ILLINOIS POLLUTION CONTROL BOARD
November
7,
1985
IN THE MATTER
OF:
R84—4
ALGICIDE
CHEMICALS,
AMENDMENTS TO
)
(Consolidated)
35
ILL. ADM, CODE 602,103 AND 602,110
)
R84-19
PROPOSED
RULE,
FIRST NOTICE,
OPINION AND
ORDER OF THE BOARD (by J, Marlin):
This
matter comes before the Board upon the
filing of
separate proposals
to amend
35
Ill, Adm, Code
602,103 by Applied
Bjochemists
Inc.
(Applied)
on December 14,
1983
(R
84—4)
and by
Carus Chemical
Company
Inc.
(Carus)
on May
23,
1984
(R 84—19).
Applied amended
its proposal on January 10,
1984,
Both proposals
were consolidated
for hearing by Hearing Officer
Order on June
8,
1984 after
Board discussion,
Merit hearings were
held
in
Springfield,
Illinois on July 24,
1984 and
in
Chicago,
Illinois
on July
31,
1984.
The Illinois Department of
Energy and Natural
Resources
on November 27,
1984 found that
an
economic impact
study was not necessary and stated that
~the
cost of making
a
formal study
is
economically unreasonable
in
relation
to the
value
of
the study to
the Board in
determining the adverse
economic impact of
the regulation.~
(November
27,
1984 Negative
Declaration),
The Economic Technical Advisory
Committee
concurred
in this finding
on January 23,
1985,
A supplemental
hearing called by the Board
to address informational deficiencies
was held May 20, 1985
in
DeKalb,
Illinois,
The participants
submitted additional
information after hearing.
The Agency
comments
were received on October
7,
1985,
The current
algicide permit section
602,103 allows the use
of only copper
sulfate
in
treating algae problems
in bodies of
water used as public water supplies.
The petitioners request
that
the
regulations be modified
to allow the use
of other
products for
this purpose.
Applied~s original proposal would
amend
the
section to include
all algicides registered with the
USEPA
for use
in potable water,
Its
amended proposal narrowed
that
scope
to include only copper
sulfate, copper carbonate
(malachite),
copper monoethanolamine
and copper triethanolamine
compounds.
Applied!s two copper
ethanolamine products are liquid
Cutrine~Plus
and granulated Cutrine—Plus.
These are registered
with
the USEPA pursuant to the Federal
Insecticide,
Fungicide and
Rodenticide Act
(FIFRA,
7 U.S.C. §136
et seq.,
1982)
for use
in
bodies
of water that are potable
water supply sources,
(Reg. Noes
8959—1OAA
and 8959~12AA),
They are also
registered with the
Illinois Department
of Agriculture
(as
of December
28,
1983;
Applied
Exhibit
20) pursuant to the Illinois
Pesticide Act
(IPA)
Ill,
Rev, Stat,
1985,
ch,
5,
par.
801
~
These
are chelated
66~379
2
copper
compounds which use ethanolamine complexes
to keep
otherwise
insoluble copper carbonate
in solution
(JR.
30,
31)1.
This results
in a rather uniform copper
concentration throughout
the water
(App, Exhs,
16,
9,
13, 14).
The
liquid form
contains
nine percent
elemental copper (0.909 lbs,/gal
Cu).
The
granulated
form contains 3,7 percent
active copper material
(App.
Exh,
14, JR.
15).
Carus~proposal would amend section 602,103
to include
its
two potassium
permanganate products, Cairox
Technical and Cairox
FF,
These are registered with the USEPA
(Reg.
No.~s
8429—6,
8429—7)
under FIFRA and with the Illinois
Department of
Agriculture
(as of November
9,
1983;
Carus Exhs.
C,D) for use
in
potable
water treatment
systems.
Under this
registration,
they
may
not
be used
in open bodies of water,
Cairox Technical
contains
98 percent potassium permanganate and
two percent inert
ingredients
while Cairox FF contains 95,6 percent
potassiui~
perrnanganate and 4,4 percent
inert ingredients, which
includes
a
food—grade
additive (Exhs, A,B,C;
JR.
38),
The record does not support the proposal
to amend
sections
602,103
and 602,110 to encompass those potable water
supply
algicides
registered with the USEPA for use
in
Illinois.
In
order
to
incorporate algicides registered with
the USEPA pursuant
to
40
C,F.R. Part
162
(1984),
the Board
is
statutorily mandated
to have
on file
a list of those chemicals,
(Ill,
Rev.
Stat.
1985,
ch.
127,
par.
1006.02,
35
Ill, Adm,
Code 100.385).
The
Board
attempted
to obtain the list of algicides
approved for use
in potable
water supplies from the USEPA.
It
was not possible
to
secure
a complete listing.
Board exhibits
1,
2,
5,
6,
7,
and
8
as
well
as the Hearing Officer Report of March
1,
1985 document
the
difficulties encountered during the attempt.
The USEPA has
been
mandated by Congress to review all algicides
currently
registered
with
it and to reregister those
that
merit
reregistration based on the latest scientific data
7
U.S.C.
136a(g)
(P,L, 95—396
eff,
9—30—1978).
The USEPA has not yet been able to complete
this task.
There
is
no evidence
in the record
to show that
the products
of
Carus
and Applied have been reregistered
(See
Carus Exh,
A, B
p.l;
App.
Exh,
1).
Based
on
the record before
it,
the Board
declines
to incorporate all potable water supply
algicides
registered
with the USEPA,
It will,
however,
incorporate
individual chemical compounds where the record
contains
sufficient information to justify such action,
which
is consecutively paginated.
MR.
refers
to the
May
1985 hearina transcript.
3
~siumPermananate
Potassium permanganate
is currently used
at water treatment
plants
to treat drinking water
at the raw
water
intake.
It
is
a
strong
oxidizing agent which
degrades
in
water in less than a
minute
(MR.
129).
The
principal degradation product
is manganese
dioxide which
is highly insoluble and biologically
inert
(MR.
107
)
The labels for Cairox FF and
Cairox Technical
state
that
they
are for use
in potable water
treatment systems to be applied
only
by trained water treatment plant operators
or persons under
their
direct sup?~rvisiOn (Carus,
Exh,
C),
Mammalian
and aquatic
toxicity
studies were performed
(Carus Exh,
E),
Acute oral
(rat)
and
dermal
(rabbit:)
toxicity studies show that the
Carus products
are
corrosive
to skin
(Carus Exh,
E),
The lethal
concentration
of
Cairox Technical
in fifty percent of the bluegill
sunfish
(~~ismachrochirus) exposed
in
a
96
hour static
exposure study
was
determined
to he 2,7 mg/I
(Carus Exh,
E,
Summary).
The LC5O
for
Cairox FF was 3,6 mg/I.
The LC5O
(48 hr.)
for the
macroinvertebrate :~afl~a
na was
84 mg/l
Technical Grade with
no
effect
at
56 mg/I.
An LC5O
(96
hr.)
value
for the green algae
Selenastrurn~yJ~orjp~~
Printz
was
210
mg/l
Technical Grade
with
no effect below 100
mg/l.
Id.
Carus would like
to
expand the use
of potassium permanganate
to
include
its application
to public surface water supply
sources,
The
current USEPA
registration allows
its use only
in
water
treatment systems
(MR.
121).
Even
if
the Board approves
Carus’
request,
the Company
will need a Federal
label change
before
the product
can be used
in
water
supply
reservoirs.
Carus
intends
to pursue this matter
with the USEPA,
Carus submitted
a
paper
by Dr. Jerome Carr
entitled
“Integrated Iron and Nitrogen
Control
for
Lake Restoration”
which
is now made Carus Exhibit
F,
Dr. Carr studied
the use
of potassium permanganate
as
an
algicide
in Morses Pond,
a
102 acre pond
in Massachusetts.
The
study
showed a reduction
in
the amount
of iron
in the pond
available
for macrophytic
uptake after application of potassium
permanganate which
in turn
limited
the amount
of algae present
(Carus Exh,
F).
Potassium perrnanganate
has been successfully used as
an
algicide
in water treatment
plants when
it
is applied
continuously.
In open water,
treatment
will
be infrequent
and
the
product concentration will
be tailored to the chemistry of
the
receiving water
(MR.
135),
The
immediate effect
of the
treatment
is largely limited
to the upper portion of the water
column
in the area behind the
applicator’s
boat,
Given
this
situation,
the potential
for widespread harm to the
aquatic
fauna
in
a
lake
is remote,
The Board finds
that potassium permanganate
is
suitable for
use
as
an algicide
in public water supplies.
In
so finding,
the
Board
notes
that this compound must also be approved
by the USEPA
86~381
4
for this
purpose
prior
to such use,
The Board further
finds
pursuant
to
Section
27(b)
of
the Act that the allowance
of
potassium
permanganate
as
a public water supply algicide will
have
no
adverse
economic impact on the people of this State
and
will
in fact
foster
competition between approved public wal:er
supply algicides.
~22~~bona(Malach
ite)
Applied,
while
proposing copper carbonate
as
an algicide,
provided
no
information on
it,
The Agency
in
its comments stated
that beq~use
malachite
is
“insoluble with
a solubility
fact~orof
1
x 10~’~and
because
it
does not possess
any algicidal
properties,
it should
not be included
in the list
of acceptable
algicides.”
(Age Comments,
October
4,
1985).
Because
of the
lack
of any
data
supporting
the inclusion of malachite,
the Board
will not
include
it as
a
public water supply algicide.
Copper
Monoethanolamine/Triethanolamine
Both
products of
Applied contain copper
in the form of mixed
copper—ethanolamine complexes,
Some of the breakdown products of
Cutrine—Plus
include
diethanolamine, monoethanolamine, ammonia,
acetic
acid,
hydroxyacetic acid,
glyoxal, glyoxylic
acid,
oxalic
acid,
formaldehyde gas and formic acid.
Cutrine—Plus
is
a slight
skin irritant
and
is
moderately
toxic
if swallowed.
It
is less
corrosive
than copper sulfate.
Toxicological data show Cutrine—Plus
to
be
“generally
nontoxic
to fish
and
wildlife at recommended dosages,” although
“trout.
,
,
and certain
other sensitive
fish species may be
adversely affected
in very
soft water
(below
50 ppm of CaCo3).”
(App.
Exh,
13).
Toxicity
data for the bluegill sunfish and for
the fathead
minnow
(Pimephales promelas) appear
in Exhibits
11
and 17 while
data on
oral dose,
single skin penetration,
single
inhalation,
primary
skin irritation
and eye injury from animal
studies appear
in Applied
Exhibit
12.
At 45
Fed, Reg,
53478 (August
12,
1980),
the USEPA mentions
that
it was
concerned
with the presence
of
2,1 ppm of N—
nitrosodiethanolamine
in
an original Applied formulation
“since
80 percent
of known
N—nitrosoamine compounds have been shown to
be carcinogenic
in
a variety of species.”
(App,
Exh,
7).
The
formulation
was revised
by Applied
and now contains less than
1/ppm of N—nitrosodiethanolamine which represents
a
risk
level
acceptable
to the USEPA,
Id.
Prior
to
the May
20 hearing,
the Board
raised the question
of
the possible
mutageriicity
and carcinogenicity
of
triethanolamine
(TREA),
A scientific paper on that topic
by
Hoshino and
Tanooka was
placed
in the record
(Board Exh.
4),
The
researchers
reported that mice
fed on
a diet including TREA
developed
tumors and that TREA
in combination with sodium nitrite
caused
mutations
in bacteria,
66-382
5
The Board retained Dr.
William Hallenbeck, who has done
research involving animal toxicology and human health effects
to
evaluate the
Tanooka paper,
He pointed
out that the controls
used
in the test
made
it impossible
to conclude with certainty
that TREA caused
the
tumors,
He also stated that,
“a stable and
direct,
but
unidentified,
mutagen was found under
test conditions
which approached
normal
physiological parameters”
(MR.
16 and
17).
In answer
to
a question he replied,
“,,.my overall
conclusion
about
TREA
is that
at this point you could only go so
far
as
to
characterize
it
as
a potential animal carcinogen and,
therefore,
a
potential
human carcinogen”
(MR.
26),
Regarding
mutagenicity
he
pointed
out that the Tanooka paper reported
a
four
to five—fold increase in mutagenicity
for the combination of
TREA and sodium
nitrite
over sodium nitrite alone,
He also
stated that
sodium
nitrite
is common
in the human diet
(MR.
56
and 57).
In response
to the
Tanooka paper, Applied presented
two
letters critical
of
the
paper and entered
a paper by Inone et.
al. which
considered
the mutagenicity of TREA
(Applied Exh.
25),
This study
found
no evidence that TREA by itself was
mutagenic
It
also
suggested further study to determine
the
exact
cause of
the
tumors reported by Tanooka,
Applied’s
Exhibit
9 which was introduced
at the July
24,
1984 hearing
stated:
In an effort
to find any and all available
references
on chronic data on monoethanolamine and
triethanolamine APPLIED BIOCHEMISTS,
INC.
contacted
the
environmental and
toxicology branches of
the
ethanolamine manufacturers and suppliers,
DOW
CHEMICAL,
UNION
CARBIDE,
OLIN CORPORATION, TEXACO
INC.
and its
subsidiary JEFFERSON CHEMICAL.
Based on our efforts,
there
apparently
is no chronic data on ethanolamines.
However,
these
contacts yielded significant information
and insight
into
ethanolamines,
their biodegradation
and
toxicology,
No mention was
made of
the Tanooka paper
or the Inone paper which
were published
in 1978
and 1982 respectively.
Applied’s
representative
said at
hearing that Applied was
not
informed of
the Tanooka
paper by the TREA manufacturers and first
learned of
it
in the
hearing officer
order,
He also indicated that the
information had not
been
supplied to the USEPA during the Federal
registration process
(MR.
69),
Applied
Exhibit
10 lists
the expected concentration of TREA
in treated water as between 0,48 ppm and 2,4 ppm (see MR.
75 for
correction).
Applied gave no data as
to how long TREA persisted
in
the body of
water after treatment and
in what concentration
(MR.
66),
66-383
6
The USEPA approved Cutrine
and Cutrine—Plus for use in
public water
supplies and the Illinois EPA has recommended that
they be approved
in
Illinois,
The Board notes that Federal
approval was based
largely upon information supplied
by Applied,
who
in turn relied on data provided by TREAwsuppliers.
The
Applied products have not yet been reregistered by the USEPA.
The Tanooka
paper indicates that TREA
is
a possible
carcinogen.
The
controls
in that
study
were inadequate to
determine whether
TREA
or TREA in combination with the heated
diet,
or some
other combination
of
factors caused the reported
tumors.
Applied~s
rebuttal
of the Tanooka paper failed to dispel
the concerns
raised,
The
questions raised can best be addressed
by
an experiment
with
proper controls,
Regarding mutagenicity,
there
is reason
to believe
that TREA
in conjunction with sodium
nitrite (which
is
common
in the diet)
has mutagenic properties.
In the
absence
of additional
substantive data,
the Board believes
it
is unwise
to place
this chemical
in water supplies which are
consumed by the
public,
The Board has no reason to conclude that
the use
of
Applied~sproducts
containing TREA pose
a threat
in
other bodies
of water,
The Board
finds that Applied has failed
to demonstrate
that
TREA can be applied to public water supplies without posing
a
threat to the public health,
Pursuant
to Section 27(b)
of the
Act, Applied’s data indicate that its product
is competitive with
the approved algicide
(JR. 90—99).
However, given the
uncertainty over potential public health impacts
of
the product,
the Board cannot find that approving Applied’s petition will not
have an overall adverse economic impact.
The Agency
has suggested
deleting the phrase “supervising
the application
of the
algicide” from current Section 602.110.
No reason
for
deleting the
phrase was provided.
The Board
believes that the
phrase
is helpful and declines to delete
it in
the absence of
a justification for doing so.
ORDER
The Board
hereby
directs the Clerk to cause
first notice
publication of
35
Ill, Adm,
Code 602.103 and 602.110 as amended
in
the
_____________
TITLE
35:
ENVIRONMENTAL PROTECTION
SUBTITLE
F:
PUBLIC WATER SUPPLIES
CHAPTER
I:
POLLUTION CONTROL BOARD
PART 602
PERMITS
Section 602.103
Algicide
Permits
No algicide
shall be applied
to
any stream,
reservoir,
lake,
pond,
or other
body of water
used
as
a
public
water supply source
88-384
7
without
an Algicide Permit issued by
the Agency.
Copper
sulphfate
t~
and potassium permanganate are
the only algicides
which may
be used
in public water supplies.
Permits issued under
this Section will
be valid
for public water supply sources
only.
Section 602,110
Algicide Permit Applications
a.
All applications for algicide permits shall contain:
1.
the name
and certificate number
of the certified
operator supervising
the application
of the algicide,
2.
a
statement
describing
the extent of the algae problem,
history
of
any past algae problems,
and algicide
treatments,
and
a description of any fish kills which
have
resulted
from treatments
in the past;
and
3.
adequate information to support exceeding the
limits
as
stated
in
35
Ill. Adm. Code
302:
Water Quality
Standards,
b.
After any algicide permit
is issued,
and before
the permit
expires
by
its stated terms,
if there
is any major change
either
in the operation of the public water
supply,
or
in
algae growth,
which affects the use of cepper ~
the
algicide
as outlined
in the permit,
the public water supply
shall submit an application
for modification of
its permit.
This application shall
contain all
of the information
required by this subsection
(b) and subsection
(a)
above.
c.
Any algicide permit
issued under
this Section shall exempt
permittee from obtaining an aquatic pesticide permit as
provided
in
35
Ill. Adm. Code 652.601.
IT
IS SO ORDERED.
I,
Dorothy
M.
Gunn, Clerk of
the Illinois Pollution Control
Board,
hereby certify that the above Opinion and Order was
adopted on the
day of
~
,
1985
bya voteof
____________•
,~).
Dorothy M/ Gunn, Clerk
Illinois Pollution Control Board
86-385