BEFORI~THE ILLINOIS POLLUTION CONTROL BOARD

iN THE

MATTER OF:

WATER QUALITY AMENDMENTS TO

35

Iii. Adna. Code 302.208(e)-(g),

302.504(a),

3 02.575(d), 303.444, 309.141(h); and

PROPOSED 35 111. Adm. Code 301.267,

301.3 13, 301.413, 304.120, and 309.157

NOTICE OF FILING

~~CEIVEj~

CLERK’S O~’~

SEl-’ 062002

S~TEOF ILLINOIS

Pollution Control Board

Dorothy Gurm, Clerk

Pollution Control Board

100 West Randolph Street

Suite 11-500

Chicago, Illinois 60601

Mathew Dunn

illinois Attorney General’s Office

Environmental Control Division

James R. Thompson Center

100 West Randolph Street

Chicago, Illinois 60601

Attached Service List

Marie E. Tipsord

Illinois Pollution Control Board

James R. Thompson Center

100 West Randolph Street, Suite 11-500

Chicago, Illinois 60601

Legal Service

illinois Department ofNatural Resources

524 South Second Street

Springfield, Illinois 62701-1787

PLEASE TAKE NOTICEthat I have today filedwith the Office ofthe Clerk ofthe Pollution Control

Board the

COMMENTS OF ILLINOIS

ENVIRONMENTAL

PROTECTION AGENCY,

copiesof

which are herewith served upon you.

ILLINOIS ENVIRONMENTAL PROTECTION AGENCY

By:___________________________

SanjayK Sofat

Assistant Counsel

Division ofLegal Counsel

Dated: September 6, 2002

Illinois Environmental Protection Agency

1021 North Grand Avenue East

Springfield, Illinois 62794-9276

(217) 782-5544

)

)

)

)

)

R02-l1

(Rulemaking

-

Water)

~Z7

THIS FILING

PRP~TED

ON RECYCLED PAPER

---

BEFORE

THE

ILLINOIS POLLUTION CONTROL BOARD

RECEIVEDCLERK’S

OFETCE

SEP

0

62002

IN THE MATTER OF:

Pollution

STATE OF

Control

ILLINOIS

Board

WATER QUALITY AMENDMENTS TO

)

35 ill. Adm. Code 302.208(e)-(g), 302.504(a),

)

R02-l 1

2-

7

302.575(d),

3 03.444, 309.141(h); and

)

(Rulemaking

-

Water)

17 ~

PROPOSED 35111. Adm. Code 301.267,

)

301.313, 301.413, 304.120, and 309.157

)

AGENCY’S COMEMNTS

THE ILLiNOIS ENVIRONMENTAL PROTECTION AGENCY (the “Agency” or “Illinois

EPA”) respectfully submits these comments on the hearing held on July

25,

2002, in the Illinois

Pollution Control Board’s (the “Board”) R02-1 1 rulemaking proceeding. The Agency filesthe

comments to provide additional information on the Agency’s proposed cyanide standard and address

the issues raised by Albert Ettinger, attorney forthe Environmental Law & Policy Center, the Sierra

Club, and Prairie Rivers Network atthis hearing. The Agency is thankful to the Board for holding

the third hearing on this important rulemakingproceeding and providing this opportunity to file

comments.

Inrulemaking proceedings, the Agency has always ensured that the Board has access to the

necessary and available information for its consideration. This rulemaking proposal was no

different. To ensure that the Agency has the most current information, it contacted several

organizations including industry groups, agencies, and environmental groups fortheir comments on

the Agency’s draft proposal. (See Public Participation section ofthe Original Petition) Based on

the comments received, the Agency made essential changes to its draft before filing it with the

Board. The first time the Agency heard about the USEPA’s new laboratory method for cyanide was

2

---

at the July 25 hearing. At that hearing, Albert Ettingerintroduced the document, Method OIA-1677

Available Cyanideby Flow Injection, LigandExchange, and Amperometry, EPA-821-R-0l3,

August 1999, into the hearing record as Exhibit 18. The Agency wishes that in the future

rulemakings, the stakeholders bring the new information to the Agency’s attention at the earliest

possible time rather than wait until the First Notice period. However, since the hearing, the Agency

has been gathering facts regarding this new laboratory method.

NEW LABORATORY METHOD FOR CYANIDE

-

The new method was promoted several years ago by USEPA as the solution to the difficulties of

cyanide laboratory analysis and correlationto the USEPA national criteriafor cyanide. Within

USEPA RegionV (the six Westernmost Great Lakes states), Michigan is the only stateto adopt this

method. For some reason, Region V water quality coordinator, who usuallypasses such information

down to the states, was not aware ofthis new method. The Michigan representatives indicated that

the newmethod, in theory, was attractive for use in cyanide standards, but due to budgetary

concerns, the state had not proceeded to use the method. Further, the representatives did not know

of any discharger using the new method in Michigan, nor were theyaware ofany consulting

laboratories capable ofperformingthe analysis.

To find out about the capabilities ofthe new method, the Agency contactedtwo sources that

were key players in the development, testing, and USEPA adopting process. Mr. Jim Boiani of

Dyncorp participated in the testing process as a USEPA contractor. Ten laboratories were given the

instruments and reagents necessary for the newmethod and were instructed in its use. The

laboratories also participated in an evaluation process. USEPA found that the new method did

indeed have fewer problems with interferences and had a better minimum detection limit than

previously approved methods. As the method passed USEPA criteria for reliability, it was adopted

as an approved method.

3

---

The Agency also contacted Mr. Jason Gray of01 Analytical Co., the company that actually

developed the method. According to Mr. Gray, the new method measures the same forms of

cyanide as does the weak acid dissociable method. Essentially, both methods, the new method and

weak acid dissociable method, exclude the iron-cyanide complexes that are not toxic to aquatic life,

but commonly are found in cyanide solutions. The tightly bound iron-cyanide complexes do not

revert to free cyanide, the toxic form, unless strong-acidic conditions are present or, as explained

later, they are exposed to ultraviolet light. All other cyanide present in the solution, i.e., the cyanide

directly toxic to aquatic life or what maybe conceivably be converted to a toxic form, is measured

by both methods. Both methods measure the bound forms ofcyanide present in other metal

complexes, e.g., copper, zinc, silver, etc.

01

Analytical makes the proprietyreagents forthe test and sells the instruments neededto

run the test. Mr. Gray indicatedthat these instruments are also available from other manufacturers.

According to Mr. Jim Boiani ofDyncorp, the cost ofthe instrumentation is about $34,500 before

discounts. The reagent cost for approximately 100 samples is $320. Mr. Boiani believes that that

private laboratories would charge about $50 per sample analyzed. The approximate cost for

analyzing a sample with the weak acid dissociable method is about

$35.

The City ofNew York and Cincinnati Metro Water District and a number ofindustrial

laboratories are currently using the new method. The newmethod is said to be much easier to

perform than the old weak acid dissociable or cyanide amenable to chlorinationmethods. The

minimum detection limit of2 ~.tg/Lhas been achieved with this new method. Mr. Pfeifer, Region V

standards coordinator, has indicatedthat USEPA would have no objection to states adopting the new

method since it came from USEPA’s research arm.

One practical problem that exists with the newmethod, as well as with all newmethods, is

that most commercial laboratories in Illinois are not equipped to run the test. The Agency surveyed

4

---

three major commercial laboratories (Suburban Labs, EMT, Inc., and PDC Laboratories, Inc.) in

Illinois and foundthat none ofthese laboratories conduct the cyanide test using this new method. In

fact, these laboratories do not even have the necessary equipment to do so. All echoedthe sentiment

that unless their clients ask for this method or show a tremendous interest in the newmethpd, the

laboratories would not be making such a considerable investment.

It is clear from the above discussion that sufficient benefits exist from the use ofthe new

method. Therefore, the Agency supports the use ofthis newmethod. The Agency recommends that

both the weak acid dissociable method and the new cyanide method should be referenced as

appropriate tests in the Board’s cyanide standard. As the new method provides less interference and

a lower detection limit, the dischargers, given the option ofthe new method, may beginto demand

that laboratories use this method instead ofthe weak acid dissociable method. As the demand grows

for the newmethod, the commercial laboratories mayconsider it worthwhile to invest in the

necessary equipments to runthe cyanide test.

ENVIRONMENTAL IMPACTS

OF

IRON-CYANIDE COMPLEXES

At the July 25 hearing, Albert Ettinger raised issues concerning the impact ofiron-cyanide

complexes on the aquatic system. Neitherthe weak acid dissociable method nor the new method

measure the iron-complexed forms ofcyanide. A publication by the US Fish& Wildlife Service

addresses the issues raised by Mr. Ettinger at the hearing. (Cyanide Hazards to Fish, Wildlife, and

Invertebrates: A Synoptic Review, Ronald Eisler, Biological Report 85 (1.23) December, 1991).

The author reports that cyanide in general does not persist very long in surface waters, at most a few

days. Volatilization and microbial decomposition are two ofthe main ways that waters are naturally

cleansed of cyanide. The publication refers to the ferricyanides and ferrocyanides as “sparingly

decomposable” and that these iron complexes “do not release free cyanide unless exposed to ultra

violet light.” Further, the author states, “~t~hemuch lower toxicities ofthe ferrocyanide and

5

---

ferricyanide complexes- which are ofhigh stability but subject to extensive and rapid photolysis,

yielding free cyanide on direct exposure to sunlight- and the nickelocyanide ion complexes are not

likely to be ofpractical importance.”

(~

Attachment A)

Clearly, the iron-cyanide complexes are more persistent in the environment than other forms

ofcyanide. Any cyanide that becomes free from the iron-cyanide complexes due to extensive

exposure to ultraviolet light would not persist very long in surface waters. As the author indicates,

the iron forms ofcyanide are not likely to be ofpractical importance because actual photolysis

(chemical decomposition due to exposure to sunlight) would occur at relatively slow rates. The

National Criteria Document for cyanide explains that “rlease ofcyanide ion by

photodecomposition might be important in relatively clear waters.” Apparently, the relative clarity,

depth, and exposure to sunlight (i.e., degree ofshading) all would be significant factors in

photolysis. Since most waters in illinois are not sufficientlyshallow, clear and unshaded, photolysis

is probably not ‘rapid’ in illinois waters. Therefore, there is no need to consider the impact ofthe

iron-cyanide complexes on the aquatic system. The Agency recommends the use ofweak acid

dissociable standard, the existing standard. This recommendation is further supported by the fact

that even the USEPA’s new cyanide method does not measure the iron form ofcyanide.

HUMAN HEALTH IMPACTS OF CYANIDE

The issues related to human health impacts ofcyanide were also raised at the July 25 hearing. The

USEPA MCL for total cyanide is 0.2 mgfL, several times the level ofthe proposed aquatic life

standards.

CONCLUSION

The Agency wishes to remind the Board that this rulemaking concerns the proposing ofnew

standards for cyanide. The Agency has explained in detail the process for updating the General Use

standards for cyanide, a process that has nothing to do with laboratory analytical methods. The

6

---

addition ofa better laboratory method does not change the appropriateness ofthe numeric values of

a standard that have been found to be protective ofaquatic life. While supplemental reasons for

changing the water quality standard for cyanide no longer exist, given the existence ofnew

laboratory method, the primaryreason is still pertinent. The warm water aquatic organisms found in

General Use waters are not as sensitive to cyanide as the existing standard implies; and therefore,

the cyanide standards should be updated to reflect “the latest scientific knowledge.”

Proposed Update:

Constituent

STORET

AS

CS

Number

(j.tg/L)

(~.tg/L)

Cyanide

00718

49

11

(Weak acid dissociable

or Available Method OJA-l677)

The Agency appreciates this opportunity to comment in this proceeding. As set forth in detail

above, the Agency urges the Board to adopt the proposed cyanide standard.

Respectfully Submitted

ILLINOIS ENVTRONMENTALPROTECTION AGENCY

By:______________________

Sanjay K Sofat

Assistant Counsel

Division ofLegal Counsel

DATED: September 6, 2002

Illinois Environmental Protection Agency

1021 North Grand Avenue East

P.O.Box 19276

Springfield, Illinois 62794-9276

(217) 782-5544

7

---

Exhibit A

---

---

Biological Report 85(1 23)

Contaminant Hazard Reviews

Invertebrates: A Synoptic Review

574 526321j

23) ~ Department of the Interior

I

• ..

.-

. -

LIBRARY

EnV1roflm~talprotec~ttøfl

~

-.

.

State

of

UILno(9

~pr1ngftetd1WlnO~ ~:

---

6

BIoLoGIcAL REPORT 85(1.23)

and is also one ofthe most toxic cyanide species, it acrylonitrile, propionitrile, and succinonitrile, are

is noteworthy that the toxicity of simple cyanides nitrile-containing materials of varying complexity

will not be affected measurably below pH 8.3. and lability, and can liberate free and toxicologi-

Acidification of dilute (milligrams per liter) cya- cally available amounts of cyanide. But the non-

nide solutions will not intiate any greater release nitrile portion ofthe cyanogenmoleculemay exert

of HCN, but acidification of concentrated (grams an independent or interactive toxicity, causing a

per liter) solutions promotes HON formation and complex response.

release.

Cyanates contain the OCN group. Inorganic

Complex cyanides are compounds in which cyanates that are formed industrially by the oxida-

the cyanide anion is incorporated into a complex or tionofcyanide salts hydrolyze inwaterto form am-

complexes; these compounds are different in monia and bicarbonate ion. Alkyl cyanates are

chemical and toxicologic properties from simple insoluble in water and form cyanurates. Alkyl

cyanides. In solution, the stability of the cyanide isocyanates contain the OCN radical, are formed

complex varies with the typeofcation andthe com- from cyanates, and, like cyanates, are readily hy-

plex that it forms. Some ofthese are dissociable in drolyzed. Thiocyanates (SCN group) are formed

weak acids to give free cyanide and a cation, while from cyanides and sulfur-containing materials

other complexes requiremuch stronger acidic con- and are relatively stable.

ditions for dissociation. The least-stable complex

Total cyanidesrefers to all cyanide-containing

metallocyanides include Zn(CN)42, Cd(CN)i~,and compounds, including simple and complex cya-

Cd(CN)42-; moderately stable complexes include nides, cyanoglycosides, and free cyanide. Total

Cu(CN)2, Cu(CN)32,Ni(CN)42, andAg(CN)2; and cyanides is a chemical measurement of free cya-

the most stable complexes include Fe(CN)6~and nide p’~’~

-

- ~

~

Co(CN)&1. The toxicity ofcomplex cyanidesis usu- or dige

ally related to their ability to release cyanide ions

~

~-~------—-

in solution, which then enter into an equilibrium 1

~c~ircumstances, the concentra-

with HON; relatively small fluctuations in pH sig- tion of total cyanide will exceed that ofHON. In

nificantly,affect their biocidal properties.

some waters, however, the total cyanide concen-

Cyanogen (CN)2~is the simplest compound tration may consist almost entirely offree cyanide,

containing the cyanide group. Cyanogen is an ex- or it may contain cyanides that readily photo-

tremely toxic, flammable gas that reacts slowly decompose ordissociate to yield HON. The relation

with water to form HCN, cyanic acid, and other between total cyanide and free cyanide in natural

compounds; it is rapidly degraded in the environ- waters varies with receiving-water conditions,

ment. Cyanogen and its halide derivations are type ofcyanide compounds present, degree ofexpo-

comparable in toxicity to hydrogen cyanide.

sure to daylight, and presence of other chemical

Nitriles are defined as organic compounds compounds.

(RCN) containing the cyanide group. Cyanide

Hydrogen cyanidehas frequently been associ-

bound to carbon as nitriles (other than as cyano- ated with the odor of bitter almonds (Ballantyne

genic glycosides) are comparatively innocuous in 1983; Gee 1987). The threshold odor for olfactory

the environment, and are low in chemical reac- detection ofatmospheric HCN is 1 mWL, but the

tivity and are biodegradable. For simple mono- odor may not be detected for various reasons, in-

nitriles there is a clear progression,with more cya- cluding the presence of other odors and the fact

nide being released as chain length increases. ,A that only 20 to 40 ofthose tested could detect a

similar pattern exists in diñitriles, but corres- cyanide odor.

ponding compounds require a longer carbon chain

Analytical methods for determining free and

than mononitriles before free cyanide is produced. bound cyanide and cyanogenic compounds in bio-

Based on studies with chicken liver homogenates logical materials are under revision. Current

(Davis 1981), mononitriles were more toxic than methods include chromatography; enzymic post-

dinitriles, and within each group the order oftoxi- column cleavage; electrochemical detection; and

city was OH3 O2H5 C3H7 04119 C5H11 C7H15. ultraviolet, infrared, proton, and carbon-13 nu-

Cyanohydrins R2O(OH)CNJ

and cyanogenic clear magnetic resonance spectroscopies (Brimer

glycosides R1R2C(0R3)CN are special classes of 1988). Proposed newer analytical methodologies

nitriles, in that under appropriate conditions they include chemiluminescence (Wu et al. 1989);

will decompose to HON and cyanide ions. Cyano- deproteinization techniques (Krynitsky et al.

gens (not to be confused with cyanogen), such as 1986); thin film dissociation coupled with prefer-

---

18

BIoLoGIcAL REPORT 85(1.23)

low in winter owing to dilution by high runoff, but

peaked in summer because of cyanide production

by plants (Leduc 1984). Cyanides do not seem to

persist in aquatic environments. In small, cold

oligotrophic lakes treated with 1 mg NaCN/L,

acute toxicity was negligible within 40 days. In

warm shallow ponds, toxicity disappeared within 4

days after application of 1 mg NaCNIL. In rivers

and streams, toxicity rapidly disappeared on dilu-

tion (Leduc 1984). Cyanide was not detectable in

water and sediments ofYellowknife Bay, Canada,

between 1974 and 1976, although the bay receives

liquid effluents containing cyanides from an oper-

ating gold mine. Nondetection was attributed to

rapid oxidation (Moore 1981). Severalfactors con-

tribute to the rapid disappearance ofcyanide from

water. Bacteria and protozoans may degrade cya-

nide by converting it to carbon dioxide and ammo-

nia. Chlorination of water supplies can result in

conversion to cyanate (EPA 1980). An alkaline pH

favors oxidation by chlorine, and an aôidic pH fa-

vors volatifization of HON into the atmosphere

(EPA 1980).

Persistence in Water, Soil,

andAir

In water, cyanides occur as free hydrocyanic

acid, simple cyanides, easily degradable complex

cyanides such as Zn(CN)2,~

-

. - -

v

~

ation is the dominant mechanism for re-

moval offree cyanide from concentrated solutions

and is most effective under conditions ofhigh tem-

peratures, high dissolved oxygen levels, and at in-

creased concentrations, of atmospheric carbon

dioxide (Leduc et at 1982; Simovic and Snodgrass

1985). Loss of simple cyanides from the water col-

umn is primarily4 oigla~dimentation,micro-

bial degradation, and volatilization (Leduc et al.

1982; Marrs and Ballantyne 1987)1

-~

1982; Simovic and Snodgrass 1985; Marrs and Bal-

lantyne 1987).

Alkaline chlorination ofwastewaters is one of

the most widely used methods of treating cyanide

wastes. In this process, cyanogen chloride, (CNC1)

is formed, which at alkaline pH is hydrolyzed to

the cyanateion(CNO). Iffree chlorine is present,

CNO can be further oxidized (Way 1981; Leduc et

al. 1982; Simovic and Snodgrass 1985; Marrs and

Ballantyne 1987). Other methods used in cyanide

waste management include lagooning for natural

degradation, evaporation, exposure to ultraviolet

radiation, aldehyde treatment, ozonization, acidi-

fication—volatilization—reneutralization, ion ex-

change, activated carbon absorption, electrolytic

decomposition, catalytic oxidation, and biological

treatment with cyanide-metabolizing bacteria

(Towill et al. 1978; EPA 1980; Way 1981; Marrs

and Ballantyne 1987). In the case of Canadian

gold-mining operations, the primary treatment for

cyanide removal is to retain gold millwastewaters

in impoundments for several days to months; re-

moval occurs through volatilization, photo-

degradation, chemical oxidation, and, to a lesser

extent, microbial oxidation. Microbial oxidation of

cyanide is not significant in ‘mine tailing ponds,

whichtypically have pH 10, a low number of mi-

croorganisms, low nutrient levels, large quiescent

zones, and cyanide concentrations 10 mgfL

(Simovic and Snodgrass 1985).

Cyanide seldom remains biologically avail-

ablein soilsbecause it is either complexed by trace

metals,metabolized byvariousmicroorganisms, or

lost through volatifization (Towill et al. 197.8;

Marrs and Ballantyne 1987). Cyanide ions are not

strongly adsorbed or retained on soils, and leach-

ing into the surrounding ground water will prob-

ably occur. Under aerobic conditions, cyanide salts

in the soil are microbially degraded to nitrites or

form complexes with trace metals. Under anaero-

bic conditions, cyanidesdenitrif~rto gaseousnitro-

gen compounds that enter the atmosphere.

Volatile cyanides occur only ‘occasionally in

the atmosphere, due largely to emissions from

plating plants, fumigation, and other special op-

erations (Towill et al. 1978). Under normal concli-

tions cyanide has relatively low persistence in air,

usually between 30 days and 1 year (Way 1981), al-

,‘

though some atmospheric HCN maypersist forup

to 11 years (Marrs and Ballantyne 1987). Data are

lacking on the distribution and transformation of

cyanide in the atmosphere (Towill et al. 1978) and

should be acquired.

-

~t maylead

to

-J

~ iormation in wastes containing iron—

cyanide complexes (Towill et al. 1978; Leduc et al.

---

20

BIoLOGICAL REPORT 85(1.23)

resistant to 65 mg KCNIL at low temperatures

(13°C) than were seedlingsfrom cold-susceptible

cultivars (25°C), as judged by respiratory activity

of mitochondria (Van De Venter 1985). Results

suggest that cyanide-resistant respiration may

play arole in coldresistance in maize seedlings, al-

though more evidence is needed to demonstrate

that cold-resistant plants actually use their

greater potential foralternative respiration at low

temperatures (Van De Venter 1985).

The cyanogenic system comprising cyano-

genic glycosides, cyanohydrins, betaglucosidases,

and nitrile lyases is widespread in plants, but also

occurs in several species of arthropods,. including

the tiger beetle

(Megacephala virginica),

leaf bee-

tie

(Paropsis atomaria),

zygaenid moths, and cer-

tain butterflies (Nahrstedt 1988). In

Zygaena

trifolii,

cyanide compounds seem to function as

protection against predators (Nahrstedt 1988). De-

fensive secretions of cyanide have also been re-

ported in polydesmid millipedes, and these

organisms seem to be more tolerant than other

species whenplacedinkillingjars containingHON

(Towiul et al. 1978). In amillipede

(Apheloria

sp.),

cyanide is generated in atwo-compartment organ

by hydrolysis of mandelonitriie; cyanide genera-

tion occursoutside the glandwhen the components

ofthe two compartments are mixed during ejection

(Towill et al. 1978).

-

Highly toxic substances, such as cyanides, are

sometimes feedingcues and stimulants for special-

ized insects. For example, instar larvae of the

southern armyworm

(Spodoptera eridania)$

strongly prefer cyanogenic foods, such as foliage of

thelima bean, a plant with comparativelyelevated

cyanide content—up to 31 mg/kg in some varie-

ties—in the form of linamurin (Brattsten et al.

1983). Feeding was stimulated in southern ar-

myworms at dietary levels up to 508 mg KCN/kg

(208 mg HON/kg) for first to fourth ‘instar larval’

stages, and between 1,000 and 10,000 mg KCN/kg

diet for fifth and sixth instar larvae (Brattsten‘et

‘al. 1983). Sixth instar larvae preexposed to diets

containing 5,000 mg KCN/kg showed no adverse

affects at dietary levels of 10,000mgKCNIkg; how-

ever, previously unexposed larvae showed revers-

ible signs of poisoning at 10,000 mg/kg diet,

including complete inhibition of oviposition and

83 reductionin adult emergence (Brattsten et al.

1983). Experimental studies with southern ar-

myworm larvae and tbiócyanate—one of the in

vivo cyanide metabolites—showed that 5,000 mg

thiocyanate per kilogram diet reducedpupationby

77,

completely inhibited oviposition, and re-

duced adult emergence by 80 (Brattsten et al.

1983), strongly suggesting that thiocyanate poi-

soning is the primary effect ofhigh dietary cyanide

levelsin southern armyworms.

Resistant species, such as southern ar-

myworins, require injected doses up to 800 mg

KCN/kg BW (332 mg HON/kg BW) or diets of

3,600 mg KCN&g for 50 mortality (Brattsten et

ai. 1983), but data are scarce for other terrestrial

invertebrates. Exposure to 8 mg HCN/L air inhib-

its respiration in the granary weevil

(Sitophilus

granarius)

within 15 mm and kills 50 in 4 h;

some ‘weevils recover after cessation of 4-h expo-

sure (Towill et al. 1978).

Aquatic Organisms

Numerous accidental spills of sodium cyanide

or potassium cyanide into rivers and streams have

resulted in massive kills of fishes, amphibians,

aquatic insects, and aquatic vegetation; sources of

poisonings were storage reservoirs ofconcentrated

solutions, overturned rail tank cars, or discharge

of substances generating free HON in the water

from hydrolysis or decomposition (Leduc 1984).

Data on the recovery of poisoned ecosystems are

scarce. In one case, a large amount ofcyanide-con-

taining slag entered a streamfrom the reservoir of

a Japanese gold mine as a result ofan earthquake

(Yasuno et al. 1981). The, slag covered the

streambed for about 10 km from the point ofnip-

ture, killing all stream biot~d

~

covering the above-water stones, but there was lit-

tle underwater growth.After 6—7 months, popula-

tions of fish,, algae, and invertebrates had

recovered, although species composition of algae

was altered (Yasuno et al. 1981).

Fish were the most sensitive aquatic organ-

isms tested under controlled conditions. Signifi-

cant adverse nonlethal effects, including reduced

swimming performance and inhibited reproduc-

tion, were observed in the range of 5.0—7.2 pg free

cyanide per liter; deaths were recorded for most

species between 20 and 76 pgfL (Table 3). Among

invertebrates, adverse nonlethal effects were

documentedbetween 18 and 43 ~ig/L,and lethal ef-

fects between 30 and 100 ~ig/L—although some

deaths were recordedin the range 3—7 pg/L for the

amphipod

Gammarus pulex

(Table 3). Algae and

macrophytes were comparativelytolerant;adverse

effects were reported at 160 pg free cyanide per

liter (Table 3).

---

CYANIDE

27

C

C)

U

C)

C.

C

Ui

0

z

.~

0

U.

Ui

0.

w

I-

-J

Ui

100

FREE CYANIDE, in ug/L

hepatic damage. Exposure of fish for 9 days to 10

pg HCN/L was sufficient to induce extensive

necrosis inthe liver, although gill tissue showedno

damage. Intensification ‘of liver histcipathology

was evident at dosages of 20 and 30 ~igHCN/L and

exposure periods up to 18 days (Leduc 1984). Cya-

nidehas a strong, immediate, andlong-lasting in-

hibitory effect on the swimming abifity of fish

(Leduc 1984). Free cyanide concentrations as low

as 10 ~ig/Lcan rapidly and irreversibly impair the

swimming ability of salmonids in well-aerated

water (Doudoroff 1976). Osmoregulatory distur-

bances recorded.at 10 pg HCNIL may affect migra-

tory patterns, feeding, and predator avoidance

(Leduc et al. 1982; Leduc 1984). In general, fish ex-

perience a significant reduction in relative per-

formance (based on osmoregulation, growth,

swimming, and spermatogenesis) at ‘10 pg HCN/L,

and although fish can survive indefinitely at 30 jig

HCN/L in the laboratory, the different physiologi-

cal requirements necessary to survive in nature

could not be met (Leduc 1978, 1981; Leduc et al.

1982; Fig re~.Increase’dpredatIoii~bygreen sun-

fish

(Lepomis cyanellus)

on fathead minnows

(Pimephalespromelas)

was noted at sublethal con-

centrations of HCN, but it was uncertain if fat-

heads became easier prey or if green sunfish had

greater appetites (Smith ,et al. 1979).

-

Sodium cyanide has stimulatory effects on

oxygen-sensitive receptors in lungfish, amphibi-

ans, reptiles, birds, and mammals (Smatresk

Figure. Summary of lethal and sub-

lethal effects of free cyanide on fresh-

water fish. Modifiedfrom Leduc etal.

(1982).

1986). Facultative and aquatic air breathers ap-

pear to rely on air breathing when external•

chemoreceptors are stimulated, whereas obligate

air-breathing fish are more responsive to internal

stimuli (Smatresk 1986). Gill ventilation fre-

quency oflongnose gar

(Lepisosteus osseus),

for ex-

ample, was little affected by external cyanide’

application, but responded strongly when cyanide

was administered internally by injection

(Smatresk 1986Y. Cyanide, like many other chemi-

cals, can stimulate growth of fish during exposure

‘to low sublethal levels. This phenomenon, referred

to as hormesis, is little understood and warrants

additional research (Leduc 1984).

The observed toxicity to aquatic life of simple

and complex cyanides was attributed ‘almost en-

tirely to molecular (undissociated) HCN derived

from ionization, dissociation, and photodecomposi-

tion ofcyanide-containing compounds. The toxic-

ity of the cyanide ion, CN, which is a minor

component of free cyanide (HON

+

CN) in waters

that are not exceptionally alkaline is of little fin-

portance (Doudoroff 1976;Towill et al. 1978;Smith

et al. 1979; EPA 1980). The acute toxicity ofstable

silver cyanide andcuprocyanide complexanions is

much less thanthat ofmolecular HCN, but is nev-

ertheless important; these ions can be the princi-

ts~eveninjj&lut~o~ions.

r~—~’~

~

~c~©

90

80

70

60

50

40

30

20

10

10

20

30

40

-

50

100

150

---

BIoLoGIcAL REPORT 85(1.23)

1910). ‘1

~

~~isms

of organic

cyanide compounds, suchaslactonitrile,is similar

to that of inorganic cyanides because theyusually

undergo rapid hydrolysis in water to free cyanide

(Towill et al. 197~’

-

~sanal.,

rde-

t~1In6..~.

~entration in cyanide-polluted

waters is considered to be the mostreliableindex of

toxicity (Doudoroff 1976; Smith et al. 1979; EPA

1980; Abel and Garner 1986).

Cyanide acts rapidlyin aquatic environments,

does not persist for extended periods, and is highly

species selective; organisms usually recover

quickly on removal to clean water. The critical

sites for cyanide toxicity in freshwater organisms

include the gills, egg capsules, and other sites

where gaseousexchange and osmoregulatory proc-

esses occur. On passing through a semipermeable

membrane, the HON molecules are usually dis-

tributed by way of the circulatory system to vari-

ous receptor sites where toxic action or

detoxification occurs (Leduc 1984). Once in the

general circulation, cyanide rapidiy inhibits the

electron transport chain ofvital organs. Signs of

distress include increased ventilation, gulping for

air at the surface, erratic swimming movements,

muscular incoorclination, convulsions, tremors,

sinking to the bottom, and death with widely ex-

tended gill ,covers (Leduc 1981, 1984). The acute

mode of action of HCN is limited to binding those

porphyrins that contain Fe~3,such as cytochrome

oxidase, hydroperoxidases, and methemoglobin.

At lethal levels, cyanide is primarilya respiratory

poison and one of the most rapidly effective toxi-

cants known (Leduc et al. 1982). The detoxi-

fication mechanism of- cyanide is mediated by

thiosuifate sulfur transferase, also known as

rhodanese. This enzyme is widely distributed in

animals, including fish liver, gills, and kidney.

Rhodanese plays a keyrole in sulfur metabolism,

and catalyzes the transfer of a sulfane—sulfur

group to a thiophilic group (Leduc 1984). Thio-

sulfate administered in the water with cyanide re-

duced the toxicityofcyanide to fish, presumably by

increasing the detoxification rate of cyanide to

thiocyanate (Towill et al. 1978).

Additive or more-than-additive toxicity offree

cyanide to aquatic fauna has beenreported in com-

bination with ammonia (Smith et al. 1979; Leduc

ret al. 1982; Alabaster etal. 1983; Leduc 1984) or ar-

senic (Leduc 1984). However, conflicting reports

on the toxicity of mixtures of HON with zinc or

chromium (Towiul et ai. 1978; Smith et al. 1979;

Leduc et al. 1982; Leduc 1984) require clarifica-

tion. Formation of the nickelocyanide complex

markedly reduces the toxicity of both cyanide and

nickel at high concentrations in alkaline pH. At

lower concentrations and acidic pH, solutions in-

crease in toxicity by more than 1,000 times, owing

to dissociation of the metallocyanide complex to

form hydrogen cyanide (Towill et al. 1978). Mix-

tures of cyanide and ammonia may interfere with

seaward migration of Atlantic salmon smolts un-

der conditions of low dissolved oxygen (Alabaster

etal. 1983). The 96-h toxicity ofmixtures ofsodium

cyanide and nickel sulfate to fathead minnows is

influenced bywateralkalinity and pH. Toxicity de-

creased with increasing alkalinity and pH from

0.42 mg CN/L at 5 mg CaCOaIL and pH 6.5; to 1.4

mg CN/L at 70 mg CaCO3/L and pH 7.5;to 730 mg

CN/L at 192 mg CaCO3/L and pH 8.0 (Doudoroff

1956).

-

Numerous biological and abiotic factors are

knownto modif~-the biocidal propertiesoffree cya-

nide,includingwaterpH, temperature, and oxygen

content; life stage, condition, and species assayed;

previousexposure to cyanide compounds; presence

ofother chemicals; and initial dose tested. There is

general agreement that cyanide is more ‘toxic to

freshwater fish under conditions of low dissolved

oxygen (Doudoroff 1976; Towill et al. 1978; Smith

et ai. 1979; EPA 1980; Leduc 1984); that pH levels

within the range 6.8—8.3 had little effect on cya-

nide toxicity but enhanced toxicity at acidic pH

(Smith et al. 1979; EPA 1980; Leduc et al. 1982;

Leduc 1984); that juveniles and adults were the

most sensitive life stages tested and embryos and

sac frythe most resistant (Smith et al. 1978, 1979;

EPA 1980; Leduc 1984); and that substantial in-

terspecies variability exists in sensitivity to free

cyanide (Smith et al. 1979; EPA 1980). Initial dose

and water temperature both modif~rthe biocidal

properties ofHCN to freshwater teleosts. At slowly

lethal concentrations (i.e., 10 j.tgHCN/L), cyanide

was more toxic at lower temperatures; at high, rap-

idly lethal HCN concentrations, cyanide was more

toxic at elevated temperatures (Kovacs and Leduc

1982a, 1982b; Leduc et al. 1982; Leduc 1984). By

contrast, aquatic invertebrates were most sensi-

tive to HCN at elevated water temperatures, re-

gardless of dose (Smith et al. 1979). Season and

exercise modif~rthe lethality of HCN to juvenile

---

)

STATE OF ILLINOIS

)

)

SS

COUNTY

OF SANGAMON

)

)

PROOF OF SERVICE

I, the undersigned, on oath statethat I have served the attached COMMENTS

OF

TilE

ILLINIOS ENVIRONMENTAL

PROTECTION AGENCY

upon the person to whom it is

directed, by placing a copy in an envelope addressed to:

Dorothy Gunn, Clerk

Pollution Control Board

100 West Randolph Street

Suite 11-500

Chicago, illinois 60601

(OVERNIGHT MAIL)

Mathew Dunn

Illinois Attorney General’s Office

Environmental Control Division

James R. Thompson Center

100 West Randolph Street

Chicago, Illinois 60601

(FIRST CLASS MAIL)

Attached Service List

(FIRST

CLASS MAIL)

Marie E. Tipsord

illinois Pollution Control Board

James R. Thompson Center

100 West-Randolph Street, Suite 11-500

Chicago, Illinois 60601

(OVERNIGHT MAIL)

Legal Service

Illinois Department ofNatural Resources

524 South Second Street

Springfield, illinois 6270 1-1787

(FIRST CLASS MAIL)

and mailing it from Springfield, Illinois on September 6, 2002, with sufficient postage affixed as

indicated above.

OFFICIAL SEAL

~3REND~BOEHNER

NC1AI~PUBLIC.

STATE OF ILLINOIS ..

+r,4y

COMMISSION EXPIRES ll-14.20051•

SUBSCRIBED AND SWORN TO

BEFORE ME

this day ofSeptember 6, 2002.

3~ (B~Q~\QX’

Noi’ary Public

TillS FILING PRINTED ONRECYCLED PAPER

8

---

R02-l1

Rulemaking

Notification List

September 6, 2002

Mike Callahan

Bloomington Normal Water Reclamation District

Post Office Box 3307

Bloomington, illinois 61702-3307

Larry Cox

Downefs Grove SanitaryDistrict

2710 Curtiss Street

Downer’s Grove, Illinois 60515

Dennis Daffleld

Department of Public Works City of Joliet

921 East Washington Street

Joliet, illinois 60433

Matthew Dunn Chief,

Environmental Bureau

Qffice ofthe Attorney General

188 West Randolph Street, 20th Floor

Chicago, illinois 60601-3218

Albert Ettinger

Environmental Law andPolicy Center

35 East Wacker Drive, Suite 1300

Chicago, illinois 60601-2110

Lisa Frede

ChemicalIndustry Council

9801 West Higgins Road, Suite 515

Rosemont, Illinois 60018

James T. Harrington

Ross & Hardies

150 North Michigan, Suite 2500

Chicago, illinois 60601

Roy Harsch

Gardner, Carton andDouglas

321 North Clark Street, Suite 2400

Chicago, illinois 60610-4795

Ron Hill

MetropolitanWater Reclamation District of Chicago

600 iWest Pershing Road

Cicero, illinois 60804-4112

Katherine Hodge

Hodge, Dwyer and Zeman

3150 Roland Avenue, Post Office Box 5776

Springfield, illinois 62705-5776

Robert Lawley

Chief Legal Counsel

illinois Department of Natural Resources

524 South Second Street

Springfield, illinois 62701

RobertMessina

illinois Enviommental RegulatoryGroup

215

East Adams Street

Springfield, illinois 62701

Tom Muth

Fox Metro Walter Reclamation District

682 State Route 31

Oswego, illinois 60543

Irwin Polls

Metropolitan Water Reclamation District of Chicago

600 lWest Pershing Road

Cicero, illinois 60804-4112

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