ILLINOIS POLLUTION CONTROL BOARD
March
6,
1975
IN THE MATTER OF:
PROPOSED AMENDMENTS TO RULES
)
R73-15
203 AND 408 OF THE ILLINOIS
WATER POLLUTION CONTROL
REGULATIONS
OPINION AND ORDER OF
THE
BOARD
(by
Mr.
I-Ienss):
Ozark-Mahoning Company and Minerva Oil Cornoany filed
a joint
proposal seeking changes
in Rules 203 and 408 of the Water Pollution
Control Regulations as those Rules pertain to fluoride.
The
proposal was
to relax the standard for mining companies by adding
the
sentence
which
has been underlined.
Rule 203(f) Water Quality Standards
—
General
Standards
Constituent
Storet
Number
Concentration
(mg/i)
Fluoride
00950
-
1.4*
*Except that fluoride
derived
from mmmc
and concentratina
the
mineral
fluorspar
(CaF~))
shall
not
exceed
15
ma/i.
Rule
408(a)
Effluent
Standards
-
Additional Contaminants
Constituent
Storet
Number
Concentration
(mg/i)
Fluoride
(total)
00951
2,5*
*Except that fluoride derived from mining
and
concentrating
the mineral fluorspar
(CaF2)
shall not exceed
15 mg/l.
The proposed amendments
and a statement of reasons supporting
the proposal were published in Board Newsletter ~78, dated December
29,
1973.
Public hearings on the proposal were held in Elizabethtown on
March
29, 1974 and in Chicago
on April 19, 1974.
Pursuant to its
Petition to Intervene, Olin Corporation was designated
a party in
interest and granted leave to participate in the hearings.
Other
participants included the
U.
S.
Environmental Protection Agency,
the Illinois Environmental Protection Agency, Allied Chemical
Company and private citizens.
The existing effluent limitation of 2.5 mg/i for fluoride was
adopted by the Board on January
9,
1972 following extensive public
hearings through the State.
In setting this limitation
the Board
stated:
16
—61
—2—
“Fluoride.
Our initial proposal for a fluoride effluent
standard was 1.0 mg/i.
This was somewhat tighter then
the water quality standards we later proposed
(1.4)
for
both aquatic life and public water supply, and it posed
problems for municipal treatment plants whose infiuent
has been deliberately dosed with as much as 1.0 mg/i of
fluoride for dental purposes.
Patterson reported that
1.0 mg/i was achievable only through relative exotic and
costly methods,
such as ion exchange, and that 10.0 mg/i
was a more appropriate standard to achieve by ordinary
precipitation.
Weston and Dodge both said,
however,
that
1.0 was readily achievable, Weston specifying the use of
alum at cost less than those for achieving most of the
metals concentrations here proposed.
The most specific
information in the record came from Olin, which reports
that its fertilizer works at Joiiet consistently reduces
fluoride concentrations by standard treatment from an
infiuent of 15 mg/i to an effluent of
2.5, but that other
ions present prevent reduction as low as
1.0.
We have accepted Olin’s figure of
2.5 mg/i,
in recognition
of the difficulties encountered in going lower and of the
likelihood of dilution in many instances to achieve a
relatively lenient stream quality standard.1’
A water quality standard of 1.4 mg/i fluoride was adopted on
March
7,
1972,
again following extensive public hearings through-
out the State.
On the fluoride water quality standard the Board
stated:
“Fluoride.
Fluoride can delay the hatching of fish eggs
and has been reported by McKee and Wolf to kill trout at
concentrations ranging from 2.3 to
7.2 mg/i.
They recom-
mend a standard of 1.5 mg/i.
The figure of 1.4, here
repeated from the May 12 draft,
is in line with that
recommendation and also should assure a potable supply.”
Both proponents in this matter are actively engaged in the
mining and processing
of fluorspar
(also known as fluorite)
for
various industrial uses.
Operating in Pope and Hardin Counties
in Southern Illinois, Proponents extract the fluorspar from bedded
and vertical vein deposits 350 to 850 feet below surface.
They
are the only fluorspar producers in Illinois and their combined
production accounts for 80
of the entire amount produced in the
United States.
Ozark—Mahoning processes about 17,000 tons of crude
ore per month at its Rosiclare mill.
Minerva processes from 900
to 1300 tons of crude ore per month,
from which about 157 tons of
fluorspar concentrate,
20 tons
of zinc concentrate and 30 tons of
barite
(BaSO4)
are extracted.
16—62
—3-.
During the concentrating processes,
part of the fluorspar in
the crude ore is dissolved and discharged
in the mill effluent.
Some fluoride is also contained in the discharges from the fluorspar
mines.
The two counties in which the fiuorspar industries operate are
described as two of the smallest and most sparsely populated counties
in Illinois.
The 1970 Census showed that Hardin County had 4914
people on 183 square miles while Pope County had 3,857 people on
381 square miles.
Ozark-Mahoning employs 220 persons directly and
another 55 to
60 on contract.
Minerva employs 210 persons directly
and 40 persons indirectly.
The majority of the workers reside in
either Hardin or Pope County.
The only other industries
in the
two—county area ate quarrying,
farming and cattle raising.
Pro-
ponents state that the economy of
these two counties is largely
dependent upon the fluorspar industry as are the users of the
fluorspar product insofar as total domestic production is concerned.
Fluoride—bearing effluent from proponent’s mines and mills
is discharged to receiving streams which vary from intermittent
drainage ditches or creeks to flowing rivers as
follows:
OZARK-MAHONING COMPANY
Parkinson Mine
-
To Big Grand Pierre Creek to
Ohio River.
Barnett Mine
-
To Big Grand Pierre Creek to
Ohio River.
Barnett Air Shaft
-
To unnamed creek to Little
Grand Pierre Creek to Big Grand
Pierre Creek to Ohio River.
Oxford Mine
ff7
-
To unnamed creek to Duck Creek
to Rock Creek to Harris Creek
to Saline River to Ohio River.
Knight Mine
-
To unnamed creek to Mud Creek
to Three Mile Creek to Ohio
River.
W.
L. Davis Mine #1
-
To Davis Branch to Big Sinks to
Ohio River
(possibly)*
Rosiclare Lead and Fluorspar Mine
-
To Willow Creek to Ohio
River
Rosiclare Flotation Plant
-
To settling pond to Ohio River
North Green Mine**
-
To Sheridan Branch to Haney Creek
to Ohio River
West Green Mine**
-
To Sheridan Branch to Haney Creek
to Ohio River
MINERVA OIL COMPANY
Mine ~l
-
To Running Bear Creek to Rock
Creek to Saline River.
16—63
—4—
MINERVA OIL COMPANY
(continued)
Mill
#1
-
To Rock Creek to Saline River.
Crystal Mill
-
To unnamed creek
(sometimes
called Davis Creek)
to Big Sinks
to Ohio River*
(possibly)
Gaskins Mine
-
To Big Grand Pierre Creek to
Ohio River
Tucker Hill Area
—
To unnamed creek to unnamed creek
to Rock Creek to Harris Creek to
Saline River to Ohio River.
Spivey
Mine
-
To
Goose
Creek
to
Harris Creek to
Saline
River
to
Ohio
River.
Deardorff
Mine
-
No
discharge***
*The Big Sinks, a natural sinkhole, drains periodically to an
unknown receiving stream.
It is believed that water drains
from Big Sinks through an underground stream to the Ohio River,
although dye tests have been unsuccessful in confirming the
location of the ultimate receiving stream.
**Initial information showed that both the North and West
Green Mines were not consistently discharging water.
When
operating conditions required the pumping of water from these
mines,
it was done on an intermittent basis only
(1 to
4 hours
per day)
and the mine water was discharged to the streams
shown.
New information shows that these mines are now dis-
charging water consistently at
a combined rate of 100,800 gpd.
***Mine water from this mine flows underground through depleted
excavations
to Ozark-Mahoning’s W.
L.
Davis Mine.
Such flow is
minimal.
The other industrial firms participating in this matter have
fluoride problems significantly different from those of the mining
companies and from each other.
At its Blockson Works in Joliet,
Olin imports calcium phosphate rock,
soda ash and sulfuric acid which
are used to manufacture sodium phosphate.
Fluoride—based
products
are also produced at the Blockson Works
through the reaction of
sulfuric acid and fluorspar to form hydrofluoric acid.
The hydro-
fluoric acid is then reacted
with other materials to form the
desired fluoride-based final product.
Fluoride-bearing effluent
from
Olin’s
Blockson
Works
is
discharged
to
the
Des
Plaines
River.
Allied Chemical operates a facility for the production of
uranium
hexafluoride
(UF6)
,
sulfur hexafluoride
(SF6)
,
fiuorene,
antimony pentafiuoride and iodine pentafluoride in Metropolis,
Illinois.
Allied’s liquid discharge, which consists of spent
ammonium sulfate solution, sulfide liquors, hydrofluoric acid
solution,
spent potassium hydroxide solution and uranium recovery
leach liquors, flows
to the Ohio River through two industrial
ditches.
16—64
—5—
Corporate positions
on these matters vary
as widely as do
the processes in which the fluoride bearing wastes are generated.
As earlier noted, Ozark-Mahoning and Minerva propose to amend
the standards only as
those standards apply to the fluorspar
industry.
Olin’s position was one of disagreement with Ozark-
Mahoning and Minerva over the proposed changes in Rule 408.
Olin proposes
to change Rule 408
to allow
a fluoride effluent
concentration of 10 mg/i for all industries.
Olin took no
position on the proposed change in Rule 203.
Allied first contended that the effluent standard should be
revised to allow 15 mg/l fluoride based on an average of
24 hour
composite analysis for 30 consecutive days and 30 mg/i maximum for
any one 24 hour composite.
Allied took no position on the proposed
revision of Rule 203.
Neither the U.
S. environmental Protection
Agency nor the Illinois Environmental Protection Agency took a
position on the proposed changes prior to the public hearings.
Their post hearing comments will be discussed elsewhere in this
Opinion.
Of the two Agencies, only the
U.
S. EPA chose to present
any testimony.
Fluorides are widely distributed in the earth’s crust,
occurring in both igneous and sedimentary rocks.
Among the more
common
fluoride
minerals
are fiuorspar
(CaF9), viliiaumite
(NaF)
cryolite
(Na3A1F6) and fiuorapatite
CaF2.3~a3(PO4)2.
Fluorides
in high concentrations are not a common constituent of natural
surface waters but they may be prevalent in detrimental concen-
trations in ground waters.
Small concentrations of fluoride
(0.6 mg/l to 1.7 mg/i)
in
drinking water have been shown to effectively reduce the prevalence
of dental carries while excessive amounts cause effects
in humans
varying from mottled teeth to death.
When fluoride is
2.5
mg/i 75
to 80
of children have mottled teeth.
In drinking water,
fluoride
of 180 mg/i is toxic and 2000 mg/i
is lethal to man.
Snlubility of a fluoride varies according to the nature,
pH
and temperature of the solvent, cationic partner and prevalence of
other chemical constituents in the solvent.
The two most discussed
fluoride compounds during these proceedings,
soc1ium fluoride and
calcium fluoride, vary significantly in their solubility.
The
solubility of calcium fluoride at 18°C.
(64.4° F)
is
16 ppm (about
8 ppm fluoride ion) whereas the soiubility of sodium fluoride is
about 19,000 ppm.
This means that sodium fluoride is inherently
more soluble in water than is calcium fluoride.
Neither Ozark-Mahoning nor Minerva discharges
any effluent that
approaches
the proposed effluent limit of 15 mg/l fluoride.
Dis-
charges from the mines and mills operated by these two companies
are less than
5 mg/i,
as shown below, with a single exception of
16—65
—6—
the discharge from the Ros~ciareflotation plant settling pond.
0 ZARK-MAHON ING
Parkingson
Mine
-
4_Q~~
Barnett
Mine
-
50
gpm
Barnett
Air
Shaft
-
4G
gpxr
Fluoride,
mg/i
Big
Grand
Pierre
above
discharge
0.28
Parkinson
discharge
to
Big
Grand
Pierre
1.40
Barnett
Nine
discharge
to
Big
Grand
Pierre
2.40
Big
Grand
Pierre
below
Parkinson
and
Barnett
0.30
Barnett
air
shaft
discharge
to
unnamed
creek
3.10
Unnamed.
creek
at
confluence with Little Grand Pierre
0.50
Little
Grand
Pierre above confluence with unnamed creek
0.25
Litt~e
Grand
Pierre
below
confluence
with
unnamed
creek
0.40
Pig
Gr~~nd
Pierre
below
all
discharges
0.28
Oxford Mine
#7
-
10
gpm
Pine
discharge
to
unnamed
creek
2.20
Unnamed
creek
at
confluence
with
Duck
Creek
0.25
Duck
Creek
above
confluence
with
unnamed
creek
1.50
Duck
Creek
below
confluence
with
unnamed
creek
1.00
Duck
Creek
above
confluence
with
Rock
Creek
0.97
Bock
Creek
above
confluence
with
Duck
Creek
0.25
Rock
Creek
below
confluence
with
Duck
Creek
0.63
I~night
Mine
-
90
gpm
Knight
discharge
to
unnamed
creek
1.40
Unnamed
creek
above
confluence
with
Mud Creek
0.75
Mud
Creek
thove
confluence
with
unnamed
creek
0.25
Mud
Creek
below
confluence
with
unnamed
creek
~h25
W.
L.
Da’iis
Mine
#1
—
1200
gpm
Mine
discharge
to
unnamed
creek
1.4
Unnamed
croci-
above
entry
to
Big
Sinks
1.2
RosiclareL?~ad
and
Fluorspar
Mine
-
20
gpm
~ne
discha”ce
to
Willow
Creek
1.3
Willoi~7Cree~~
above
confluence
with
Ohio
River
1.4
Ro
siciara FLotation Plant
-
650
gpm
2~ant d!~charge
to
settling
pond
—-
Settlina
pond
discharge
to
Ohio
River
10.0
16
—
66
—
7—
Mine #1 and Mill
-
368 gpm
MINERVA
Fluoride, mg/l
#3 pond discharge to Rock Creek
Rock Creek above
#3 pond discharge
Rock Creek below
#3 pond discharge
Harris Creek below confluence with Rock Creek
Saline River above confluence with Harris Creek
Saline River at confluence with Harris Creek
Crystal Mill
-
52 gpm
Heavy-media-separation tails
Unnamed creek above HMS tails
Big Sinks
Tucker Hill Area
-
150 gpm
4.5
(avg.)
0.6
(avg.)
2.5
(avg.)
0.45
0.40
0.47
3.62
(avg.)
1.34
(avg.)
1.51
(avg.)
Churn Drill Hole, underground water
Unnamed creek upstream
Unnamed creek downstream
Gaskins Mine
-
875 gpm
3.02
(avg.)
No flow
1.14
Gaskins Shaft
Big
Grand
Pierre
Creek
above
discharge
Big Grand Pierre Creek below discharge
Spivey Mine
-
80 gpm
1.58
(avg.)
0.39
(avg.)
0.50
(avg.)
Spivey Shaft
Goose Creek above discharge
Goose Creek below discharge
2.75
(avg.)
0.51
(avg.)
0.66
(avg.)
C.
B.
Rash,
Ozark-Mahoning’s
Superintendent
of
Milling,
explained
that
the
proposed
15
mg/i
effluent
limitation
was
necessary
as
a
“safeguard”
in
the
event
recycling
of
effluent was imposed upon the
industry
(R.
41).
Ozark-Mahoning’s
plant
in
Colorado
attempted
a
waste
water
recycling effort when the Colorado Department of Public
Health
requested
an
effort
to
achieve
“zero
flow”.
Although
“zero
flow”
was
not
achieved,
the
effort
resulted
in
the
recycling
of
80
of
the
waste
water——but
at
a
price.
This
price
was
an
increase
in
fluoride
concentration
to
32
ppm.
When
the
Board
set
the
effluent
standard
at
2.5
mg/i
it
relied
heavily
upon
the
testimony
of
an
Olin
employee,
Emil
Stoitz,
regarding
16—67
—8—
the technology available to reduce fluoride in waste water.
Stoltz had testified that while Olin had not been able to
“obtain it in our specific effluent” th~ydid have the technology
to “get down to
2 to
2 1/2 mg/i.”
Stoltz
testified
in
the
current
proceedings
that
he
had
meant
to
inform
the
Board
that
this
level
of
fluoride
reduction
was
only
a
technical
feasibility
based
on
laboratory
studies
made
at
the
corporation’s
research
headquarters
in
New
Haven,
Connecticut.
This
research
was
primarily
based
on
a
lime
treatment
process
which
Olin
has
not
used
at
its
Blockson Works.
Stoltz testified that,
based
on
the
research
program,
he
now
believe’s
that
Olin
could
reduce
the
fluoride
in
waste
water
from
15
mg/i
to
2.5
mg/i.
Blockson
Works
waste
water
currently
contains
about
20
mg/i
fluoride
before
treatment
(R.
224).
At
this
point,
it
is
necessary
to
review
the
health
related
information
about
fluorides
in
order
to
provide a balance to the
later
discussion
on
feasibility
and
economic
reasonableness
of
fluoride
treatment.
In setting
a
1.4
mg/i
fluoride
water
quality
standard,
the
Board
cited
a
report
by
McKee
and
Wolf
(McKee,
J.
E.,
and
Wolf,
H.
W.,
Water
Quality
Criteria,
California
State
Water
Resources
Control
Board,
Second
Edition,
1963)
showing
that
fluoride
can
delay
the
hatching
of
fish
eggs
and
that
concentrations
ranging
from
2.3
to
7.2
mg/i
can
kill
trout.
These
references,
p.
191
of
the
McKee—
Wolf
report,
also
show
that
in
15
studies
the
majority
involved
the
use
of
sodium
fluoride
and
none
of
the
studies
is
shown
to
have
involved
calcium
fluoride.
Under
Sodium
Fluoride,
McKee-Wolf
cite
research
showing
the
following
effects
of
sodi~m fluoride
on
certain
aquatic
bacteria,
algae and small crustaceans:
Species
Results
(an
order
of crustaceans
Threshold of NaF at 23°C. was
wllcth
includes
water
fleas,
found
to
be
270
mg/l
for
a
2
day
found
everywhere
in
fresh
exposure.
waters)
Scenedesmus
(a
fresh
water
algae,
Threshold
of
toxic
effect
was
95
most
common
and
best
known
of
mg/l
during
4
days
at
24°
C.
all algaes,
found almost
anywhere algae grows)
Microregina
(A single cell
Threshold of toxic effect was 226
protozoan often found in
mg/l during
4 days at 24°C.
fresh water)
16—68
—9—
____
Results
Escherichja coli
(a bacteria
Threshold of toxic effect was 180
found abundantly in verte-
mg/i during
4 days at 27°C.
brate intestine)
Free—living protozoa and
Survived and reproduced in water
fresh water rotifers
containing 1000 mg/l but were
killed at 1700 mg/i.
This
information
tends
to
show
that
low
concentrations
of
sodium
fluoride
probably
would
not
present
any
significant toxicological
difficulties
for
at
least
some
of
the more common lower aquatic
organisms
expected
to
inhabit
Illinois
streams.
Based
on
research
reported in McKee-Wolf,
the same
is not true for higher aquatic
organisms.
This
research
reported
the
following
effects
of
sodium
fluoride on fish:
Concentration, mg/l
Type Fish
Effect
2.3
to
7.3
Trout
TLm
at
18°
C.
in
soft
water
2.6
to
6.0
Trout
TLm
at
13°
C.
in
soft
water
2.7
to
4.7
Trout
TLm
5.9
to
7.5
Trout
TLm
at
7.5°
C.
in
soft
water
Thus,
it
would
appear
that
some
lower
aquatic
organisms
are
able
to
tolerate
sodium
fluoride
concentrations
on the order of
100 times
that
tolerated
by
trout,
Although
time
of exposure
for determining
TLm
is
usually
specified,
this
parameter
was
not
provided
for
the
data
above,
making
comparison
of
results
impracticable.
Reasons
for
these
phenomenal
differences
in
survivability
(for
example,
osmotic capabilities of membranes of
lower aquatic
forms vs. higher
aquatic forms, significant physiological differences,
etc.) were
not stated.
In this proceeding,
expert testimony indicates that sodium
fluoride concentrations in natural waters should be minimal in
comparison
to
concentrations
of
calcium
fluoride.
Dr.
W.
F.
Sigler,
head
of
the
Wildlife
Science
Department
at
Utah
State
University,
testified
that
all
research
conducted
in
the
U.
S.
on
fish
fluorosis
“was done by me and under my direction”.
Dr. Sigler noted that while
small amounts of sodium fluoride might exist, larger amounts do not
exist
naturally because it dissociates to form calcium fluoride.
A number of opinions on the relative toxicities of sodium and
calcium
fluoride
were
aired
during
the
hearings.
C.
B.
Rash
testified that his opinion of available research was that sodium
16
—
69
*
10—
fluoride “would be more toxic than calcium fluoride even at
the
same
concentration,
because
there
is
indication
that
the
calcium present with the fluoride ion reduces the toxicity”
(R.
45)
Dr. Sigler first testified
that sodium fluoride and
calcium fluoride have equal toxicities at equal concentrations.
(R.
120)
Admittedly not a chemist, Dr. Sigler later qualified
this statement by testifying that the toxicities would be equal
except when other positive ions were present
(R.
155)
.
Then
later, Dr. Sigler testified that calcium fluoride would be the
less toxic of the two fluorides because “calci~umand the fluoride
have an affinity for each other and reduces the toxicity”
(R.
206).
Dr. Sigler indicated his preference
to let Franklin Davis
of the Colorado School of Mines Research Institute answer the
questions relating to the chemistry of fluorides.
When called
upon, Davis testified that he could not “answer that with the
proper credentials” because he was not a toxicologist
(R.
164).
Significant testimony on fluoride toxicity was produced by
Dr. Leonard Krause of Olin Chemical Company.
Dr. Krause testified
that fluoride entering the system of any living organism will
combine with the most prevalent tissue around it, usually tissue
containing calcium such as cartilage or bony tissue.
Such a
combination is known as fluorosis.
Fluoride interferes with
enzyme systems at the cellular level and interferes with the
oxygen uptake in organisms by some mechanism that toxicologists
don’t yet understand
(R.
322).
Fluoride taken into a body in the form of calcium fluoride
tends to be excreted almost exclusively as calcium fluoride.
This occurs, according to Dr. Krause, because very little,
if
any,
of the fluoride will combine with the body calcium since
sufficient calcium is already available for combining with the
fluoride.
Dr. Krause testified that his research work involving humans
showed that 14 mg/l of calcium fluoride was not toxic to humans.
He did not think
a toxic level of calcium fluoride in solution
could be reached because it would be precipitating out.
Dr. Krause
stated that he would not hesitate to drink water containing 14 mg/i
of calcium fluoride but would never put the same amount of sodium
fluoride into his body
(R.
332).
Fluoride in water containing
sodium fluoride would not be excreted as would the calcium fluoride.
It would be available to bony tissues and kidneys.
Another of the body elements that could be affected by the
ingestion of calcium fluoride is potassium,
an essential element
in nerve tissues.
At first Dr. Krause stated unequivocally that
potassium in the body would not be replaced by the calcium in
16—70
—ii—
calcium fluoride because of the tight chemical bond found in
calcium fluoride
(R.
335).
He later acknowleöqed that such
a
replacement possibility did exist
(R.
342) although the
fluoride itself is more available to cartilaginous and bony
tissue than for nerve tissue
(R.
351)
Table 6-5 of the McKee-Wolf report shows various levels of
fluoride concentrations that caused mottled teeth.
In the range
from 0.2 to 1.0 mg/i fluoride the mottling is mild with
a con-
centration of 1.0 mg/i listed as the “threshold for mottling”.
One study reveals
a mild to moderate degree of mottling from 1.0
to 2.0 mg/i fluoride.
At 6.0 mg/i the references reported pitting
and chipping of teeth and that 100
of children had mottled teeth.
E.
F.
Carter, Jr., Rosiclare postmaster, testified that he
knew of no mottling of teeth in the Pope-Hardin County area cau~ed
by the discharges
of Ozark-Mahoning or Minerva.
N. N. Fowler,
Ozark—Mahoning Vice President and General Manager, testified that
he knew of no adverse effects, including mottling of teeth, that
had been suffered by any of his employees.
He added that miners
have drunk water from the mine seams and wails for a number of
years.
The highest fluoride concentration in such water was
found to be 2.5 mg/i.
C.
B.
Rash also testified that he had ob-
served no ill effects or mottling of teeth in the area.
Rash testified that several farmers in the area depend on the
mine discharge water as
a source of water for their livestock.
The
farmers had informed Rash that they had never observed any ill
effects in their cattle as
a result of drinking the mine discharge
water.
Proponents submitted a letter from Truman Louderbach,
a
Research Biologist at the Colorado School of Mines Research Institute
(CSMRI), reporting on results of bioassay testing conducted at CSMRI
at the request of Ozark-Mahoning Company
(Petitioner’s Exhibit 4).
For the test,
samples were drawn from the tailings dam effluent
of Ozark—Mahoning’s Cowdrey, Colorado operation and from Pinkham
Creek above the confluence with the tailings dam effluent.
These
samples had the following properties:
Tailings Dam Effluent
Pinkham Creek
Temperature
7°C.
(44.6°F.)
6.5°C.
(43.7°F.)
pH
7.6
7.5
D.O., ppm
8.3
7.0
F,ppm
32
2.6
16—71
—12—
Six-month-old fingerling rainbow trout were acclimatized for
10 days in Pinkham Creek water at 15°C.
±
2°(59°F.) with a
dissolved oxygen concentration above 7 ppm.
Following the ac-
climatization the trout were subjected to testing using various
mixtures of Pinkham Creek water and tailings dam effluent up to
100
tailings dam effluent.
The tests showed a 100
survival
of
trout for 96 hours in all mixtures including the undiluted tailings
dam effluent.
No evidence of distress
in the behavior of fish
specifimens was observed.
Also submitted by proponents was a report by CSMRI’s Senior
Research Biologist,
Dr.
Gary D. Boss,
in which Boss summarized his
findings on fluoride toxicity based on published reports.
According
to the Boss report, assignment of specific toxic levels is difficult
because of the following major factors:
1.
Fish species,
race,
or strain
2.
Fish size and stage of development
3.
Physiological state, including age of fish
4.
Level, type and solubility of fluoride and
fluoride containing compounds
5.
Water temperature
6.
Individual biological response
7.
Composition of the water,
in particular the
content of calcium, magnesium and chloride
Boss cites a Utah State University study
(Neuhold and Sigler,
1960)
conducted on carp and rainbow trout, using fluoride containing
water with
a calcium and magnesium content of less than
3 ppm.
Results were reported as follows:
Species
Temperature, °F.
TL50* at Fion conc.
(ppm)
Trout
55
2.7 to 4.7
Carp
65—75
75.0
to 91.0
*TL50
-
Tolerance limit at which 50
of the fish survived and is
nearly
equal to LD50
(lethal dose)
and LC50
(lethal concen-
tration)
Boss qualifies the above results by stating
“Fish populations in-
cluding rainbow trout flourish in Wyoming and Nevada where fluoride
concentrations are 13.0
-
14.0 ppm.
Yet reared trout have displayed
TL50’s of about 3.0 ppm of fluoride
(Sigler and Neuhold, 1972)”.
The Boss report cites another study of response of rainbow
trout eggs in water containing less than 3.0 ppm of calcium and
magnesium under varying temperatures
(Neuhold and Sigler,
1960).
Reported results were as follows:
16 —72
—13—
Temperature, °F
Hours
46
222—273
424
55
242—261
214
60
27—281
167
These data show that fluoride toxicity increases for trout
eggs
with increasing tertiperature.
Information was also reported on efforts to determine
the
effect of chloride concentration on rainbow trout (Neuhold and
Sigier,
1962).
In
water
containing measured amounts
of fluoride
and
chloride
ions,
the
following
results wore obtained:
Cl
ion, ppm
0
_____
(Deaths)
0
0
0
4
0
0
7
1
0
13
6
1
25
10
1
Boss states that such evidence indicates that the presence of
either calcium, magnesium or chloride ion decreases the toxic level
of fish to the fluoride ion,
While admitting that the effect of the
chloride ion is conditional, Boss asserts that
“the weight of the
experimental evidence supports the contention that fish acclimated
to moderate concentrations of cJ~Jonideion have increased resistance
to fluoride toxicity.”
Summarizing,
Boss
states:
“Fluoride
~on
has
a
high
affinity
for ..calc~iumand its
presence
in
the
water
in
significant
amounts
seems to reduce the
effective
concentration
of
calcium
in
the
body
of the fish.
CaF2,
however,
dissociates
to
form
so
few
fluoride
ions that evidently only light symptoms of fluorosis are produced.
Moreover,
the calcium ion made available by the dissociation of
CaF2 would seem to provide a replacement for any calcium extracted
from the body of the fish.”
Boss”s overall conclusion based on available
information
was
that “in our opinion, data on fluoride toxicity are too general and
vague to establish a valid toxicity level for aquatic life at
this
time”.
As will be noted in the following
table,
waters
used
in
the
tests just described bear little,
if any, resemblance to stream
conditions applicable to the parties in this proceeding.
This table
provides definitive stream values
in
relation
to various streams
16—73
—14—
receiving proponents effluent, the Des Plaines River near Olin’s
Blockson Works and the Ohio River near Allied’s Metropolis plant:
Average Stream
Big Grand
(2)
Saline River
Saline
(4)
value
(1)
—
Pierre Creek, ALO1
South Fork
(3)
River, ATO4
ph
7.5
6.5
D.O.
7.9
8.0
Fluoride
0.6
0.3
0.4
Chloride
13
.,
49
Hardness
160
Saline
(5)
Ohio
(6)
Ohio
(7)
River, ATO2
River, A08
River, A07
ph
7.6
7.9
7.8
D.O.
8.2
8.4
8.6
Fluoride
0.2
0.2
0.1
Chloride
23
100
22
Hardness
Ohio
(8)
Ohio
(9)
Ohio
(10)
River
River AOl
River, A02
ph
7.7
7.6
D.O.
8.6
8.7
Fluoride
0.6
0.2
0.1
Chloride
24
19
Hardness
160
Ohio
(II)
Ohio
(12)
Ohio
(13)
River, A06
River, A04
River
ph
7.5
7.6
D.O.
7.6
7.8
Fluoride
0.2
0.2
0.3
Chloride
22
20
Hardness
178
Des Plaines
(14)
Des Plaines
(15)
River, Gl2
River, GOl
ph
7.3
7.4
D.O.
7.0
7.3
Fluoride
0.8
0.8
Chloride
120
165
Hardness
320
290
16—74
—15—
(1)
Stream identification followed by an
“A” or “G”
identification number
(i.e., ALO1,
G12) represents
data taken from IllInois EPA Nater Quality Network,
Summary of Data,
1972.
Stream identification with-
out an
“A” or
“G” identification number represents
data taken from Illinois EPA Public Water Supplies
Data Book,, 1973
(Allied Exhibit #2).
Values reported
in mg/i.
(2) Below discharge from Minerva’s Gaskins Mine.
At or
near discharges from Barnett Air Shaft, Barnett Mine
and Ozark-Mahoning’s Parkinson Mine.
(3) Above fluorspar mine discharges.
(4) Far above fluorspar mine discharges.
(5) Mouth of River below fluorspar mine and mill discharges.
(6) Near Shawneetown,
above fluorspar mine and mill discharges.
(7) Near Cave-In-Rock, below confluence of Saline and Ohio
Rivers.
(8)
Rosiciare water intake below discharge from Ozark-
Mahoning’s Rosiclare Mill.
(9) Golconda water intake below fiuorspar mine and mill
discharges.
(10) Brookport below all fluorspar mine and mill discharges
but above discharge from Allied plant.
(ii) Oimsted below Allied plant discharge.
(12)
Cairo water intake.
(13) Cairo water intake.
(14)
Above discharge from Olin’s ~lockson Norks.
(15) Below discharge from Olin’s Blockson Works.
From the record it is apparent that the determination of
toxicity in this matter depends largely upon the concentration of
ions in the receiving waters, particularly calcium and magneisum
ions.
The reports refer to the concentration of these ions as
hardness.
(Water hardness in the Des Plaines River near Olin’s
Blockson Works
is about 90% calcium and 10% magnesium
[R.
2221).
As the above Table shows,Illinois streams are not deficient in calcium
and magnesium ion concentrations.
On this basis, toxicity data submitted by Allied Chemical
appear to be more pertinent to this proceeding than any other data
submitted.
Allied contracted Industrial Bio-Test Laboratories
Inc.
to conduct a 4-day static fish toxicity study using bluegill sunfish
(Lepomis macrochirus) and channel catfish
(Ictalorus punctatus)
.
A
test solution was prepared by using de-ionized water and measured
amounts of calcium and magnesium sulfate, sodium bicarbonate and
potassium chloride.
Water taken
from the Ohio River near Metropolis
was used as a dilutant.
16—75
—l~—
Sodium fluoride, calcium fluoride and hydrofluosilicic acid
were added at test concentrations of 2.5,
10.0 and 20.0 ppm
fluorine to separate vessels, each containing
10 specimens of
each àspecies of fish.
An untreated sample containing only river
water
was
used
as
a
control.
Water temperature was maintained at
about 18°C.
(64.4°F.).
In
the
test
using
sodium
and calcium fluoride no fish
fatalities
had
occurred
after
96
hours
exposure
to
the
calcium
fluoride
test
solution.
One
bluegill
died
after
24
hours
exposure
to
the
10.0
ppm
sodium
fluoride
solution
and
another
died
after
72
hours
exposure
to
the
20.0
ppm
sodium
fluoride
solution.
No
catfish
fatalities
occurred
in
the
sodium
or calcium fluoride
solutions.
Investigators concluded
that
the
96-hour
TLç0
of
both
sodium and calcium fluoride for unacciimated native fish is in
excess of
20 mg/l
These results are particularly important and directly
relatable
to
Illinois
streams.
They
again
point
to
the
importance
of
associating
fluoride
toxicity
levels
with
calcium
and
magnesium
concentrations in surface streams.
Another document which provides additional insight into the
effect
of
fluoride
on
stream
quality
was
submitted
as Proponent’s
Exhibit
#14.
This docurnenL reports the results of
a biological
survey conducted by the Illinois EPA on February 6-7,
1974
to
determine
the
condition
of
stream environments relative to dis-
charges from Minerva’s Gaskins Mine.
The survey reveals well
balanced benthic invertebrate populations both upstream and
downstream from the mine discharge.
(An unnamed tributary re-
ceiving effluent from the mine was reported to be “semi—polluted”
with the cause appearing to be of an “organic origin”).
Although
fluoride concentrations are not reported in the biological survey,
data reported earlier in this Opinion indicate that the fluoride
water quality is being met and this receiving stream is adequately
protected.
Turning now to the question of economic reasonableness and
technical feasibility, we shall first review Proponents’ Exhibit
#8.
Under the direction of Franklin T. Davis, CSMRI,
a report
titled “Capital and Operating Cost of a Suggested Process for the
Removal of Fluoride Ion from Tailings Water” was prepared.
The
report shows applicability of currently available methods of
fluoride
removal
and
also
details
an
as
yet
unproven
method
which
has
a
potential
of
reducing
fluoride
content
from
10
ppm
to
about
1
ppm
at
a
rate
of
one
million
gallons
per
day.
The
Davis
report
disposes
of
“state—of-the-art”
systems
as
follows:
—17—
A.
CaF2 precipitation
—
economically unreasonable because
of excessive calcium requirements.
B.
Contacting beds of activated alumina, calcium phosphate,
calcium super phosphate or bauxite
-
prohibitively large
bed volume required to treat large amounts of
10 ppm
fluoride water,
loss of bed material in regeneration
and probable addition of phosphate ion to water.
C.
Combined magnesia-lime system
—
restricted
to water
containing less than
3 ppm fluoride,
large amounts of
magnesium
co-precipitated.
D.
Carbon, zeolites and activated bone
-
best suited for
low volume of water with
a fluoride concentration of
less than
5 ppm and a pH of
7 or
less, regeneration
losses.
E.
Ion exchange
-
low capacity, slow exchange,
low fluoride
selectivity and economics.
F.
Reverse osmosis and ion selective membrane
—
economically
unattractive and not proven technology.
An alternate method proposed by Davis, but not yet tested,
could be labeled
as the “Hydroxyapatite Method”.
In that method
water and lime are mixed to produce
a 10
slurry which
is reacted
with 85
phosphoric acid to produce hydroxyapatite by the
following reaction:
5Ca(OH)2
+
3H3P04
~
Ca5(OH) (P04)3
+
9H20
Twice the stoichiometric amount of hydrated lime is added to favor
complete reaction of the phosphoric acid in the 1 hour reaction
time.
Hydroxyapatite slurry is then pumped to an agitated reaction
vessel where it contacts the incoming fluoride-bearing waste
water.
Reaction tank volume allows
1 hour for reaction of the
fluoride to fluorapatite.
From the reaction vessel the slurry
flows to
a floculator
tank where
a fiocculating polymer is added.
After 15 minutes
the treated slurry flows to
a clarifier where
suspended solids are settled.
Overflow from the clarifier is
discharged from the plant at
a rate of 693 gpm.
Sludge from the
clarifier is pumped to the tailings dam but can be recirculated
in varying amounts
to the reaction tank in order to react any
remaining unreacted hydroxyapatite.
Sludge generation is small
for this process and should not present any major disposal problem.
While Davis thinks the method looks good on paper, he quickly
adds that additional
laboratory studies are required to finalize a
numer of parameters before final evaluation is possible.
Among
the parameters to be determined are:
16
—
77
—18—
1.
Ratio of lime to phosphoric acid and required reaction
time,
2.
Rate and absorbtion capacity of the hydroxyapatite,
and
3.
Optimum quantity of flocculant, floccuiating time and
settling time in the clarifier.
Capital investment for use of the hydroxyapatite method to
treat one million gallons per day would be $287,300, exclusive of
roads, power lines and pipe lines.
Operating costs for the plant
were listed as $11,278 per month or $O.376 per 1,000 gallons.
Davis testified that Ozark-Mahoning would require three such
plants since
3 million gallons of waste water must be treated
(R.
172).
Therefore,
capital cost for Ozark-Mahoning would be in
excess of $1 million and operating costs would be $45,000 per month
(R.
171).
Similar costs on
a percentage basis would apply to
Minerva’s operations
(R.
172).
Full-scale laboratory testing remains
to be done for the hydroxy-
apatite method.
Davis has performed some laboratory experiments
using “artificial hydroxyapatite” with the result being a reduction
to less than 1 ppm fluoride
(R.
172).
As
to other processes for removal of fluorides as described in
Waste Water Treatment Technology,
Second Edition, IIEQ Document 73-i
(Petitioner’s Exhibit
#9)
Davis testified that none of the processes
would be effective on mill tailings water.
Davis stated that the
processes would not be effective because most of the processes treat
water that
is relatively free of turbidity.
Mill tailings water
would have to be clarified or filtered in order to use the process
and this “is expensive”
(R.
168).
Another reason for nonacceptance,
according to Davis, was “although they don’t say this,
..
.it is
pretty obvious that after they removed it
fluoride
they dumped it
back into the river downstream”
(R.
167).
This option is not open
to Proponents.
After reviewing the various methods in the IIEQ document, the
Board agrees that they do not directly relate to the fluorspar
industry.
However,
a possible exception might be the use of contact
beds of activated alumina.
Without committing to the applicability
of this process, the Board notes that one such unit in Bartlett,
Texas has operated since 1952 on a municipal water plant to reduce
fluoride from
8 mg/i to
1 mg/i.
Noticeably absent from discussion
on the Bartlett plant are flow rates and cost data.
According to
the report, two investigators experimented with an alumina bed as a
polishing unit following lime precipitation.
They found that a 30
mg/i residual fluoride concentration could be reduced to
2 mg/i.
At
a pH of 11.0 to 11.5 they were able to reduce fluoride from
9 mg/i
to 1.3 mg/i.
Regenerative losses were cited as
4
alumina lost per
100 regenerative cycles.
16—78
—19
—
While such information is far too skimpy,
it certainly raises
the possibility of use on Proponent’s mine waters, which
are
“reasonably clear”
CR.
200),
or on mill tailings water after
clarification.
Further, the Board finds nothing in the IIEQ
document to indicate that any of the methods discussed involves
subsequent dumping of removed contaminants “back into the
river downstream”.
In his letter dated April
26, 1974
(Petitioner’s Exhibit #11),
Davis said that new information supplied to Davis showed the mine
waters
to be free of turbidity.
On this basis Davis
states that
the best process would be the one reported in “Defluoridation of
Municipal Water Supplies”, by F.
J. Maier in the Journal of the
American Water Works, August 1953.
This
is the same alumina
contact bed process used in Bartlett,
Texas and discussed just
above.
Davis states the process has a potential for lower capital
cost than the hydroxyapatite method but laboratory verification
would be required.
A set of figures based on the alumina bed process for mine
waters and the hydroxyapatite method for tailings water, adjusted
to 1974 prices, was supplied by Davis.
These figures show
a one
million gpd tailings treatment plant with
a fixed capital invest-
ment of $298,000 and operating costs of $12,800 per month.
A
650,000 gpd mine water treatment plant to treat water from #7
Oxford Shaft, North Green Mine and West Green Mine and a 650,000
gpd mine water treatment plant to treat water from the Parkinson
Mine and Barnett Air Shaft would require a fixed capital invest-
ment of $568,800.
Adjusted operating costs are shown as $0.25l
per 1000 gallons
for the two mine water treatment plants and
$O.427 per 1000 gallons
for the tailings plant for a total of
$O.328 per 1000 gallons.
These costs exclude about 10,100 feet
of right-of-way for pipeline which Davis warns may be “very
substantial”.
James
N.
Pappas,
a Sanitarian with the U.
S. EPA, attacked
Davis’ estimates of capital operating cost for the hydroxyapatite
method.
Pappas testified that these costs most likely would be
considerably different if Proponents only treated the blow-down
from a recycling process and where fluoride concentration was to
be reduced to 2.5 mg/l rather than
1 mg/i.
He stated that Pro-
ponents had not proved that recycling would be required and had
failed to provide data relative to marketing of recovered fluorides
as a possible cost reduction.
Davis responded
(Petitioner’s Exhibit
#11) by stating that
prior testimony had established “that recycling of tailings water
in this type of flotation system is not compatible with the
flotation system”.
He admitted that the water could be purified
for recycling purposes but added that such
a process would probably
16—79
—20--
be more expensive than the hydroxyopatite method because sodium
ions
and organics would have to be removed.
C.
B. Rash had
testified that recycling adversely affected the efficiency of
the flotation process
(R.
41)
.
Davis
added that recycling
efforts
at
the
Colorado
plant
were not very
successful.
Solar
evaporation ponds were required, which Davis
adds,
would
not
be practical in Illinois.
As to the possible sale of recovered ~iuoride, Davis re-
sponded that recovery of acid grade OaF2 from two million gallons
of water would
amount
to about 240 poun~lsner day with
a market
value of about $10.00.
He added that he knows of no process from
which CaF2
is recovered in
a marketable form and that the whole
idea
is
“a
most
impractical
consideration”.
In
a
letter
dated
May
16,
1974
Chris
Potos,
Chief
of
Water
Quality
Standards,
U.
S.
EPA, suggested several possible
methods
of
treatment
which,
in
his
opinion,
raised
doubts
regarding
the
claim of economic hardship.
Responding
to
the
concern
that during
periods of low flow
the
water
quality
standard
of
1.4
mg/i
could
be violated by an effluent which would he acceptable during periods
of normal
flow,
Potos suggests
that
retention
basins
or lagoons
could be utilized to
store
mine
~iaters
until
sufficient
flows
upstream are available to allow release of mine waters
without
contravention of water quality standards,
Potos hastens to add
that the U.
S. EPA does not necessarily recommend such a
solution
but merely raises the question “as to consideration of alternatives”.
Other alternatives suggested by
Potos
included
relocation
of
mills to sites near the Saline or Ohio Rivers and transmission of
mill waste water from existing sites to the larger receiving streams.
Petitioner’s Exhibit #11 was of particular concern to Potos.
He questions whether generalized cost figures
are
applicable
for
specific projects.
He states that treatment costs for reducing
fluoride
in
mill
tailings from 5 mg/I at the Minerva Mine
#1
Mill
to
2.5
mg/i
at
580,000
gpd
would
probably
be
different
than
the
cost
of
reducing
fluoride
in
miii
tailings
from
10
mg/I
to
2.5
mg/i at Ozark-Mahoning’s Rosiciare Miii at 980,000 gpd.
Further
reduction
of
fluoride
to
1
mg/l
could
amount
to
90
of
the
total
treatment
cost
according
to
Potos.
In his statement of treatment cost,
Davis assumed that mine
water
flows
from
the
Oxford,
North
Green
and
West
Green
Mines
were 650,000 gpd.
Potos states that Federal NPDES files show the
flows
to be only about 116,000 gpd.
U.
S.
EPA files containing
this information were not made a part of the record.
16 —80
—21—
The
Davis
estimate also cited a 650,000 gpd flow to the
“Barnett
area
waste
treatment
plant”
from
the
Parkinson
Mine
and
the Barnett air shaft.
As Potos points out, Petitioner’s
Exhibit #13 shows flows from the Parkinson Mine, Barnett Mine
and Barnett air shaft as 187,200 gpd.
If we were dealing with another type of industry it would
be
a simple matter at this point to combine the flows each
proposed plant was
to receive.
These figures would show that
the two proposed 650,000 gpd plants are substantially larger than
required thus showing that the estimates of cost are overstated.
However, this industry must contend with substantial changes
in mine discharges.
In their Supplemental Submission Petitioners
insist that a plant capacity of 650,000 gpd is necessary.
Assuming
for purposes of argument that it were both possible and practical
to combine mine discharges from several mines at one
(or more)
location, Petitioner states that history would show the inability
of the fluorspar industry, or anyone else for that matter,
to
anticipate increases in mine water as new veins are mined and new
faces opened.
For examples of the above, Petitioner cites the
current discharge from Ozark-Mahoning W.
L.
Davis Mine which is
now three times
larger than the original discharge ievel.
Minerva’s
older Gaskins Mine has a 1,260,000 gpd discharge as opposed to the
115,000 gpd discharge from the new Spivey Mine.
Another example
is the Crystal Mill
facility which has a current discharge of
75,000 gpd during intermittent operations.
If both the heavy media sep-
aration
and flotation miii were placed into operation,
this dis-
charge would increase to as much as 480,000 gpd.
Thus, Petitioners
argue,
it would be sheer folly to construct
a treatment plant based
on current operating requirements when these requirements might
increase two,
three, or more times in the months and years to come.
The basic premise necessary for such regional treatment plants
is that the discharge flows from several points must be combined.
Petitioner’s concede that
a project of this
type might be accom-
plished if reasonableness and ability to finance the project were
not to be considered.
Hurdles to be overcome by Petitioners
in such
a project are
numerous and varied.
Petitioners would have to commit finances
covering the cost of land,
easements,
pipelines,
electrical dis-
tribution lines, storage facilities, buildings,
labor and maintenance
for a theoretical process without any reasonable assurance that
compliance would be achieved.
Pipelines and electrical distribution lines would have to
cross
land in the Shawnee National Forest.
Petitioners state
that past experiences considered, the U.
S. Forest Service would
be reluctant and probably unwilling to issue the permits necessary
for such
a project.
16—81
—22—
Petitioners also believe the concept of ponding or lagooning
mine discharge is not a feasible alternative.
Of the 15 discharge
points from Petitioners mines and mills, one flows to the Ohio
River and the remaining 14 flow to streams classified as inter-
mittent streams.
These discharge points-are widely separated in
the rock and hill terrain of Hardin and Pope Counties mak~Lng
centralization or combining of discharges
impracticable.
Numerous
small treatment plants would have to be built.
Petitioners state
that 10 of the 15 discharges are currently in violation of the
effluent or water quality standards.
As an example of the problems
to be encountered if the
ponding concept were implemented,
Petitioners cite the following
estimated cost for impoundment of discharge water from the Gaskins
Mine for a 90 day period:
Total discharge for period
=
113,400,000 gallons
Estimated evaporation
—
22,000,000 gallons
Volume
to be retained
=
91,400,000 gallons
Requires a 60 acre pond with average depth of
4.67 feet.
Estimate need to purchase or lease 180 acres for pond
site.
Levee requires two feet of freeboard
-
6.67 feet levee
height.
Requires moving approximately 31,000 cubic yards
of
dirt.
Cost:
Building levee at 60’~per yard
=
$
18,400
180 acres of land at $300/acre
=
54,000
Cost of pipeline and pumps
=
55,000
Major expense total
=
$127,000
In addition to the above estimated cost Petitioners would incur
fees of $200 per acre for land leased from the U.
S. Forest Service
(assuming such leases could be arranged)
as well as cost for seed
and fertilizer, pipeline right-of-way and maintenance.
However, Petitioner states that the major problem in ponding
is that they are simply unaware of any land in the area suitable
for ponds or lagoons.
One alternative available to Petitioner is to pump the dis-
charge waters from Gaskin’s Mine to the Ohio River, a distance of
7 miles.
This project would require a 10” pipe,
40,000 feet long,
costing $320,000 according to Petitioner’s estimates.
Estimated
total cost of this alternative including right—of—way, survey costs,
legal fees,
leases, piping, pumps and installation is in
excess of
$420,000.
16 —82
—23—
A second alternative would be to pump the Gaskin’s Mine
discharge to a central treatment plant serving all Minerva
discharges.
If this central plant were located at the Minerva
Mill,
the cost of pipe alone for the 15 mile project would be
in excess of $600,000 at
$8 per foot.
Petitioners believe that
a project of this magnitude would take longer than the reamining
productive life of the Gaskin’s Mine.
Responding to the suggestion that Petitioners consider
relocation of mills near the Saline or Ohio Rivers, Petitioners
state that they have no way of estimating the cost of such a
project and that the project would be comparable
in difficulty
to relocating the Sears Tower.
The Board feels that Petitioners have shown that the many
alternatives suggested are not practicable or economically
feasible solutions to this complex problem.
Hillsides blighted
with pipelines and electrical power lines, especially
in a national
forest, makes these alternatives particularly displeasing from an
aesthetic viewpoint in addition to the other drawbacks.
Olin’s fluoride problem, as earlier noted,
is substantially
different from that of Ozark-Mahoning, Minerva or Allied Chemical.
Nicholas J. Barone testified that Olin had investigated numerous
fluoride removal techniques which were found to be unacceptable
from an economic consideration.
Olin’s corporate engineering
department devoted the efforts of some
50 people over a period of
years on scaling up laboratory data to
a full-scale operation
intended for purchase and installation if the effluent standard
was not changed.
Waste water from Olin’s plant contains phosphate in proportions
which enhance utilization of the lime process.
Barone testified
that the Olin fluoride removal process requires a ratio of phosphate
to fluoride of
20 to
1 or greater or the process will fail to
achieve the desired reduction
(R.
232).
An excess of lime of about
200over
stoichiometric is required to reach 2.5 mg/l fluoride.
The Olin process will require a capital investment of $1.4
million and annual operating costs are estimated to be $450,000
(R.
238).
When operating,
the Olin process will require
7 tons
of lime and
28 tons of phosphate per day to treat the 1200
gpm waste water flow.
About 70,000 lbs.
of 35
solid sludge per
day will be generated which will either be impounded or hauled to
a landfill.
Sludge disposal will cost an estimated $80,000 to
$90,000 a year exclusive of land requirement cost
CR.
240).
Weighed
against these factors will be the removal of an estimated 100 to
200 lbs. per day of fluoride CR.
288).
Even with these process
disadvantages, Olin believes it has a significant economic advantage
over the other parties in this matter because of the phosphate
16—83
—24—
content of its waste water.
The other parties would have to
add phosphate to their waste water to make them treatable.
Barone estimated that phosphate addition would increase
operating cost by an additional
10 to 20
(R.
257).
The U.
S.
EPA’s criteria for best practicable treatment
of fertilizer industry effluent calls for achieving 15 ppm
fluoride or a maximum of
30 mg/l fluoride for any 24 hour
period
(R.
243).
The U.
S.
EPA’s best available technology
for the steel industry calls for reduction to levels of 4.2
to 8.3 mg/i fluoride on a 30-day average and 10 to
20 mg/i as
maximum
allowable
for
a
24-hour
period
(R.
246).
However,
if the effluent standard were changed to Olin’s
proposed level of
10 mg/i,
Olin could reach this level through
“in-process controls”
(i.e. pump leakage control, recycling,
etc.).
Fluoride in Olin’s waste water comes
in large part from
leakage from over 800 pumps at the Blockson Works
(R.
241).
Barone
testified that the reduction to
10 mg/i
is
a “very reliable
number”
CR.
269) based on actual experience at the plant
CR.
254).
Obviously the cost for in—process control would be far cheaper
than installation and operation of a
lime treatment process.
Allied Chemical’s Metropolis plant effluent currently contains
about 410 mg/i fluoride wh~.chis equivalent to
a discharge of
7,000
lbs.
per day fluoride
(P..
375).
Richard J. Sobel, Director
of Environmental and Process Technology for Allied’s Special
Chemicals Division, testified that it
is Allied’s belief that
technology
is available to achieve 15 mg/i fluoride levels in the
presence
of
calcium
CR.
370).
Allied
is
committed
to
a
program
aimed at an over-all level of
7 mg/i fluoride in the Metropolis
plant
effluent
(R.
370).
Allied presented testimony in 1971 when the Board was con-
sidering the fluoride effluent standard.
A.
J. von Frank, Allied’s
Director of Air and Water Pollution Control, testified that it was a
practical impossibility to achieve a fluoride level of less than
8.3 mg/I.
This
level represents
the theoretical minimum that can
be achieved in a water solution of calcium fluoride from the
conventional lime method of fluoride removal
(R.
371).
Sobel testified that Allied began a search of technical
literature and an intensive in-house development program immediately
after the Board adopted the 2.5 mg/i standard.
This effort was
directed toward discovery of a technically feasible and economically
reasonable method of achieving the 2.5 mg/i standard.
After
two years of research and thousands of manhours, Allied concluded
that there was no such method available.
Allied sought and was granted a variance from the fluoride
effluent standard
(and others) on February 28,
1974 upon satisfying
—25—
the Board that it was diligently working on fluoride abatement
technology.
Sobel testified that the abatement program approved
in that variance will require about
two
years for completion at
a cost in excess of $4 million
(R.
375).
Research on fiuoride
removal technology will continue during the two year period.
Allied Chemical estimates that it would remove 6,880
lbs.
per day of fluoride to achieve
7 mg/i.
The capital investment
for doing this would be $2,683,200 and the operating costs would
be $660,000 per year.
If the control equipment had a life
expectancy of
10 years then capital costs would be approximately
$.107 per lb.
of fluoride removed.
Operating costs would be
approximately $0.26 per lb.
of fluoride removed.
If Allied Chemical then used the most promising and techni-
cally feasible method to achieve 4.1 mg/i fluoride (filtration)
an additional
33 lbs. of fluoride per day would be removed at
a
capital cost of $220,110
($1.83 per
lb. over a
10 year period)
and an operating cost of $73,000 per year
(R.
377).
If Allied
then used a fixed alumina bed process
to reach 2.5 mg/i, an
additional
25 lbs. of fluoride per day would be removed at a
capital cost of $330,000
($3.62 per lb. over
a 10 year period)
and operating cost of $99,000 per year
(R.
378).
If the life expectancy of the abatement equipment is
10
years Allied Chemical would have capital costs of $0.127 per lb.
of fluoride removed.
If the life expectancy
of the equipment
is
20 years
then the capital costs for fluoride removal would be
just $0.064 per lb.
The claim of Allied Chemical that capital
costs would amount to $9,480 per lb. per day is absurd.
Allied’s
mistake was in failing to allocate the cost of the plant over
the entire life expectancy.
It seems obvious
that the entire cost
of the capital outlays should not be assigned to the first day of
operation.
The other companies which were participating in the
hearings did not make this same mistake, but Allied Chemical made
the mistake for them.
(See Appendix A attached to Allied’s final
position paper).
For instance, Allied claimed that capital costs
for Ozark-Mahoning would amount to $11,110 per pound of fluoride
removed,
apparently assigning a life expectancy
of only one day
for that proposed facility.
Franklin Davis, the designer of the
proposed Ozark-Mahoning system indicated that it would have
a
life expectancy of 20 years.
Over a 20-year period the Ozark-
Mahoning capital costs per pound of fluoride removed would be
around $1.50.
Allied Chemical did not tell us what the useful life of its
control equipment will actually be.
We doubt that the equipment
installed at the Allied plant would have a life expectancy of
20
years.
The U.
S.
EPA allows a depreciation factor of
10 years, and
we have already noted that capital costs over a 10—year period
would be less than $.l3 per pound of fluoride removed.
16—85
—26—
The Internal Revenue Code allows companies to take de-
preciation deductions for pollution control facilities over
a five year period instead of the “estimated useful life” of
the equipment.
This practice inflates the cost figures
attributable to the equipment during the period of depreciation,
a fact Allied Chemical readily concedes.
However, such costs
could not under any acceptable accounting practice reach $9,480
per pound.
Proponents mine water discharges do not appear in danger of
violating the Mine Related ~ffluent criteria of
8 mg/l.
No
testimony relating to the Mine Related Pollution Control Regu-
lation was presented by proponents.
A remaining problem unique to Ozark—Mahoning and Minerva
comes about as
a result of mine discharges.
Proponents contend
that Rule
302(k)
of
the
Water
Pollution
Control
Regulations
“proceeds to designate” as Secondary Contact and Indigenous
Aquatic Life Waters
“all waters in which, by reason of low flow
or other conditions,
a diversified aquatic biota cannot be satis-
factorily maintained even in the absence of contaminants”.
Rule
302(k)
(As amended February 14,
1974)
states:
“Secondary Contact and Indigenous Aquatic Life Waters”
Secondary contact and indigenous aquatic life waters
are those waters which will be appropriate for all
secondary contact uses and which will be capable of
supporting an indigenous aquatic life limited only by
the physical configuration of the body of water, char-
acteristics and origin of the water, and the presence
of contaminants in amounts that do not exceed the
applicable standards.
The following are designated as secondary contact and
indigenous aquatic life waters;
(k) All waters in which by reason of low flow or
other conditions,
a diversified aquatic biota cannot
be satisfactorily maintained even in the absence of
contaminants.”
In
its
Opinion
on
this matter the Board stated:
“Part III contains water use designations.
All waters
are
designated
for
general
use
except
those
in
the
restricted category, which has here been broadened in
response
to testimony to include waters whose flow
is
too low to support aquatic life.
This should relieve
the burden of treatment beyond the effluent standards
16—86
—27—
for discharges to intermittent streams.
Such extra
effort is difficult to justify when it will not result
in a satisfactory aquatic life because of insufficient
flow.”
(Vol.
3,
p.
765).
The request of the mining companies that certain waters be
designated “Secondary Contact and Indigenous Aquatic Life Waters”
is important,
because such designation would substantially increase
the allowable fluoride levels in the stream.
Rule
402 of the Water Pollution Regulations provides:
“In addition to the other requirements of this Part,
no
effluent shall, alone or in combination with other sources,
cause a violation of any applicable water quality standard.
When the Agency finds
that a discharge that would comply
with effluent standards contained in this Chapter would
cause or is causing a violation of water quality standards,
the Agency shall take appropriate action under Section 31
or Section
39 of the Act to require the discharge to meet
whatever effluent limits are necessary to ensure com-
pliance with the water quality standards.
When such
a
violation is caused by the cumulative effect of more than
one source, several sources may be joined in an enforce-
ment or variance proceeding, and measures for necessary
effluent reductions will be determined on the basis of
technical feasibility, economic reasonableness,
and
fairness to all discharges.”
Therefore,
if we adopt an effluent standard of 15 mg/l,
the
discharges must meet that effluent standard and also must not
cause
a violation of the Water Quality Standard beyond the mixing
zone.
The mining companies could meet a Water Quality Standard
of
5 mg/i fluoride.
If on the other hand,
the water quality standards were held
at the present 1.4 mg/i criteria while the effluent standard is
changed to
15 mg/i,
the mining companies would still have a problem
during periods of low flow when effluent from the mines is pro-
portionately a larger part of the stream.
Several alternatives
would have to be considered by the mining companies:
1.
The mining companies could petition to have the stream
declared a “Secondary Contact and Indigenous Aquatic Life
Water” under Rule 302(k).
Water so designated would have a
water quality standard identical to the new 15 mg/i
effluent standard
(See Rule 205).
2.
Ponding—-This concept has already been discussed and
found to be impracticable for the mining companies.
16—87
—28—
3.
Treat
the
effluent
down
to
the
water
quality
standard
of 1.4 mg/i.
This alternative would cause undue hardship
on the mining
companies.
4.
Variance-—This is available only on
a temporary basis
while
permanent
solutions
to
the
problem are brought into
play.
The
record
for
reclassification
of
the
streams
is
woefully
inadequate.
While numerous streams are known to he receivers of
the
mine
water
discharges,
proponents
sole
presentation
on
the
issue
is
a
copy
of
an
Agency
report
on
biological
samples
taken
on
Big
Grand
Pierre
Creek.
As
earlier
noted,
results
of
this
survey indicate well—balanced benthic invertebrate populations
both
upstream
and
downstream
from
the
mine
discharge.
One
stream
was found to be “semi—polluted”.
If
the
Board
were
to
act
at
this
time
on
the information
presented,
the obvious decision would be to deny the “secondary
contact’1
classification.
However,
the
Board
feels
that
no
decision
is required at this time on the Rule
302(k) matter simply because
Rule
302(k)
was
not
adequately addressed as an issue during these
proceedings.
Our
ruling
does
not
preclude Proponents
from raising
the
Rule
302(k)
issue
at
some
later
date.
Our
decision
only
relates to the inadequacy of the record now before the Board on
that
matter.
It
is the Board’s finding that Proponents, with the aid of
Olin and Allied, have presented proof sufficient
to warrant changing
the fluoride effluent limit from 2.5 mg/i
to
15
mg/l.
Effluent
of
that
quality
should
be
acceptable
in
Illinois
waters.
The
Water
Quality
Standard
for
fluoride remains unchanged at 1.4 mg/l
for all dischargers other than the fiuorspar mining and concen-
trating industry.
The Water Quality Standard becomes
5 mg/i
fluoride in waters which receive effluent from the mines and mills
of the fluorspar mining and concentrating industry,
and have been
designated by the Illinois State Water Survey as streams which
once in 10 years have an average minimum seven day low flow of
zero.
Throughout these proceedings some degree of importance was
attached
to
information
in
the
Illinois
EPA’s
Public
Water
Supplies
Data
Book,
July
1973.
In
that
document,
fluoride
levels
in
drinking
water
as
high
as
7.7
mg/i
fluoride
for
Bureau
Junction
and
5.8
mg/i
for Parkersberg are shown.
Proponents state that they are not
aware
of
any
Agency
initiated proceedings,
enforcement or otherwise,
because of the fluoride level in these public water supplies.
How-
ever no evidence was introduced regarding the impact of these
fluoride
levels
in
these
communities,
and
we
certainly
do
not
infer
from the lack of legal action that 5.8 mg/i
-
6.6 mg/I is an
appropriate
standard
for
the
entire
state.
16—88
—29--
It is
the responsibility of this Board,
as charged by the
Environmental
Protection
Act,
to
protect
the
quality
of
the
environment.
Having reviewed all aspects of these proceedings,
the Board feels
that an increase in the general water quality
standard for streams receiving fluoride containing discharges
from the fluorspar mining and concentrating industry, without
change for
other
streams in the
State,
would
not
create
signif-
icant
and unwarranted effects on the environment.
Unrefuted
testimony and evidence in the record shows
that no apparent
environmental damage has occurred
in these streams because of
continuous mine discharges over a number of years.
In raising the water quality standard and the effluent
limitation for fluoride, the Board has carefully taken into
consideration the expected impact upon the receiving streams
and the economic impact of the Regulation.
Ozark—Mahoning and
Minerva will receive relief for operation of their mines and
concentrating mills.
Ozark-Mahoning’s current discharge level
of
10 mg/i
is below the new effluent limit and should not require
any additional treatment barring a major process upset.
Minerva,
on the other hand, discharges water from its Mill
#1 and Crystal
Miii that are well within the 15 mg/i limit.
Thus, Minerva will
not be required to provide any additional fluoride control treat-
ment unless process changes cause the fluoride concentration to
increase significantly above the current concentrations.
In those instances where Proponent’s mines discharge to
flowing streams, current effluent levels appear to be low enough
iopreciude violation of the 15 mg/i effluent criteria.
A
different situation confronts proponents when and if their mine
discharges
go to dry or intermittent streams.
For the most part,
mine discharges are well below the new 5 mg/i water quality
standard for such streams.
Pond
#3 of Minerva’s Mine #1 and
Mill now average 4.5 mg/i and Minerva will have to monitor this
discharge closely to insure that this discharge does not violate
the new standard.
With proper chemical treatment Minerva should
be able to maintain this discharge concentration within the new
limits.
Increasing the effluent limit to 15 mg/i will provide signifi-
cant relief for Olin since that level can be reached by implementing
“in process controls”.
In process controls,
according to Barone’s
testimony, will involve some repiping, recycling of certain waste
streams, elimination of chronic leaks and possibly some equipment
modifications or replacement.
Barone testified that Olin considered
in process controls to be
“a very attractive thing” since the
operating costs would be so low as
to not even show up as
a
separate cost
(R.
242).
Through the recycling effort Olin would actually receive some
benefit since phosphate materials now being discharged would be
recovered and end up as product instead of waste.
Olin did not
16—89
—30—
have any cost figures relating to in process control but Barone
testified that the capital investment would be “much lower”
than installing
a lime treatment plant
CR.
242).
This change in effluent criteria for fluoride affects Allied
differently since the current fluoride concentration in Allied’s
effluent is significantly higher than that of any other party in
this matter.
At one time in these proceedings Allied sought to change
the effluent standard to allow 15 mg/i fluoride based on the
average of
24 hour composite analysis for thirty consecutive
days and 30 mg/i maximum for any one 24 hour composite.
In its
last submission Allied states that its recommended standard of
30 mg/i for any one 24 hour composite may prove to be too re-
strictive for some industries such
as hydrofluoric
acid manu-
facturers.
Allied now seeks to change the effluent limit to
30
mg/i as the average of
24 hour composites
for 30 consecutive
days and 60 mg/l for any one 24 hour period.
Allied’s original recommendation was based upon criteria
published in Volume 39, No.
49 of the Federal Register on March 12,
1974 by the U.
S. Environmental Protection Agency.
The reason-
ableness of this
U.
S. EPA criteria was challenged by the hydro-
fluoric acid manufacturers in the Fourth Circuit Court of Appeal.
One result
of
this
action,
according to Allied,
is that the U.
S.
EPA now plans to revise the fluoride effluent limitations to the
same limits Allied now seeks in this matter.
Although the U.
S.
EPA has not yet proposed any new limits,
Allied states that Region
VI of the U.
S. EPA granted Allied a permit for its Baton Rouge
Works on December 9,
1974 using the new limit.
Allied is now committed to a fluoride reduction program
designed to achieve a fluoride concentration in its effluent of
7 mg/i.
Undoubtedly, Allied will modify this program to meet the
fluoride level now permitted and we would expect this modification
to reduce cost.
Having considered all information in this record concerning
the technical feasibility and economic reasonableness of alternative
methods of fluoride abatement in conjunction with the data from
a commercial lime treatment facility now in operation at another
Allied
facility
it
is
our finding that the 15 mg/i fluoride is
both economically reasonable and technically feasible when applied
to Allied Chemical.
16—90
—31—
ORDER
It is the Order of the Pollution Control Board that the
Water Quality Standards and the Effluent Standards of the
Illinois Water Pollution Control Regulations be amended to
specify the following limitations for fluoride:
PART II
WATER QUALITY STANDARDS
203.1 Exceptions
to Rule 203
(a) The fluoride standard of Rule 203(f)
shall not
apply to waters of the State which:
(1) receive effluent from the mines and mills
of the fluorspar mining and concentrating
industry,
and
(2) have been designated
by the Illinois State
Water Survey as streams which once in ten
years have an average minimum seven day low
flow of
zero.
Such waters shall meet the following standard with
regard to
fluoride:
Constituent
Storet Number
Concentration
(mg/i)
Fluoride
00950
5
PART IV
EFFLUENT STANDARDS
408
-
Additional Contaminants
(a) The following levels of contaminants shall not
be exceeded by any effluent:
Constituent
Storet Number
Concentration
(mg/I)
Fluoride
(total)
00951
15
I, Christan L. Moffett, Clerk of the Illinois Pollution Control
Board, hereby certify the a ove Opinion and Order was adopted
this __________day of
çr’~
,
1975 by a vote of
4
toO.
QJ~
16—91
