ILLINOIS POLLUTION

CONTROL BOARD

September

7, 1978

IN THE MATTER OF :

)

WATER POLLUTION CONTROL

)

R74-15, -16

AMENDMENTS : CYANIDE

)

OPINION OF THE BOARD (by Mr

. Goodman) :*

The original Petitions for a Regulatory Amendment in this

matter

Corporation

were

and

filed

the

approximately

Illinois Petroleum

four years

Council

ago

(R74-15

by Republic

and R74-16,Steel

respectively)

. The Petitions sought changes in the Board's Water

Quality, Effluent and Sewer Discharge Standards for cyanide

.

BACKGROUND AND PROCEDURES

This Board inherited the substance of its cyanide regulations

from its predecessor in water pollution control, the Illinois

Sanitary Water Board

. The Sanitary Water Board's cyanide water

quality and effluent standards were contained in various individual

regulations, applying to various river basins and dischargers, as

well as in rules of general applicability

. See, e.g., SWB 5

; SWB

10, at Rule 1

.04(d)(1966) ; T .R . 20-19, Rule 1

.01 (1964)

; SWB T.R .

20-22, at 2 (1968)

. The last of those references limited efflu-

ents, discharged to waters of the state, to cyanide concentrations

of 0

.025 mg/1, with the footnote, "reduced [sic**] at least to

cyanate and approaching zero as CN ."

In 1972, as part of its codification and general review/

revision of existing Water Pollution Regulations, this Board

adopted the same general standard of 0

.025 mg/l for water quality

* The Board wishes to thank Vincent P

. Flood, Jr., Attorney, and

Carolyn Hesse, Technical Assistant to the Board for their assist-

ance in the preparation and drafting of this opinion and order

.

** "Reduced" is probably used colloquially, and not to indicate a

chemical reaction .

---

-2-

and effluent use, but revised the old SWB standards for sewer dis-

chargers . In making that decision, the Board cited as its justi-

fication the work of the Ohio River Sanitary Commission (ORSANCO),

carried on in the late 1950's and early 1960's, (See, eg . Ex . 10,

11, 12) .

ORSANCO's uncertainty in two areas -- distinction between

various

thoseforms

0techniques.025

.

mg/l

the

uncertainties,

cyanide

basis

standard--

therefore

forms

for

.

the

An

along

and

led

regulatory

attempt

the

with

to

availability

the

other

by

Board's

proposals

industry

technical

adoption

of

and

now

adequate

and

others

before

of

economic

the

measurementto

the

generalresolveBoardfactors,

.

The proponents, along with various other participants in this pro-

ceeding, contend that the 0 .025 mg/l standard can and should be

changed for the following reasons :

1 .

discharge

The existing

standards

effluent,

for cyanide

water

fail

quality

to distinguishand

sewer

between various cyanide chemical forms which are

significantly different in terms of toxicity and

treatability ; and

2 .

Any need for those standards which may have

existed as a result of testing procedure inadequacy

or other uncertainty no longer exists, since tech-

nology has advanced to the degree necessary for

such measurement determinations (although complete

accuracy was not alleged at any point) .

At hearing, evidence was also presented to support the follow-

ing additional contentions :

3 .

In many cases, individual industries or dis-

chargers cannot, using practical technology, comply

with the existing 0 .025 mg/l effluent standard for

"total" (a term defined below) cyanide .

4 .

cyanide

Even

to

in

meet

those

the

cases

0.025

in

mg/l

which

standard

the removal

is tech-of

nically

economically

practicable,

unreasonable

it is

to

for

require

many industriessuch

treat-

ment .

5 .

Since cyanide is more readily and economically

treated in municipal treatment works, it is unreason-

able to severely limit discharges of cyanide into

33.64

---

-3-

sewers tributary to such municipal treatment plants,

(in accord with the existing sewer discharge criteria

of

presently

Rule 703)

meet

whether

the existing

or not

0a

.025

municipal

mg/1 standarddischarger

.

can

In addition to the general relief asked in the original

Petitions, various other proposals and amendments were offered

during the hearings in this matter . For example, the Metropolitan

Sanitary District of Greater Chicago (MSDGC) requested special

relief for the secondary contact and indigenous aquatic life

waters

charge

.

to

(It

which

was

certain

the MSDGC's

of its

contention

treatment

that

plants

the

presently

existing,

dis-or

mental

even

those

the

watersProtection

proposed,

.) In

Agency

a

levels

separate

(IEPA)

of protection

proposal,

made particularly

the

are

Illinois

not necessary

specific

Environ-forpro-

posals on the issue of testing and measurement for various

cyanide chemical forms and quantities

.

Fifteen hearings on the various proposals and submissions were

held

1977 .

in

The

Chicago

IIEQ filed

and Springfield

its study,

from

IIEQ

June

Doc

.

16,

No1975

. 77/3,

until

"EconomicMay

17,

Impact

25, 1977of

.

Alternative

In addition,

Cyanide

various

Standards

participants

in Illinois",

introduced

on

extensiveFebruary

economic data throughout the "merit" hearings . At the conclusion

of the hearings on this matter, the record consisted of thousands

of pages of testimony and documentary exhibits . Republic Steel

Corporation and the Illinois Environmental Protection Agency (IEPA)

also filed thorough, extensive briefs summarizing that evidence .

In addition to the Regulatory Proposals filed by Republic

Steel and the Illinois Petroleum Council, various other partici-

or

pants

other

proposals

recommended

also filed,

are summarized

presented

standards for

in

on

testimony

the

cyanidefollowing

.

or

Those

supported

page,

recommendations(Table

varioustaken

from Appendix 4, Brief of Republic Steel Corporation) .

DISCUSSION

Chemical forms of cyanide

Much of the testimony in the record centered on the differ-

ences in toxicity, treatability and formation of various cyanide

containing molecules . The principle forms of cyanide discussed

follow :

1 .

Free cyanide includes the triple bonded carbon-

nitrogen anion (C

N- ) and hydrogen cyanide (HCN), also

33-65

---

- 4 -

1According

to Rule 401(c), compliance with the effluent standard shall be determined

on the basis of 24-hour

Lu site sammples (i .e .,

daily average)

. In addition, for any given grab sample (daily maxvmm), the total

cyanide concentration shall not exceed 0

.125 total (five tines the nu erical standard)

.

2NO

permit reTuired, but violation must not occur "at any tine"

. This provision governs sewer discharges which

are not subsequently treated .

3With

permit only if no violation of the effluent standard by the downstream sewage treatment plant occurs

.

4

Without permit if no violation of the effluent standard by the downstream sewage treatment plant occurs

.

SFor secondary contact and indigenous aquatic life waters (include the Calumet River)

. The [SD's original

proposed water quality standard of 0

.025 "sinple" was withdrawn in April, 1976

.

6

FOr sewage treatment works other than the Caluret River S7W

. The PSD's original proposed effluent standard

of 1 .0 total/0

.1 "simple" was withdrawn in April, 1976 .

7For the Calumet STW only

.

BAs part of the

IEPA's

proposed water

quality standard, the coefficient of variation (which is a measure of the

single operator-single laboratory precision) shall not exceed 20% at the 0

.025 mg/l level and the bias shall

not exceed 10% of this level .

9The

IEPA effluent standard proposal provides that compliance neasurarent shall be with such precision that the

coefficient of variation does not exceed 10% and the bias does not exceed 20%

.

l 0

Campliance is to be determined by

24-hour canposite samples averaged over 30 days

. No single 24-hour aaposite

sample shall exceed 0

.2 total (Twice the nurerical standard), and no single grab sample shall exceed 0.5

total

(5 tines the nurerical standard) .

llCcmpliance is to be determined by 24-hour samples

. No single grab sample shall exceed 0

.050 total (twice

the nurerical standard)

. The IIEQ proposal also provides for site-specific effluent

s tanda

rds

in certain

cases where a less stringent effluent standard would be appropriate

.

-2Effluent

limitations to be established

on

a case-by-case basis to insure that the water quality standard

within reasonable mixing zone, is not exceeded

.

(CYANIDE mNCENTRAfas IN luLuGpA B PER LITER)

WATER QUALITY

E FISIEN'T

SEVER DISCH%RC£

(Rule 203(f))

Rule 408(a))

(Rule 703(a) and (b))

PRESENT

REGULATIONS

0 .025 total

0 .025 totall

0 .025 total (Rule 703(a))

2

10 total/2 readily releasable (Rule 703(b))

3

REPUBLIC

S"gEL

1

.0 total/0 .025 free

2 .0 total/0

.1 free

2

.0 total/0 .1 free (Rule 703(a)

2

10 total/2 readily releasable (Rule 703(b))

4

10 total/2 readily releasable (Rule 703(b))

3

ILLINOIS

PETR E2P1

COUNCIL

0 .025 free

0 .1 free

10 total/2 readily releasable

4

METROPOLITAN

SANITARY

0 .1 total

6

DISTRICT

0 .1 totals

0 .3 total

7

ILLINOIS EPA

0 .025 total

8

0 .1 total9

0 .1 total (Rule 703(a)) 2

10 total/2 readily releasable (Rule 703(b))

3

ILLINOIS Ig4

0 .1 totall

0

U .S . EPA

0 .025 total"

DUPONT

0 .025 free

12

---

-5-

referred to as hydrocyanic acid when dissolved in water .

These two forms of cyanide exist in equilibrium in aque-

ous solutions . HCN is the predominant form in neutral and

acidic solutions ; at higher pH's hydrogen cyanide dissociates

to form cyanide ion .

2 .

positive ion

Simple

(cation)

cyanidesand

x

are

number

compounds

of cyanide

that contain

ions wherea

x is equal to the valence state of the cation

. The cation

could be an ammonium group, alkali (metal), alkaline earth

or heavy metal . Generally, the cyanide compounds can dis-

sociate in water to release the cation and the cyanide

ion(s) . The range of solubility and dissociation depends

on the molecular structure of the given compound .

3 .

Complex cyanides are compounds in which one or

more cyanide ions are joined with a metal atom to form

a complex negative ion, which may in turn join with a

positive ion to form a molecule . Complex cyanide can be

represented as Ay [M(CN) x] t where A represents the cation,

CN is the cyanide group, M(CN) x is the metal-cyanide com-

plex ion, and x, y, and a represent the numbers of ions

in the molecule . When dissolved in water, complex cyanide

molecules

and the positive

may dissociate

ion

. The

to

metal-cyanide

release the complex

complex

ion,

ion

M(CN)may x

and

further

degree

dissociate

of dissociation

to release

under

the

various

cyanide

conditions,

ion . The ratesuch

as temperature and pH, depends on the cyanide complex ; some

complexes readily dissociate while others are stable .

4 .

accurate chemical

Readily

definition

releasable cyanidesand

are defined

are not

strictly

subject toby

regulation . In the existing Rule 703(b), readily releas-

cyanide

able cyanides

compounds

would

in

include

a sample

any

which

free,

release

simple,

free

and

cyanidecomplex

when subjected to a temperature of 150°F

. at a pH of 4 .5 for

thirty minutes .

5 .

Total cyanide is simply the sum of all of the

above

cyanide

cyanide

forms

forms,

which,

along

depending

with

on

any

the

other

testing

compounds

methodor

used, are recorded as cyanide

. Throughout the hearings

in

all

this

cyanide,

matter,

in any

total

form,

cyanide

present

was

at

used

any

to

timedenote

.

any and

---

-6-

6 .

Other cyanide forms, e .g .,

organic cyanides such

as

cyanohydrins, are important only insofar

as they fall

into

one of the above categories or act

as interferences in

various analytic or treatment methods .

Toxicity

to aquatic

Although

life,

some

(Rcomplex

.1364-1365)

cyanides

it is

have

generally

been shown

agreed

to

thatbe

toxic

hydrocyanic acid (HCN) is the most toxic form of cyanide

. There

is some information which indicates that the toxicity of complex

cyanides is related to their dissociation to form free cyanides

which in turn depend on water conditions such as pH, turbidity,

and temperature (R .1540)

. Cyanide intoxication results in cellu-

lar asphyxia and leads to death (R.990) .

Several witnesses presented testimony on cyanide toxicity

for aquatic life ; four of them, Pipes, Doudoroff, Broderius, and

Lue-Hing had actually performed cyanide toxicity testing on

various organisms . It appears that fish are the most important

organism that would be affected by cyanide in the concentrations

discussed in this proceeding

. Generally, cold water fish, such

as trout and salmon, are more sensitive to cyanide than are warm

water fish, such as fathead minnows, bluegills, and bullheads .

Pipes found a four day LC50* of 0 .05 to 0

.1 milligrams HCN per

liter for trout and salmon and an LC50 of 0 .16 to 0

.24 mg/l for

warm water fish (bluegill, sunfish, fatheat minnows)(R

.95) .

Doudoroff reported toxicity tests using bluegills which showed

48 hour LC50 values for free cyanide of 0

.15 mg/l, for cupro-

cyanide ion (complex copper cyanide) of 4 mg/l and for nickel

cyanide complex and iron cyanide complex on the order of 400

mg/1 . Lue-Hing, of the Metropolitan Sanitary District of

Greater Chicago, exposed fathead minnows to unchlorinated

sewage treatment plant effluents for 96 hours and reportedly

did not obtain fish kills (R .1118-1119)

. However, it should be

were

noted

less

that

than

the

the

cyanide

reported

concentrations

96 hour LC50

used

of

in

0 .18-0the

MSDGC

.23 mg/l

testas

free cyanide for fathead minnows and less than the standard set

forth in this opinion .

Broderius has done and, at the time of the hearings, was

still doing an extensive amount of research on cyanide . Table

1 of his testimony (R.854) is based on the work of others and

presents minimum lethal threshold concentrations of free cyanide

A four day LC50 is the lethal concentration that would kill

half of the test organisms within four days (96 hours) .

33-68

---

-7-

for various species of fish

. Based on his own work using con-

tinuous flow bioassays, Broderius has found minimum lethal

threshold concentrations to be generally less than the concen-

trations reported in Table 1 (R.851)

. The differences in data

are probably due to significant changes in the cyanide level in

the water produced by the metabolism and absorption of cyanide

by fish and by loss of cyanide (HCN) to the atmosphere (R

.853) .

Hence, data from static bioassays would tend to indicate that

would

fish could

data from

tolerate

the more

a higher

accurate

concentration

continuous

of

flow

cyanide

tests

thanin

which

the cyanide concentration is kept constant . Broderius concluded

that free cyanide concentrations near 0 .1 mg/l as CN have

eventually proven fatal to a high percentage of cold and warm

water fishes and that levels greater than 0 .2 mg/l are most

likely rapidly fatal for most fish species (R.855) .

Exposure to free cyanide at levels less than minimum lethal

threshold concentrations has been shown to produce sub-lethal

effects . Broderius reported finding biochemical changes, avoid-

ance reactions, reduction in swimming performance, and reduced

fertility and fecundity at levels of HCN as low as 0 .012 mg/l in

the laboratory (R .863-869) . Pipes also testified that fish avoid

toxic concentrations of free cyanide (R .104) .

Human toxicity was discussed by two witnesses, Hermann and

which

Carnowmay

. Hermann

produce

noted

a fatality

that the

in

"minimum

adult humans

oral

has

dose

been

of

reported

free cyanideto

range from 20 mg to 100 mg," (R.82) which is far in excess of any

of the standards being set forth in this matter . Although he did

not have data to substantiate his claim, Carnow argued that there

may be human chronic toxicity effects from exposure to sub-lethal

unlikely

concentrations

that these

of cyanide

effects

(Rwould

.2015-2076)occur .

at

However,

the low

it

concentrationsseems

set forth as standards in this proceeding

.

Hermann also testified that the sewer discharge limitations

would

would

be

protect

expected

sewer

in

workers

a sewerunder

. According

the worst

to his

conditions

calculations,that

if the wastewater has a pH of 4 .5 and a temperature of 150°F

(65

.5°C) and the sewer is completely unventilated, HCN in the

sewer air could not exceed 10 ppm (the threshold limit value

set by American Conference of Governmental Industrial Hygenists)

unless the wastewater contained free cyanides in excess of

sewer

3 .8 mg/l

discharge

for an extended

standard

period

of 2 mg/l

of timereadily (R .85)releasible

. The cyanideand

10

mg/l total should provide an adequate margin of safety .

---

-8-

MeasurementTechniques

There was much testimony

presented

in the record on the

various measurement

techniques for cyanide

. The following is

a brief summary of the material

in

the record ; for more detail,

see the testimonies of the following witnesses : Caruso,

Doudoroff, Lee, Hernandez, Mathre, Lue-Hing, Broderius, and

Schaeffer .

Measurement techniques for total cyanide involve liberating

cyanide from the sample as HCN then collecting and analyzing this

D2035-Acyanide

by the USEPA

:

by

Total

using

for

Cyanide,

measurement

various

1972proceduresof

; (2)

total

Standard

. The

cyanide

three

Methods

aremethods

: (1)

for

ASTMapprovedthe

Exam-

Cyanide

Cyanideination ;

(Rof

and

.662)Water

(3)

.

and

USEPA

Reportedly,

Wastewater,

Methodthe

- STORET

13th

tests

Edition,

Nohave

. 00720,

a

1971precision

1971-

Total-(repro-Total

ducibility)

methods

concentration

for

of

measuring

of

plus

0.025

or

total

minus

mg/l

cyanides

(R80

.663)to

100

.

(Exhibit

Hernandez

percent

Noat

evaluated

.

a

31)

total

and

cyanidethecon-

cluded that the USEPA method is the best available method for

measuring total cyanide since thiocyanate can reportedly inter-

fere with the ASTM-A method and the Standard Methods measurement

as

technique

the recoveries

does not

reported

achieve

for

recoveries

the USEPA

of

method

total cyanide

(20 to 80as

high

percent recovery for Standard Methods versus 90 percent for

the USEPA method) .

Although some of the proposed standards would set limits

on free cyanide, there is no generally accepted method of

analyzing a water sample for free cyanide (R.65, R.1712, R.1441) .

However,

D2036-Bmated

cyanides

Method

:

four

were

Cyanides

;

identified

methods

(3) AISI-Modification

Amenable

of

(Rapproximating

.669-670)to

Chlorinationof

. They

the

ASTM

concentration

;

areD2036-A(2) :

Technicon

(1)

; and

ASTMof

(4)

Auto-freeWood

River

also involve

Modification

liberating

of the

cyanide

Roberts-Jackson

from the solution

Method .

as

These

HCN and

methodsthen

collecting and analyzing it . The major difference between the

methods for measuring total cyanide and the methods for estimating

free cyanide is that the distillation step in the former is more

severe in order to break down the complexed cyanide . Even though

these methods are said to be conservative because they measure

some complex cyanides as well as free cyanides, the particular

unknowncomplexes

. An

included

additional

and the

problem

extent

with

to

these

which

four

they

methods

are included

is that,is

according to IEPA testimony, the technique for preserving the

33-70

---

-9-

samples

destroys free cyanide and

disturbs

the equilibrium which

causes

(R.1441)

the

.

complex

In addition,

cyanide

some

to

of

convert

these

from

test

one

methods

form

are

to anotherplagued

by

interference or poor sensitivity (R

.670-672, R

.1382-1384, R .1427) .

It appears that none of these procedures is generally applicable

to samples of all wastes

. Hence, the IEPA does not support any

method which supposedly measures "free" cyanide

(R

.1392) .

Sources

-Although cyanide is a naturally occurring compound and may

at times reach levels in water which are toxic to aquatic life

as a result of natural processes, such occurrences are unlikely

in Illinois . Despite some anamolies in Metropolitan Sanitary

District figures, indicating unusually high cyanide levels from

non-industrial areas, the bulk of cyanides present

- whether

free or complex -

in Illinois waters result from industrial pro-

cesses

of iron

associated

and steel,

with

or petroleum

the metal

refiningplating .

industry, the manufacture

the minor

Of the

exception

various industries

of steel case

discussed

hardening

at these

operations,

hearings,

onlywith

the metal plating industry purposely uses cyanide in high concen-

plating

trationsshops,

. Cyanide-containing

although other

plating

technologies

vats are

have

still

been

used

investigatedin

most

.

(In many cases, no substitute for cyanide has been found

.) Cyanide

bearing wastes originate in the vats themselves, subsequent rinses,

drippings and spills . Although cyanide wastes from the plating

industry typically contain high concentrations, they are

relatively low in volume .

Cyanide is generated in the iron and steel industry in four

operations (of which the first three are significant in terms of

quantity of cyanide produced) :

1 .

centrations

Large

of cyanide

volumes

wastes

of typically

are generated

low (1 mg/1)

in thecon-

scrubbing steps for blast furnace gases .

2 .

Blast furnace gas cooling water also contains

large quantities of wastes with a relatively low (2 mg/1)

concentration of cyanide

. The source of the cyanide in

these wastes is the same as that in blast furnace gas

scrubber water, above .

33.71

---

-10-

3 .

By-product coke operations produce, in the

cooling process, relatively high (e .g

., 90-100 mg/1)

concentration cyanide wastes, typically composed of a

mixture of simple, free, and complex (including iron)

cyanides .

4 .

Steel case hardening often involves the use

of sodium cyanide vats ; cyanide bearing waste waters

are generated in subsequent rinses .

In the petroleum refining industry, cyanides are generally

formed in the cracking and coking operations

. The amount of

cyanide

amount of

produced

nitrogen

varies

present

greatly,

in the

apparently

crude oil

dependent

being refinedon

the

. Oil

refinery cyanide wastes are often complex cyanides and include

ferricyanide and/or ferrocyanide .

In addition to the above sources of cyanide, other unknown

sources contribute to cyanide discharges from municipal treat-

ment plants, (e .g ., R .1113) . Even completely domestic,

"bedroom type" communities without a significant industrial

waste load may, at times, exceed the current 0 .025 mg/l limi-

tation for cyanide (R .1148) .

Fates of Cyanide in the Environment

Free and complex cyanides are subject to alteration from

their original state upon introduction to the aquatic environment

.

Free and simple cyanides may be oxidized biologically, escape to

the atmosphere, or combine with other substances to form complex

cyanides ; cyanides already in complex form may, on the other hand,

dissociate to form toxic free cyanides

. The reactions involved

are all reversible, accelerable, and interactive

.

The importance of these reactions is that they are central

to the primary contention of the proponents and several other

participants

: that complex cyanides, if allowed to enter the

environment in increased quantities, will not cause environmental

damage

. The Board, therefore, must determine whether complex

cyanides, especially iron cyanides, will be converted in the

environment to toxic free cyanide in quantities sufficient to

cause problems . The Petitioners argued at length, and presented

testimony and evidence accordingly, that many complex cyanides

--

in particular, iron cyanides --

dissociate very slowly, if at all,

in the environment .

---

Although there are many forms of complex cyanide,

discussion

at hearing

and in the exhibits entered in this matter centered

upon iron cyanides since, as mentioned above, alkaline

chlori-

nation does not destroy iron cyanides and the iron

cyanides appear

to

be one of the less toxic forms . The principal

forms under dis-

cussion were ferrocyanide (hexacyanoferrate

(II)) and ferricyanide

(hexacyanoferrate (III)) .

Although the former may be transformed

forms

to the

may

latter

be treated

and other,

as a

minor

single

differences

form for regulatory

may exist,

purposesthe

two

.

'iron

-Much

cyanides

discussion

to free

revolved

cyanide .

around

(See testimonies

the photodissociation

of Broderius,of

Caruso, and Lue-Hing

.) In short, it is clear that laboratory

conditions,

give photodissociation

with distilled

results

water

quite

and

possibly

iron complex

toxic

cyanides,

to aquaticwill

life, starting with iron cyanide complex concentrations of less

than 1 .0 mg/1 and possibly down to 0 .1 mg/l

. However, it is

difficult to extrapolate these findings to the natural environ-

ment .

Only one study has been done to date using natural waters

and existing discharges and was performed by MSDGC . Dr

. Lue-Hing

contended that MSDGC's measurements in the Illinois River, when

compared with upstream discharge and water quality data, indicate

slow and insignificant photodissociation

. (The MSDGC found an

average of 17%, with a range of 4 to 30%, "simple" cyanides down-

stream in the Illinois River .) (Exhibit #51)

. That conclusion

was, however, strongly rebutted by IEPA since the Illinois River

is not necessarily representative of all the waters of the state

.

It should also be borne in mind that the river was only sampled

on one occasion .

It appears that the photodissociation of iron cyanide com-

plexes may indeed cause the release of significant amounts of

toxic, free cyanides under some circumstances

. The reaction

involved, however, is inhibited or accelerated by many factors,

including pH, temperature, sunlight, and the presence of other

compounds

.

Treatment Technology

There was general concurrence among all witnesses discussing

the subject that no generally applicable treatment process is cap-

able of consistently producing an effluent meeting the existing

0

.025 mg/l standard . In addition, it was also agreed that it is

not possible to eliminate cyanide use or formation from most of the

33-13

---

-12-

industrial processes discussed

above . The various

available treat-

ment

methods are, therefore, discussed

briefly .

Seemingly contrary to

the general consensus

just described,

complete cyanide destruction has been

achieved by at least one

method currently in use in Illinois

. Incineration is presently

being employed by one refinery, which has a nearby heat source

available

. This is not, however, a generally applicable tech-

nologyheat

source(s),

. Few dischargers

and few (if

have

any)

available

of those

the

who

necessary

do also

surplushave

a

high-concentration, low-volume waste stream such as that currently

being incinerated

. Steel industy wastewater streams in Illinois,

for example, generally exceed 10,000 gallons per minute, and some

may exceed that figure by orders of magnitude .

Alkaline chlorination, on the other hand, is the most commonly

used method for the treatment of cyanide-bearing

wastewater . i t

involves

greater)

the

wastewaters

addition

to

of

oxidize

chlorine

the

to

cyanide

highly alkaline

present

.

(pH

While

of

free10

or

cyanide concentrations of 0

.1 mg/1 or less can be obtained by

alkaline chlorination, it is not generally considered effective

for the control of iron cyanides

. (See generally, testimony of

Dr . Patterson and Exhibit 49) .

Other treatment methods are rarely used . In general, they

are either experimental, inadequate to achieve sub-milligram per

liter effluents, or are considered too costly for reasonable use

.

They are :

(1) Alkaline ozonation is merely the use of ozone instead

of chlorine to oxidize cyanides . This method has diffi-

culties resulting from the inability to oxidize certain

complex cyanides, high capital and operating costs, and

sludge production .

(2) Oxidation with permanganate, still in the laboratory

development stage, will not destroy several important com-

plex cyanides

. It also suffers from high cost and sludge

production .

(3) Electrolysis is capable of destroying almost

all cyanide species, including complex iron cyanides

.

However, costs would obviously be quite high for any

except high-concentration, low-volume waste streams, as

with incineration, (e .g., R.150 et seq .

; Ex . 16) . it

was only suggested for metal plating wastes

.

33.74

---

-13-

(4) Precipitation does not destroy cyanides, instead

it merely concentrates them for disposal by other means .

In addition to a very large sludge accumulation, this

method is not practical because it has not been shown

to achieve effluent cyanide concentrations below 4 or

5 mg/l

.

waste

(5) Ion

streamsexchange

. In

would

addition,

be applicable

the method

only

is

to

impracticallow-volume

due to interferences, which include almost any other

_impurity in the water being treated .

(6) Adsorption with catalytic oxidation requires the

addition of copper in large quantities, probably with

resulting violations of copper effluent standards . In

addition, the method is not applicable to steel industry

or oil industry wastes as a result of interferences .

(7) Conventional biological treatment has removed approxi-

mately 55% of influent cyanide at MSDGC's Calumet STP . How-

ever, excessive influent loading can impair the biological

removal mechanism and interfere with plant operations, and

shock loadings are a serious problem (as described by the

Rockford Sanitary District) . Some of the cyanide removal

may be due simply to concentration in sludge . This method

cyanidesis

not generally

.

effective for some strongly complexed

(8) Other methods are detailed in Ex . 16 and elsewhere

in the record, including IIEQ Doc . No . 76/22 . These

include such exotic techniques as gamma ray irradiation

and are not beyond laboratory testing ; most would, even

volume

if proven

waste

successful,

streams .

be applicable only to very low-

In summary, it is clear that -- except in very-high-concentra-

tion situations such as might exist in the metal plating industry --

alkaline chlorination is the only practical treatment method and

destroys approximately 80% of all cyanides amenable to chlorination

(R .760) . While it has problems, including particularly inter-

ferences in oil and steel industry wastes, it is the only method

reasonably available for high-volume wastes . Dr . Patterson's

testimony indicated that alkaline chlorination may be considered

available, practical treatment technology, capable of allowing most

dischargers to meet his recommended standard of 0 .1 mg/1 total

cyanide .* Steel industry witnesses, including Drs . Gurnham and

* Given averaging, as discussed below .

33.75

---

-14-

Becich,

argued on the other hand that alkaline chlorination is not

acceptable

for steel industry wastes and will not produce results

much better than the proposed 2 .0 mg/l total and 0

.1 mg/l free

cyanide . It could, however, meet a 10 mg/l total, 2 mg/l simple,

sewer discharge standard, (R .754) . (Wisconsin Steel presently

approaches 0 .1 mg/l total cyanide at times using air-stripping,

alkaline chlorination and sand filtration, (Ex

. 32), although

there is also some dilution of the cyanide-bearing waste streams,

(R .758) .)

Averaging

The averaging proposal before us here is in fact taken from

hearingsanother

proceeding,

. The proposal

R76-21,

was prepared

and was introduced

by the Illinois

only at

Effluentthe

later

Standards Advisory Group, with the support of the Illinois Insti-

tute for Environmental Quality and IEPA

. In addition, its adopt-

ion was supported by essentially all the proponents and partici-

pants in the proceeding .

In short, the averaging proposal propounds a mechanism

whereby an effluent standard is not an absolute discharge limit,

but is rather a measure of required average performance over a

monthly period based on composite samples . There are also pro-

visions in the proposal to prevent environmentally damaging

excursions beyond the monthly average, which might otherwise be

mathematically allowed ; daily composite samples cannot be more

than twice the stated limit, and grab samples cannot exceed the

limit by more than a factor of five .

Because treatment plants must operate under widely differing

ment

conditions,

of a very

from

low

day-to-day

concentration,

and from

absolute

minute-to-minute,

effluent limit

achieve-requires

over-design . To stay under an effluent ceiling, the plant must,

on the average, discharge cyanide at a level far below the ceiling

.

Hence,

eliminate

we find

the need

the averaging

to over-design

proposal

a treatment

sensible,

plant,

since

though

it wouldthis

finding is limited here to cyanide effluents .

ECONOMIC IMPACT

The Economic Impact Study required by P .A . 79-790 was sub-

mitted by the Illinois Institute for Environmental Quality (IIEQ)

on February 11, 1977.* Huff and Huff, The Economic Impact of

Alternative Cyanide Standards in Illinois, IIEQ Doc . No . 77/03,

Exhibit E-4, the earlier study, Huff and Huff, Analysis of

the Benefits and Costs of Alternative Cyanide

Standards in

Illinois, IIEQ Doc . No . 75 24 1976 , was withdrawn by IIEQ .

33-76

---

Proj . No

. 20

.065 (1976) [Ex .

E-1] . The Study concentrated prin-

cipally on costs and benefits associated with the various proposed

effluent standards**, generally assuming water quality levels to

be a direct function of effluent levels and emphasizing the pro-

posed changes to Rule 703 (sewer discharge criteria) to the extent

that costs were imposed upon sewer dischargers as a result of vary-

ing the potential effluent standards for direct dischargers, who

would "pass along" stricter effluent standards in the form of

stricter sewer discharge limits .

.The Study's conclusions are sgmmarized in Table 2-10, p .22 .

Because much of the testimony and argument regarding the Study

concerned this Table (or its equivalent, Table 7-1), it is repro-

0.025 mg/l total

cyanide - daily

maxi nm

0.1 mg/l total

cyanide - daily

maxi-nun

0

.1 mg/l total

cyanide daily

maximum with 0

.3

mg/l total cyanide

for Calunet SIP

0.1 m3/l single

cyanide - daily

maxilmnn

-15-

131,000,000 -

Protection of all waters

580,300,000

for all use .

Protection of all waters ex-

7,200,000

cept the Chicago-Illinois

456,400,000 River System where loss of

recreation valued at $0 to

$62,000 occurs . Also, aes-

thetic losses are possible .

3,400,000

Protection of all waters ex-

cept the Chicago-Illinois and

Calumet River Systems where

loss of recreation valued from

$0 to $89,000 is possible . Aes-

thetic losses are also possible

.

** The IIEQ Study pre-dated several proposals, including the IIEQ/

SAG proposal which introduced averaging concepts, and thus did

not consider the effects of such later proposals

. However, as

noted above, averaging may in fact render the study more mean-

ingful, as real effluent levels would be closer to those pro-

posed .

33-77

390,000

Loss of recreation on the

Calumet and Chicago-Illinois

River System valued from $0 to

$700,000 is possible . Also,

aesthetic and commercial fish-

ing

losceq are possible .

duced here :

Effluent

Annual Direct

Annual Projected

Regulation

costs, $

Benefits

---

Turning first to the costs

associated with cyanide regulation,

the study indicates that there are 13

major

sources of cyanide

which would be impacted economically by either enforcement of the

existing standard (0 .025 mg/1) or some other "tight" standard

:

three steel companies, eight refineries and two sanitary districts

(MSDGC and Rockford) (Ex . E-1, pp .47, 42, 61, 59)

. Including those

two sanitary districts, however, includes a significant number of

smaller, indirect dischargers, many of them metal electroplating

firms .

who

-are In

responsible

addition, there

for relatively

are also other

low volume

minor,

cyanide

direct dischargersdischarges

(Ex . E-1, pp .75, 73) . It should be noted, however, that smaller

dischargers may be more seriously affected by a lower treatment

standard ; at an effluent standard of 0 .025 mg/l (daily maximum)

total cyanide, some small plating operations might have to cease

operations altogether as the only possible compliance method

.

In the steel industry, there are 8 significant cyanide

four

sourcesplants

: blast

. Of

furnace

these,

and

five

coke

discharge

plant discharges

to MSDGC, one

from

to

each

the

of

Calumet River, and two (already in compliance) to Horseshoe Lake .

(The two complying sources, which are owned by Granite City Steel

and discharge to Horseshoe Lake, were shown to be unusual cases .)

Compliance costs for the steel industry in Illinois, for varying

5-13

levels

of

of

ExRegulation,

. E-1

. Compliance

are set

by

out

all

in

steel

tables

industry

5-7, 5-10,

dischargers5-12

and

total

with

of 0

.025

existing

(the

mg/1)

latter

regulations

would

indicating

cost

(including

between

closure

$56

a

of

million

sewer

all coke-dependentdischarge

and $506

limitationmillion

presumably,

operations

unavailability

resulting

the

of

sewer

coke)from

discharge

. As

an

the

inability

standard)

effluent

to

standard

comply,

is relaxed,

and

(and

industrymarkettherefore,

costs are more than proportionately reduced . Coke plant discharges

would

to MSDGC,

require

currently

capital

in

investment

violation of

of

permitted

approximately

0.025

$5

mg/l

million

levels,and

releasable

with

operating

a sewer

costs

cyanidedischarge

in

.

excess

Those

standard

of

figures

$100,000

of

constitute

10

annually,

mg/l total

the

for

and

majority

compliance2

mg/l

ofreadily

industry costs associated with a looser effluent standard for

MSDGC's discharges .

Compliance with existing standards by petroleum refineries

would

costs

costs,

(tablecost

in addition

in

5-6)excess

.

to

In

of

approximately

addition,

$8 million

considerable

per

12 million

year in

output

annual

in initial

would

operatingcapitalbe

33-78

---

-17-

lost

.

Again, as the standard is

relaxed, compliance

costs are

more

than proportionally reduced as

treatment technology

becomes

more readily

available . However, some

costs remain

even with a

0

.3 mg/l effluent standard .

Compliance costs for sewer dischargers in the electroplating

industry are presented in table 5-5 of the report

. Costs for

compliance with 0

.025 mg/1 (as now required when the receiving

sanitary district is not itself meeting that same standard) would

exceed $66 million

; at an effluent standard of 0

.1 mg/1 total

cyanide, costs drop to $0

.09 million .

As the study notes, however, direct costs to dischargers of

cyanide --

whether to waterways or to sewers and whether directly

for compliance or due to lost output --

are not all the economic

costs associated with a given level of regulation

. The authors

present

from lost

macroeconomic

output and reduced

costs, including

employment,

indirect

for various

costs

standards

resultingin

table 5-15 (apparently the source of cost figures in table 2-10,

reproduced above)

. These figures indicate, for example, that the

lower expected

indirect economic impacts of enforcing the existing

0 .025 mg /l standard would exceed $31

.8 million ; the range of

possible indirect costs to the state goes considerably higher

.

As the standard is relaxed, and particularly as fewer cyanide

indirect

sources are

costs

forced

decrease

to cease

significantly

operations

(although

as a compliance

not proportion-option,

ately to direct costs) .

Turning to benefit analysis, the Study's authors identified

a considerable number of beneficial uses of Illinois waters poten-

tially affected by varying levels of cyanide regulation, (Ex

. E-1,

§ 6 .1, table 6-1) .

For quantification purposes, however, the study

concentrated on recreational/fishing activity and the possible

waters

gain or

increased

loss of such

or decreased

activity

(as

as cyanide

a function

levels

of effluent

in the receivinglimits)

.

In the table reproduced above, the figures shown in the "benefit"

column are derived from this analysis .

There was some question as to the adequacy of such a limita-

tion on benefit quantification, (See, eg

., cross examination of

the Huffs and Dr . Harberger by Mr

. Park, IEPA)

. However, it

should be noted that environmental benefit analysis is a new

field, not easily given to any quantification

. However, the

willingness of Illinois citizens to pay for the use of clean

water resources at varying levels of protection is a valuable

approach .

33-79

---

-18-

It is

not, however, a complete

approach . As

the authors

note, at

three of the four

regulatory effluent levels considered

in table 2-10, aesthetic losses are possible, even though not

quantifiable . In addition to recreation and aesthetics, the Board

is constrained to consider the perhaps unquantifiable goals in § 2

of the Environmental Protection Act, Ill .Rev

.Stat ., Ch . 111-1/2,

§ 1002 (1975), that environmental quality be "restored, protected

and enhanced" .

sequent

As Republic

brief, a

Steel

purely

noted

economic

in its

decision

economic

on

presentation

cyanide regulationand

sub-

might indeed favor a standard looser than 0 .1 mg/1 total cyanide

.*

However, we find that such an argument could also rationally lead

to the conclusion that a far more liberal standard should be

chosen, or perhaps none atall, (See, eg ., R .2210-11 ; see also

R

.2193, "I doubt that there is a benefit associated with fish life

on

million

these

perwaterways

yr] .")

that would warrant that kind of price [$2 or $3

As required by § 27(b) of the Environmental Protection Act,

we find that any standard for cyanide protective of aquatic life

will have some "adverse economic impact on the people of the State

of

same

IllinoisAct

requires

." The

it)

benefits

are not

of

amenable

such protection

to complete

(even

or

though

adequatethat

,quantification, especially when compared to potential costs .

We feel, however, that the Institute's study presents suffi-

cient data to choose a standard offering adequate environmental

protection

An effluent

without

standard

requiring

of 0

.1 mg/1

unnecessary

total cyanide,

control

given

at excessive

the averag-cost

.

ing techniques for compliance measurement discussed above, was

not even among the possibilities discussed in the study, but is

maximum)

the one we

total

choosecyanide

. It is

standard

less stringent

which the

than

study

the

would

0.1

lead

mg/1

us

(dailyto

choose (from among the alternatives presented) and should involve

the

stringent

considerably

3 million

necessary

than

dollars

less

environmental

a 0compliance

annually

.1 mg/l free

(although

protection,

costcyanide

. On

this

the

standard,

at

cost

other

a cost

may

hand,

but

betweenin

will

fact

it

provideis

.3

be

moreandfar

Plant

lower,

and

as

sources

a result

that

of the

discharge

separate

to

provisions

sewage treatment

for the

plantsMSD

Calumet

.

*

nation

For

an economic

a thorough

of Drbasis,

. Harberger)discussion

see R

.

.2214

of optimal

and following

cyanide

(cross

standards

exami-on

33

.80

---

-19-

THEREGULATION

The

evidence before the Board justifies a change in the

existing standards for cyanide

. The reasons for the Board's

decision follow :

1 .

Although much testimony was presented in the

record that separate standards for free and

total cyanide are scientifically justifiable,

the Board has adopted a cyanide standard based

on only total cyanide since the only generally

accepted methods for determining cyanide are

methods that measure total cyanide

. The methods

that estimate free cyanide are not generally

accepted and do not necessarily reflect the

potential toxicity of complex cyanides that may

be present

. For example, these methods do not

measure

decompose

iron

and

cyanide

release

complexes

free cyanidewhich

.

may photo-

2 .

The use of a single cyanide standard

(i .e .,

total cyanide) will provide for rational com-

pliance planning and monitoring .

3 .

The general use water quality standard for total

cyanide is set at 0.025

mg/l in order to protect

the warm water fish found in Illinois . Such a

standard would be too high to protect cold water

fish such as salmonids ; however, although salmon

are being stocked in Lake Michigan and trout are

being stocked elsewhere in Illinois, these are

not fish that are native to Illinois at the

present time

. Although some sub-lethal effects

due to cyanide at this concentration may occur

such as avoidance reactions or a reduction in

fertility and fecundity, no fish kills due to

cyanide would be expected

. A general use water

quality standard for cyanide (total) of 0 .025

mg/l was supported in the record, as discussed

comments

above (see

from

Toxicity

the IEPA,

section)

USEPA,

and

and

by

otherspublic

(PC# 36, 40, 41, 45) .

4 .

The secondary contact and indigenous aquatic life

water quality standard is set at 0 .10 mg/l since

much of the water in this river system is from

effluents and because these waterways are already

of limited recreational value

. Although it was

stated in the record that free

cyanide concentra-

tions near 0 .10 mg/l (as CN) are eventually fatal

---

-20-

to

a high percentage of fishes, it

is thought

that such high concentrations of total

cyanide

would be found only in limited reaches

of these

waterways as indicated in

data presented by the

MSDGC (R .1768) and that fish would probably avoid

areas with toxic levels of cyanide

. It is also

unlikely that all the cyanide in a waterway would

be present as free cyanide .

5 .

At present, the IEPA has the authority to deter-

mine if an apparent water quality standard vio-

lation falls within the margin of error inherent

in the testing procedure . Hence, no separate

provision that the "coefficient of variation

shall not exceed 20% at the 0 .025 mg/l level and

the bias shall not exceed 10% of this level" has

been set .

6 .

No technically feasible and economically reason-

able method of compliance with the existing 0

.025

mg/l total cyanide effluent standard is available

for all sources

. Most dischargers will, however,

be able to meet the effluent standards adopted at

a reasonable cost in light of the environmental

protection achieved .

7 .

Complete assurance that free cyanide concentra-

tions will never even potentially

reach possibly

chronic-damage levels in general wastwaters

cannot be achieved without significant, unreasonable

economic disruption, (realizing that chronic effects,

and the levels at which they occur, are uncertain)

.

8 .

An effluent requirement of 0 .1 mg/l total cyanide

will require removal of most toxic cyanide species

and will require that the strongly complexed

cyanides discharged be at levels low enough to

prevent damage to downstream aquatic life .

9 .

The MSDGC Calumet plant is allowed a higher

effluent limitation than other sources since

it receives cyanide effluents from steel mills

and other industrial sources and generally has

a higher cyanide influent loading than any of

the other treatment plants in the state .

83-82

---

-21-

10 .

The use of averaging

for effluent

standard compli-

ance testing will assure the necessary environmental

protection, while allowing for good engineering

practice and preventing uneconomical overbuilding

of treatment facilities .

11 . The standards adopted will not require unnecessary

pretreatment by sewer dischargers . By eliminating

certain of the permit requirements of Rule 703

(without limiting the authority of the receiving

sewage system operator), we will eliminate un-

necessary paperwork . The original purpose of

the Sewer Discharge Criteria will still be met,

while

consideration

own influent

allowing

problemsany

localities

federal

. (We

to

pretreatment

have

analyze

not taken

and

requirementssolve

intotheir

;

obviously, our decision in this regard will have no

effect on federal requirements .)

12 .

to

The

protect

sewer discharge

sewer workers

standards

from exposure

should be

to

sufficienttoxic

concentrations of cyanide gas

.

of law

This

of the

Opinion

Board

constitutes

in this matterthe

findings

.

of fact and conclusions

Control

on theI,

7

Christan

Board,

hereby

day

L .

ofMoffett,

certify

Clerk

the above

of the

Opinion

Illinois

was

Pollutionadopted

, 1978 by a vote of

4-6 .

Christan L . Mof

t, Clerk

Illinois Pollut

Control Board

33-83