OPTIMAL CHELANT/COPPER
RATIOS FOR MAXIMIZING
COPPER SOLUBILITY IN
NATURAL WATER USING CITRIC
ACID AND TRIETHANOLAMINE
ILENR/RE-EH-86 09
Illinois Department of
Energy and Natural Resources
James R Thompson, Governor
Don Etchison, Director
Printed by the Authority of the State of Illinois
ILENR/RE-EH-86/09
September 1986
Contract EH 22; EH 22
Project 85/6005; 86/6005
OPTIMAL CHELANT/COPPER RATIOS
FOR MAXIMIZING COPPER SOLUBILITY IN NATURAL WATER
USING CITRIC ACID AND TRIETHANOLAMINE
Prepared by
Illinois State Water Survey
Water Quality Section
Foot of MacArthur Hwy
P.O. Box 697
Peoria, IL 61652
Principal Investigators
Raman K. Raman
Billy K. Cook
Prepared for
Illinois Department of
Energy and Natural Resources
Energy and Environmental Affairs Division
325 W. Adams
Springfield, IL 62704-1892
James R. Thompson, Governor
State of Illinois
Don Etchison, Director
Illinois Department of
Energy and Natural Resources
NOTE
This report has been reviewed by the Illinois Department of
Natural Resources (ENR) and approved for publication.
Energy
and
Printed by the Authority of the State of Illinois.
Date Printed:
September 1986
Quantity Printed:
120
Referenced Printing Order:
IS 36
One of a series of research publications published since 1975.
This
series includes the following categories and are color coded as follows:
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- RE-ER
- Red
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- RE-WR
- Blue
Air Quality
- RE-AQ
- Green
Environmental Health
- RE-EH
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Economic Analysis
- RE-EA
- Brown
Information Services
- RE-IS
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Insect Pests
- RE-IP
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Illinois Department of Energy and Natural Resources
Energy and Environmental Affairs Division
325 W. Adams
Springfield, Illinois 62704-1892
217/785-2800
i
CONTENTS
Introduction
Acknowledgments
Page
1
7
Objectives and Scope
8
Materials and Methods
9
Results and Discussion
Optimal copper/chelant
Particulate adsorption
Cutrinestudy
Regression analysis
ratio
12
12
15
16
17
Summary
18
Tables and Figures
20
References
40
Appendix
43
ii
OPTIMAL
CHELANT/COPPER
FOR M A X I M I Z I N G COPPER
SOLUBILITY
USING CITRIC ACID AND
by R a m a n K
RATIOS
IN NATURAL WATERS
TRIETHANOLAMINE
R a m a n and B i l l y K.
Cook
INTRODUCTION
Taste
and
odor
problems
i m p o u n d m e n t s as a s o u r c e
can m o s t
blooms, mainly blue-greens
odor
problems
filter
to
runs,
are
excessive
nutrient
consuming
Although
copper
compounded
such
several
to
their
particularly
(Mackenthun
The
reflected
by other
when
Cooley,
relatively
in
These
problems
etc.
of
Physical
algae
or
costly
m e t h o d s of
commercially
to
the
greatest
low t o x i c i t y
applied
at
to
taste and
reduced
solutions
control
and
of
time
bloom control.
are
enjoy
using
to a l g a l
such as
algicides
available,
popularity due
higher
organisms,
accepted algicidal
levels
1952).
low
toxicity
finished water
of
quality
maximum allowable
concentrations
(Pollution Control
Board,
Treatment
copper may
(1950),
attributed
1957).
costs,
chemical
relatively
fish,
and
seem
be
waterworks
can b e e x t r e m e l y
to
types of
often
harvesting
inputs
formulations
in p a r t
as
in c o m p a r i s o n
plague
(Sigworth,
increased chemical
the p r o b l e m s
that
1982).
of
copper
standards,
copper
According
be
at
humans
which
set
is
the
5.0 m g / l i t e r
t o W a t e r Q u a l i t y and
beneficial
1
to
or
even essential
for
the
RMCL
growth of
(i.e.,
of
1.3 m g / L
of
copper
in
drinking water.
from water
and
14-day
TL-50
(.i.e.,
bluegill
14
populations
in
Kellerman,
widely
in
an
higher
of
since
1904).
used
copper
to
and
alkaline,
northern
copper
sulfate
(Mackenthun,
of
copper
to
possibly
adsorption,
common
in
to
typical
changes
in
non-toxic
in
the
1
(from S y l v a ,
f r e s h w a t e r s as
copper
due
by
1976).
alkalinity
7.5
chemistry
shows
in
2
has
has
is
been
(Moore
been
an
and
yearly
1971).
in
central
require
greater
algicidal
action
complexation,
inorganic
species
This
is particularly
and
hardness
the
the
an
the m o s t
with
found
hydrolysis,
f u n c t i o n of
occur
test)
to rapid c o n v e r s i o n of
true
are
high,
s p e c i a t i o n of
copper
t o 8.5 ( S t i f f ,
1976)
a
to
reactions with
(Sylva,
range of
those
effective
1971)
mortality
(Fitzgerald,
are known
forms
precipitation
Illinois where
Figure
in
Fitzgerald,
fresh waters
central
with pH's
and
lakes
States,
pounds
such as
for
the
phytop lankton
century
United
lakes,
that
50%
nuisance
the
hard w a t e r s ,
a
2-5 m g .
a lgici dal l e v e l s .
turn
the
about
Illinois,
sulfate pentahydrate
"loading"
1969;
intake
to
supply
in
Illinois
human
flow-through
and w a t e r
applications approaching 20 million
However,
daily
which
native
accepted
Copper
algicide
at
than
the
copper
demonstrated
toxicity
catfish,
p r o p o s e d an
for
generally
also
acute
recreational
fact
have
is
has
Level)
average
concentration
and channel
toxicity
accepted
the
The
foodstuffs
(1978)
days
of m a g n i t u d e
The
and
Roseboom
occurs within
order
The USEPA
Recommended Maximum Contaminant
Richey
for
living organisms-.
1971a).
pH.
pH
The
range
most
6.5 -
rapid
8
such
that
of
less
than
cupric
the
tons.
chemistry
Stable
waters,
such
of
also
pH
in
6.5
the
this
fulvic
to
reduce
Woodward,
acids
the
copper
CJames
of
onto
total
be
of
physical
state of
best
effects
of
Currently,
aquatic
solids
and
is
plays
dissolved copper
indicated
slower
considerable
a
significant
(TDCu).
that
in
in
aquatic
for
Studies
the
rate
of
filtered
than
in
0.3 m g / L
in order
and d o s a g e s
specific
to
on
the
the
environments.
"loss"
algicidal
in
organisms.
effect
precipitation,
no
significant
profound
to
frequency
to
the
organic
having a
a 0.1
increased
macromolecular
solids
to m a i n t a i n
But
to
also point
copper
1978).
point
(1971b)
copper
Muchmore,
(1978)
Sylva,
by Stiff
suspended
necessary
1981;
Results
These m e c h a n i s m s of
copper
McKnight,
1972)
copper was always
fresh
available
suspended
(1979)
of
c o n c e n t r a t i o n of
copper
d i s a p p e a r a n c e of
presence
typical
ecologically
Barica
samples.
form
decaying
by
by W a g e m a n n and
unfiltered
the
products dominate
produced
others
and H e a l y ,
reduction of
in
by
1977;
and
may
is
pH.
and
water
of
pH 8
copper with organics
availability
Adsorption
at
precipitation
complexation
lake
the
present
and
Gachter
that
in
regulating
role
tend
and
at
of
humic
Likewise,
material
above
copper
as
possibility
copper
Hydrolysis
CShuman
1976).
the
complexes
vegetation,
copper
1 0 % of
make
it
difficult
concentration
action
of
at
dissolved
(Mackenthun,
1969;
to do s o , a p p l i c a t o r s have simply
in
order
to
complexation,
guidelines
3
exist
"overpower"
and
for
the
the
adsorption.
amount
or
frequency
of
chemical
impoundments.
Mackenthun
at a
upper
2
than
feet
of
recommend
each
sulfate
raising
copper
dosages,
Stefan,
as
such as
1984).
algae,
c)
from game
e)
Iskander
fish
to
reduction
species
rough
to
s o l u b i l i t y of
Although
monohydrate
application
Fair
by
reduce
copper
shift
rates
as much
to
not
in an
more
only
depth
of
less
0.3
(1971)
as
5 % for
even
larger
resistant
include a)
d)
green
increases
impoundment;
of
but
elevated
Lakes, Minnesota
from
the
also
copper
(Hanson
and
copper accumulation
certain s p e c i e s of
t o b l u e - g r e e n a l g a e and
d i s a p p e a r a n c e of
macrophytes,
(Gibson,
1972;
These c u m u l a t i v e side effects point
dosage
requirements
in a n a t u r a l
the u s e o f
the
al.
In a d d i t i o n ,
adjustments
fish,
1974).
for
rates of
et
in benthic m a c r o i n v e r t e b r a t e s
and K e e n e y ,
Cu+2)
alkalinities
associated with
the F a i r m o n t
tolerance
shift of
the n e e d
quality
These effects may
b)
sulfate
1984).
in a p p l i c a t i o n
in
copper
actual
with
CaCO3.
algae
long-term effects
in s e d i m e n t s ,
to
indicated
40 m g / L ,
concentration amounts
pentahydrate.
as
supply
than
as
the
sulfate dosages
of m a i n t a i n i n g w a t e r
intensifies
waters
of
mg/L
this
recommends
copper
increase
(0.25
basis,
For
( H a n s o n and S t e f a n ,
This
5H 2 O
r e g a r d l e s s of
10 m g / L of a l k a l i n i t y
species
and
water
Mackenthun
dosages may be
cost
CuSO4
lbs/surface acre.
as
water
the a p p l i c a t i o n
On an acreage
40 m g / L ,
mg/L
advocates
1 m g / L as
impoundments.
t o 5.4
to
For w a t e r s w i t h a l k a l i n i t y g r e a t e r
C1969)
r a t e of
application
by
enhancing
the
system.
chelating agents,
(Kothandaraman et a l . ,
4
1980;
such as citric
Stern
et a l . ,
acid
1978)
and
triethanolamine,
has
been
water
demonstrated
impoundments
Gelfand,
most
the
1946),
cases.
algal
lack
the p H
research
copper/chelant
formulations,
in
the
accompany
country
Sylva
treated
the
for
the
(1976)
need an
on
than o t h e r s
the
indicates
can
in
non-uniform
made
it
i.e.,
maintain
commercial
an
initially
or m a y
not
be
which
makes
regions
the
of
copper
disclaimers
of
to
and
advantage
different
stability
chelants
can e n s u r e
in
partly
some
of
the
complex
vs.
copper.
effective
ions
to
which may
outlined
case
optimal,
Non-uniform speciation
that
at
formation
free copper
no m e a n s a h a r d - a n d - f a s t
copper
etc.,
that w h e n
has
the
chelants,
in
imminent.
the
the
ratios
1975;
alone
is due
latter
Given
of
is
to
determine
surface
in w h i c h
desirable
The
complex,
lake as
effective
to e f f e c t i v e l y bind
is by
of
8.0,
mainly
e.g., C u t r i n e , A V - 7 0 ,
depending
competition
would
levels
these algicides.
products more
but
concentration.
concentrations
fact
copper
outlining
copper/chelant
and e l e v a t e d
the
sulfate alone
empirically
effective,
copper
premixing
copper
ratios,
to
used
of
in
1976)
Survey,
to be
the
surface w a t e r s .
difficult
algicidal
light
c o m p l e x a t i o n of
published
in U . S .
History
typically about
of
cost
stable
is
of
extremely
high
in
Inc.,
solubility
sulfate continues
is p u z z l i n g
form,
copper
Natural
continued use
speciation
most
enhance
(Illinois
p r e c i p i t a t i o n and
optimum
free
to
copper
This
blooms
The
the
or TEA (Applied B i o c h e m i s t s ,
pH 8 a
constant
ions
rule,
vary greatly
prospective
on
the
in a natural
as
5
1 05
of
system.
This
competition effects
from s y s t e m to
5
order
ligand
system,
but
for
it
does
place
some
monohydrate
their
and
doubt
on
the
triethanolamine
relatively
small
as
stability
efficacy
of
chelating
agents
constants
citric
CSillen
acid
considering
and M a r t e l l ,
1964) .
Another
of w h e t h e r
retain
chelated
their
the
toxicity
not
by
(1979)
the
important
.
copper
total
is
copper
copper
chelation
or
McKnight
d e t e r m i n e d by
"total
chelating
and H o m e
the
issue
copper
salts
(1981) maintains
cupric
ion
that
activity
Wagemann
toxic c o p p e r "
agents,
is
soluble
concentration.
their
From Elder
of
effect.
copper
introduced
the a b s e n c e o f
CuOH
forms of
algicidal
of
aspect
and
Barica
concept, which,
Cu+2
included
and
in
, C u ( O H ) 2 , and
(1978):
C o m p l e x a t i o n of copper is g e n e r a l l y a s s u m e d
to
reduce
the a v a i l a b i l i t y o f the m e t a l for
biological
u p t a k e , a l t h o u g h not n e c e s s a r i l y
by removing it from
s o l u t i o n (Horne and
Goldman,
1974).
On
the o t h e r
hand, Gachter
and
others
(1974)
and
Sylva (1976)
c o r r e c t l y p o i n t e d out
that
this
a s s u m p t i o n h a s not
been
experimentally
verified
and
it
is
entirely
p o s s i b l e that s o m e
or
all
natural copper complexes
are a c t u a l l y a v a i l a b l e .
Some
and
studies
have
indicated
copper-citric
acid
complexes
agents
even when
concentrations
tested with
for
toxicity
sulfate/L
(Fitzgerald,
conducted
by
copper
Fitzgerald
that
are
precipitated
no
different
varied
1963).
(1963)
to b l u n t n o s e m i n n o w and
It
less
algae
f r o m 0.5
several
6
salts
effective
as
in which
required
to
should be noted
indicated
copper
that
1.0
mg
that
the
sunfishes was
toxic
copper
the s t u d y
toxicity of
reduced
in
the
presence
being
Kean
of
citric
affected.
Stern
(1979),
adverse
effects
On
known
have
the
to
a
on
other
an
added
in
biological
razor's
algicidal
hand,
strong
or
to
uptake.
as
be
no
several
1978)
sought
acid
as
EDTA are
toxicity-
This would
and
appears
no
sulfate.
copper
the
and
has
NTA or
between
precipitation
information
its
success
algicide.
is
available
complexes
formulations
(Environmental
in
are
the
However,
Register,
to
indicate
ability
of
its
interference
to
lie
the
Illinois
November
water
because
algicides
health
effects
Citric
acid,
relating
on
to
the o t h e r
Food
on
on
the
of
hand,
Chemical
even
the m a r k e t .
its
In
efficacy
not
suitable
as
public
possibility
of
adverse
and
no
Federal
found
Board
1985)
the
the
algae
of
7,
presents
in
toxicity
Pollution Control
mutagenicity
c o n s u m p t i o n as o u t l i n e d
Administration's
the
field one would assume
complexes were
supply
on
blue-green
currently
copper/triethanolamine
human
such
Guy
copper
counteract
acid
with
citric
of
properties
edge.
of
an
chelants
Citric
copper-triethanolamine
light
along
that
Gachter,
inhibit
algicidal
properties
completely
1974;
its
(1978),
verified
balance must
ligand
Virtually
though
others
the
partially
delicate
and
without
similarly
( H o m e and G o l d m a n ,
that
acid
that
carcinogenicity.
such
problem with
Food
and
Drug
Codex.
Acknowledgments
This
investigation
was
sponsored
7
and
financially
supported
by
the
Illinois Department
study was
conducted
of
J.
Richard
under
Schicht,
of
E n e r g y and Natural
the
general
Acting Chief
Resources.
guidance
of
the
The
and
supervision
Illinois
State Water
Survey.
Our
appreciation
Chemistry
Section
consultation
on
contributed
the
special
thanks
Illinois,
in
this
of
the
goes
Illinois
this
is
due
and
the
Survey
Survey
include
computer
plotter
for
for
his
who
Taylor,
who
typist.
A
our
College,
Aquatic
personnel
Gail
Johnson,
Central
the
East
the
Peoria,
graphics
report.
This
study
is
dissolved
algicidal
inhibited
concerned
copper
by
of
the
the
necessary
to
would
only
sulfate
reduction
applications
in water
surface
The work
primarily
by
chelation
the v a r i o u s
of
a
algicidal
the
but
by
forms
involved
it
action
costs
can
the
of
copper.
anions
of
incurred
If
can
such as
that
be
citric
dosages
This
long-term copper
result
correlation
8
than with
be minimized.
drinking water
the
of
follows
impact
also
enhancement
rather
chelating agent
would
as
with
inorganic
ecological
treatment
impoundments
itself
SCOPE
triethanolamine,
maintain
reduce
AND
copper
presence
acid m o n o h y d r a t e or
not
(TDCu)
e f f e c t i v e n e s s of
precipitation
using
of
State Water
Linda
Illinois
providing
Holm
Other Water
OBJECTIVES
total
Tom
investigation
manuscript,
for
to
the p r o j e c t .
to
edited
also
in
by
an
enormous
municipalities
sources.
of
percent
copper
loss w i t h
hardness,
with
determination
the
necessary
report
to
is
maximize
a
acid
guidelines
c o n c e n t r a t i o n s of
copper
of
and
suspended solids along
cheI a n t / c o p p e r
solubility.
of
the
relative
in
this
stability
of
copper-triethanol amine
were
established
under
and
for
copper
given water
complexes.
the
relative
necessary
quality
ratios
Included
vs.
chelant
solubility
pH,
minimum
copper
comparison
copper-citric
Thus,
alkalinity,
for m a x i m u m
conditions.
MATERIALS AND METHODS
For
the
laboratory
lakes w i t h
typically
accurately
simulate
evaluation
h i g h a l k a l i n i t y and
real
r a n g e of
8.4,
for
to 2 3 0 m g / L as
providing ample
the p u r p o s e s o f
Rend Lake
40-75
(Benson,
mg/L
alkalinity
Both
as
CaCO 3 .
was
chosen
blooms with copper
Canton
w i t h a pH r a n g e of
complexation
to
C230
in
7.4
to
reactions
To provide c o m p a r i s o n ,
as a
Canton
sulfate
installation
destratification/aeration
Bulk
order
18,900 a c r e s ) with alkalinities of
Lake E u r e k a and Lake
the
treatments
CaCO3
experiment.
Illinois,
Lake
in
both exhibit alkalinities
p r e c i p i t a t i o n and
this
hardness
to c h o o s e
relatively soft,
low
lake.
treat a l g a l
with
160
necessary
lake c o n d i t i o n s .
a c r e s ) and Lake E u r e k a (37 a c r e s )
the
it w a s
have
have
in
in
systems
had
the
past.
recent
in
occasion
both
to
However,
years
lakes,
of
these
been m i n i m i z e d .
samples
(approximately
60
9
liters)
were obtained
from
the
top 2
Table
1
feet
of
the
contains
sample
total
pH,
All
Methods
1980).
Bulk
from
subsamples which were
sulfate
mg/L
each
chelating
incremental
sulfate
amounts
spikes were allowed
recovery
premix,
(0.45
copper
by
1980).
analysis
was
E a c h and
to
repeated with
also
copper
1:0
portions of
(1 ml
atomic
table
for
each
1:9.
24
hours
the
of
0.1
acid
spikes
of
copper
a
to
a
provide
copper/chelant
to equilibrate
subsample were
analyzed
per
by
for
filtered
for
Standard
inhibit
in
addition,
copper
agitated
to
copper
These premixed
In
of
absorption as
250-mL
citric
ratios
with
1+1 H N O 3 ) , a n d
were
into
sulfate
to
and
Standard
sufficient
minutes.
dosed
per
concentration
m i x e d and a l l o w e d
The subsamples
shaker
triplicate
SO-ml
flame
15
sulfate,
example,
Following addition
acidified
Eberbach
provide
blank was
Next,
from
stand
samples were well
µm),
(APHA,
to
comparison.
2 hours.
the
copper
lake
hardness,
as
with
(for
bulk
divided
providing weight/weight
pentahydrate/chelant
distilled water
chloride,
dosed
agent
m o n o h y d r a t e ) was premixed with
each
performed
theoretical
(figure 2 ) .
metals,
lake w e r e
initially
to p r o v i d e a
as Cu+2 .A
were
points
of
soluble
solids,
analysesr
samples
deepest
analysis
and
suspended
conductivity.
(APHA,
their
the b a c k g r o u n d
including
alkalinity,
lakes at
soluble
Methods
means
of
an
settling,
and
the
repeated.
every
copper/chelant
e n s u r e a c c u r a c y and
copper
theoretical
sulfate
copper
ratio experiment was
precision.
These
pentahydrate
dosages
concentrations
of
10
0.2
run
in
tests were
sufficient
and
to
0.3 m g / L
Cu+2
as
All
of
triethanolamine
Spring
Eureka,
the
(TEA)
bulk
above
as
the
samples
procedures
Aiso,
three
June 2 8 ,
lakes on
repeated
with
chelating agent.
were
collected
and Rend Lake on April
respectively.
were
summer
from Lake
12, May 3,
samples
September
and
were
10,
Canton,
June
collected
and
Lake
7,
1985,
from
these*
14,
1985,
August
respectively
A
follow-up
commercially
required an
The pH,
included
the w a t e r
study,
0.2,
sampling of
and
250-ml
Cutrine
0.5,
and
run
the
in
triplicate
subsamples were
2 hours.
Next,
quality data
these
for
mg/L
Cu+2
as
the
Identical
volumes
experiments,
to
ensure
then well
50-ml
samples.
each
by
atomic
1
absorption
concentrations
range
the
listed
f r o m 0.4 m g / L
distilled
served as
In
spiked with
requirements
of
water,
control.
copper
concentration was
precision.
Cutrine-spiked
m i x e d and a l l o w e d
aliquots of
This analysis was
copper
manufacturer,
8.02,
v a l u e s a r e not
bulk
Cdosage
13.
were
theoretical
provide
a c i d i f i e d (1 ml
1980).
table
on December
sampling
and
a
algicide,
to
( 0 . 4 5 urn),
flame
this
respectively,
same c o n c e n t r a t i o n s ,
in previous
Cutrine,
from Lake Eureka were
0.8
As
of
subsamples
1.0 m g / L a s C u + 2 ) .
spiked at
use
Lake Eureka
hardness of
by Applied B i o c h e m i s t s ,
to
the
copper/triethanolamine
and 228 m g / L ,
sufficient
of
additional
in
involving
available
alkalinity,
181 m g / L ,
this
study
each
to
equilibrate
subsample were
for
filtered
+ 1 H N O 3 ) a n d a n a l y z e d for c o p p e r
as
per
Standard
repeated at 2 4 ,
11
48,
Methods
and
96
(APHA,
hours
to
provide a
look
complex when
at
the
v i a b i l i t y of
extended equilibration
the
copper/triethanolamine
time
for
the
complex
is
allowed.
In order
an
to m o n i t o r
experiment
March
18)
involving
the
to p r o v i d e
a
to
addition,
this
solids
in
the
Average
(w/w)
ratio
order
to
loss o f
an
Eureka
and 9 6 - h o u r
look
the
another
monohydrate
5H2O/C6H8O7H2O)
TDCu
was
analyses.
with a portion
at
and
acid
CuSO4
period,
(collected on
spike
citric
(as
split,
extended
sample
Cu+2
sufficient
include 48-hour
in
over
0.25-mg/L
with
sample was
loss
Lake
a
copper
1:1.25
extended
spiking
one
containing
containing
to
copper
filtered
r o l e p l a y e d by
In
prior
suspended
soluble copper.
r e s u l t s of
each
copper
analysis
can be seen
in
the
a p p e n d i x.
RESULTS
Optimal
Copper/Chelant
Background
Canton,
and
chloride,
m e t a l s can b e
dissolved
seen
copper
subsamples with
citric
Lake
suspended
acid
quality
for
pH,
conductivity,
table
1.
concentration
copper/chelant
and
data
including
solids,
in
DISCUSSION
Ratio
water
Rend
AND
ratios
12
and
for
the
of
Eureka,
alkalinity,
Figures
in
triethanolamine
Lake
total
3a-3f
hardness,
and s o l u b l e
indicate
aforementioned
1:0
three
to
Lake
1:9
different
for
the
lake
both
initial
copper
plot
c o n c e n t r a t i o n s and
indicates
equilibration
mixing.
dissolved
period
where
However,
combined
in
the
these
if
copper
remaining
in
has an
soluble copper
copper
resulting
24
very
fact
low
not
no
2-hour
constant
the
lakes
reveal
added
the
are
4a-4d
level
in
appears
solution
for
all
the
that
near
to be
average
lakes
the
versus
0.3-mg
enhancement
a
1:5
the c a s e
(w/w)
for
vs.
higher
the
the
spiked at
off
enhancement
indicate
for
a clear
lake e x p e r i m e n t s a r e
remaining
indicate
to
This
in
than
did
loss o v e r
comparable
hours.
that
of
these
initial
hours
is
stability
is
indicates
Cu/L
of
the
r a t i o of
both
the
first
less
for
citric
stable
and begins
higher
2
on
levels
hours,
for
both
for
the
(Merck
the
chelants
these
could be
in a q u e o u s
to d e g r a d e
Triethanolamine,
13
this
although
the T E A s a m p l e s ,
constants
similar,
not
that
maintaining
concentrations
relatively
concentrations
C h e m i c a l s and D r u g s ) .
the T E A for
copper
citric acid
plots
tenacity,
24
Since
chelating agents are
the
Each
triethanolamine.
citric acid
after
do
has
solution
These plots
A close examination
rate of
copper
ratio ( w / w ) when
CuSO45H2O:chelant.
of
chelant
Figures
solubility begins
and
a
of
of
a plateau does emerge
concentrations.
concentration.
acid
after
hours
each
experiments
percent
ratio,
copper/chelant
copper
24
for
the d a t a f r o m all
terms of
copper/chelant
percent
after
runs
additional
effect.
copper
periods.
concentrations
again
summer
contact
separately.
Individually,
"plateau"
different
copper
and
Spring and
illustrated
two
due
two
to
s o l u t i o n at
Index
other hand,
of
is
more
stable
It
over
extended
is
clear
enhancement
effect
concentrations
copper
of
contribution
Even
should
to
the
lake,
remain
available
indicate
total
expected
at
the
for
of
or
agent,
dissolved
rates
dissolved copper
in
all
three
copper
spike
all
three
lakes
and
0.1
show a
copper
by
0.1
the
hours,
a
copper
spring
as
higher
initial
at
concentrations,
copper
in
seen
concentration
the
study of
and
mixtures
the
of
algicidal
copper
vary
treated
from
lakes
Figures
in
effect
but
solution
runs.
for
The
both
the p l a t e a u
for
to
the
first
chelant
ratio
the
is
higher
few
ratio
the m a x i m u m e f f e c t
necessary
for
include
representing
that
7a-7d
for
increasing
decreases.
I t s h o u l d b e n o t e d h e r e that
their
those
1:5 p r o v i d e s
with
in
no
complexes
summer
pentahydrate
least
these
and
enhancement
can be
sulfate
( w e i g h t / w e i g h t ) of
the
it
clear
or
These averages
as
Still,
little
remaining
not
concentrations.
no
at
concentrations
effects.
triethanolamine,
defined
copper
that
frequency may
c i t r i c acid m o n o h y d r a t e and
nearly as well
this
to 0.3 m g / L as b i o l o g i c a l l y
copper
definite
these
is
concentrations.
both
show
mg C u / L ,
there
and
that
initial
6a-6d
concentrations
r a n g e of
percent
6a-6d
when
near
required algicidal
the a v e r a g e
and
Figures
that
application
copper
resulting plots
as
the order
chelating
though
to
on
low c o n c e n t r a t i o n s .
5a-5d
decreased.
indicating
and
and
figures
decreases
concentrations
copper
lake
from
are
plateau exists,
periods
Stern
effects
of
et
copper
sulfate-citric
14
al.
(1978),
sulfate
acid,
in
alone
used
a
weight/weight
ratio
equivalent
0.5 m g / L
addition
to
of
on
the
In
1:8
with
at
no
copper
field
pentahydrate-citric
1:0.5
ratio
inhibition
acid
a
over
Par t i c u l a t e
et
for
both
a
8
a
on
clear
and
sediments
and
both
presence
copper,
but
in
the
citric
copper
formulations
of
alone
presence
and
Evans,
a
were
These
the
citric
a
copper
on
dissolved
acid
percent
enhanced
significantly
solids.
in
a
a
copper
absence of
the
higher
COn
studies
of
citric
1980).
period
with
can
have
of
96
and
hours
without
effect
sediments,
solubility
concentration
no
a
remaining
concentrations.
of
have
concentration.
significant
overall
solution with
(1978)
copper
suspended
the o r d e r
15
solids
copper
subsamples,
indicate
and
remains
dissolved
of
and Barica
by
analyzed over
results
seston
the a b s e n c e of
initial
in
copper
comparison
unfiltered
These
of
to
using
Illinois).
and W a g e m a n n
the
sample
chelant.
addition
copper
of
pentahydrate
(Kothandaraman
a d s o r p t i o n of
Eureka
filtered
the
studies
(Antioch,
C1978)
effect
shows
Lake
al.
that
significant
Figure
effects
the
sulfate.
precipitation
period
of
that
Adsorotion
Gachter
pointed out
of
toxicity
adverse
sulfate
Lake Catherine
24-hour
the
concentration
indicated
acid m o n o h y d r a t e
copper
indicated
sulfate
study
application
sulfate
in
Their
increased
of
addition,
performed
copper
detectable
efficacy
and
a
Cu+2
as
citric acid
Microcystis,
acid
of
50%
was
a
of
In
the
the
maintained
more
solids.)
of
for
of
the
These plots
about
48
hours.
stability
C1978)
of
steady-state
The
presence
in
of
solids
suspended
role
in
the
close
reveals an
agent
most
in
of
the
in
terms
attained
as W a g e m a n n
in
their
first-order
after
10
copper
implies
l o s s of
after
of
and
the
Barica
spiked
lake
decay
with
days.
concentrations
that
copper
of
adsorption
in
the
plays
a
in n a t u r a l w a t e r s .
allowing an
competition
for
Our
copper/triethanolamine
Although
copper
this
to
time a f f o r d e d
the
Illinois,
treatment
used.
the
of
"tank
Dosage
the m a n u f a c t u r e r ,
unless
requirements
as
concentrations
agent
once
introduced
into a
of
Cutrine,
a
in
only
1:10
the
complex
mixing"
is
period
costly
ensures
not
i s not
commercial
listed by Applied
indicated earlier,
16
range
ratio
a
of
concentrate.
1:2.5
indeterminate
the
chelating
chelating
shows
of
the
copper
the
agent
pre-equilibration
operators
for
copper
ratio
to TEA,
Since
this
the
chelating
formation
concentrations.
advantage
of
initial
examination
a
available
concentration
formulation,
represents
pentahydrate
commercially
This ensures high
system.
elemental
of
elevated
cases.
complex,
natural
are
nearly
TDCu
indication
concentrations
dissolved
examination
complexes
water
an
of
Study
A
sulfate
be
complexes,
follow a
concentrations
l e v e l l i n g off
also
copper
copper
to
a
may
5 0% d e c r e a s e
significant
Cutrine
two
that
continued
indicate
This
these
reported
samples
also
as
copper
equilibration
high
initial
allowed
in
available
to
formulations
Biochemists,
f r o m 0.4 m g / L
to
1.0 m g / L as Cu + 2
The
laboratory
subsamples
of
sufficient
Cutrine
0.5,
and
off"
copper
in
of
figure
the
However,
there
l e v e l e d off
the
to
of
a
higher
pre-equilibration
s o l u b i l i t y of
the
using Cutrine
than
of
that
Regression
The
between
and
results
used
of
suspended
solids.
in
all
this
dependent
percent
analysis
shown
for
to
this
toss and
spikes
time was
as
short.
to a
copper
results
are
algal
hours.
concentrations
previous
this
extent,
blooms
sulfate
48
initially high
Although
greater
"levelling
about
in
0.2,
for
a
copper
than
control
current
copper
are
levels
after
of
the
studies
enhances
cost
is m u c h
per
higher
treatments.
Analvsi s
regression
loss
other
indicate
with
analyzed
the
to u s i n g an
complex,
copper
treatment
also
benefit
the C u - T E A
were
96 h o u r s ;
spiking
sample
concentrations
concentration
clear
Eureka
samples
results
copper
at m u c h
copper
These
involved
Lake
a period of
These
is
13
provide
Cu+2.
over
9
experiment
December
soluble
concentration
where
the
0.8 m g / L a s
dissolved
shown
Cutrine
in
percent/day.
pH,
Results
table
three
2.
The
the
both
Column
24
second
and
hours,
third
17
strong
hardness,
a
above
correlation
conductivity,
stepwise
parameters
data
from
multiple
to
the
copper
0.3-mg Cu/L
spring and summer
runs,
were
1
lists
the
of
including percent
at
a
of
Only
lakes,
analysis.
loss
out
alkalinity,
applying
variables,
copper
study bear
and
the
table
copper
loss
rate of
columns
show
at
2
copper
the
hours,
loss
in
regression
equations
for
correlation
coefficients.
The
dependent
regression
hours
shows
with
pH,
a
equation
representing
independent
equations
possible
and
percent
copper
for
order
of
without
physical
be
noted
dependence
to
and
that
to
and
it
exist
24
= 0.974),
significance
reference
relationships,
statistical
(r
at
solids,
decreasing
should
multiple
loss
suspended
It
developed
and
for
the
the
correlation
hardness,
variables.
were
biological,
variable
high d e g r e e of m u l t i p l e
conductivity,
alkalinity
the
each
of
these
causal,
is e n t i r e l y
without
causal
dependence.
SUMMARY
It
is e v i d e n t
formation
of
from
copper
copper-TEA does
the
results
complexes
slightly
such
inhibit
from natural
waters.
However,
as
toxicity
of
to
the
algicides.
Regardless
proportions
of
water
This
either
copper
or
chelated
treatment
study
no
sulfate
sulfate
that
as
copper-citricacid
is
copper
still
complexes
issue,
in
formulations
greater
than
a
the
relative
of
copper
stability
18
of
their
for
are
a
"on-site"
pentahydrate:citric
inhibition
that
the
and
copper
a m a t t e r of d e b a t e
guidelines
involving
any
study
precipitation
1:5
acid
pentahydrate:triethanolamine
additional
Regarding
this
operations
indicates
copper
of
this
the
it
these
of
role
as
the p r o p e r
necessity
in
preparations.
(w/w)
ratio of
monohydrate
results
in
or
little
precipitation.
of
these
two
formulations
in
natural
the
citric
to
the
waters,
acid
TEA
enhancement
or
TEA
complex
copper
not
concentrations
complexes
24
those
samples where
to
hours,
health
point
and
solids
the
loss
of
as
much
dissolved
Topics
for
premixing
making
copper,
copper
this
study
investigations
range
is
to
This
chelant
to
play
filtered
as
a
of
debate
higher
as
organisms
is obviously
Cu+2
Both
dissolved
copper
to
higher
retained
in
However,
the
seem
the
to
in
twice
samples.
viability
of
rather
than
present.
Of
toxicity of
their
fundamental
the
at
role
nearly
agents
case
and
than
unfiltered
include
the
copper
significant
chelating
is
acid
choice.
corresponding
as
citric
triethanolamine
very
samples
with
the
of
the
as
absent.
with
that
chelated
effectiveness
further
as
research
field.
This
a
the
sulfate
complexes
concentrations
of
comparison
dissolved
0.2mg/L
investigation might
importance
algicides.
as
as
copper
further
copper
until
associated
appear
separate additions
primary
in
now
in
chelation with
chelating agents were
effects
tenacity
indicate
concentrations were
to c i t r i c acid as
Suspended
by
approximately
these
power
also
evident
comparable
initial
staying
Results
solubility
reach
reached
indicate an
little
clearly
after
adverse
but
formulation.
of
is
the.results
chelant
(1:0.5
points
to
determine
within
to
to
1:3)
an
of
the
need
the
carry out
efficacy
economically
copper
to
and
sulfate
ratios.
19
of
field
using
ecologically
pentahydrate
scale
citric
acid
reasonable
to
chelant
TABLES AND FIGURES
20
Table 1.
Water Quality Characteristics of Bulk Samples
Lake Canton
First Run
Second Run
pH
Alkalinity (mg/L
CaCO3)
Hardness (mg/L
CaCO3)
Chloride (mg/L)
Sulfate (mg/L)
Suspended solids (mg/L)
Conductivity
(µmho/cm)
NH3-N (mg/L)
PO4-P (mg/L)
7.95
130
190
10.0
51.0
28.0
314
-
Lake Eureka
First Run
Second Run
Rend Lake
First Run
Second Run
8.38
141
199
12.8
53.0
11.0
413
0.03
0.02
7.99
158
240
20.6
40.0
23.0
387
-
8.12
255
245
25.0
2.50
42.0
562
0.44
0.22
7.78
53.0
87.0
6.0
50.0
19.0
212
-
7.70
48.0
92.0
21.0
51.0
17.0
286
0.02
0.01
<0.05
<0.0l
0.04
0.01
43.0
18.0
0.07
0.38
<0.05
<0.01
0.04
0.02
55.0
24.0
0.07
1.00
<0.05
<0.01
0.05
<0.01
46.0
22.0
0.14
0.13
<0.05
<0.01
0.05
0.01
20.0
5.6
0.21
0.33
<0.05
<0.01
0.04
<0.01
22.0
6.0
0.37
0.24
<0.05
<0.01
0.04
0.01
42.0
17.0
<0.01
0.10
<0.05
<0.01
0.03
0.02
55.0
23.0
0.01
0.10
<0.05
<0.01
0.09
<0.01
44.0
21.0
0.04
0.17
<0.05
<0.01
0.05
0.01
19.0
5.4
<0.01
0.02
<0.05
<0.01
0.04
<0.01
22.0
5.8
<0.01
0.01
Total Metal Concentrations (mg/L)
Pb
Cd
Zn
Cu
Ca
Mg
Mn
Fe
<0.05
<0.01
0.04
0.02
47.0
19.0
0.08
1.70
Soluble Metal Concentrations (mg/L)
Pb
Cd
Zn
Cu
Ca
Mg
Mn
Fe
<0.05
<0.01
0.03
0.01
44.0
18.0
0.01
0.11
Table 2.
Regression Analysis of Copper Loss with Respect to Water Quality Parameters
Dependent Variable
Regression
Equations
Multiple
Corr. Coef.
Percent TDCu Loss at T=2 hr
41.43 X1 + 2.542 X4 - 74.78 X2 + 0.2331 X3 + 0.1074 X5 - 349.3
0.890
Percent TDCu Loss at T=24 hr
23.29 X1 + 0.1822 X5 + 0.0871 X3 + 2.221 X4 - 69.75 X2 - 190.7
0.974
ATDCu/At (%/day)
-0.1452 X3 + 0.0696 X5 - 22.66 X1 - 0.3906 X4 + 74.28 X2 - 194.9
0.906
X1 = pH (unitless)
X2 = Alkalinity (mg/L as CaCO3)
X3 = Hardness (mg/L as CaCO3 )
X4 = Suspended solids (mg/L)
X5 = Conductivity (µmho/cm)
ATDCu/At = Rate of soluble copper loss
PH
Figure 1. Speciation of copper (II)
(total concentration 2 ppm) and carbonate
as a function of pH (from Sylva, 1976)
23
Figure 2. Sampling locations on Lake Canton, Lake Eureka, and Rend Lake
24
Figure 3a. Lake Canton TDCu analysis of April 12, 1985 sampling
25
Figure 3b. Lake Eureka TDCu analysis of May 3, 1985 sampling
26
Figure 3c. Rend Lake TDCu analysis of June 7, 1985 sampling
27
Figure 3d. Lake Canton TDCu analysis of June 28, 1985 sampling
28
Figure 3e. Lake Eureka TDCu analysis of September 10, 1985 sampling
29
Figure 3f. Rend Lake TDCu analysis of August 14, 1985 sampling
30
Figure 4. Average percent copper remaining in solution vs.
CUSO4•5H20/chelant ratio (w/w) for all lakes, both
runs and 0.3 mg Cu/L spike
31
Figure 4.
Concluded
32
Figure 5. Average percent copper remaining in solution vs.
CuS04•5H2O/chelant ratio (w/w) for all lakes, both
runs and 0.2 mg Cu/L spike
33
F i g u r e 5.
34
Concluded
Figure 6. Average percent copper remaining in solution vs.
CuS04●5H2O/chelant ratio (w/w) for all lakes, both
runs and 0.1 mg Cu/L spike
35
Figure 6. Concluded
36
Figure 7. Average percent copper remaining in solution vs.
CUSO4•5H20/chelant ratio (w/w) for all lakes, both
runs and all spike concentrations
37
Figure 7.
38
Concluded
Figure 9. Percent copper remaining in solution vs. time for
Cutrine dosages of 0.2, 0.5, and 0.8 mg Cu/L
39
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41
Water Survey Circular
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Sillen, A.G., and A . E .
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enhancement of copper sulfate toxicity to blue-green algae
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42
1950.
(II)
in
rate of loss
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American
Water
APPENDIX
43
Average Data for Lake Eureka - First Run (May 3, 1985)
Ratio+
T=2 hr
Citric Acid Monohydrate
0.3 mg/L Spike 0.2 mg/L Spike 0.1 mg/L Spike
TDCu* %Cu REMt TDCu
%Cu REM TDCu
%Cu REM
Ratio
Tnethanolamine
0.3 mg/L Spike 0 2 mg/L Spike
TDCu %Cu REM TDCu
%Cu REM
0.1 mg/L Spike
TDCu
%Cu REM
Control
1:0.0
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.283
0.235
0.245
0.260
0.272
0.272
0.274
83.0
86.6
91.8
96.2
96.1
96.8
0.194
0.148
0.153
0.155
0.164
0.167
0.176
76.6
78.8
80.0
84.7
86.1
90.7
0.093
0.096
0.098
0.094
0.094
0.090
0.101
104
106
101
101
96.8
109
Control
1:0.0
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.295
0.233
0.231
0.239
0.240
0.245
0.253
78.9
78.3
80.8
81.2
83.0
85.8
0.192
0.149
0.159
0.170
0.177
0.172
0.185
77.9
83.0
88.9
92.3
89.6
96.5
0.092
0.096
0.087
0.086
0.080
0.078
0.080
104
94.6
93.5
87.0
84.1
87.0
T=24 hr Control
1:0.0
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.302
0.210
0.218
0.227
0.245
0.244
0.243
74.1
77.1
80.2
86.5
86.2
85.7
0.193
0.131
0.130
0.137
0.136
0.138
0.142
67.5
67.0
70.7
70.1
71.3
73.5
0.094
0.076
0.075
0.079
0.078
0.075
0.082
82.0
80.6
85.3
84.2
81.3
88.5
Control
1:0.0
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.302
0.208
0.221
0.228
0.237
0.247
0.245
70.5
74.7
77.3
80.1
83.7
83.0
0 188
0.135
0.136
0 150
0.152
0.158
0.167
70.4
71.1
78.4
79.5
82.6
87.1
0.093
0.069
0.071
0.070
0.062
0.067
0.071
74.7
76.5
75.5
67.5
72.9
76.9
+
*
†
Ratios are calculated on a weight/weight basis as CuS04•5H2O/chelant
TDCu represents the average total dissolved copper of triplicate trials
%Cu REM represents percent dissolved copper remaining in solution vs. control
Averaqe Data for Lake Eureka - Second Run (September 10, 1985)
T=2 hr
T=24 hr
RatlO+
Citric Acid Monohydrate
0.3 mg/L Spike 0.2 mg/L Spike 0.1 mg/L Spike
TDCu* %Cu REMt TDCu
%Cu REM TDCu
%Cu REM
Control
1:0.0
1:0.5
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.263
0.202
0.204
0.207
0.217
0.226
0.234
0.236
Control
1:0.0
1:0.5
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.320
0.159
0.160
0.156
0.162
0.154
0.153
0.152
76.7
77.4
78.6
82.3
85.7
88.8
89.7
60.5
60.8
59.4
61.4
58.4
58.2
57.6
0.179
0.147
0.143
0.145
0.146
0.147
0.147
0.148
0.158
0.114
0.116
0.113
0.114
0.114
0.108
0.115
82.3
80.1
81.0
81.5
82.0
82.3
82.8
0.086
0.088
0.087
0.086
0.081
0.082
0.079
0.081
-
0.089
63.6
64.8
63.4
64.0
63.7
60.6
64.3
0.064
0.060
0.061
0.057
0.059
0.057
0.059
102
101
99.6
94.0
95.2
91.3
93.8
73.6
69.1
70.1
66.4
68.1
66.2
68.0
Ratio
Triethanolamine
0.3 mg/L Spike 0.2 mg/L Spike 0.1 mg/L Spike
TDCu
%Cu REM TDCu
%Cu REM TDCu
%Cu REM
Control 0.276
1:0.0
0.227
1:0.5
0.229
1:1.0
0.230
1:3.0
0.229
1:5.0 0.228
1:7.0 0.231
1:9.0
0.231
Control
0.268
1:0.0
1:0.5
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.178
0.179
0.178
0.191
0.192
0.194
0.202
82.0
82.8
83.4
82.9
82.7
83.5
83.6
64.3
64.9
64.6
69.2
69.3
70.1
73.1
+ Ratios are calculated on a weight/weight basis as CuS04●5H2O/chelant
* TDCu represents the average total dissolved copper of triplicate trials
† %Cu REM represents percent dissolved copper remaining in solution vs. control
0.179
0.161
0.163
0.165
0.159
0.165
0.162
0.170
0.182
0.116
0.123
0.115
0.127
0.126
0.133
0.138
90.1
91.4
92.5
89.2
92.4
90.7
95.0
65.0
68.8
64.6
70.8
70.3
74.6
77.1
0.090
0.086
0.084
0.088
0.088
0.086
0.084
0.085
95.6
92.4
96.9
96.9
95.0
92.6
94.1
0.087
0.059
0.060
0.064
0.061
0.063
0.064
0.066
64.8
66.4
70.3
67.3
70.1
70.7
72.7
Average Data for Lake Canton - First Run (April 12, 1985)
Ratio+
T=2 hr
Control
1:0.0
1:0.5
1:1.0
1:2.0
1:3.0
1:3.5
1:5.0
1:7.0
1:9.0
T=24 hr
Control
1:0.0
1:0.5
1:1.0
1:2.0
1:3.0
1:3.5
1:5.0
1:7.0
1:9.0
Citric Acid Monohydrate
0.3 mg/L Spike
0.2 mg/L Spike 0.1 mg/L Spike
TDCu*
%Cu REM† TDCu
%Cu REM TDCu
%Cu REM
0.295
-
0.171
0.217
0.208
0.225
0.250
0.242
0.265
-
73.6
70.5
76.4
84.7
_
82.1
90.0
_
-
0.131
0.139
0.152
_
0.162
0.160
0.157
0.269
0.178
0.175
0.195
0.208
0.209
0.232
-
60.3
59.5
66.1
70.5
70.8
78.6
-
0.191
0.125
0.121
0.120
0.117
0.113
0.121
-
0.093
-
76.8
0.080
86.3
81.5
0.080
86.0
88.9
94.9
93.8
91.6
0.075
0.083
0.041
0.094
81.3
89.2
98.2
101.4
72.9
0.096
0.072
71.0
_
70.0
_
68.6
66.3
70.6
0.077
_
0.076
_
0.079
0.079
0.085
77.7
83.1
_
81.7
_
85.3
85.6
91.4
Ratio
Triethanolamine
0.3 mg/L Spike 0.2 mg/L Spike 0.1 mg/L Spike
TDCu
%Cu REM TDCu
%Cu REM TDCu
%Cu REM
Control
0.263
1:0.0
1:0.5
1:1.0
1.2.0
1:3.0
1:3.5
1:5.0
1:7.0
1:9.0
0.164
Control
1:0.0
1:0.5
1:1.0
1:2.0
1:3.0
1:3.5
1:5.0
1:7.0
1:9.0
0.183
0.201
0.229
0.225
0.234
0.291
0.155
0.165
0.204
0.223
0.217
0.218
-
0.203
-
0.093
62.3
_
69.5
_
76.2
_
87.1
85.6
88.9
0.156
77.0
_
_
_
0.176
86.7
_
_
_
0.186
91.5
0.203 100.0
0.185
91.0
0.181
89.3
0.068
_
0.072
_
0.072
0.071
0.080
0.084
77.5
_
77.5
_
77.5
_
76.4
85.4
90.4
58.7
_
62.5
_
77.5
_
84.7
82.5
82.9
0.178
0.126
_
_
0.140
_
_
0.139
_
_
0.147
0.144
0.152
0.091
0.058
_
0.056
_
0.062
_
0.062
0.062
0.075
62.1
_
60.0
_
66.8
_
66.4
66.8
79.8
+ Ratios are calculated on a weight/weight basis as CuS04•5H2O/chelant
* TDCu represents the average total dissolved copper of triplicate trials
† %Cu REM represents percent dissolved copper remaining in solution vs. control
61.9
_
69.0
_
68.3
_
72.6
70.9
74.9
Averaqe Data for Lake Canton - Second Run (June 28, 1985)
T=2 hr
T=24 hr
,
Ratio+
Citric Acid Monohydrate
0.3 mg/L Spike
0.2 mg/L Spike 0.1 mg/L Spike
TDCu*
%Cu REM† TDCu
%Cu REM TDCu
%Cu REM
Control
1:0.0
1:0.5
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.283
0.257
0.266
0.265
0.289
0.286
0.289
0.293
Control 0.283
1:0.0 0.209
1:0.5 0.209
1:1.0 0.225
1:3.0 0.234
1:5.0 0.245
1:7.0 0.242
1:9.0 0.252
Ratio
Triethanolamine
0.3 mg/L Spike 0.2 mg/L Spike 0.1 mg/L Spike
TDCu %Cu REM TDCu
%Cu REM TDCu
%Cu REM
91.0
94.1
93.9
102
101
102
104
0.188
0.181
0.178
0.182
0.180
0.186
0.193
0.189
96.3
94.5
96.6
95.7
98.9
103
101
0.088
0.086
0.087
0.088
0.090
0.091
0.090
0.109
97.4
98.5
99.2
101
103
102
123
Control
1:0.0
1:0.5
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.281
0.244
0.252
0.245
0.260
0.262
0.262
0.264
86.7
89.6
87.2
92.6
93.4
93.4
94.1
0.187
0.180
0.186
0.184
0.188
0.188
0.187
0.191
96.4
99.6
98.6
101
101
100
102
0.091
0.086
0.085
0.085
0.084
0.088
0.087
0.085
95.2
93.8
93.8
92.3
96.7
96.3
93.8
73.9
73.9
79.6
82.8
86.7
85.5
89.0
0.188
0.159
0.156
0.161
0.159
0.150
0.166
0.170
84.6
82.8
85.8
84.6
79.8
88.3
90.6
0.085
0.074
0.075
0.075
0.073
0.073
0.074
0.072
83.8
84.5
84.9
82.3
82.3
83.8
81.1
Control
1:0.0
1:0.5
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.283
0.224
0.224
0.225
0.244
0.242
0.245
0.250
79.8
79.8
8.01
86.8
86.1
87.1
89.0
0.179
0.154
0.157
0.157
0.154
0.163
0.157
0.168
82.2
83.8
84.1
82.4
87.0
84.1
89.7
0.090
0.072
0.072
0.077
0.077
0.074
0.080
0.085
79.8
79.4
84.6
84.6
82.0
87.9
93.8
+ Ratios are calculated on a weight/weight basis as CUSO4•5H2O/chelant
* TDCu represents the average total dissolved copper of triplicate trials
† %Cu REM represents percent dissolved copper remaining in solution vs. control
Average Data for Rend Lake - First Run (June 7, 1985)
T=2 hr
T=24 hr
Ratio+
Citric Acid Monohydrate
0.3 mg/L Spike 0.2 mg/L Spike 0.1 mg/L Spike
TDCu* %Cu REMt TDCu %Cu REM TDCu
%Cu REM
Control
1:0.0
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.281
0.225
0.245
0.258
0.275
0.278
0.279
80.1
87.2
91.9
97.8
98.8
99.5
0.185
0.145
0.156
0.165
0.178
0.175
0.179
78.1
83.9
89.0
95.9
94.5
96.3
0.092
0.077
0.079
0.082
0.084
0.088
0.087
84.1
86.2
89.5
91.7
95.3
94.0
Control
1:0.0
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.279
0.197
0.206
0.202
0.216
0.211
0.208
70.4
73.7
72.4
77.2
75.4
74.6
0.182
0.140
0.144
0.145
0.151
0.149
0.145
77.1
79.1
79.5
82.8
81.9
79.9
0.096
0.078
0.073
0.080
0.076
0.072
0.077
81.6
76.0
83.3
79.5
75.3
79.9
Control
1:0.0
1.1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.284
0.172
0.185
0.184
0.190
0.197
0.209
61.3
65.9
65.4
67.5
70.2
74.5
0.205
0.118
0.118
0.120
0.121
0.119
0.118
63.7
63.6
64.6
65.2
63.9
63.4
0.093
0.062
0.064
0.066
0.067
0.064
0.068
67.8
69.9
71.4
73.2
69.6
73.9
Control
1:0.0
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.281
0.153
0.166
0.175
0.187
0.194
0.196
54.8
59.5
62.5
66.8
69.5
70.2
0.180
0.104
0.114
0.114
0.119
0.119
0.130
57.1
62.5
62.5
65.4
65.4
71.4
0.092
0.061
0.058
0.063
0.060
0.059
0.062
63.2
60.8
65.3
62.8
61.8
64.2
Ratio
Triethanolamine
0.3 mg/L Spike 0.2 mg/L Spike
TDCu
%Cu REM TDCu
%Cu REM
0.1 mg/L Spike
TD6u
%Cu REM
+ Ratios are calculated on a weight/weight basis as CuSO4●5H2O/chelant
* TDCu represents the average total dissolved copper of triplicate trials
† %Cu REM represents percent dissolved copper remaining in solution vs. control
Average Data for Rend Lake - Second Run (August 14, 1985)
Ratio+
T=2 hr
Citric Acid Monohydrate
0.3 mg/L Spike 0.2 mg/L Spike 0.1 mg/L Spike
TDCu* %Cu REM† TDCu
%Cu REM TDCu
%Cu REM
Ratio
Triethanolamine
0.3 mg/L Spike 0.2 mg/L Spike 0.1 mg/L Spike
TDCu
%Cu REM TDCu
%Cu REM TDCu
%Cu REM
Control 0.297
1:0.0 0.212
1:0.5 0.224
1:1.0 0.228
1:3.0 0.249
1:5.0 0.263
1:7.0 0.259
1:9.0 0.261
71.4
75.5
76.7
83.8
88.4
87.2
88.0
0.195
0.149
0.147
0.150
0.156
0.165
0.163
0.168
76.7
75.7
77.1
80.0
84.5
83.9
86.4
0.098
0.082
0.083
0.077
0.076
0.084
0.082
0.087
83.5
85.2
78.4
78.0
85.3
84.2
89.3
Control
1:0.0
1:0.5
1:1.0
1:3.0
1:5.0
1:7.0
1:9.0
0.293
0.206
0.209
0.206
0.212
0.212
0.213
0.216
70.2
71.3
70.3
72.3
72.1
72.5
73.7
0.182
0.152
0.150
0.150
0.146
0.144
0 151
0.152
83.5
82.4
82.4
80.0
79.2
82.6
83.2
0.098
0.084
0.083
0.079
0.080
0.077
0.077
0.078
85.2
84.4
80.1
81.0
77.9
78.8
79.1
T=24 hr Control 0.291
1:0.0 0.135
1:0.5 0.138
1:1.0 0.139
1:3.0 0.153
1:5.0 0.135
1:7.0 0.159
1:9.0 0.150
45.3
46.3
46.8
51.5
45.3
53.4
50.4
0.200
0.130
0.095
0.103
0.101
0.102
0.105
0.106
52.7
48.8
53.0
51.6
52.6
53.9
54.4
0.096
0.058
0.056
0.056
0.056
0.053
0.053
0.057
58.6
56.9
56.9
56.9
54.3
54.3
58.6
Control
1:0.0
1:0.5
1:1.0
1:3.0
1:5.0
1.7.0
1:9.0
0.283
0.142
0.154
0.146
0.156
0.166
0.166
0.179
48.6
52.6
49.7
53.1
56.7
56.7
61.2
0 167
0.109
0.108
0.106
0 108
0.109
0.121
0 120
59.9
59.4
58.0
59.4
60.0
66.3
65.9
0.096
0.059
0.058
0.055
0.060
0.054
0.060
0.058
60.4
58.7
55.5
60.8
55.2
61.0
59.3
+ Ratios are calculated on a weight/weight basis as CuSO4●5H2O/chelant
* TDCu represents the average total dissolved copper of triplicate trials
† %Cu REM represents percent dissolved copper remaining in solution vs. control
Average Data for Filtered and Unfiltered Lake Eureka
T=2 hr
Lake Eureka*
Lake Eureka (Citric Acid)**
Filtered Lake Eureka*
Filtered Lake Eureka (Citric Acid)**
TDCu
0.147
0.179
0.232
0.241
%Cu REM
58.8
71.6
92.8
96.4
T=48 hr
TDCu
0.104
0.118
0.221
0.224
%Cu REM
41.6
47.2
88.4
89.6
T=96 hr
TDCu
0.099
0.117
0.212
0.236
%Cu REM
39.7
46.8
84.8
94.4
* Samples were spiked with sufficient CuSO4•5H2O to provide 0.250 mg/L as Cu+2
** Copper spike was premixed with sufficient citric acid monohydrate to provide a 1:1.25 (W/W) ratio of
CuSO 4• 5H 2 O to C6H8O7•H2O
Average Data for CutrineR Analysis
T=2 hr
Lake Eureka (a)
Lake Eureka (b)
Lake Eureka (c)
(a)
(b)
(c)
TDCu
0.207
0.540
0.810
%Cu REM
98.6
100
100
T=24 hr
TDCu
0.181
0.463
0.751
%Cu REM
86.2
86.3
93.6
T=48 hr
TDCu
0.187
0.444
0.666
%Cu REM
89.0
82.8
83.0
T=96 hr
TDCu
0.190
0.432
0.660
Spiked with sufficient Cutrine to provide approximately 0.2 mg/L as Cu+2 (0.210 mg/L)
Spiked with sufficient Cutrine to provide approximately 0.5 mg/L as Cu+2 (0.536 mg/L)
Spiked with sufficient Cutrine to provide approximately 0.8 mg/L as Cu+2 (0.802 mg/L)
%Cu REM
90.5
80.6
82.3
ILENR/RE-EH-86/09
Optimal Chelant/Copper Ratios for Maximizing Copper
Solubility in Natural Water Using Cxtric Acid and
Triethanolamine
September 1986
Raman K. Raman and Billy K. Cook
Illinois State Water Survey
Water Quality Section
Foot of MacArthur Hwy
P.O. Box 697
Peoria, IL 61652
85/6005 and 86/6005
(C)EH 22 and EH 22
(G)
Illinois Department of Energy and Natural Resources
Energy and Environmental Affairs Division
325 W. Adams
Springfield, IL 62704-1892
Taste and odor problems that plague waterworks using impoundments as a source can most
often be attributed to algal blooms, mainly blue-greens (Sigworth, 1957). These taste and
odor problems are compounded by other problems such as reduced filter runs, increased
chemical costs, etc. Physical solutions to the problems such as harvesting of algae or
control of excessive nutrient inputs can be extremely costly and time consuming in
comparison to chemical methods of bloom control. Although several types of algicides are
commercially available, copper formulations seem to enjoy the greatest popularity due
in part to their relatively low toxicity to higher organisms, particularly fish, when
applied at accepted algicidal levels (Mackenthun and Cooley, 1952). It is evident from the
results of this study that the formation of copper complexes such as copper-citric acid
and copper-TEA does slightly inhibit the precipitation of copper from natural waters.
However, it is still a matter of debate as to the toxicity of these complexes in their
role as algicides. Regardless of this issue, guidelines for the proper proportions of
chelated copper formulations are a necessity in water treatment operations involving
"on-site" preparations. This study indicates that any greater than a 1:5 (w/w) ratio of
either copper sulfate pentahydrate:citric acid monohydrate or copper sulfate pentahydrate:
triethanolamine results in little or no additional inhibition of copper precipitation.
This study points to the need to carry out field scale investigations to determine the
efficacy of using citric acid as a chelant within an economically and ecologically
reasonable range (1:0.5 to 1:3) of copper sulfate pentahydrate.to chelant ratios.
Algal Bloom; Algicides; Lakes; Illinois; Algae
Illinois; Lakes; Lake Canton; Lake Eureka; Triethanolamine; Copper Sulfate
Rend Lake; Chelanting Agent; Blue Green Algae
07 B
No restriction on distribution.
Available at IL Depository Libraries or from National
Technical Information Service, Springfield, VA 22161
Unclassified
Unclassified
50