ILLINOIS POLLUTION CONTROL BOARD

September

29, 1975

IN THE MATTER OF

PROPOSED AMENDMENTS TO

)

R75-3

CHAPTER

2:

AIR POLLUTION

REGULATIONS

)

OPINION OF THE BOARD

(by Mr. Dumelle):

This matter concerns proposed amendments to the definitions

of photochemically reactive material and volatile organic material

contained in Rule 201: Definitions of Chapter

2:

Air Pollution

Regulations of the Board’s Rules and Regulations.

The amendments were proposed by Chairman Jacob

D. Dumelle

of the Pollution Control Board and, pursuant to Rule

204 of the Board’s

Procedural Rules, were set for hearing.

The proposal, with an

accompanying statement of need, was published on March 10,

1975 in

Environmental Register *99

(Exhibit 1).

Public hearings on the proposed amendments,

designated R75-3,

were held on April

11,

1975 in Belleville and on April 18 and

29,

1975 at the Chicago Circle Campus of the University of Illinois.

Much

interest in the proposal was evidenced by the 350 people who

attended the April

18 hearing alone.

The record from these

hearings consists of 18 exhibits and over 500 pages of testimony

by witnesses from industry, city,

state, and federal government,

academia, and medicine.

Public comments, numbering 142, were

also received by the Board and are part of the official record.

The proposed amendments were intended to reduce the emissions

of hydrocarbons to the atmosphere and thereby reduce the atmospheric

levels of ozone

(Exhibit 1).

The emission reduction would occur as

a

result of more emissions being defined as being photochernically

reactive and/or volatile organic, and thus subjected to the emission

limitations

of Rule 205 of the Air Pollution Regulations.

In

particular,

the present rule defines photochemically reactive

material in terms of concentrations of certain organics, with the

result that many emissions contain compounds thought or known

to participate in the formation of ozone and other oxidants, but

are not, however, defined as being photocheinically reactive

and thus not regulated.

The proposed definition of photochemically

reactive material would include almost all organic emissions,

The Board expresses its appreciation to Mr. Edward H.

Hohman,

Assistant to the Board,

for his work in this proceeding.

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except for those specifically exempted, and would therefore

regulate the compounds that form oxidants.

Similarly,

the proposed

change in the definition of volatile organic materials,

from

2.5 pounds per square inch absolute

(psia)

to 1.5 psia, would

subject more emissions of organics

to the limitations of Rule

205,

and would therefore also tend to decrease the formation

of oxidants according to Chairman Dumelle’s proposal.

Our basic concern was with the excessive oxidant levels in

Illinois.

The air quality standard for photochemical oxidants

measured as ozone,

state and federal,

is

160 micrograms per

cubic meter

(or 0.08 ppm) maximum 1-hour concentration not to be

exceeded more than once per year.

During July and August of 1974,

several areas

in Illinois exceeded this standard.

According to the

report

“Oxidarits in the Urban Atmosphere”

(Exhibit

3), peak hour ozone

levels equalled or exceeded 0.1 ppm on 24 occasions in Chicago,

on

15 occasions in Joliet; and on

3 occasions in July in Cahokia,

and on

4 occasions in July in Springfield.

Since the air quality

standard of 0.08 ppm can be exceeded only once a year, violations

of the photochemical oxidant air quality standard occurred at each

of these locations

in Illinois.

Furthermore, according to Exhibit

3,

the levels of oxidants hadn’t changed significantly during the period

of 1964 to 1972 based on Continuous Air Monitoring Program

(CAMP)

data,

and the oxidant levels had exceeded the air quality standard.

The relation between ozone and oxidants has recently come under

scrutiny.

It had been felt that ozone was the major constituent

of photochemical oxidants; Exhibit

3 for example cites data that

shows 70

of total oxidants to be ozone.

Recent studies in California

and Texas

(part of Comment lii), however, show ozone levels

significantly higher than oxidant levels, based on simultaneous

measurements.

In any case,

the 1974 data does show ozone

levels exceeding the standard.

It therefore seems that there

is and has been an oxidant/ozone problem in Illinois.

The importance cf minimizing oxidants and ozone

is based

on their adverse effects on health and welfare.

Exhibit 16,

‘tAir Quality Criteria for Photochemical Oxidants”,

is the

federal criteria document that summarizes the effects on

human health,

vegetation,

and materials.

Based on this

document the air quality standard of 0.08 ppm was established.

Comment 100,

“Health Effects and Recommended Alert and

Warning Systems for Ozone’1, prepared by the Environmental

Health Resource Center, contains recent information regarding

the effects of ozone on the pulmonary system, nervous system,

and others.

Finally, Dr.

Gross of the University of Chicago

testified that while the irritating effects of pollen may be

worse than that of ozone,

there

is permanent damage to the

respiratory system with ozone but not with ragweed pollen

(R.

455—457)

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Our proposal. would, we believe, decrease the ozone levels

by decreasing

the emissions of certain precursor compounds that

undergo atmospheric reactions to form ozone.

Basically, photochemical

oxidants are formed by the reactions between nitrogen oxides and

certain organic compounds

in the present of sunlight.

The exact

details of all the atmospheric reactions are not known, but the

important features are the following

(Exhibit

3,

pp.

35 to 46):

a)

the photolysis of nitrogen dioxide

(NO2)

in the

presence of sunlight,

hv

N02

NO

+

0

b)

the formation of ozone

(03)

utilizing the free oxygen

liberated in the previous reaction,

0+02

-03

c)

the destruction of ozone by the nitric oxide

(NO)

emitted to the atmosphere,

NO

+

03

NO2

+

d)

reactions competing with

c)

between organics,

03,

0,

and nitrogen oxides to form photochemical oxidants including

1.

Ozone,

2.

Nitrogen dioxide and nitrogen containing products

such as peroxyacetyl nitrate

(PAN),

and nitric acid,

and

3.

Partially oxygenated organics such as acrolein.

The organics that participate in the above atmospheric reactions

are characterized as being photochemically reactive.

Smog chamber

studies, performed to identify the reactive organics, consist of

irradiating a mixture of organics and nitrogen oxides with artificial

sunlight for a certain period of time and measuring the oxidants

produced.

The record contains the smog chamber studies performed

by Batelle-Columbus Labs (Exhibit

8), National Air Pollution Control

Administration (Exhibit 13), Bureau of Mines

(Exhibit 13), Shell

Development Company

(Exhibit 13), Los Angeles Air Pollution Control

District

(Exhibit 13), and Stanford Research Institute

(Comment 89).

A summary of the data into reactivity classes has been performed

by the U.S. Environmental Protection Agency

(U.S.

EPA)

(See pages

13 to 22 of Exhibit

5 “Proceedings of the Solvent Reactivity Con-

ference”).

While there were inconsistencies in the data from test

to test,

the U.

S. EPA felt that

5 classes of reactivity were justified,

with Class

I containing compounds considered to be non—reactive

(See

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Table

5 of Exhibit

5).

These Class

I non-reactive compounds are

contained in the proposed definition of photochemically reactive

material as exemptions.

Since they do not form significant

quantities of oxidants,

they do not have to be controlled,

unless

they create problems because of their odor or toxicity.

There

is apparently littie atmospheric data showing the reactions that

form oxidants,

so it is necessary to rely on smog chamber studies,

which for the most part are based on 6-hour irradiation times.

The U.S.

EPA points out, however,

in Exhibit

5,

that during long

distance transport and extended irradiation times, even low reactivity

organics may form appreciable quantities of oxidants.

It may be

necessary,

therefore,

to control the emissions of all organics except

the non-reactive ones.

A recent document received by the Board, of which we hereby take

official notice,

is a draft document dated August 13, 1975 and published

by the U.S.

EPA entitled “Guidelines on Use of Reactivity Criteria

in Control of Organic Emissions for Reduction of Atmospheric Oxidants”.

It classifies organics into

3 photochemical reactivity classes

categorized as follows:

Class

I

(low reactivity)

—

Emissions need not be controlled,

unless exposed to temperatures exceeding 175°F.

Class II

(moderate reactivity)

—

Control

is necessary.

Oxidants

are formed gradually and will contribute to atmospheric levels both

at the point of release as well as at downwind locations, rural and

urban.

Class III

(high reactivity)

—

Control is necessary.

Oxidants

are formed rapidly in the vicinity of their release, and are major

contributers within urban source areas.

The Class

I compounds listed in this document contain the exemptions

listed in our proposal plus several more not previously classified.

The draft guideline states that the emission of any Class II or III

compound must be considered an interim measure, and that the long

range solution

to an oxidant problem must be either the reduction

of emissions or the substitution of Class

I compounds.

Our proposed arrendment to the definition of photochemically

reactive materials is consistent with these goals,

and were

it not for other considerations to be described below,

including

the incompleteness of the record, we would be inclined to adopt

the amendment as modified to include the following additional

exemptions:

partially halogenated paraffins

(see discussion by

Dow Chemical in

Comitient 89), acetic acid,

aromatic amines, and

hydroxyl amines.

As stated previously,

the precursors, nitrogen oxides and

reactive organics,

form oxidants in the atmosphere.

Thus to

reduce oxidant levels, one should presumably reduce the emissions

of reactive organics, nitrogen oxides, or both.

The testimony

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of Professor Quon was that reducing hydrocarbons alone would result

in lower concentrations of ozone than reducing both hydrocarbons and

nitrogen oxides simultaneously,

based on the present atmospheric

concentrations of these two pollutants at the Chicago CAMP station

(R.

45).

The degree of reduction in emissions required to achieve

compliance with the oxidant air quality standard is not known,

although it

is estimated to be large

-

in excess of 50

(R.

37).

Dr. Quon believed that the proposed amendment would reduce the

atmospheric levels of oxidants, including a “significant” reduction

in the peak levels

(R.

65-66).

However,

it is not known whether

the proposed amendment would result in attainment of the air

quality standard.

Dr. Quon was of the opinion that it wouldn’t

and that amendments to reduce the emissions allowed by our Rule

205

(of the Air Regulations) were also necessary

(R.

73—74).

Regarding the relationship between emission reduction and changes

in ambient levels of oxidants, much was made of a Texas

report

that purportedly showed no decline in the frequency of high ozone

levels even though hydrocarbon emissions were reduced by 80

in some

areas

CR.

239).

Our review shows this document (Comment

114) does

not contain sufficient data to confirm this statement,

in that

only the highest ozone values are given.

Testimony also concerned the high “natural” levels of ozone;

levels that on occasion exceed the standards.

Papers from New York

State, Indianapolis, and Texas, submitted by DuPont as part of

Exhibit

9,

show ozone levels

in rural areas and in air masses entering

urban areas exceeding 0.08 ppm on occasion.

Although one could argue

that this was due

to

rural emissions of the precursor compounds

reacting to form high levels of ozone,

this

is not necessarily

the primary mechanism.

The oft cited paper by Coffey and Stasiuk

(Environmental Science and Technology Vol.

9,

p.

59)

contained in

this record as part of Comment 41,

indicates a belief that no

significant ozone production occurs at their rural sites;

the

cause of high rural ozone levels say Coffey and Stasiuk,

in another

paper included as part of Exhibit

9,

is

long distance transport from

emission sources and “a net generation of ozone

in urban plumes at

some distances downwind of the source area”.

Other papers contained

in Exhibit

9 also show the regional characteristics

of ozone,

and

indicated transport into rural areas.

The truly “natural”

ozone,

that due to stratospheric leakage and naturally emitted organics,

is

in the range of 0.01 ppm to 0.07 ppm (Exhibit

2, enclosure to Comment

41).

This ozone,

upon entering urban areas,

is scavenged by nitrogen

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oxides and aerosols so that the net “natural” ozone input in urban

areas

is nearly zero; and an urban ozone problem is therefore

caused primarily by the net formation of ozone from emitted

precursors.

Thus while many argued at the hearings that the ozone

problem is due to

‘natural”

inputs, the problem seems to be one

of emissions of precursors from one geographic area contributing

to ozone problems in a distant area.

We do not know, numerically,

the impact the amendments would

have in reducing emissions of photochemically reactive materials.

The

problem seems to be with the emission inventory.

The Agency

suggested that an updated, comprehensive hydrocarbon emission

inventory is necessary

(R.

338), which would presumably include

information relating to reactive and non-reactive organics.

The

Agency attempted to estimate the reduction in Cook County

(Exhibit

6).

A discussion of this exhibit revealed the estimations and

approximations used, and the incompleteness of the inventory

(R.

311-337).

Nevertheless it is a useful indicator of the

emission reductions that could result from the adoption of the

proposal.

The estimated reduction is 6.5

of the total organic

emissions in Cook County, including automobiles, or 13

of the

non-automotive emissions

(R.

322—323).

This represents, according

to Exhibit

6,

a decrease in yearly emissions of organics of

26,340

tons.

Similar estimates were not prepared for other areas

of the state.

While we do not know whether a reduction by

6.5

of the organic emissions in Cook County will solve the

ozone problem, the U.S. EPA witness called the proposal “a

step in the right direction...that should be incorporated

into the overall oxidant strategy”

CR.

357).

His calculations

were that a 68

to

70

reduction would be required

(R.

367).

We turn now to a consideration of the proposed

amendments

themselves.

As pointed out in Chairman Dumelle’s proposal

(Exhibit 1), not all emissions of reactive organics are included

in the existing definition of photochemically reactive

material.

For example, an emission could contain 19.99

toluene,

a known reactive organic,

and not be defined as

being photocheinically reactive.

As pointed out by Professor

Quon,

it is the mass emission rate that is important rather

than the percentage

(concentration in the effluent) (R.

104).

The proposed amendment defines photochemically reactive

material in terms of participating in atmospheric reactions

to form oxidants.

However, the definition

is probably too

inclusive because nearly every organic might react with

“excited oxygen”

(atomic oxygen) (R.

101).

A revision of the

proposed definition would then be warranted.

The exemptions to

the definition were criticized as being unusable in industrial pro-

cesses for various reasons, including toxicity, gaseous phase,

and

odor.

The properties of the exempted compounds and classes ol

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compounds are discussed in several portions of the record

(R.

131—133,

153, Comment

9, Comment 22).

In only two cases,

that of Dow

Chemical’s recommendation regarding chlorinated paraffins and the

printing industry recommendation of isopropyl alcohol, were suggestions

made regarding either additions to the exemption list or changes

to

the proposed definition;

other witnesses supported the existing

definition of photochemically reactive material.

It was pointed

out by some that our existing regulation

is being used in Los

Angeles and is reducing ozone levels out there; but that may be

due to Los Angeles levels being much higher

(R.

85—88).

Finally,

although witnesses seemed to be under the impression that the

proposal to amend the definition of photochemically reactive

material would forbid the use of certain chemicals, we indicated

at the hearings that our concern was with the emissions complying

with the standard

(R.

108).

The proposed amendment to the definition of volatile organic

material is also intended to be more inclusive.

It is consistent

with the federal new source standard, and if nearly all organics

are photochemically reactive, will decrease vapor emissions from

storage and loading that could form oxidants

(R.

34—35).

The Agency

supplied a list of chemicals that would be defined as volatile

using the amendment (Exhibit 7).

Some of them,

for example methanol

and benzene,

have been exempted as being non—photochemically reactive,

so there may be some inconsistency between the amendments to the

two definitions.

The emissions from bulk storage and handling

facilities are estimated to represent 0.2

of the total organic

emissions in the Chicago area

CR.

492).

The economic impact of the proposed amendments could not

be determined due to the incompleteness of the record.

We were

not successful

in obtaining industry—wide statistics that would

allow us to make the determination.

The following discussion

is,

therefore,

a qualitative discussion of the impact of the

proposal.

The industries that would be affected by the proposed

amendment include the following:

paints and coatings manufacturing,

painting and coating, asphalt manufacturing, asphalt roofing,

printing, bulk storage,

tire manufacturing, dry cleaning and

degreasing.

For those not in compliance with Rule 205:

Organic

Material Emission Standards and Limitations if the amendments were

adopted,

two compliance techniques are available:

emission reduction,

and reformulation or process modification.

Examples of the

former include incineration and carbon adsorption; and examples

of the latter include water based paints and high solids coatings.

In order to reduce emissions of organics from stationary

sources,

one must collect the emissions from the source so that they

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can be treated.

Testimony was that in many cases there are

multiple emission sources at a facility, for example paint spray

booths or tire making machines,

so that the collection equipment

would consist of multiple hoods manifolded together;

a system

that may not be practical or feasible

CR.

409).

In addition,

the

testimony was that the volumes of exhaust air required to purge

the organic emissions from the equipment may be large, which

means that the concentrations of organics in the exhaust would be

low

(R.

135—136)

The two emission reduction techniques,

incineration and

carbon adsorption,

have been and are being used to control certain

emissions.

Incineration is not applicable in all cases due to the

unavailability of natural gas and the low concentration of organics

in the exhaust that is incinerated

(R.

136—137).

Carbon adsorption

has not been tried in all cases, although the solvent recovery

feature seems attractive.

In Chicago, there are two printing

companies that practice solvent recovery, the first company uses

a single solvent and is able to recover 85

of it for reuse, the

second company is able to recover usable solvents unless the

process is using a mixed solvent

(R.

395-396).

These companies

are saving money as

a result of the recovery systems

(R.

188).

As

pointed out by one witness, the vapor recovery and reuse aspect

of carbon adsorption is not applicable to mixtures of

solvents;

the same witness stated, however, that the solvents

recovered could be and have been used as supplementary fuel

(R.

270,

274).

Reformulation,

in this proceeding,

means modifying a process or

product so as to reduce the amounts of certain organic compounds

being used and emitted to the atmosphere; two possibilities being

water based products and high solids products.

Most of the testimony

concerning reformulation involved paints and coatings, although there

was testimony concerning degreasing agents.

The coatings and paints

used currently are formulated so that the volatile portion,

the

solvent,

is by the present definition not photochemically reactive.

Because of the various properties of the solvents currently used,

and the properties of the proposed exemptions,

it is impossible

to reformulate all the paints and coatings using only the exemptions

listed.

Thus if one wanted to comply with the regulations

as

amended by the proposal, and the compliance technique selected

was reformulation, water based or high solids coatings would

be used.

Water based coatings have been in use for several years,

for example Lucite house paint and emulsion type roofing

materials

(R.

226).

It has been estimated that by 1978 to 1980,

water based coatings will have replaced 30

of the solvent based

variety

(R.

170).

However,

the use of water based coatings in

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industrial situations is hampered by the drying rate, which depends

on temperature and humidity,

arid

the resulting necessity to air

condition the facility ~where

the

coatings are applied

(R.

246-247).

Water based roofing materials are expensive and are not suitable

below 50°F (Comment 23).

High solids coating would be desirable because much less

solvent would be used.

Exhibit 17 shows the reduction in solvents

usage by converting to high solids coatings.

The Ford Motor

witness described a program wherein Pintos were sold with

powdered coatings that had been applied electrostatically

(R.

294-295).

The coating showed good survivability, and

the main problem with the use of this coating technique seems

to be the manufacturing application.

Many witnesses suggested that our existing Rule 205(f) (2) (D)

be modified to increase the allowable organic content contained

in the exception from 20

to

30.

We should do this,

they

say,

to encourage the use of low solvent coatings

CR.

139).

Neither the decrease in development time nor the additional

numbers of coatings that could be reformulated was known

(R.

212—215).

However, one witness testified that while only

2 of 35 industrial

customers

in Illinois can use c~oatingshaving organic contents of

20

or less,

another

8 customers could use organic coatings having

organic contents of 30

or less

(R.

502-503).

We believe

Rule 205(f) (2) (D)

to be an important

alternative to the use of high

solvent coatings,

arid we will therefore extend the deadline for

the utilization of this coating method by two years in order to

allow addition time for technOlog~to develop.

We find the recoi~din this proceeding to be inadequate for

supporting the propos~d~definit’ionchanges.

The main deficiencies

are the impact of the amendment iiri reducing the emissions of reactive

organics, and~theeffect of reducing precursoremissions in reducing

atmospheric levels of oxidants.

~

will fherefore dismiss the

proceeding and request the ~IliinoisIn~titutefor Environmental

Quality and the Illinois Environmental Protection Agency to

undertake studies to cure the above deficiencies.

The record

in this proceeding will’be~avai1ableto the public for future

proposed amendments.

This Opinion constitutes~theBoard’s findings of fact and

conclusions of law.

I, Christan L. Moffett, Clerk of the Illinois Pollution Control

Board, hereby certify the above Opinion was adopted on the

~)9~

day

of September,

.1975 by a vote bf

4/-C)

trol Board

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