
Precedence
for
the
use
of
values
gleaned
from
graphical
data
is
provided
in
the
2001
Update
of
Ambient
Water
Quality
Criteria
for
Cadmium
(
U.
S.
EPA
2001).

2.12
Cl
and
Na
Concentrations
Cl
and
Na
ion
concentrations
of
the
tap
water
used
for
testing
in
Rice
and
Harrison
(
1983)
were
derived
from
the
addition
of
20
mg/
L
sodium
chloride
(
NaCl).
What
are
the
specific
concentrations
of
the
individual
ions
from
the
addition
of
the
salt?
What
concentrations
do
you
suggest
using
for
K
and
SO4
in
this
water?

Recommendation:
The
Cl
content
of
the
tap
dilution
water
used
in
Rice
and
Harrison
(
1983)
was
reported
as
having
been
derived
from
the
addition
of
20
mg/
L
of
NaCl.
Assuming
that
the
initial
Na
and
Cl
concentrations
in
tap
water
were
essentially
zero,
the
concentrations
of
these
ions
can
be
calculated
in
the
following
way:

The
molecular
weight
of
NaCl
is
58.44
g/
mol.
The
atomic
weight
of
Na
is
22.98
mg/
L
and
the
atomic
weight
of
Cl
is
35.453
mg/
L.

The
concentration
of
Na
is:

20
mg
NaCl/
L
*
1
mmol
NaCl/
58.44
mg
NaCl
=
0.342
mmol
NaCl/
L.
0.342
mmol
NaCl
*
1
mmol
Na/
1
mmol
NaCl
*
22.98
mg
Na/
1
mmol
Na
=
7.86
mg
Na/
L.

The
concentration
of
Cl
is:

20
mg
NaCl/
L
×
1
mmol
NaCl/
58.44
mg
NaCl
=
0.342
mmol
NaCl/
L.
0.342
mmol
NaCl
×
1
mmol
Na/
1
mmol
NaCl
×
35.453
mg
Cl/
1
mmol
Cl
=
12.12
mg
Cl/
L.
D­
16
Given
the
potentially
large
dichotomy
between
the
default
ion
concentrations
and
measured
hardness
of
the
water
used
in
this
study,
we
recommend
adjusting
the
default
SO4
concentration
according
to
measured
hardness
as
in
Section
2.1.
We
do
not,
however,
recommend
adjusting
the
current
default
value
of
1.0
mg/
L
for
K.

2.13
Calculating
DOC
in
Dilution
Water
The
dilution
water
used
in
the
acute
copper
toxicity
tests
with
cutthroat
trout
in
Chakoumakos
et
al.
(
1979)
was
a
different
mix
of
spring
water
and
de­
ionized
water
for
each
test.
Ca
and
Mg
concentrations
were
measured
and
reported
for
each
of
the
test
waters
used,
but
measurements
of
the
other
ions
were
reported
only
for
the
undiluted
spring
water.
Based
on
a
percentage
dilution,
ions
other
than
Ca
and
Mg
were
estimated
in
the
following
way:
hardness
was
measured
in
the
spring
water
and
in
each
of
the
test
waters;
the
proportion
of
spring
water
was
calculated
for
each
test
using
these
measured
hardness
values;
this
proportion
was
then
multiplied
by
the
concentration
of,
for
example,
Na
in
the
spring
water
to
get
an
estimated
Na
value
for
each
test.
TOC
in
the
spring
water
was
3.3
mg/
L.
Should
the
same
approach
as
that
used
to
estimate
the
other
ions
be
used
to
calculate
DOC,
which
was
only
measured
in
undiluted
spring
water?

Recommendation:
The
concentrations
of
the
major
cations
and
anions
in
the
dilution
water
used
by
Chakoumakos
et
al.
(
1979)
were
calculated
based
on
the
percent
dilution
of
natural
spring
water
with
deionized
water.
The
same
correction
can
be
used
to
estimate
DOC,
with
the
following
assumptions.
First,
the
TOC
in
spring
water
was
100
percent
dissolved.
Second,
the
DOC
of
de­
ionized
water
was
0.5
mg/
L.
If
these
assumptions
are
acceptable,
the
DOCs
for
H/
H,
M/
H,
L/
H,
H/
M,
M/
M,
L/
M,
H/
L,
M/
L,
and
L/
L
would
be
3.3,
1.5,
0.75,
3.3,
1.7,
0.94,
2.8,
1.5,
and
0.87
mg/
L,
respectively.

2.14
Ionic
Composition
of
Chehalis
River
Water
The
ionic
composition
of
Chehalis
River,
WA,
water
is
needed
to
fill
in
existing
data
gaps
used
for
BLM
analysis
of
acute
toxicity
reported
in
Mudge
et
al.
(
1993).
The
publication
states,
"
Water
quality
data
collected
during
this
bioassay
program
is
similar
to
historical
data
for
Chehalis
River
(
WPPSS
1982)
and
other
Pacific
NW
streams
(
Samuelson
1976)."
Are
data
from
Samuelson
(
1976)
acceptable
for
use
in
approximating
these
ion
concentrations?
Furthermore,
are
there
any
dissolved
or
ionic
LC50s
available
other
than
those
reported
in
the
publication?

Recommendation:
The
following
additional
water
chemistry
information
for
the
Chehalis
River
dilution
water
used
in
the
studies
reported
by
Mudge
et
al.
(
1993)
was
provided
by
the
author
on
20
November
2000.
These
measurements
were
made
on
Chehalis
River
water
at
the
time
of
testing.
A
corresponding
value
for
DOC
was
obtained
from
the
NASQAN
dataset.

Recommended
spreadsheet
addition
for
Chehalis
River
dilution
water
Applied
to:
DOC
(
mg/
L)
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Mudge
et
al.
1993
3.2a
7.1
2.4
1.8
5.1
0.65
4.5
(
May)
4.2
(
Jun)
3.1
(
Sep)
4.0
(
May)
3.5
(
May­
Jul)
2.3
(
Sep)

a
Value
from
the
USGS
NASQAN
dataset,
1980­
1982,
when
the
tests
were
conducted.

2.15
Chemistry
of
Water
in
Howarth
and
Sprague
(
1978)
D­
17
What
is
the
ionic
composition
and
organic
carbon
content
of
test
waters
used
in
Howarth
and
Sprague
(
1978)?
The
waters
used
for
testing
were
various
mixes
of
University
of
Guelph
(
Guelph,
ON,
Canada)
well
water
and
de­
ionized
well
water.
The
de­
ionized
well
water
was
reported
as
"
having
retained
its
original
chloride
content
(
22
mg/
l),"
but
the
values
for
the
other
major
anion
and
cation
concentrations
were
not
reported.
Furthermore,
the
equation
provided
for
calculating
alkalinity
from
pH
and
hardness
(
supposedly
accounting
for
96.7
percent
of
the
variability)
appears
unreliable.
For
example,
using
the
equation
and
a
total
water
hardness
of
364
mg/
L
CaCO3
at
pH
9,
one
obtains
an
estimated
alkalinity
value
of
341
mg/
L
CaCO3.
In
contrast,
the
measured
alkalinity
reported
in
the
text
for
this
level
of
hardness
and
pH
was
263
mg/
L
CaCO3.

Recommendation:
The
equation
provided
in
the
text
of
Howarth
and
Sprague
(
1978)
for
calculating
alkalinity
appears
unreliable.
The
calculated
alkalinity
does
not
approximate
measured
alkalinity
within
a
reasonable
degree
of
accuracy.
Values
of
hardness,
pH,
and
alkalinity
in
Dixon
and
Sprague
(
1981a),
which
used
the
same
water
source
in
their
toxicity
tests,
give
greater
evidence
of
this;
i.
e.,
using
the
measured
value
of
hardness
of
374
mg/
L
CaCO3
and
a
pH
of
7.75,
the
alkalinity
calculated
with
the
equation
is
98
mg/
L
CaCO3.
This
compares
rather
poorly
with
the
measured
alkalinity
of
223
mg/
L
CaCO3.
Instead,
alkalinity
can
be
estimated
using
the
nomograph
from
Faust
and
Aly
(
1981)
as
in
Section
2.8.

It
is
possible
to
apply
the
procedure
used
with
the
Chakoumakos
et
al.
(
1979)
data
here,
i.
e.,
using
the
ratio
of
hardness
in
full­
strength
well
water
and
de­
ionized
well
water
to
calculate
the
dilution
of
the
other
major
ion
concentrations.
However,
no
values
are
given
for
Na
or
K
in
University
of
Guelph
well
water.
This
study
is
also
complicated
by
the
reverse­
osmosis
unit
used
to
create
the
de­
ionized
well
water.
In
particular,
the
statement
concerning
the
retention
of
the
original
Cl
concentration
in
the
de­
ionized
well
water
implies
an
ionic
exchange
that
would
also
require
a
cation
(
to
maintain
charge
balance).
The
cation
involved
is
unknown.
As
discussed
in
a
phone
conversation
with
John
Sprague
on
17
November
2000,
and
later
that
day
with
Scott
Howarth
(
Environment
Canada),
NaCl
may
have
leached
through
the
RO
unit.
Assuming
that
Na
and
Cl
leached
through
the
unit
in
equivalent
proportions,
a
value
of
14
mg/
L
for
Na
can
be
back­
calculated
from
the
reported
Cl
concentration
of
22
mg/
L.

Default
DOC
concentrations
of
1.6
and
0.5
mg/
L
were
assumed
for
the
well
water
and
de­
ionized
water
used
in
the
tests,
respectively
(
see
Section
2.3).
The
DOC
concentrations
were
adjusted
for
each
particular
test
water
hardness
level
based
on
the
proportion
of
well
water
and
de­
ionized
water
used
to
achieve
the
desired
test
hardness
level.
In
the
example
provided
in
Table
9,
the
dilution
factor
of
0.27,
based
on
the
ratio
of
the
average
hardness
of
well
water
(
366
mg/
L
CaCO3)
versus
the
average
hardness
of
well
plus
de­
ionized
well
water
(
100
mg/
L
CaCO3),
was
applied
to
the
starting
DOC
concentrations
to
achieve
an
estimate
of
the
DOC
concentrations
at
100
mg/
L
CaCO3).
Table
9
shows
the
results
of
similar
adjustments
made
for
the
major
anions
and
cations
based
on
the
data
reported
in
Howarth
and
Sprague
(
1978).

2.16
Default
Values
for
Analyte
Concentrations
What
value
should
be
used
when
a
specific
analyte
is
not
detected
at
its
designated
detection
limit?

Recommendation:
The
use
of
half
the
detection
limit
(
DL)
is
most
appropriate
when
the
concentration
of
an
analyte
is
not
detected.
One­
half
the
DL
will
closely
approximate
a
replacement
value
for
censored
data
in
a
log­
normally
distributed
population
that
includes
several
measured
values
(
Berthouex
and
Brown
1994;
Dolan
and
El­
Shaarawi
1991).
This
way
some
of
the
"
nondetect"
samples
will
actually
be
counted
as
detected.
D­
18
Table
9.
Example
Calculations
to
Estimate
Water
Chemistry
of
Tests
Conducted
at
100
mg/
L
CaCO3
by
Howarth
and
Sprague
(
1978)
Using
a
Mixture
of
University
of
Guelph
Well
Water
and
De­
ionized
Water
Parameter
(
units
in
mg/
L)
De­
ionized
water
Well
Water
Example
Calculations
for
Mixture
Hardness
0
366
100
(
i.
e.,
0.27
dilution
factor)

Ca
0
77
(
from
Dixon
&
Sprague
1981)
21
Mg
0
43
(
from
Dixon
&
Sprague
1981)
12
Na
14
(
assuming
NaCl
used
for
the
softening
process)
14
(
estimated
from
[
Cl])
14
K
0
2.4
(
based
on
personal
communication
from
Dr.
Patricia
Wright,
Univ.
of
Guelph,
Guelph,
ON)
0.66
Cl
22
(
stated
as
not
having
changed
from
the
water
softening
process)
22
22
SO4
0
129
35
DOC
0.5
(
default
value
for
deionized
waters)
1.6
(
default
value
for
well
waters)
0.8
Alkalinity
(
calculated
using
ratios
as
in
Section
2.8):

at
pH
6
0a
81.5
22
at
pH
7
0a
205
55
at
pH
8
0a
250
N/
A
at
pH
9
0a
263
70
a
Alkalinity
in
de­
ionized
well
water
is
assumed
to
be
0.0
mg/
L.

2.17
Organic
Carbon
Content
of
Samples
Can
any
information
be
obtained
on
the
organic
carbon
content
of
the
spring
water
/
City
of
Cincinnati,
OH,
tap
water
mixes
used
in
Brungs
et
al.
(
1973),
Geckler
et
al.
(
1976),
Horning
and
Neiheisel
(
1979),
Mount
(
1968),
Mount
and
Stephan
(
1969),
and
Pickering
et
al.
(
1977)?

Recommendation:
The
water
used
for
all
tests
was
a
mixture
of
spring­
fed
pond
water
(
originating
at
the
Newtown
Fish
Farm)
and
carbon­
filtered,
demineralized
Cincinnati
tap
water.
The
water
was
mixed
to
achieve
the
desired
test
hardness
level
and
discharged
to
a
large
(
several
thousand
gallon)
concrete
reservoir
that
fed
the
test
system.
The
detention
time
varied
anywhere
from
30
to
90
days,
depending
on
the
study,
which
was
sufficient
to
allow
the
growth
of
phytoplankton
and
zooplankton
in
moderate
abundance.
No
additional
information
regarding
the
TOC
(
DOC)
concentration
or
treatment
of
this
water
is
available
at
this
time.
The
recommended
organic
carbon
content
of
spring/
city
water
mix
is
currently
a
conservative
1.6
mg/
L,
but
could
be
as
high
as
2.5
mg/
L,
the
highest
DOC
concentration
recorded
for
a
natural
surface
or
well
water
used
for
studies
included
in
this
report
(
see
Section
2.3).
Considering
the
long
retention
time,
D­
19
and
the
fact
that
the
natural
water
was
spring­
fed
pond
water,
the
more
conservative
DOC
value
of
2.5
mg/
L
is
recommended
for
this
water.

2.18
Additional
Water
Chemistry
Data
Needed
Additional
water
chemistry
data
are
needed
for
Bennett
et
al.
(
1995)
and
Richards
and
Beitinger
(
1995).
In
the
case
of
Richards
and
Beitinger
1995,
only
the
ranges
of
measured
pH,
alkalinity,
and
hardness
across
all
tests
were
given.

Recommendation:
Detailed
pH,
alkalinity,
and
hardness
values
were
provided
by
both
Bennett
et
al.
(
1995)
and
Richards
and
Beitinger
(
1995)
(
Appendixes
D­
7
and
D­
9,
respectively).
The
studies
performed
by
Bennett
et
al.
were
conducted
using
dechlorinated
City
of
Denton,
TX,
tap
water
(
from
Lake
Roy
Roberts).
The
author
was
not
able
to
provide
any
additional
data
regarding
the
ionic
composition
of
this
water;
however,
based
on
supplementary
data,
mean
values
of
pH,
alkalinity,
and
temperature
were
8.07
and
89.7
mg/
L
CaCO3
and
21.4
C,
respectively.
Richards
and
Beitinger's
studies
were
conducted
using
standard
reconstituted
(
hard)
water.
To
estimate
the
ionic
composition
of
this
water,
refer
to
recommendations
provided
in
Section
2.1.

2.19
Estimating
Data
for
Waters
Values
for
DOC,
TSS,
Ca,
Mg,
Na,
K,
SO4,
and
Cl
are
needed
for
the
following
natural
waters:

Water
Body
Reference
American
River,
California
 
sand
filtered
Finlayson
and
Verrue
1982
Clinch
River
 
11
µ
m
filtered
Belanger
et
al.
1989
Belanger
and
Cherry
1990
Amy
Bayou
Belanger
and
Cherry
1990
Blaine
Creek,
Kentucky
 
1.6
µ
m
filtered
Dobbs
et
al.
1994
S.
Kawishiwi
Lind
et
al.
manuscript
St.
Louis
River
Lind
et
al.
manuscript
Lake
One
Lind
et
al.
manuscript
Colby
Lake
Lind
et
al.
manuscript
Cloquet
Lake
Lind
et
al.
manuscript
Greenwood
Lake
Lind
et
al.
manuscript
Embarrass
River
Lind
et
al.
manuscript
Green
Duwamish
River
Buckley
1983
Chehalis
River
Mudge
et
al.
1993
Pinto
Creek,
AZ
Lewis
1978
Naugatuck
River
Carlson
et
al.
1986
Recommendation:
On
the
following
pages
are
data
(
current
and/
or
historical,
presented
as
arithmetic
means)
from
selected
natural
waters
that
were
retrieved
from
NASQAN,
STORET,
or
a
secondary
source
(
as
indicated).
As
mentioned
earlier
(
see
Sections
2.6
and
2.7),
given
the
reasonably
good
correlation
between
most
of
the
major
anion
and
cations
(
except
K)
and
water
hardness
in
natural
surface
and
well
waters,
we
recommend
using
the
ion
and
hardness
values
retrieved
from
these
various
sources
to
estimate
the
ion
concentrations
in
the
test
water
used
in
the
previous
studies.
The
operation,
again,
is
simply
to
multiply
the
ion
concentrations
listed
below
by
the
ratio
of
hardness
values
presented
below
and
the
earlier
test
waters.
D­
20
Note
that
additional
data
were
not
available
for
Blaine
Creek,
KY,
or
Pinto
Creek,
AZ,
and
although
additional
data
were
obtained
from
the
City
of
Sacramento,
CA,
regarding
the
American
River,
the
default
DOC
value
(
8.2
mg/
L)
for
California
streams
may
be
artificially
high
on
the
basis
of
reported
values
of
DOC
in
the
Sacramento
River
(
1.2
mg
C/
L),
of
which
the
American
River
is
a
tributary.
Therefore,
the
data
from
Finlayson
and
Verrue
(
1982)
have
been
relegated
to
"
other
data."
Likewise,
Amy
Bayou
is
a
highly
contaminated
and
dynamic
system
(
Don
Cherry,
personal
communication),
and
BLM
normalization
is
not
recommended
for
these
data.
A
large
annual
variability
in
water
quality
also
excludes
the
use
of
surrogate
STORET
data
for
the
Embarrass
River,
MN,
for
BLM
analysis
(
Lind
et
al.
manuscript).

American
River,
CA
(
Appendix
D­
9).
Source:
Ron
Myers,
City
of
Sacramento,
CA,
Water
Quality
Laboratory
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Finlayson
and
Verrue
1982
21
22
7.5
­
a
5.6
1.8
2.0
3.0
­
2.6
3.8
a
DOC
and
K
data
for
the
American
River
were
not
available.

Clinch
River,
VA
(
Appendix
D­
5):
Source:
Don
Cherry,
VA
Poly.
Inst.
&
State
Univ.,
Blacksburg,
VA
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Belanger
et
al.
1989,
and
Belanger
and
Cherry
1990
150
150
8.3
2.3
42
11
2.3
12
2.4
9.2
19
S.
Kawishiwi
River,
MN
(
Appendix
D­
10).
Source:
STORET
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Lind
et
al.
manuscript
24
18
6.6
­
a
5.6
2.4
1.5
1.3
0.5
1.0
4.9
a
DOC
data
for
this
river
were
not
available.
TOC
measurements
reported
by
Lind
et
al.
(
manuscript)
should
be
adjusted
based
on
a
mean
DOC:
TOC
ratio
(
0.8721)
in
Minnesota
streams
(
see
Section
2.3
and
Appendix
D­
2).

Lake
One,
MN
(
Appendix
D­
10).
Source:
STORET
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Lind
et
al.
manuscript
10
15
6.7
­
a
2.8
0.7
1.8
0.1
0.3
0.2
4.2
a
DOC
data
for
this
lake
were
not
available.
TOC
measurements
reported
by
Lind
et
al.
(
manuscript)
should
be
adjusted
based
on
a
mean
DOC:
TOC
ratio
(
0.9677)
in
Minnesota
lakes
(
see
Section
2.3
and
Appendix
D­
2).
D­
21
Colby
Lake,
MN
(
Appendix
D­
10).
Source:
STORET
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Lind
et
al.
manuscript
56
33
7.1
­
a
13.3
5.4
1.6
4.0
1.4
7.3
23
a
DOC
data
for
this
lake
were
not
available.
TOC
measurements
reported
by
Lind
et
al.
(
manuscript)
should
be
adjusted
based
on
a
mean
DOC:
TOC
ratio
(
0.9677)
in
Minnesota
lakes
(
see
Section
2.3
and
Appendix
D­
2).

Cloquet
Lake,
MN
(
Appendix
D­
10).
Source:
STORET
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Lind
et
al.
manuscript
27
21
7.2
­
a
6.9
2.3
1.4
1.9b
1.4c
1.2
5.6
a
DOC
data
for
this
lake
were
not
available.
TOC
measurements
reported
by
Lind
et
al.
(
manuscript)
should
be
adjusted
based
on
a
mean
DOC:
TOC
ratio
(
0.9677)
in
Minnesota
lakes
(
see
Section
2.3
and
Appendix
D­
2).
b
Na
data
for
this
lake
were
not
available.
The
Na
value
given
here
is
based
on
data
for
Colby
Lake,
MN,
and
was
scaled
on
the
basis
of
hardness
(
see
Section
2.1):
Na
=
4.0
mg
Na/
L
*
(
27
mg/
L
CaCO3
/
56
mg/
L
CaCO3).
c
K
data
for
this
lake
were
not
available.
The
K
value
given
here
is
from
data
for
Colby
Lake,
MN.
This
value
was
not
scaled
on
the
basis
of
hardness
(
see
discussion
of
K­
hardness
relationship
in
Sections
2.1
and
2.7).

Greenwood
Lake
(
Appendix
D­
10),
MN.
Source:
STORET
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Lind
et
al.
manuscript
17
11
6.4
­
a
4
1.8
2.4
0.2b
0.3c
1.7
7.6
a
DOC
data
for
this
lake
were
not
available.
TOC
measurements
reported
by
Lind
et
al.
(
manuscript)
should
be
adjusted
based
on
a
mean
DOC:
TOC
ratio
(
0.9677)
in
Minnesota
lakes
(
see
Section
2.3
and
Appendix
D­
2).
b
Na
data
for
this
lake
were
not
available.
The
Na
value
given
here
is
based
on
data
for
Lake
One,
MN,
and
was
scaled
based
on
hardness:
Na
=
0.1
mg
Na/
L
*
(
17
mg/
L
CaCO3
/
10
mg/
L
CaCO3).
c
K
data
for
this
lake
were
not
available.
The
K
value
given
here
is
from
data
for
Lake
One,
MN.
This
value
was
not
scaled
on
the
basis
of
hardness
(
see
discussion
of
K­
hardness
relationship
in
Sections
2.1
and
2.7).

St.
Louis
River,
MN
(
Appendix
D­
6).
Source:
NASQAN
Note:
for
the
St.
Louis
River
dataset
(
1973
to
1993),
a
question
arose
as
to
which
data
would
be
most
representative
for
estimating
the
ion
concentrations
in
St.
Louis
River
water
for
BLM
analysis.
In
order
to
determine
this,
the
relationship
between
hardness
and
Na
ion
for
all
20
years
was
plotted.
Linear
regression
was
used
to
fit
the
data.
Most
data
showed
very
high
coefficient
correlation
(
0.8­
0.94).
For
each
of
these
20
regression
lines,
the
slope
and
intercept
coefficients
were
plotted
on
separate
graphs
as
functions
of
time
(
Figures
7
and
8).
The
following
conclusions
were
derived:


A
significant
event
occurred
in
1976
and
perhaps
1977
that
affected
the
water
balance
of
the
St.
Louis
River.
A
wastewater
treatment
plant
was
built,
which
substantially
improved
the
water
quality
(
Jesse
Anderson,
Minn.
Pollution
Control
Bd.,
personal
communication).
D­
22

For
the
1979­
1993
period,
hardness
and
ion
concentrations
did
not
change
significantly
as
absolute
values.
Therefore,
general
equations
(
which
could
be
used
to
extrapolate
water
chemistry
data
till
year
2000
and
before
1979)
can
be
obtained
connecting
hardness,
alkalinity,
pH,
and
the
major
ion
concentrations.


The
exponential
growth
in
the
values
between
1973
and
1979
shows
that
averaging
values
on
seasonal
and
annual
basis
is
not
appropriate.
The
constant
values
for
the
slopes
and
intercepts
for
1979­
1993
allow
mean
monthly
and
annual
interpretation
of
the
data.


The
regression
equations
derived
for
1977
alone
are
recommended
to
predict
ion
concentrations
based
on
the
water
hardness
levels
measured
in
the
Lind
et
al.
(
manuscript).
The
equations
derived
for
each
ion
are
provided
in
Appendix
D­
6
with
the
corresponding
figures.

Green­
Duwamish
River,
WA.
Source:
James
Buckley
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Buckley
1983
33
29
7.2
3.2a
8.9
2.8
2.0
7.5
1.2
7.0
6.3
a
Value
given
as
TOC.
DOC
data
for
this
river
were
not
available.
TOC
measurements
reported
by
Buckley
et
al.
(
1983)
should
be
adjusted
on
the
basis
of
a
mean
DOC:
TOC
ratio
(
0.7803)
in
Washington
streams
(
see
Section
2.3
and
Appendix
D­
2).

Naugatuck
River,
WA.
Source:
STORET
Applied
to:
Hardness
(
mg/
L
CaCO3)
Alkalinity
(
mg/
L
CaCO3)
pH
DOC
Specific
Ions
(
mg/
L)

Ca
Mg
Ca:
Mg
Na
K
Cl
SO4
Carlson
et
al.
1986
39
20
6.4
3.7a
9.9
3.3
1.9
9.9
2.3
­
22
a
Value
given
as
TOC.
DOC
data
for
this
river
were
not
available.
TOC
measurements
reported
by
Carlson
et
al.
(
1986)
should
be
adjusted
on
the
basis
of
a
mean
DOC:
TOC
ratio
(
0.8711)
in
Connecticut
streams
(
see
Section
2.3
and
Appendix
D­
2).
D­
23
Total
Hardness
(
mg/
L
as
CaCO3)
Figure
1.
Relationship
between
Ca
and
hardness
in
WFTS
well
water
D­
24
D­
25
D­
26
Figure
4.
Relationship
between
K
and
hardness
in
WFTS
well
water
Total
Hardness
(
mg/
L
as
CaCO3)
D­
27
D­
28
Figure
6.
Relationship
between
SO
and
hardness
in
WFTS
well
water
4
Total
Hardness
(
mg/
L
as
CaCO3)
D­
29
Figure
7.
Slopes
of
the
regression
equations
derived
for
Na
concentration
in
St.
Louis
River,
MN,
water
versus
water
hardness
from
1973
to
1993.
D­
30
Figure
8.
Intercepts
of
the
regression
equations
derived
for
Na
concentration
in
St.
Louis
River,
MN
water
versus
water
hardness
from
1973
to
1993.
D­
31
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