Part I: Regulations

MNL17-EB/Jun. 1995

Regulation of Volatile Organic

Compound Emissions from 1
Paints and Coatings
by J. John Brezinski I

PRIORTOTHE 1960S the coatings industry enjoyed a somewhat TABLE 1--Federal environmental laws administered by the U.S.
predictable regulatory and economic environment. The paint Environmental protection agency.
formulator developing a solvent-based coating selected sol- Law Abbreviation
vents on the basis of evaporation rate, solubility parameter, Clean Air Act, 1970 CAA
density, flammability, and, of course, cost. There was no ap- Amendments of 1977 CAAA-77
parent need to consider the relative photochemical reactivity Amendments of 1990 CAAA-90
of these materials, nor was there any appreciable incentive to Clean Water Act of 1972 CWA
Amendments of 1977
reduce the solvent content of commercially acceptable coat-
Safe Drinking Water Act, 1974 SDWA
ings. Toxic Substances Control Act, 1975 TSCA
It was, of course, recognized that objectionable odors were Resource Conservation and Recovery Act, RCRA
released from some paints and coatings. Further, air emis- 1980
sions resulting from the evaporation of solvents during high- Comprehensive Environmental Response CERCLA
Compensation and Liability Act, 1980 (Superfund)
temperature processing of oils and resins caused occasional Superfund Amendments and Reauthorization SARA
complaints from persons living near the coatings plant. The Act, 1986
prevailing view of this period was summarized by Francis Title III, Emergency Planning and Community SARA, Title
Scofield in his article in the 13th edition of the Paint Testing Right-to-Know, 1986 III
Manual entitled "Atmospheric Pollutants" [1].
These "nuisance" types of pollution are a continuing The discussion in this section will focus on the Clean Air
problem but, in general, can be dealt with by dilution and Act and its amendments that, in the author's opinion, have
dispersion of the objectionable materials to bring the
had (and will continue to have) the greatest impact on coat-
concentration below a level that can be detected by the
neighboring citizenry. Fortunately, most of the materials ings.
used by the paint industry are not toxic at concentrations
significantly below the range at which they can be de-
tected by the human nose, and sophisticated analytical
procedures are rarely needed to deal with these "nui-
sance" problems. T H E CLEAN AIR ACT AND ITS
Since the 1960s societal concern about health and the envi- AMENDMENTS
ronment has increased appreciably. Actions taken by federal
and state legislative bodies have resulted in a steady ava- California Smog
lanche of new laws and associated regulations that affect
A precipitating factor influencing the basis for selection of
virtually all industry. Among the new federal laws adminis-
solvents for coatings in the 1960s and early 1970s was the
tered by the U.S. Environmental Protection Agency (EPA)
recognition that the emission of solvents from coatings to the
that impact significantly on the coatings industry are those
atmosphere contributed to the growing "smog" problem in
shown in Table 1. They are designed to control the emission
Southern California. The frequency of smog conditions in
of pollutants to air, to water, and to soil.
this area had increased steadily during the 1950s and 1960s
In addition, among the new federal standards administered
as the number of automobiles, trucks, buses, and airplanes
by the Occupational Safety and Health Administration are
increased and as industrial development expanded with the
those that require manufacturers--including those making
accompanying growth of petroleum and chemical processing
paints and coatings--to evaluate the hazards of products
and power plant utilization.
they make and to provide appropriate safety information to
The smog problem was (and is) most acute in the Los
employees and users through the Material Safety Data Sheet
Angeles air basin, an area uniquely situated in a series of
(MSDS) and product labels.
plains that originate in the high mountains to the east. The
9 Hazard Communication Standard (HCS), 1983 basin enjoys predominantly sunny days with cool moist air
9 Occupational Exposure to Hazardous Chemicals in Labo- flowing with a light westerly wind most of the year. These
ratories, 1990 factors cause a nearly permanent temperature inversion
layer, trapping air emissions that combine to produce a per-
11046 College Circle, St. Albans, WV 25177. sistent eye-irritating smog in the basin.

Copyright9 1995 by ASTMInternational www.astm.org

4 PAINT AND COATING TESTING MANUAL
In a presentation entitled "Solvent Restriction--Problem
or Opportunity," Dr. John Gordon, then of the University of
Missouri-Rolla, discussed the major sources of hydrocarbons
and nitrogen oxides, which together in the presence of UV
radiation react to produce oxidants and ozone, major compo-
nents of smog [2].
Sunshine
HC + NOx UV Radiation Smog (03)
Sources of NOx: Flame of almost any kind, volcanoes, inter-
nal combustion engines, forest fires, cig-
arettes, boilers, space heaters.
Processes that Produce Hydrocarbons
9 Petroleum production, refining, transport
9 Internal combustion engines
9 Natural processes--forests and plants (isoprene and ter-
penes)
9 Surface coatings
A 1962 estimate of the contaminants discharged into the
Los Angeles air during the summer period revealed that mo-
tor vehicles accounted for about 60%, while the use of or-
ganic solvents (for all purposes) accounted for about 18% of
the organic gases. About one half of the organic solvent
emitted was attributed to the coatings industry, chiefly to the
use in paint and coatings. Approximately 66% of the NOx
released was assigned to gasoline (motor vehicle) combus-
tion, while the combustion of fuels (energy supply) accounted
for about 26% [1].
Based on the results of laboratory studies in "smog cham-
bers," in which a mixture of a solvent and nitrogen oxide was
exposed for 6 h to light approximately the intensity of noon
sunlight, the solvents could be classified as "low" or "high" in
photochemical reactivity related to the amount of peroxides
and ozone produced. These studies formed the basis for the
well-known Rule 66, an air pollution control regulation
passed by the Los Angeles Air Pollution Control District. Rule
66 identifies an "approved" solvent as one that contains less
than 20% by volume of specific chemicals and is further
limited to certain combinations of these chemicals. Thus,
approved solvents can contain no more than designated
amounts of the combinations shown in Table 2.
In effect, Rule 66 promoted the use of specific solvents such
as aliphatic and naphthenic hydrocarbons, alcohols, esters,
normal ketones, chlorinated hydrocarbons (except trichloro-
ethylene), and nitroparaffins. Rule 66, superseded in 1976 by
Rule 442, Usage of Solvents, by the California South Coast Air
Quality Management District, was subsequently adopted by
various other state jurisdictions. Renewed interest has devel-
oped recently in the consideration of solvent photochemical
TABLE 2--Rule 66--Limits of solvent categories in approved
mixtures.*
5% 8% 20%
Hydrocarbons, alcohols, Aromatic Ethylbenzene,
aldehydes, e s t e r s , hydrocarbons branched
ethers or ketones (W/8 C ketones,
having an olefinic or atoms) toluene, or
cycIoolefinic trichloroethane
unsaturation
*Calculated as the percent by volumeof the total solvent.
reactivity in state, federal, and international programs re-
lated to air quality control.
VOC Definition
The United States Environmental Protection Agency (EPA)
was created in 1970 by Congress as part of a plan to consoli-
date several federal environmental activities. Studies directed
by the EPA laboratories in Research Triangle Park, NC of the
photochemical reactivity of materials in a laboratory smog
chamber revealed that when organic materials and nitrogen
oxide were irradiated for periods of up to 36 h, even those
solvents considered acceptable under Rule 66 reacted to form
peroxides and ozone. Only a few materials showed negligible
photochemical reactivity, among which were: methane, eth-
ane, methylene chloride, 1,1,1-trichloroethane, and fluorin-
ated compounds. These studies, which were prompted in part
by the passage of the Clean Air Act of 1970, led to the conclu-
sion that most organic compounds emitted to the atmosphere
contribute to the formation of ozone. On this basis, EPA
adopted as a regulatory objective the limit of essentially all
volatile organic compounds emitted to the atmosphere from
all sources, including paint and coatings applications [3].
Regulatory Definition o f VOC
The regulatory definition of volatile organic compounds
(VOC) was revised by EPA in 1992. A part of this definition is
as follows:
Section 51.100 Definitions 2
Volatile organic compounds (VOC) means any compound
of carbon, excluding carbon monoxide, carbon dioxide,
carbonic acid, metallic carbides or carbonates, and am-
monium carbonate, which participates in atmospheric
photochemical reactions.
(1) This includes any such organic compound other than
the following, which have been determined to have negli-
gible photochemical reactivity: methane; ethane; meth-
ylene chloride (dichloromethane); 1,1,1-trichloroethane
(methyl chloroform); 1,1,1-trichloro-2,2,2-trifluoro-
ethane (CFC-113); trichlorofluoromethane (CFC-11);
dichlorodifluoromethane (CFC-12); chlorodifluoro-
methane (CFC-22); trifluoromethane (FC-23);
1,2-dichloro- 1,1,2,2-tetrafluoroethane (CFC-114);
chloropentafluoroethane (CFC-115); 1,1,1-trifluoro 2,2-
dichloroethane (HCFC-123); 1,1,1,2-tetrafluoroethane
(HF-134a); 1,1-dichloro 1-fluoroethane (HCFC-141b); 1-
chloro 1,1-difluoroethane (HCFC-142b); 2-chloro-
1,1,1,2-tetrafluoroethane (HCFC- 124); pentafluoro-
ethane (HFC-125); 1,1,2,2-tetrafluoroethane (HFC-134);
1,1,1-trifluoroethane (HFC- 143a); 1,1-difluoroethane
(HFC-152a); and perfluorocarbon compounds which fall
into these classes:
(i) Cyclic, branched, or linear, completely fluorinated
alkanes;
(ii) Cyclic, branched, or linear, completely fluorinated
ethers with no unsaturations;
240 Code of Federal Regulations (CFR) Part 51; Requirements for
Preparation, Adoption and Submittal of Implementation Plans; Ap-
proval and Promulgation of Implementation Plans. FederalRegister,
Vol. 57, No. 22, 22 Feb. 1992, pp. 3941-3946.

(iii) Cyclic, branched, or linear, completely fluorinated
tertiary amines with no unsaturations; and
(iv) Sulfur containing perfluorocarbons with no unsat-
urations and with sulfur bonds only to carbon and fluo-
rine.
(2) For purposes of determining compliance with emis-
sions limits. VOC will be measured by the test methods in
the approved State implementation plan (SIP) or 40 CFR
part 60, appendix A, as applicable. Where such a method
also measures compounds with negligible photochemi-
cal reactivity, these neglibflity-reactive compounds may
be excluded as VOC if the amount of such compounds is
accurately quantified and such exclusion is approved by
the enforcement authority.
(3) As a precondition to excluding these compounds as
VOC or at any time thereafter, the enforcement authority
may require an owner or operator to provide monitoring
or testing methods and results demonstrating, to the
satisfaction of the enforcement authority, the amount of
negligibly-reactive compounds in the source's emissions.
(4) For purposes of Federal enforcement for a specific
source, the EPA will use the test methods specified in the
applicable EPA-approved SIP in a permit issued pursu-
ant to a program approved or promulgated under title V
of the Act, or under 40 CFR part 5 I, subpart I or appendix
S, or under 40 CFR parts 52 or 60. The EPA will not be
bound by an State determination as to appropriate meth-
ods for testing or monitoring negligibly-reactive com-
pounds if such determination is not reflected in any of
the above provisions.
The Ozone Standard
The Clean Air Act of 1970 targeted six criteria pollutants for
control: carbon monoxide, lead, nitrogen dioxide, ozone, par-
ticulates, and sulfur dioxide. Criteria pollutants are those for
which criteria were issued by EPA. These documents include
national ambient air quality standards (NAAQS)--levels that
protect against adverse effects to health and to plants and
materials [4]. Standards for ozone and nitrogen oxides are:
Ozone The ozone concentration in the atmosphere can-
not exceed 0.12 p p m as a daily m a x i m u m one-hour
average more than once per year.
Nitrogen Dioxide The nitrogen dioxide concentration in
the atmosphere cannot exceed 0.053
p p m as the annual arithmetic mean con-
centration.
CONTROL OF VOC E M I S S I O N S F R O M
COATINGS
The Clean Air Act addressed air pollution eminating from
both existing sources and that from future new plant con-
struction or significant modification of existing sources.
States with areas that did not comply with the ozone standard
were given primary responsibility to develop appropriate reg-
ulations for existing sources to meet the time schedule for
compliance specified by Congress. The Federal EPA was as-
signed oversight responsibility for the state programs that
were described in "State Implementation Plans" (SIP).
CHAPTER 1--REGULATION OF VOC EMISSIONS 5
Control Technique Guidelines
In 1977, the Agency issued the first of a series of guidance
documents for the states related to various industrial coating
operations or end-use categories. These documents, called
"Control Technique Guidelines (CTG) Series, Control of Vola-
tile Organic Emissions from Stationery Sources," include rec-
ommended VOC emission limits, based on EPA's assessment
of Reasonably Available Control Technology (RACT): the lim-
its are expressed as pounds of VOC per gallon of coating
(minus water), as applied.
The Clean Air Act Amendments of 1977 directed that states
had to revise their implementation plans for areas out of
compliance with the national ozone standard. The revised
SIPs were to include sufficient control of VOC emissions from
stationery sources, such controls to incorporate the RACT
limits for coatings operations for which a CTG was pub-
lished.
The CTG documents relating to surface coatings opera-
tions issued through 1992 are shown in Table 3 with recom-
mended limits for VOC content.
NEW SOURCE PERFORMANCE
STANDARDS
The control of VOC emissions from new coatings plants
and from significant modifications of existing plants was
addressed by EPA in a series of New Source Performance
Standards (NSPS), the first of which issued in 1980. These
mandatory standards, which apply uniformly to all parts of
the country, define the emission sources more narrowly and
impose a tighter level of emission control than that for related
existing sources. The VOC limits defined in the NSPS, ex-
pressed as kilograms of VOC per liter of applied solids, are
based on the best demonstrated technology (BDT) for the
specific coating operation.
The New Source Performance Standards for surface coat-
ings operations issued through 1992 are shown in Table 4.
The emission limits in both the CTG and NSPS documents,
in the majority of cases, focus on restricting the VOC content
per unit of coating or of coating solids applied in the opera-
tion, rather than placing a ceiling on individual plant emis-
sions. The responsibility for establishing emission limits for
particular plants, if appropriate, was left to the states [5].
D E T E R M I N A T I O N OF VOC C O N T E N T
Federal Reference Method 24
The procedures specified by the federal EPA for testing
paint products for compliance with VOC limits are described
in Federal Reference Method 24 [6]. This standard employs
several ASTM test standards, including those shown in Table
5.
Method D 2369 is a key procedure of Federal Method 24.
Since 1980, several important revisions have been made in
this standard to make it compatible with revisions in Method
24, including the addition in 1990 of instructions for testing
multicomponent coatings and the deletion of sections dealing
with testing at shorter times. The revised version of Federal
6 PAINT AND COATING TESTING MANUAL

TABLE 3--VOC content limits in control technique guidelines (CTG) for surface coating operations.
Allowable Limitsb
Lb VOC/Gal Kg VOC/L
Coatings Operation CTG Date" Minus H20 Minus H20
Appliances, large Dec., 1977 2.8 0.34
Auto and light duty trucks May, 1977 Primer, electrodeposit 1.2 0.14
Prime coat 1.9 0.23
Guidecoat (surfacer) 2.8 0.34
Topcoat 2.8 0.34
Final repair 4.8 0.58
Cans May, 1977 Sheet basecoat 2.8 0.34
Interior body spray 4.2 0.51
Side seam 5.5 0.66
End seal compound 3.7 0.44
Fabric May, 1977 Fabric coating 2.8 0.34
Vinyl coating 3.8 0.45
Graphic arts--rotogravure and Dec., 1978 (Consult CTG or state regulations)
flexography
Magnetic tape See Paper coating
Magnet wire Dec., 1977 (Based on the use of an incinerator) 1.7 0.20
Metal coil May, 1977 Prime and topcoat or single coat 2.6 0.31
Metal furniture Dec., 1977 3.0 0.36
Miscellaneous metal parts and June, 1978 Air dry 3.5 0.42
products
Clear coat 4.3 0.52
Extreme performance 3.5 0.42
Powder coatings 0.4 0.05
All others 3.0 0.36
Paper, film and foil May, 1977 2.9 0.35
Plastic parts for business machines None
Polymeric coatings of supporting None; may be
substrates considered
fabric coating
Pressure sensitive tapes and labels See Paper coating
Vinyl and urethane, flexible Fabric: May 1977 Vinyl 3.8 0.45
and/or Graphic
Arts Packaging
Rotogravure,
Dec. 1978
Wood paneling, flat June, 1978 Printed interior panels: 6.0 lb/1000
sq. fl of surface coated
Natural finish plywood: 12.0 lb/
1000 sq. ft of surface coated
Class II finishes 10.0 lb/1000 sq. ft
of surface coated
NOTE:The information presented in this table is not complete. Persons subject to emission control for any of the operations are advisedto consult the state/local
regulations for details.
aCTG documents are available from the National Technical Information Service, 5285 Port Royal Road, Springfield,VA 22161.
bReasonably available control technology (RACT)limits recommended in CTG and, in most cases, adopted in state/local regulations.

Reference M e t h o d 24 is also included in the ASTM Manual on Weight % total volatiles

Determination o f Volatile Organic Compound (VOC) Content less w a t e r less | (Density of coating)
in Paints, Inks, and Related Coating Products, 2nd ed., 1993 e x e m p t solvent ]
VOC =
[7]. (Volume% 1 _ ( Volume% 1
Substantial revisions during 1989-1991 were also m a d e in 100% - \ w at er ] \ e x e m p t solvent]
ASTM D 3960, Practice for D e t e r m i n i n g Volatile Organic or
C o m p o u n d (VOC) Content of Paints and Related Coatings, a voc - (Wo)(Oc)
standard developed in ASTM S u b c o m m i t t e e D01.21 to pro- 100% - Vw - vex
vide a guide for the calculation of VOC and to establish a base (W~ - W~ - W~x)(Dr (1)
for the investigation in ASTM of the precision of VOC co n t en t 100%- (Ww)(Dc/D~)- (W~)(D~/Dr
determination. The definitions a n d symbols used in D 3960 where
are those ad o p t ed by the EPA and included in the Agency
VOC = VOC co n t en t in g/L of coating less w a t e r and ex-
d o c u m e n t "Procedures for Certifying Quantity of Volatile Or- e m p t solvent,
ganic C o m p o u n d s E m i t t e d by Paint, Ink a n d Other Coatings" 141o = weight % of organic volatiles = Wv - Ww - Wex,
that was published in 1984 [8]. Wu = weight % of total volatiles = (100% - weight %
The general expression for calculating VOC c o n t e n t in nonvolatiles), (ASTM D 2369),
gr a m s p er liter of coating less w a t e r and e x e m p t solvent Ww = weight % of w at er (ASTM D 3792 or ASTM D
specified in the EPA Control T e c h n i q u e Guidelines issued 4017),
t h r o u g h 1991 is: 14~x = weight % of e x e m p t solvent (ASTM D 4457),
 CHAPTER 1--REGULATION OF VOC EMISSIONS 7

TABLE 4 - - V O C limits in New Source Performance (NSPS) for surface coatings operations.
Allowable Limitsb
Lb VOC/Gal Kg VOC/L
Coatings Operation NSPS Date~ Applied Solids Applied Solids
Appliances, large Oct.,1982 7.5 0.90
Auto and light duty trucks Dec., 1980 Prime coat
1.3 0.16
Guide coat
11.7 1.40
Top coat
12.2 1.47
Cans (beverage cans only) Aug.,1983 Exterior base
2.4 0.29
Clear base coat
3.8 0.46
Inside spray
7.4 0.89
Fabric (coating) See Polymeric
coating of
supporting
substrate
Graphic a r t s - - r o t o g r a v u r e and Rotogravure only Consult NSPS d o c u m e n t
flexography Nov., 1982
Magnetic tape Oct,, 1988 1.7 0.2
Consult NSPS
Magnet wire None . . . . . .
Metal coil Nov., 1982 w/o emission control device
2.3 0.28
With emission control device
1.2 0.15
Metal furniture Oct., 1982; Apr., 1985 7.5 0.90
Miscellaneous metal parts and None . . . . . .
products
Plastic parts for business machines Jan., 1988 Prime a n d color coat
12.52 1.5
Texture and touch-up
19,2 2.3
Polymeric coatings of supporting Sept., 1989 90% control from process:
substrates Consult NSPS
Pressure sensitive tapes Oct., 1983 1.67 0.20
Vinyl and urethane, flexible June, 1984 8.3 1.0
Wood paneling, flat None . . . . . .
NOTE: The information presented in this table is not complete. Persons subject to emission control for any of the operations are adv/sed to consult the specific
language of the referenced documents and state and local regulations.
~NSPS documents are available from the National Technical Information Service (NTIS), 5285 Port Royal Road, Springfield, VA 22161.
bBest demonstrated technology (BDT) emission limits established as NSPS standards. In the NSPS, the limits are expressed as kilograms of VOC per liter of
applied solids.

Vw = volume % o f w a t e r -- (Ww)(Dc/Dw),
TABLE 5 - - A S T M standards referenced in Federal Reference Vex = volume % of e x e m p t s o l v e n t = (Wex)(Dc/Dex),
Method 24. Dc = density o f c o a t i n g a t 25~ i n g/L ( A S T M D 1475),
ASTM Method Test Method f o r - Dw = density o f w a t e r a t 25~ i n g/L -- 0 . 9 9 7 103, a n d
D,x = density of e x e m p t s o l v e n t a t 25~ i n g/L ( A S T M D
D 2369-81 Volatile Content of Coatings
1475).
D 1475-60 Density of Paint, Varnish, Lacquer, and T o c o n v e r t f r o m g/L t o lb/gal, m u l t i p l y t h e r e s u l t (VOC
Related Products
c o n t e n t ) b y 8.345 10 -3 (lb/gal)/g/L). T o c o n v e r t g/L t o kg/L,
D 3792-79 Water Content of Waterborne Paints by d i v i d e t h e r e s u l t b y 10 a.
Direct Injection into a Gas The general expression for VOC content defined in terms of
Chromatograph
the mass of VOC per unit volume of coating solids applied as
D 4017-81 Water in Paints and Paint Materials by Karl s p e c i f i e d i n t h e E P A N e w S o u r c e P e r f o r m a n c e S t a n d a r d s is
Fischer Method
( W , - Ww - We~)Dc
VOCm = (2)
D 4457-85 Analysis of Dichloromethane a n d 1,1,1- v.
Trichloroethane in Paints and Coatings by
Direct Injection into a Gas where
Chromatograph
V O C m = V O C c o n t e n t i n g/L o f c o a t i n g solids, a n d
8 PAINT AND COATING TESTING MANUAL
V, = Volume % nonvolatile content of the liquid coat-
ing, ASTM D 2697. 3
The EPA would have preferred to limit volatile organic
compound emissions in the Control Technique Guidelines on
the basis of the unit volume of coating solids applied. The
adoption in the 1970s of Eq 1, in which VOC content is
defined as mass per unit volume of coating less water and less
exempt solvents, was necessary as no acceptable consensus
procedure was available for determining the volume percent
nonvolatile content. In a presentation in Copenhagen in 1990,
James C. Berry of U.S. EPA stated: "Though certainly less
than ideal, the major attraction is that the expression permits
the determination of compliance from the analysis of a coat-
ing sample obtained during a plant inspection. In the sim-
plest case, these units require only one volumetric and one
gravimetric measurement" [5].
Studies and discussions in ASTM Subcommittee D01.21
that led to the modification and improvements of ASTM
standards referenced in Federal Method 24 and in ASTM
Practice D 3960 were conducted with the cooperation of EPA
personnel of the Office of Air Quality Standards Development
at Research Triangle Park, NC.
OTHER VOC-RELATED METHODS AND
STUDIES
ASTM development activity on other VOC-related stan-
dards has expanded significantly since 1980. Many of the
standards listed in this section have not been approved by the
Federal EPA for use in demonstration of compliance with
VOC emission control regulations. Use of any of these stan-
dards to demonstrate compliance should be coordinated with
appropriate regulatory agencies. Among the new standards
developed or in process of development are the following:
S t a n d a r d s Specific to t h e A u t o m o b i l e I n d u s t r y
9 D 5087 Test Method for Determining the Amount of Vola-
tile Organic Compounds (VOC) Released from Sol-
vent-Borne Automotive Coatings and Available for
Removal in a VOC Control Device (Abatement)
9 D 5066 Practice for the Determination of the Transfer Effi-
ciency Under Production Conditions for Spray Ap-
plication of Automotive Paints--Weight Basis
9 D 5009 Test Method for Evaluating and Comparing Tran-
sfer Efficiency Under Laboratory Conditions
These standards were developed with the cooperation of
representatives from automotive coating suppliers and the
Motor Vehicle Manufacturers Association. Method D 5009
was derived from a study of transfer efficiency conducted for
the U.S. Environmental Protection Agency [9].
Masonry Treatments
9 D 5095 Test Method for Determination of the Nonvolatile
Content in Silanes, Siloxanesl and Silane-Siloxane
3EPAReference Method 24 does not include an analytical method
for determining V~, but states that the value be calculated from the
coating manufacturer's formulation.
Blends Used in Masonry Water-Repellent Treat-
ments. 4
In this standard, a catalyst is added prior to the bake cycle
to simulate the catalytic effect provided by masonry during
actual application of the water-repellent treatment.
Aerosol Spray Paints
9 D 5200 Test Method for Determination of Weight Percent
Volatile Content of Solvent-borne Paints in Aerosol
Cans
9 D 5325 Test Method for the Determination of Weight Per-
cent Volatile Content of Water-borne Aerosol Paints
These standards were developed for potential use related to
proposed regulations in California to limit the level of volatile
organic material in aerosol paints.
General Application Standards
9 D 5201 Practice for Calculating Formulation Physical Con-
stants of Liquid Paints and Coatings
The calculation of various physical constants directly from
the paint formulation is a common practice in industry.
ASTM D 5201 describes procedures for the calculation of
formulation weight solids, volume solids, solvent content,
and density of liquid paint based on formulation data (not
analytical laboratory determinations). The values obtained
may not be acceptable for demonstrating regulatory compli-
ance.
9 D 5286Test Method for Determination of Transfer Effi-
ciency Under General Production Conditions for
Spray Application of Paints
This standard, a modification of Practice D 5066 developed
for use in the automobile industry, describes conditions for
determining transfer efficiency under production conditions
applicable to spray application of miscellaneous parts.
9 D 5327 Practice for Evaluating and Comparing Transfer Ef-
ficiency under General Laboratory Conditions
Practice D 5327 provides a useful guide for general re-
search studies related to transfer efficiency. The general
approach employed is derived from that developed in Method
D 5009 except that D 5327 employs a fixed rather than moving
spray station.
9 Revision of D 2697, Test Method for Volume Nonvolatile
Matter in Clear or Pigmented Coatings: Use of the Helium
Gas Pycnometer (Under Study)
The use of the helium gas pycnometer provides a quick,
reliable approach to the determination of the dry coating
density, a critical parameter in the calculation of volume
percent nonvolatile content.
9 Direct Measurement of Volatile Organic Material in Water-
Reducible Coatings (Under Study)
Federal EPA funds supported the preliminary investigation
of this novel approach to the "direct" gravimetric determina-
4This standard has been accepted by the Federal EPA for use in the
determination of the VOC of silane- and siloxane-based coatings:
Letter, Gary McAllister, EPA, to H. Smith, NJ Dept. of Environmental
Protection, 25 March 1992.
 CHAPTER 1 - - R E G U L A T I O N OF VOC E M I S S I O N S 9

tion of volatile organic content of waterborne coatings [10]. tants; reduction of acid rain; and the protection of ozone in
The method involves collecting, on activated charcoal in the stratosphere.
weighed tubes, the organic effluent evolved on heating a paint Features of the Act that will impact most on the coatings
specimen for 1 h at 110~ while purging the reaction vessel industry include:
with dry nitrogen. Methanol is not captured on the charcoal.
9 D 5403 Test Method for Volatile Content of Radiation Cur-
able Materials Title I m O z o n e Control in the Atmosphere
The test methods in D 5403 determine the weight percent Title I specifically directs EPA to develop control technique
volatile content of paint, coatings, and inks that are designed guidelines and maximum achievable control technology
to be cured by exposure to ultraviolet light or to a beam of (MACT) standards for aerospace coatings and for shipbuild-
accelerated electrons. After radiation cure, the specimens are ing coatings and repair. EPA was also directed to prepare new
baked at 110 + 5~ for 60 min. control technique guidelines for additional coatings uses that
include:
Inks 9 autobody refinishing
9 plastic parts (business machines)
9 D 5328Volatile Organic Compound (VOC40) Content of 9 plastic parts (others)
Non-Heatset Paste Printing Ink Systems at 40~ 9 offset lithography
This standard is patterned, in part, after Method 30 of 9 wood furniture
California's Bay Area Air Pollution Control District in which In addition, EPA plans to promulgate national rules to
the specimen is baked for 1 h at 40~ D 5328 is applicable to control VOC emissions from architectural and industrial
paste printing inks and vehicles that dry primarily by absorp- maintenance coatings and from traffic paints. Solvent emis-
tion, polymerization, or related means without the applica- sion from consumer and commercial products, including
tion of heat. that from aerosols, are currently under study, and regulation
of this broad category of products is planned. In the develop-
ment of these rules, negotiated rulemaking may be employed,
Supplementary Information a process bringing together representatives of EPA, industry,
Further information about the development, significance, the states, and environmentalist groups to negotiate the con-
and limitations of these VOC-related ASTM standards as well tent of a proposed rule.
as about the use of ASTM standards for the demonstration of In CAAA-90, ozone nonattainment areas are placed in five
compliance with VOC emission control regulations is avail- classifications based on the mid-1991 ozone level (Table 6),
able in the ASTM Manual on Determination of Volatile Or- and compliance with the national ozone standard by specific
ganic Compounds in Paints, Inks, and Related Coating years is mandated in the law.
Products [7]. Attachments in the second edition of this man- Increasingly strict provisions, including further reduction
ual include the 1992 revision of Federal Reference Number of VOC emissions, will be imposed on areas, the magnitude to
24 and a publication from EPA's Emission Standards Divi- be related to the severity of the ozone problem. Depending on
sion titled "Procedure for Certifying Quantity of Volatile Or- the area classification, several or all of the following will be
ganic Compounds Emitted by Paint, Ink and Other Coatings" required:
[8]. Included in the latter publication are "VOC Data Sheets" 9 Increased monitoring and more accurate VOC and N O 2
applicable to coatings "as supplied" by the manufacturer and emission inventory
for coatings "as applied" by the user. The form used for "as 9 Revision of state implementation plans to incorporate
supplied" coatings is patterned after a recommendation of RACT limits from previous and future CTGs for all major
the National Paint and Coatings Association. stationery sources
9 New source review and permits for new or modified sta-
tionery sources
9 Reduced emission threshold levels for the definition of
CLEAN AIR ACT A M E N D M E N T S OF 1 9 9 0 major stationery sources, ranging between 10 tons/year for
severe classification areas to I00 for marginal or moderate
The Clean Air Act Amendments of 1990 defined a compre-
areas
hensive long-term approach "to achieve and maintain a
healthy environment while supporting a strong and sus-
tainable economic growth and sound energy policy.''s A TABLE 6--Clean air act amendments--1990 ozone
nonattainment area classifications.
major impetus for these amendments was the continued in-
ability of a number of heavily populated urban areas to meet Years to Achieve
Design Value Compliance,
the requirements of the national ambient air quality stan- Classification (Ozone Level) year
dards for ozone and carbon monoxide.
Marginal 0.121-0.138 3 (1993)
Among the specific issues addressed in the Act are: control Moderate 0.138-0.160 6 (1996)
of ozone in the atmosphere; control of hazardous air pollu- Serious 0.160-0.180 9 (1999)
Severe 0.180-0.280 15 (2005)
Extreme~ 0.280 and above 20 (2010)
5U.S. EPA Office of Air and Radiation, "Implementation Principles
for the Clean Air Amendments of 1990." ~Onlythe Los Angelesarea is in this classification.
10 PAINT AND COATING TESTING MANUAL
9 Higher VOC emission offset r e q u i r e m e n t s for new or modi-
fied sources
Title III--Air Toxics Program
U n d e r Title III, EPA is directed to evaluate a n d control the
emission of hazardous air pollutants (HAPS). 189 products
are identified in the Act, a n d EPA has the authority to delete
or add additional products to this list. I n d u s t r y groups m a y
petition EPA to delist products.
Among the materials included o n the initial HAP list that
are used in paints a n d coatings are those shown in Table 7.
The control of emissions of hazardous air pollutants is to
be achieved t h r o u g h the p r o m u l g a t i o n of emission standards
for source categories a n d subcategories that emit these prod-
ucts. The initial list of categories of sources published by EPA
(57FR31576, 16 July 1992) included u n d e r Surface Coating
Processes those processes for which a CTG or n a t i o n a l rule
has b e e n issued or is planned. Also included is the Manufac-
ture of Paints, Coatings and Adhesives. A draft timetable for
regulating the categories of sources of hazardous air pollu-
tants was published by EPA in 1992 (57FR44147, 24 Sept.
1992). By the end of 1994 emission standards were due for
the following surface coating processes: magnetic tapes,
printing/publishing, shipbuilding a n d ship repair, a n d wood
furniture.
The Agency was required to p u b l i s h emission limits based
o n m a x i m u m achievable control technology (MACT) for 40 of
these categories by the end of 1992, with MACT limits to be
identified for the r e m a i n i n g categories by 2000. The Act di-
rects that the health impact a n d economic factors he consid-
ered in defining appropriate MACT limits. Further, by the end
TABLE 7--Clean air act amendments--1990 selected hazardous
air pollutants used in paints and coatings.
ORGANICMATERIALS
Bis (2-ethylhexyl phthalate)
Dibutyl phthalate
Diethanolamine
Dimethyl formamide
Dimethyl phthalate
Ethylene glycol
Formaldehyde
Glycol ethers (ethylene oxide-based)
Methanol
1,1,1-trichloroethane (methyl chloroform)~
Methylene chloride~
Methyl ethyl ketonea
Methyl isobutyl ketone~
2-nitropropane
Styrene
Toluenea
Xylenes~
INORGANICANDOTHER
Ammonia
Antimony compounds
Cadmium compounds~
Chromium compoundsa
Cobalt compounds
Lead compounds~
Mercury compounds~
~Materials included in the EPA/Industry33/50 Project, a voluntaryindustry
initiative to reduce the total release and transfer of 17 targeted chemicals by
one third by the end of 1992and by one half by the end of 1995 (using 1988as a
baseline year).
of 1995 sufficient categories a n d subcategories m u s t be listed
to ensure that 90% of the area sources that emit the 30 most
hazardous air pollutants are subjected to regulation.
Title V - - S t a t e Operating Permit Program
The state operating p e r m i t p r o g r a m is considered by EPA
as a cornerstone of the CAAA-90 a m e n d m e n t s designed to
ensure that the ozone n o n a t t a i n m e n t areas meet compliance
deadlines. This p r o g r a m will impact o n m a n y previously un-
regulated coatings m a n u f a c t u r e r s a n d users. The final rule
re the operating p e r m i t p r o g r a m was issued in 1992
(57FR32250, 21 July 1992).
The operating permit p r o g r a m has been called the "air
pollution equivalent" of the NPDES permit p r o g r a m of the
Clean Water Act, u n d e r which operating permits are required
of sources that discharge pollutants to water. I n the p r o g r a m
u n d e r Title V, all federal a n d state air pollution rules a n d
regulations will be consolidated u n d e r a single d o c u m e n t
wherein the states are given authority to m o n i t o r a n d enforce
the regulations. Sufficient funds will be available to the states
from a m i n i m u m a n n u a l fee of $25 per ton for each regulated
pollutant emitted, the fee to be assessed against all m a j o r
sources.
Major sources required to have state operating permits in-
clude those that emit 10 tons or more per year of a single
regulated hazardous air pollutant or 25 tons per year of a
c o m b i n a t i o n of hazardous air pollutants. These pollutants
include those materials for which a n a t i o n a l emission stan-
dard (NESHAP) has been established. Under Title V of
CAAA-90, a n d the final rule on operating p e r m i t programs,
EPA is to approve (or disapprove) state permit programs
w i t h i n one year of receipt; the m a j o r sources m u s t apply for
the five-year p e r m i t within one year of the EPA's approval of
the state program, a n d all permits m u s t be issued a n d be
legally b i n d i n g by the e n d of 1997. U n d e r the rule, states have
the option of exempting all n o n m a j o r sources, with some
exceptions, from requiring a permit for five years after the
state p e r m i t p r o g r a m is approved by EPA.
The characterization of a m a j o r source in ozone non-
a t t a i n m e n t areas is also based o n the a m o u n t of volatile
organic c o m p o u n d s emitted annually. The threshold a m o u n t
is related to the area classification a n d sources in ozone
n o n a t t a i n m e n t areas that emit above the designated a m o u n t
of VOC shown in Table 8 are identified as m a j o r sources.
These limits vary between 10 tons/year for the "extreme"
classification to 100 tons/year for the "marginal or moderate"
classification.
For ozone transport regions (e.g., one is established in the
Northeast), a threshold limit of 50 tons/year of VOC emission
applies.
TABLE 8--Clean air act amendments--1990 major source
identification based on VOC emissions: limits for area
classifications.
Ozone Nonattainment VOC Emission Limit,
Area Classification tons/year
Marginal or moderate 100
Serious 50
Severe 25
Extreme 10
 CHAPTER 1 - - R E G U L A T I O N OF VOC E M I S S I O N S 11

TABLE 9--Code of federal regulations subchapter topics. Title VI--Stratospheric Ozone Protection
Subehapter Subject Parts
The m o s t significant feature of the p r o g r a m to protect
C Air Programs 50-87 ozone in the s t r a t o s p h e r e is the staged p h a s e o u t of 1,1,1-
New Source Performance Standards 60 trichloroethane, a m a t e r i a l widely used in coatings a n d clas-
D Water Programs 104-149
I Solid Waste 240-281 sified as a "VOC-exempt" solvent by the EPA. P r o d u c t i o n (and
J Superfund/Right-to-Know 300- 372 use) will be r e d u c e d in i n c r e m e n t s (from the 1989 a m o u n t )
N Effluent Guidelines and Standards 401-471 b e g i n n i n g in 1993 to a 50% level for the p e r i o d 1996-1999,
R Toxic Substances Control Act 700-799 t h e n to the 20% level for the p e r i o d 2000-2001, after w h i c h
the use of the m a t e r i a l will be prohibited.

TABLE 10--Control technique guidelines and surface coating Title VII--Enforcement

operations reference documents.
EPA is g r a n t e d b r o a d n e w a u t h o r i t y to i m p o s e penalties
EPA Document Reference Coating Operation a n d substantial fines for various actions including: violations
EPA-450/2-77-008 Vol. II Auto and light duty trucks of the State I m p l e m e n t a t i o n Plan; violation of s o m e of the
Cans o p e r a t i n g p e r m i t provisions; a n d false s t a t e m e n t s in records,
Fabric m o n i t o r i n g data, a n d reports. Also i n c l u d e d are provisions
Metal Coil
Paper, film, and foil for field citations b y inspectors.
EPA-450/2-77-032 Vol. III Metal furniture
EPA-450/2-77-033 Vol. IV Magnet wire Scenario for the 1990s
EPA-450/2-77-034 Vol. V Appliances, large CAAA-90 a n d the m y r i a d of n e w federal a n d state regula-
EPA-450/2-78-015 Vol. VI Miscellaneous metal parts and
products tions associated with i m p l e m e n t a t i o n of this c o m p r e h e n s i v e
EPA-450/2-78-032 Vol. VII Wood paneling, flat law that will issue d u r i n g the 1990s will have a m a j o r i m p a c t
EPA-450/2-78-033 Vol. VIII Graphic arts--rotogravure and on the coatings industry. A m o n g the m a n y u n c e r t a i n t i e s are
flexography the n a t u r e a n d level of MACT limits to be defined for essen-
Vinyl and urethane, flexible
tially all coating operations; the level of new o r stricter VOC

TABLE I 1--Regional offices, U.S. Environmental Protection Agency.

Region States Address
Connecticut, Maine, Massachusetts, J. F. Kennedy Federal Bldg.
New Hampshire, Rhode Island, Room 2203,
Vermont Boston, MA 02203
Phone (617) 565-3715
New Jersey, New York, Puerto Rico, 26 Federal Plaza
Virgin Islands New York. NY 10278
Phone (212) 264-2515
Delaware, Maryland, Pennsylvania, Virginia, 841 Chestnut St,
West Virginia, District of Philadelphia, PA 19107
Columbia Phone (800) 438-2474
Alabama, Florida, Georgia, Kentucky, 345 Courtland St. NE
Mississippi, North Carolina, South Atlanta, GA 30365
Carolina, Tennessee Phone (800) 282-0239 in GA
(800) 241-1754 in other Region 4 states
Illinois, Indiana, Michigan, 230 S. Dearborn St.
Minnesota, Ohio, Wisconsin Chicago, IL 60604
Phone (800) 572-2515 in IL
(800) 621-8431 in other Region 5 states
Arkansas, Louisiana, New Mexico, 1445 Ross Ave.
Oklahoma, Texas 12th Floor, Suite 1200
Dallas, TX 75202
Phone (214) 655-2200
Iowa, Kansas, Missouri, Nebraska 726 Minnesota Ave.
Kansas City, KS 66101
Phone (913) 236-2803
Colorado, Montana, North Dakota, 999 18th St.
South Dakota, Utah, Wyoming Suite 500
Denver, CO 80202
Phone (800) 759-4372
American Somoa, Arizona, Nevada, 215 Fremont St.
Hawaii, Guam, California San Francisco, CA 94105
Phone (415) 974-8076
10 Alaska, Idaho, Oregon, Washington 1200 6th Ave.
Seattle, WA 98101
Phone (206) 442-5810
12 PAINT AND COATING TESTING MANUAL
e m i s s i o n limits for coating operations; a n d the time,
m a n p o w e r , a n d cost a s s o c i a t e d with c o m p l y i n g with the
m a n y new regulations a s s o c i a t e d with the a m e n d m e n t s .
As did the decades of the 1970s a n d 1980s, the 1990s will
pose a c o n t i n u i n g challenge to r a w m a t e r i a l suppliers to de-
velop a n d provide e n v i r o n m e n t a l l y acceptable m a t e r i a l s as
well as to p a i n t f o r m u l a t o r s to develop new o r modified
coatings with r e d u c e d VOC content. Additionally, i n c r e a s e d
attention to the i m p r o v e m e n t of coating processes a n d to the
use of a b a t e m e n t e q u i p m e n t for e m i s s i o n control d u r i n g the
a p p l i c a t i o n of coatings is expected.
REGULATION INFORMATION
Published Sources
F e d e r a l e n v i r o n m e n t a l regulations, including those pro-
m u l g a t e d u n d e r the Clean Air Act, are p u b l i s h e d in the Code
of Federal Regulations (CFR), a series of b o o k s that are gener-
ally available in m a j o r libraries a n d law libraries. These regu-
lations as well as those of related state a n d local codes are
also o b t a i n a b l e from the associated r e g u l a t o r y offices.
Regulations of p a r t i c u l a r interest to the coatings i n d u s t r y
can be found in s u b c h a p t e r s of the Code of Federal Regula-
tions (Table 9).
The F e d e r a l Control Technique Guidelines for coating op-
erations are not included in the CFR, b u t are available from
the National Technical I n f o r m a t i o n Service (NTIS), 5285
Port Royal Road, Springfield, VA 22161. CTG d o c u m e n t s
t h r o u g h 1991 are i n c l u d e d in the EPA p u b l i c a t i o n s listed in
Table 10.
P r o p o s e d regulations are p u b l i s h e d by the EPA in the Fed-
eral Register. Typically, a p u b l i c (written) c o m m e n t p e r i o d of
30 to 90 days on the p r o p o s a l s is allowed, a n d often a public
h e a r i n g is s c h e d u l e d at w h i c h oral c o m m e n t s can be pre-
sented. The c o m m e n t s received are c o n s i d e r e d by the Agency
in the d e v e l o p m e n t of a final regulation that is p u b l i s h e d in
the Federal Register together with the r e g u l a t i o n c o m p l i a n c e
date.
Information S o u r c e s
Questions relating to the interpretation, applicability, a n d
c o m p l i a n c e to air quality regulations m a y be a d d r e s s e d to the
U.S. EPA regional offices o r to the specific state regulating
b o d y responsible for air quality control.
The U.S. E n v i r o n m e n t a l Protection Agency has established
ten regional offices, each responsible for several states (Table
11).
A m o n g the i n d u s t r y o r g a n i z a t i o n s that provide informa-
tion to their m e m b e r s h i p a b o u t p e n d i n g regulations a n d
g u i d a n c e on c o m p l i a n c e with finalized regulations are Chem-
ical M a n u f a c t u r e r s Association (CMA), N a t i o n a l Paint a n d
Coatings Association (NPCA), Dry Colour M a n u f a c t u r e r ' s As-
sociation (DCMA), a n d Chemical Specialty M a n u f a c t u r e r s
Association (CSMA). Several coatings j o u r n a l s p u b l i s h ex-
cerpts from regulations a n d s u m m a r y reviews.
REFERENCES
[1] Scofield, F. in Paint Testing Manual, 13th ed., American Society
for Testing and Materials, Philadelphia, 1972, p. 413.
[2] Gordon, J., "Solvent Restriction, Problem or Opportunity," pre-
sentation to the Chicago Coatings Society, 13 Nov. 1978.
[3] EPA Policy Statement, Recommended Policy on Control of Vol-
atile Organic Compounds, FederalRegister, 8 July 1977.
[4] "Glossary for Air Pollution Control of Industrial Coating
Operations," EPA-450/3-83-013R, Environmental Protection
Agency, Washington, DC, December 1983.
[5] Berry, J. C., U.S. EPA, "Control of Volatile Organic Compound
(VOC) Emissions from Painting Operations in the United
States," presentation at the International Symposium on Paint
and the Environment, Copenhagen, 12-14 Nov. 1990.
[6] Code of Federal Regulations, Vol. 40, Subchapter C., Part 60,
Appendix A; Amendments in a Rule published in the Federal
Register, Vol. 57, No. 133, 10 July 1992, pp. 30654-30656.
[7] Manual on Determination of Volatile Organic Compounds in
Paints, Inks, and Related Coating Products, ASTM Manual Series,
MNL4, 1989, 2nd ed., 1993.
[8] Procedures for Certifying Quantity of Volatile Organic Com-
pounds Emitted by Paint, Ink and Other Coatings, EPA-450/3-84-
019, Environmental Protection Agency, Washington, DC, De-
cember 1984.
[9] Development of Proposed Standard Test Method for Spray Paint-
ing TransferEfficiency, Vols. I and II, EPA Publication Nos. EPA-
600/2-88-026a and EPA-600/2-88-026b, Environmental Protec-
tion Agency, Research Triangle Park, NC.
[10] Method Development for Measuring the VOC Content of Water-
Based Coatings, EPA Contract No. 68D90055, Work Assign-
ments No. 28 and 40, Environmental Protection Agency, Re-
search Triangle Park, NC.