EXTERNAL REVIEW
DRAFT
AQUEOUS AND TERPENE CLEANING
INTERIM REPORT
U.S. Environmental Protection Agency
Office of Toxic Substances
Washington. DC 20460
Printed on Recycled Paper
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EXTERNAL REVIEW DRAFT
AQUEOUS AND TERPENE CLEANING
INTERIM REPORT
October 29, 1991
U.S. Environmental Protection Agency
Office of Toxic Substances
Washington, DC 20460
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TABLE OF CONTENTS
1. EXECUTIVE SUMMARY 1
2. HAZARD ASSESSMENT 12
2.1 AQUEOUS CLEANERS 12
2.2 TERPENE CLEANERS 20
3. INDUSTRIAL APPLICATIONS AND OCCUPATIONAL EXPOSURE .... 26
3.1 SUMMARY AND CONCLUSIONS 29
3.2 AQUEOUS CLEANERS 29
3.2.1 FORMULATION OF AQUEOUS CLEANERS 34
3.2.2 PC BOARD CLEANING WITH AQUEOUS CLEANERS . . 37
3.2.3 WARM IMMERSION CLEANING WITH AQUEOUS
CLEANERS 37
3.2.4 MAINTENANCE COLD CLEANING WITH AQUEOUS
CLEANERS 38
3.3 TERPENE CLEANING 39
3.3.1 MANUFACTURE OF TERPENES 39
3.3.2 FORMULATION OF TERPENE CLEANERS 40
3.3.3 PC BOARD CLEANING WITH TERPENE CLEANERS . . 42
3.3.4 WARM IMMERSION CLEANING WITH TERPENE
CLEANERS 43
3.3.5 MAINTENANCE COLD CLEANING WITH TERPENE
CLEANERS 44
4. ENVIRONMENTAL RELEASE, FATE, AND EXPOSURE 45
4.1 RELEASES 45
4.1.1 AQUEOUS CLEANERS 45
4.1.2 TERPENE CLEANERS 45
4.1.3 DATA NEEDS 48
4.2 ENVIRONMENTAL FATE AND TRANSPORT 48
4.2.1 AQUEOUS CLEANERS 48
4.2.2 TERPENE-BASED CLEANERS 52
4.3 EXPOSURE ANALYSIS 53
4.3.1 PROBABILISTIC DILUTION MODEL 53
4.3.2 STREAM CONCENTRATIONS 56
4.3.3 EXPOSURE ANALYSIS MODELING SYSTEM 60
4.3.4 DRINKING WATER AND FISH INGESTION
ESTIMATES 60
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1. EXECUTIVE SUMMARY
BACKGROUND
Over the past decade, there has been heightened concern
worldwide over the slow but progressive depletion of the Earth's
stratospheric ozone layer, the shield which protects the Earth
from ultraviolet (UV-B) radiation. In the 1970s, scientists
hypothesized that chlorine from chlorofluorocarbons (CFCs) could
destroy stratospheric ozone, thus increasing the amount of UV-B
radiation reaching the Earth's surface. Increased UV-B radiation
can lead to increased cases of skin cancers and cataracts, and it
has been linked to crop, fish, and materials damage.
Bromochlorofluorocarbons (halons) also destroy stratospheric
ozone, and they are believed to do so at a faster rate than CFCs.
At the time that this report was prepared, substitutes for the
halons were not identified.
In 1978, the United States banned the use of CFCs in non-
essential aerosols (40 CFR 762) in an effort to halt ozone
depletion. By 1982, however, the global production of CFCs had
risen, thereby negating the decrease in use that had resulted
from the 1978 aerosol ban in the US and other nations. Uses of
CFCs include refrigeration, metal and electronics cleaning,
production of insulating foam, mobile air conditioning, and
sterilization.
Montreal Protocol
The increase in CFC production prompted officials in the
United Nations Environment Programme (UNEP) to develop and
promote a multilateral response to stratospheric ozone depletion.
These efforts resulted in the development of an international
agreement — the 1985 Vienna Convention To Protect the Ozone
Layer — which provided the framework for the eventual adoption
of the Montreal Protocol on Substances That Deplete the Ozone
Layer. The Montreal Protocol was signed in 1987, ratified in the
US in 1988, and became effective worldwide on January 1, 1989.
To date, 64 nations, 28 of which are developing countries, have
ratified the Protocol.
The Montreal Protocol, as initially ratified, requires a
freeze in production and consumption, at 1986 levels, of the
following chemicals:
CFC-11 Trichlorofluoromethane
CFC-12 Dichlorodifluoromethane
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CFC-113 1,1,2-Trichloro-l,2,2-trifluoroethane
CFC-114 1,2-Dichlorotetrafluoroethane
CFC-115 Chioropentafluoroethane
The freeze is to be followed by a phased-in reduction to 80
percent of 1986 levels beginning in mid-1993 and 50 percent
beginning in mid-1998. The Protocol also limits the production
and consumption to 1986 levels of halons 1211, 1301, and 2402,
beginning in 1992. These reductions are to be accomplished by
allocating production and consumption allowances to firms that
produced and imported these chemicals in 1986, based on their
1986 levels of activity.
On August 12, 1988, under the authority of the Clean Air
Act, EPA promulgated regulations to implement the reductions
called for in the Montreal Protocol (53 FR 20566).
London Amendments to the Montreal Protocol
Scientists measuring stratospheric ozone have concluded that
the amount of global ozone in northern hemisphere mid-latitudes
has decreased 1.7 to 3 percent from 1969 to 1986, with the lowest
levels occurring in winter. This decrease is two to three times
greater than had been predicted by atmospheric models. Several
extensive scientific investigations also produced evidence that
CFCs led to decreases in stratospheric ozone during the spring
months in the area over the Antarctic pole (sometimes called the
Antarctic ozone "hole").
Scientists believe that the naturally occurring atmospheric
concentration of chlorine is 0.7 part per billion (ppb). When
the Antarctic ozone hole was first observed in the mid 1970s, the
chlorine concentration equalled approximately 2.0 ppb; it is
currently at 3.0 ppb. EPA has concluded that levels of chlorine
and bromine in the atmosphere will continue to increase
measurably despite the reductions in CFCs required by the
Montreal Protocol. Concentrations of chlorine are predicted to
exceed 8 ppb by the year 2075.
Based on these assessments, the U.S. and other Parties to
the Montreal Protocol determined that further restrictions,
including controls on other chlorinated compounds and an eventual
phaseout of CFCs, were warranted.
In June 1990, the Parties met again in London to formally
amend the Montreal Protocol to include more stringent provisions.
Under the revised Protocol:
o all fully halogenated CFCs and carbon tetrachloride
will be phased out by 2000,
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o halons will also be phased out by 2000 with exemptions
for essential uses, and
o methyl chloroform will be phased out by 2005.
In addition, the Parties issued a non-binding declaration calling
for HCFCs to be used only when other alternatives are not
feasible, with phaseout by 2020 if possible, but no later than
2040. These restrictions are based on a series of recently
completed scientific, economic, and technological assessments
prepared by the Parties to the Protocol.
Clean Air Act Amendments
In November 1990, the Clean Air Act was amended to include a
number of provisions that will eliminate the production of CFCs,
halons, carbon tetrachloride, and methyl chloroform by the turn
of the century. One key provision requires EPA to set "Lowest
Achievable Emission Levels" for CFCs in the air-conditioning and
refrigeration sectors and prohibits venting of HCFCs in these
sectors within the next two years. In addition, the new Clean
Air Act requires recycling of all refrigerants in mobile air-
conditioning within the next five years.
INTERIM REPORTS
To increase the public's knowledge of the potential CFC
replacement chemicals, EPA has been working to characterize the
human health and environmental risks associated with the major
substitutes for CFCs and halons. In late 1989, EPA released a
draft strategy document, "CFC Substitutes Health and
Environmental Effects Program," that outlined the Agency's
approach to this task. Several offices within EPA, primarily the
Office of Toxic Substances (OTS), the Office of Air and Radiation
(OAR), and the Office of Water (OW), were involved in the
creation of the strategy document.
A focal point of the strategy was the creation of interim
reports which should help provide the public with an early
indication of the health and environmental impacts of major
chemical alternatives to the ozone depletors. Chemicals are
selected for assessment in the interim reports based on projected
use volumes and the potential for significant increases in
exposures and releases, rather than because of specific toxicity
problems associated with the chemicals.
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The interim reports are to be based on data available at the
time of publication, rather than being comprehensive documents.
Although the data in the interim reports can be expected to
change in these fast-moving fields, EPA believes that industry
and the public should have access to the information as it
becomes available. Where data for a particular chemical are not
available, EPA relies on closely related chemicals and scientific
judgment to estimate hazard and exposure factors. EPA will
prepare future reports as new data on these chemicals become
available or as other substitutes or exposure scenarios are
identified.
This interim report focuses on eight terpenes and twenty
aqueous cleaner chemicals as feasible substitutes for CFC-113 and
methyl chloroform, another ozone-depleting chemical, in metal and
electronics cleaning. These chemicals are:
Aqueous Cleaners
• Ammonium hydroxide (CAS # 1336-21-6), potassium
hydroxide (CAS # 1310-58-3), sodium hydroxide (CAS #
1310-73-2)
Diethylene glycol monobutyl ether (CAS # 112-34-5)
Dodecanedioic acid (CAS # 693-23-2)
Ethylenediaminetetraacetic acid (CAS # 60-00-4) and its
tetrasodium salt (CAS # 64-02-8)
Monoethanolamine (CAS # 141-43-5), diethanolamine (CAS
# 111-42-2), triethanolamine (CAS # 102-71-6)
Borax (CAS # 1303-96-4)
Sodium carbonate (CAS # 497-19-8)
Sodium gluconate (CAS # 527-07-1)
Sodium silicate (CAS # 1344-09-8) and sodium
metasilicate (CAS # 6834-92-0)
Sodium tripolyphosphate (CAS # 7758-29-4), trisodium
phosphate (CAS # 7601-54-9), tetrasodium pyrophosphate
(CAS # 7722-88-5), tetrapotassium pyrophosphate (CAS #
7320-34-5)
Sodium xylene sulfonate (CAS # 1300-72-7)
Terpene Cleaners
d-Limonene (CAS # 5989-27-5)
Anethole (CAS # 480-23-8)
alpha-Pinene (a-pinene) (CAS # 7785-70-8)
beta-Pinene (8-pinene) (CAS # 18172-67-3)
alpha-Terpinene (o-terpinene) (CAS # 99-86-5)
beta-Terpinene (8-terpinene) (CAS # 99-85-4)
Terpinolene (CAS # 586-62-9)
Dipentene (dl-limonene) (CAS # 138-86-3)
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For purposes of this report, the term "hazard" refers to the
potential for human health or environmental effects because of
the inherent toxicity of a chemical. "Exposure" addresses
potential exposures to workers who manufacture, process, or use
aqueous or terpene cleaners, and the general public exposed to
releases from industrial sites.
Aqueous and terpene cleaners are expected to become only
partial replacements for CFC-113 and methyl chloroform in metal
and electronics cleaning applications. Aqueous and terpene
cleaners are not expected to be used in other CFC applications,
such as mobile air-conditioning, refrigeration, foam insulation,
and sterilization. A separate EPA report, "Hydrofluorocarbons
and Hydrochlorofluorocarbons Interim Report," presents EPA's
assessment of the HCFCs and HFCs as substitutes in these major
CFC use categories.
For the purposes of this report, aqueous cleaners are
assumed to replace 30% of the CFC-113 and methyl chloroform used
in electronics cleaning and 40% of the CFC-113 and methyl
chloroform used in metal cleaning. Terpenes are assumed to
replace 25% of CFC-113 and methyl chloroform in electronics
cleaning and 10% in metal cleaning. These estimates were
developed to provide an indication of the order of magnitude of
potential total releases. The actual replacement may be higher
or lower in specific use areas.
Selection of the aqueous and terpene cleaners for this
report was based on projected use volume aggregated from
responses to letters sent by EPA's Office of Air and Radiation
(OAR) to industrial and military installations under Section 114
of the Clean Air Act. At that time, these compounds were viewed
as potential high-volume substitutes for the electronic and
metal-cleaning uses of CFCs. In this quickly changing field,
other substitutes, such as aliphatic hydrocarbons [e.g., Axeral
(trade name)] and N-methylpyrrolidone, are also being considered
by industry for these uses. These other substitutes also warrant
a similar review, but due to time constraints, they could not be
included in this report. The absence of their review does not
constitute an endorsement of their use over aqueous and terpene
cleaners. Future assessments will include, but not be limited
to, these other compounds. In the meantime, developers and users
of CFC substitutes should consider the following:
o In developing and using alternatives to the ozone depleters,
care must be taken that in solving one problem we do not
create another. Any chemical or process that takes a
significant portion of the market should be capable of being
used in a safe and environmentally acceptable manner.
o In general, when making decisions about how to replace the
ozone-depleting chemicals, EPA encourages industry to first
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consider a preventive approach that will reduce overall use
of chemicals through toxics use reduction, alternative
processes, or conservation. In situations where these
options do not exist, industry should avoid replacing ozone
depletors with chemicals that possess known hazards and that
cannot be used in a safe manner. EPA also cautions industry
to be prudent in choosing any chemical for which there is a
lack of hazard information and encourages those actions
which would reduce exposure and release to the environment.
Although chlorinated solvents such as methylene chloride,
trichloroethylene, and perchloroethylene are also used in
these applications, they are not considered good
replacements for CFC-113 and methyl chloroform due to their
potential adverse health effects.
Despite the limitations of this preliminary assessment, due
to insufficient available information, several conclusions can be
drawn. They are summarized below. This information should be
provided to formulators, users, and the workforce handling these
substitutes.
OVERALL FINDINGS OF THIS ASSESSMENT
The interim assessment evaluated the available information
on the toxicity of the aqueous and terpene cleaners, as well as
the potential exposure levels to workers and the general
population from the manufacture, formulation, and use of these
cleaners. Because many of these chemicals are not yet used
widely in these applications, the assessment necessarily rests on
incomplete data and, therefore, should not be interpreted as a
final judgment. Nonetheless, the results of these preliminary
analyses indicate that the aqueous and terpene cleaners can be
used in a manner safe to workers, the general population, and the
environment, given appropriate technological changes and exposure
control practices.
In reaching this conclusion, we must emphasize the interim
nature of this assessment in two respects. First, as more and
better information becomes available on the toxicity of the
alternatives and their likely exposures, a more definitive
assessment can be conducted. Second, the data used in these
analyses are, in many cases, limited, and assumptions are often
based more on analogy than on direct measurement. As new
equipment is developed that utilizes these chemicals, and as work
practices are modified to facilitate use of the substitute
chemicals, exposures are likely to be reduced. We urge all
companies and workers involved with the production and use of CFC
substitutes to take reasonable efforts to ensure that exposures
to these chemicals are controlled while additional data are being
developed.
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General conclusions regarding the toxicity of and exposure
to aqueous and terpene cleaner chemicals follow.
TERPENES
Toxicity
Terpenes comprise a family of unsaturated hydrocarbons that
occur in most essential oils and oleoresins of plant matter,
mainly that of pine and citrus trees. They exhibit low to
moderate toxicity to human health, moderate to high toxicity to
aquatic organisms. They are more biologically active than the
CFCs, a class of chemicals that has long been recognized as
having low toxicity. As discussed in Section 2, terpenes have
been tested for general toxicity, developmental effects,
neurotoxicity, carcinogenicity, and aquatic toxicity.
With regard to human health, d-limonene induced kidney
toxicity and kidney tumors in male rats, but not in female rats
or male or female mice. The biological significance of these
effects for humans is uncertain. Developmental effects were seen
in mice and rabbits treated with high doses of d-limonene, and
liver effects were seen in mice treated with moderate doses of d-
limonene and anethole. In the only adequate neurotoxicity study
obtained, a-pinene did not induce neurotoxic effects in rats.
Undiluted terpenes appear to be moderate skin irritants.
With regard to the environment, test data and structure-
activity relationship (SAR) predictions indicate that terpenes
present a moderate to high hazard to aquatic organisms.
Exposure
For the purposes of this report, 25% of the volume of CFC-
113 and methyl chloroform used in electronic cleaning and 10% of
their volume used in metal cleaning was assumed to be replaced
with terpene cleaners.
General Population
The physical/chemical properties of these substances,
together with known industrial use practices, indicate that
exposures to the general population resulting from cleaning
electronics and metals would be through water. Modeling
estimates of exposures to the general population from these uses
via drinking water and fish consumption do not indicate a basis
for concern and are discussed later in this document. Measured
values of terpenes in water and fish are needed to more fully
characterize general population exposures.
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Occupational
In an effort to understand occupational exposures, the
Agency estimated preliminary exposures in two occupational
settings: electronic printed circuit (PC) board and metal
cleaning. Because these compounds are not currently used for
metal and electronics cleaning to a great extent, no measured
occupational exposure data are available. EPA used exposure
information on other metal and electronics cleaning chemicals
(CFC-113 and methyl chloroform) as surrogate exposure data; in
other situations, modeling information was used to infer
potential occupational exposures. The Agency recognizes the
limitations inherent in the occupational exposure analysis, in
particular, the reliance on the existing CFC-113 and methyl
chloroform data to predict exposures for terpenes. However, the
results of this analysis can guide future and existing users of
the terpenes. Use-specific exposure information is discussed in
Section 3.
Traditionally, exposures to the CFCs have been relatively
high, compared to other industrial chemicals, because of the
well-known biological stability of the compounds. In contrast,
the physical and chemical characteristics of the terpenes (e.g.,
odor and flammability) will dictate a need to use these
substances in ways that reduce the potential for exposure.
Nonetheless, an evaluation of the available toxicity data for
most of the monoterpenes (excluding anethole, a flavoring and
fragrance agent, which is not expected to be used in cleaning
applications) and estimated occupational exposures are not
problematic for all scenarios, except manufacturing. In the
manufacturing situation, outerbound exposures could be reached
during some practices, thus suggesting the need to further
examine these levels and the need for appropriate controls.
It should be noted that terpenes will not be direct
replacements for current CFCs in many cases. New technologies
and equipment will be developed or existing equipment will be
retooled to allow the use of these cleaners. New equipment may
result in exposures that are lower than the estimated exposures
summarized above and discussed in Section 3.
Envi ronmental
Most environmental releases resulting from use of terpenes
will be to water, based on the cleaning operation and their
physical/chemical properties. Releases during manufacturing and
formulation are to air and land (landfill or incineration) and
appear to have minimal exposure potential.
The Agency believes that discharges containing terpenes will
undergo gravity separation (pretreatment) in most instances,
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followed by wastewater treatment (see Section 4). Subsequent to
these treatments, surface water concentrations resulting from
electronics and metal cleaning uses of terpenes may reach levels
that in worst case conditions (minimal dilution in receiving
streams) have been shown to cause toxicity to aquatic organisms
in limited laboratory studies. Without efficient process
controls (e.g., gravity separation, wastewater treatment,
recycling, controlled disposal), surface water concentrations
resulting from electronic and metal cleaning operations may
exceed predicted aquatic toxicity levels.
AQUEOUS CLEANERS
Toxicity
Most of the 20 aqueous cleaner chemicals addressed in this
report have been used widely in cleaning and other industrial
applications for many years. As discussed in Section 2 and
summarized below, some of the constituents used in aqueous
cleaner formulations induce adverse effects in laboratory animals
at low to moderate dose levels. These compounds include:
diethylene glycol monobutyl ether (DGBE); monoethanolamine (MEA);
diethanolamine (DBA); triethanolamine (TEA); and borax.
DGBE is currently the subject of an Agency test rule based
on the concerns for potential toxicity and widespread exposure.
Limited data on the ethanolamines indicate that liver and kidney
effects and neurotoxicity occur at low dose levels in animals.
The ethanolamines can be eye and skin irritants. However, they
are used in cosmetic preparations and are also designed for
intermittent applications (e.g., soaps and shampoos).
Exposure
General Population
The physical/chemical properties of these substances,
together with known industrial use practices, indicate that
exposures to the general population resulting from electronics
and metal cleaning would be through water. Estimated exposures,
using modeling techniques, to the general population via drinking
water and fish consumption do not indicate a basis for concern
and are presented later in this document. Measured values for
aqueous cleaners in water and fish are needed to more fully
characterize general population exposures.
Occupational
In an effort to understand occupational exposures, the
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Agency estimated exposures in occupational settings. Because
insufficient monitoring data were found for all 20 chemicals, the
Agency used monitoring data on surrogate chemicals (CFC-113 and
methyl chloroform), OSHA permissible exposure limits (PELs), or
modeling techniques to evaluate potential exposure, as
appropriate. The Agency recognizes the limitations inherent in
these approaches to exposure analysis, particularly the reliance
on existing CFC-113 and methyl chloroform data to predict
exposures for aqueous cleaner components such as DGBE and the
ethanolamines.
Although there is considerable uncertainty in the exposure
estimates, the available data suggest that formulation and use of
the cleaners represent the greatest potential exposures. Good
workplace practices should be integrated into these operations to
ensure that exposures are controlled. In the absence of
protective equipment (e.g., gloves), exposure levels due to the
formulation and use of DGBE and the ethanolamines in particular
may be inappropriate.
The assessment does not consider any reduction of
occupational or environmental exposures that would result from
the use of personal protective equipment or the use of new
cleaning processes using aqueous cleaners. Information on
exposure estimates are presented in Section 3.
Environmental
Most environmental releases of the aqueous cleaners will be
to water. Among the 20 compounds, surface water concentrations
of MEA and TEA from electronics cleaning may reach levels, on
some release days, that have been shown to cause chronic toxicity
to algae, the most sensitive freshwater species for these
chemicals.
In addition, sodium tripolyphosphate, trisodium phosphate,
tetrasodium pyrophosphate, and tetrapotassium pyrophosphate have
high potential to cause algal blooms and eutrophication in
freshwater environments. Release of these compounds to water
presents well known risks to aquatic species.
The use of appropriate process controls (e.g., wastewater
treatment, recycling, controlled disposal) is recommended to
ensure that surface water concentrations resulting from
electronics cleaning operations do not exceed predicted aquatic
toxicity levels.
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NEXT STEPS
At this early stage in the project, it is unclear as to
which terpene and aqueous cleaner chemicals will actually
substitute for CFC-113 and methyl chloroform and the relative
extent of substitution. As this situation becomes clearer,
additional toxicity and exposure data may be needed.
OUTLINE OF THIS REPORT
Section 2, Hazard Assessment, presents a summary of EPA's
hazard assessment for the 11 categories of aqueous cleaner
chemicals and eight terpenes. The term "hazard" refers to the
potential for human health or environmental effects because of
the inherent toxicity of a chemical.
Section 3, Industrial Processes and Occupational Exposure,
outlines the processes by which the aqueous and terpene cleaners
are produced, formulated and used, and estimates potential
occupational exposures of workers through dermal contact or
inhalation, during manufacture, formulation, and use.
Section 4, Environmental Release, Fate, and Exposure,
presents EPA's estimates of likely releases of the aqueous and
terpene cleaners into the environment, discusses their patterns
of persistence and accumulation in the environment, and presents
an exposure analysis of industrial releases of these chemicals
into water bodies.
More complete assessments of the human health and
ecotoxicity effects of the aqueous and terpene cleaners can be
found in EPA's support documents. The support documents and
other references are listed at the end of this report.
Additional copies of this document and EPA support documents can
be obtained through:
TSCA Assistance Information Service
U.S. Environmental Protection Agency
Office of Toxic Substances. (TS-799)
Washington, D.C. 20460
Telephone: (202) 554-1404
FAX: (202) 554-5603
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2. HAZARD ASSESSMENT
This chapter provides an overview of the health and
environmental hazard information of several candidate aqueous and
terpene cleaner chemicals. This hazard assessment is based on
readily available published literature and information obtained
from EPA program office files. For more detailed evaluation and
references, refer to EPA's support documents.
2.1 AQUEOUS CLEANERS
The 20 candidate aqueous cleaner chemicals presented in this
section are grouped into 11 categories. They were selected from
among the many chemicals that could be used in aqueous cleaner
formulations based on production volume estimates obtained from
industry.
Most of the aqueous cleaner candidates are well known,
widely used industrial chemicals, and, as to be expected, all
have some type of current application in soap or detergent
formulations.
Because of the numerous possible combinations of chemicals
present in cleaning formulations (see chapter 3 for more
discussion), this document does not attempt to evaluate the human
health or environmental effects of the aqueous cleaner
formulations themselves. Rather, it assesses the effects of the
20 chemicals separately. Only a few of these chemicals have
undergone extensive toxicity testing, and a number of these tests
suffer from shortcomings that limit their use for hazard
assessment. Nevertheless, the test data summarized below provide
a general characterization of the toxicological properties
associated with each chemical.
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2.1.1 AMMONIUM HYDROXIDE, POTASSIUM HYDROXIDE, & SODIUM
HYDROXIDE
NH4OH, KOH, NaOH
These three strongly alkaline substances, which have wide
current use as components of soaps or detergents, are well known
for their caustic nature in the presence of moisture. These
chemicals are expected to be used to clean metal surfaces.
Contact of living tissue with the pure compounds by all routes of
exposure usually produces immediate damage to living tissue, with
the extent of damage being dependent on the pH of the solution
and duration of exposure. The higher the pH (usually within the
range 10 to 14), the greater the damage. There appears to be a
latent period following skin contact to NaOH (the only compound
with such data) during which no sensation of irritation occurs,
and the duration of this period appears to be inversely related
to pH.
There are instances (suicide attempts, accidents) in which
massive oral exposure to NaOH has led to esophageal cancer, but
available information suggests that the cancer is the result of
extensive tissue destruction followed by tissue regeneration,
rather than a genotoxic mechanism.
All three compounds have moderate to low acute toxicity to
aquatic species, with vertebrates being more sensitive than
invertebrates. Available data indicate that KOH and NaOH will
not pose a hazard of chronic toxicity to aquatic organisms and
that they will not bioaccumulate or persist in the environment.
Indirectly, NH4OH is most likely to cause chronic toxicity due to
potential release of ammonia. Release of ammonia depends on the
temperature, hardness, and pH of the ambient water. There is a
chronic toxicity value of 85 Mg/1 (27-day EC50) for NH4OH and
acute toxicity values of 80 mg/1 (96-hour LC50) for KOH and 43
mg/1 (96-hour LC50) for NaOH.
2.1.2 DIETHYLENE 6LYCOL MONOBUTYL ETHER (D6BE)
HOCH2CH2OCH2CH20 (CH2) 3CH2
DGBE is widely used as a solvent for inks, dyes, enamels,
and paints and, at low levels, for hard-surface cleaning agents.
It is the subject of an Agency test rule [Federal Register Feb.
26, 1988] that requires manufacturers and processors of the
chemical to perform testing for certain health effects based on
concern for potential toxicity and concern for widespread
exposure to workers and the general population by the dermal and
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inhalational routes through manufacture, processing, and use.
Because of technical difficulties in testing low-vapor-pressure
compounds such as DGBE by inhalation, the recommended test route
is dermal.
Animal data show that DGBE has low acute toxicity by the
oral and dermal routes and is a slight skin irritant at 300
mg/kg. In undiluted form or in 50% solution, however, it is
severely irritating to rabbit eyes. There is no information on
the carcinogenicity of DGBE; three analogues are under
consideration for cancer testing by the National Toxicology
Program. The weight of available evidence indicates that DGBE is
not mutagenic. Available studies of developmental toxicity,
which suffer from various limitations, show no evidence of
developmental toxicity, but they do provide evidence of maternal
toxicity at doses as low as 25 mg/kg. Two studies of
reproductive toxicity, also inadequate for complete hazard
assessment, are negative for reproductive toxicity or parental
systemic toxicity. Data on the neurotoxicity of DGBE are
inadequate to draw any conclusions as to this effect.
Several subchronic (28- to 120-day) tests in rats and
rabbits by the oral, inhalational, and dermal routes show that
the blood is the target organ of DGBE toxicity. Dose levels at
which adverse effects are seen are 51 mg/kg/day by the oral
route, 13 mg/m by inhalation (approximately equal to 2
mg/kg/day), and 30 mg/kg/day by the dermal route. Findings in
inhalation toxicity studies indicate that DGBE may be toxic to
the liver at exposure concentrations of 40 mg/m .
DGBE exhibits a low level of acute toxicity to aquatic
organisms, with LC50 values for fish, daphnids, and algae being
>1,000 mg/1. There are no data on the chronic aquatic toxicity
of DGBE to fish and aquatic invertebrates (e.g., daphnids) or on
the bioconcentration potential or persistence of DGBE in the
environment.
DGBE is the subject of a test rule promulgated by EPA
because of toxicity concerns and exposures resulting from all its
many uses. The tests requested under the rule consist of a
subchronic test with particular emphasis on reproductive,
hematological, and kidney effects; neurotoxicity tests; a
developmental neurotoxicity test; and a pharmacokinetics test,
all by the dermal route. The satellite reproductive toxicity
test and the pharmacokinetics test have been completed.
Remaining data gaps are standard developmental and reproductive
toxicity tests by the oral route, neurotoxicity tests by the
inhalation route, and a subchronic (90-day) test for chronic
toxicity by the oral route from which a NOAEL can be obtained.
For ecological effects, data gaps are in the areas of chronic
aquatic toxicity to fish and aquatic invertebrates and
bioconcentration potential or persistence in the environment.
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2.1.3 DODECANEDIOIC ACID (DDA)
HOOC(CH2)10COOH
DDA is used as an intermediate in the manufacture of
plasticizers, lubricants, adhesives, polyesters, corrosion
inhibitors, and bleaching agents. Virtually no information was
found on the toxicity of DDA in the literature. Based on a
consideration of structure-activity relationships using data on
structural analogues and based on professional judgment, DDA is
not expected to be significantly toxic to humans.
With respect to environmental toxicity, estimations of
maximum toxicity derived from QSAR (quantitative structure-
activity-relationship) equations for neutral organics indicate
that DDA may be moderately to highly toxic to aquatic organisms.
Maximum fish 96-hr LC50 values range from 6 to 17 mg/1, the mysid
shrimp 96-hr LC50 is 2 mg/1, and the daphnid 16-day EC50 is 1.5
mg/1.
It is important to note that these values are based on the
un-ionized form of DDA; in water, where DDA will be ionized,
toxicity is expected to be reduced. There is no information on
the chronic aquatic toxicity of DDA or on its bioconcentration
and persistence in the environment.
2.1.4 ETHYLENEDIAMINETETRAACETIC ACID (EDTA) & ITS TETRASODIUM
SALT
(HOOCCH2) ^CHgCHgN (CH2COOH) 2, (NaOOCCH2) ^CHjCH^ (CH2COONa) 2
EDTA and its tetrasodium salt were selected as components
for aqueous cleaner formulations because of their well-known
ability to form chelates with di- and trivalent metal ions. In
addition, EDTA is used as an antioxidant in foods (at an
acceptable level of use of 0.01%), and both compounds are used as
chelating agents in the treatment of metal poisoning, at doses
ranging from 16 to 50 mg/kg/day.
On the basis of available data, EDTA and its tetrasodium
salt are not expected to exhibit high acute toxicity by the oral
route. EDTA has been implicated as an inducer of hypersensi-
tivity when used as an antimicrobial agent in cosmetics, but a
sensitization study in guinea pigs was negative. There are four
oral cancer bioassays of EDTA salts in rats and mice that are
inadequate for hazard assessment for various reasons.
Nevertheless, three of the assays were negative. The fourth
showed an increased incidence of neoplasms in female rats, but
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the increase was attributed to the longer lifespan of the EDTA-
treated animals. These feeding studies do show that EDTA salts
have low systemic toxicity by the oral route at doses as high as
2,500 mg/kg/day for rats. The only treatment-related effects in
rats fed this dose were reduced body weight gain and increased
blood coagulation time. Mutagenicity data are sparse and
inconclusive, and there is no information on neurotoxicity.
Several studies demonstrate that EDTA is maternally and
developmentally toxic and, additionally, that it may have adverse
effects on the reproductive system. Data are from studies in
which only one or two doses were tested, most of the test doses
are high, treatment did not occur throughout organogenesis, and
assessment of fetal development was incomplete. Doses in the
oral studies (diet and gavage) ranged from approximately 950 to
1,375 mg/kg/day. The only exception is a study in which EDTA was
applied to the eyes of pregnant rabbits (an unusual route of
administration), at an approximate dose of 3 mg/kg; this dose
resulted in 70% embryo/fetal mortality.
The apparent discrepancy between the results of the four
oral lifetime studies in rats and the oral developmental toxicity
studies in rats, at comparable dose levels, can probably be
attributed to the sensitivity of pregnant animals or to strain
differences.
Available data show that EDTA and its salts have low to
moderate acute toxicity to aquatic organisms (i.e., acute
toxicity values are >100 mg/1 for freshwater fish and aquatic
invertebrates and >1 but <100 mg/1 for green algae), and they are
expected to have low chronic toxicity based on a chronic value of
approximately 1 mg/1 for inhibition of algal growth.
Information gaps are noted in the following areas: extent
of gastrointestinal absorption, mutagenicity, developmental and
reproductive toxicity, acute toxicity to algae.
2.1.5 MONOETHANOLAMINE (MEA), DIETHANOLAMINE (DBA), &
TRIETHANOLAMINE (TEA)
NH2CH2CH2OH , NH ( CH2CH2OH) 2 , N ( CH-,CH2OH ) 3
MEA, DEA, and TEA are strong bases that are widely used in
the chemical and pharmaceutical industries as intermediates for
the production of emulsifiers, detergents, solubilizers,
cosmetics, drugs, and textile-finishing agents.
At high solution concentrations, all three compounds are
moderate to severe skin and eye irritants, and data from one
16
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study with humans indicate that TEA (2% solution) may be a weak
skin sensitizer. In rats, single oral doses of >200 and >400
mg/kg produced effects on the liver and kidney, respectively.
There is no information on the carcinogenicity of MEA and
DBA; a dermal bioassay of DBA is planned for 1990. There is
limited evidence that TEA has human carcinogenic potential, based
on the finding of an increased tumor incidence in mice and
equivocal results in rats. A dermal bioassay of TEA with rats
and mice is in progress. The weight of evidence for all three
amines indicates that none represents a mutagenicity hazard to
humans. It should be noted that DBA and TEA can be converted to
the carcinogen N-nitrosodiethanolamine (NDELA) in the presence of
nitrosating agents. The reaction can occur in the stomach, by
the reaction of ingested amines with nitrosating agents in foods
or medications. It can also occur in other, nonbiological
environments, as NDELA has been detected in consumer or
industrial products containing ethanolamines.
A developmental toxicity study of MEA shows that this
compound is maternally and developmentally toxic in rats; the
lowest effect level is 50 mg/kg for developmental effects in rats
by the oral route. Data on DBA and TEA suggest that these
compounds are also developmentally toxic. There are no
reproductive studies of MEA, DBA, or TEA but, in a subchronic
inhalation study of MEA, suppressed spermatogenesis was found in
guinea pigs and dogs exposed to 75 to 102 ppm MEA for up to 30
days.
Given available data, the most significant health effects
for these amines are neurotoxicity, organ toxicity, and
ecotoxicity. Neurotoxicity was noted in dogs, rats, and guinea
pigs exposed continuously by inhalation to MEA at concentrations
as low as 11 mg/kg/day for rats. TEA produced neurotoxic effects
in rats and guinea pigs fed doses as low as 200 mg/kg/day.
Although there are no data on the neurotoxicity of DBA, based on
structural analogy, DBA is also expected to elicit this effect.
The target tissues for all three amines, in repeated-dose
studies by the oral, dermal, and inhalational routes, are the
liver and kidney. Dose levels at which effects are seen in
animals are 170 mg/kg/day by the oral route (DBA), 145 mg/kg/day
by the inhalational route (MEA), and 4 mg/kg by the dermal route
(MEA).
MEA, DBA, and TEA show low to moderate acute toxicity (i.e.,
values are >1 but <100 mg/1) and moderate chronic toxicity to
aquatic organisms. Average chronic toxicity values for
freshwater green algae, the most sensitive freshwater aquatic
species, are 0.850 mg/1 for MEA; 6.6 mg/1 for DBA; and 1.8 mg/1
for TEA. The compounds have a low potential to bioconcentrate
and, thus, food-chain transport should be minimal.
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Areas lacking adequate information are absorption and
metabolism (DEA and TEA) , carcinogenicity (DEA and MEA) ,
mutagenicity, developmental and reproductive toxicity, organ
toxicity (i.e., 90-day test data), neurotoxicity, acute toxicity
to saltwater organisms, chronic toxicity to fish or aquatic
invertebrates, and bioconcentration in fish.
2.1.6 BORAX
10H2O
Borax, or sodium tetraborate decahydrate, is primarily used
in soaps and detergents, with lesser amounts being used in
fertilizers and Pharmaceuticals. Toxicity data on boric acid are
included here because both borax and boric acid dissociate in the
presence of body fluids to the borate ion and both compounds are
considered toxicologically equivalent. Boron is an element
normally consumed by humans in quantities ranging from 0.02 to
0.3 mg/kg/day, depending on the diet.
Human and animal data show that borax has moderate acute
toxicity by the oral route. Based on data from several animal
bioassays, there is no reason to suspect that borax has human
carcinogenic potential. The compound is not mutagenic in
bacteria, weakly mutagenic and cytotoxic in cultured mammalian
cell assays, and negative in a cell transformation assay. There
is no information on the developmental toxicity of borax or boric
acid.
Chronic and subchronic oral exposure of animals to borax or
boric acid produces toxicity to the testes, blood, kidney, liver,
spleen, brain, and adrenals, with these effects being noted in at
least two species and effects on the testes and blood being noted
in rats, mice, and dogs. In addition, there is a case study in
which an infant exposed to 43 mg boron/kg/day for 12 weeks
developed anemia. Nine case reports document neurotoxic signs in
infants at doses as low as 8 mg boron/kg/day over a 5 -week
period.
The most significant effect seen in animals is reproductive
toxicity (i.e., testicular atrophy). Doses at which no effects
were noted in chronic studies are 17.5 mg boron/kg in rats and
8.8 mg boron/kg in dogs.
Borax shows low acute toxicity to aquatic organisms, with
24-hr LC50's ranging from 162 mg/1 to 111 g/1 in tested species.
The boron equivalent range is 4.6 to 3,145 mg/1. It is
moderately toxic upon chronic exposure. Chronic exposures to
aqueous solutions of borax at concentrations >3.5 mg/1 (boron
equivalent concentration >0.1 mg/1) produced teratogenic effects
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in fish. Because of the relatively high water solubility of
borax, it will remain in the water column in dissociated form.
Areas lacking adequate information include:
pharmacokinetics, acute inhalation toxicity, mutagenicity,
developmental and reproductive toxicity, and systemic effects
(i.e., a 90-day test).
2.1.7 ADDITIONAL SODIUM & POTASSIUM SALTS
Of the remaining nine aqueous cleaner chemicals, only the
phosphates appear to be associated with significant toxicity.
The current intended use of all of these salts except sodium
xylene sulfonate is in cleaning of metal surfaces; sodium xylene
sulfonate may find application in cleaning of metal surfaces and
electronic components (e.g., PC boards).
Sodium tripolyphosphate (Na5P3O10), trisodium phosphate
(Na3PO4), tetrasodium pyrophosphate (Na4P2O7), and tetrapotassium
pyrophosphate (K4P2O7) have high potential to cause algal blooms
and eutrophication in freshwater environments, and they should
never be released to water. The concentration of concern is 100
ng/1 (PPt)/ and it is based on a phosphate concentration of 10
Mg/1 that was correlated to algal blooms and oxygen depletion
(eutrophication). Available information on health effects does
not point to any significant toxicity, but no information was
found on the carcinogenicity, developmental/reproductive system
toxicity, or neurotoxicity of these compounds.
Data on sodium carbonate (Na2CO3) and sodium gluconate
[HOCH2(COH)4COONa] show that these compounds are not highly toxic
to human health or the environment and, even though these data
are not complete, both compounds are not expected to pose any
significant toxicity. The only concern is over the alkalinity of
sodium carbonate and, thus, for irritation to skin or mucous
membranes at high solution concentrations of the chemical.
Data on sodium metasilicate (Na2SiO3) and sodium silicate
(Na2Si3O7) show that they, too, are not highly toxic to human
health or the environment. However, data are inadequate in the
areas of subchronic toxicity and developmental/reproductive
system toxicity, and uncertainty remains as to the toxicity of
the compounds in these areas. Although there are also no data on
carcinogenicity, mutagenicity, and neurotoxicity, there is low
concern for these health effects based on a consideration of the
physicochemical properties of the two compounds. Finally, the
same caution applies for irritation to skin or mucous membranes
at high concentrations of these strongly alkaline compounds in
solution.
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From the sparse available toxicity data on sodium xylene
sulfonate (CgHjgC^S.Na) and on the basis of analogue data, the
compound is not expected to be carcinogenic and it is expected to
have low toxicity to aquatic organisms. It should be noted,
however, that there are no data on the acute toxicity,
developmental/ reproductive system toxicity. neurotoxicity, or
ecotoxicity of this compound, and some uncertainty remains as to
its potential toxicity in these areas.
2.2 TERPENE CLEANERS
This section contains a summary of the potential hazards of
eight terpene compounds to human health and the environment based
on currently available data.
Available toxicity data for most of the terpenes under
review are inadequate for a full evaluation of the potential
hazards of these chemicals. However, the data indicate that the
most significant toxicity due to terpenes appears to be
environmental toxicity, specifically, moderate to high toxicity
to aquatic organisms.
At moderate doses, d-limonene and anethole may be
hepatotoxic to mice and rats, respectively, and, at high doses,
d-limonene may be a developmental toxicant in mice and rabbits.
In chronic studies with rats and mice, d-limonene induced kidney
toxicity and kidney tumors in the male rat, but the biological
relevance of the male rat kidney response to humans is uncertain.
Undiluted terpenes appear to be moderate skin irritants.
Evidence suggests that contact dermatitis, or dermal
sensitization, may develop from an impurity found in commercial
terpene formulations. The pure terpenes themselves do not appear
to cause dermal sensitization.
Additional information concerning chronic toxicity,
oncogenicity, mutagenicity, developmental/reproductive effects,
neurotoxicity, and acute/chronic aquatic toxicity is needed for
most of these terpenes for a complete hazard assessment. More
details are given below.
Absorption/Metabolism; Absorption and metabolism data are
not available for all the terpenes of interest. The data
reviewed are inadequate to fully characterize the
pharmacokinetics of the terpenes. However, based on available
data on d-limonene, anethole, and a- and 0-pinene and an
analogue, p-cymene, the terpenes are expected to be absorbed from
the skin, lungs and gastrointestinal (GI) tract. The available
data on d-limonene, a- and 0-pinene, and anethole indicate that
the terpenes may be metabolized to give hydroxy-substituted and
carboxylic acid derivatives. These derivatives may be conjugated
with glucuronic acid or excreted free in the urine.
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Acute toxicitv; Available acute toxicity studies in rodents
show that d-limonene is slightly to moderately toxic following a
single oral exposure (LD50 values range from 3.4-7.9 g/kg). a-
Pinene and anethole are moderately acutely toxic to rats (LD50 =
3.7 and 3.2 g/kg, respectively) by the oral route, and /3-pinene
and dipentene do not appear to be highly acutely toxic by the
oral route (LD50 >5 g/kg; no deaths at this dose) . Acute dermal
toxicity data on four of these terpenes show that none are highly
toxic by this route. No acute toxicity data are available for a-
and /3-terpinene and terpinolene.
Undiluted d-limonene and a-pinene caused moderate skin
irritation in primary dermal irritation studies with rabbits.
However, diluted samples of a- and /3-pinene, anethole, and
dipentene (2%-20% in petrolatum) did not produce skin irritation
in human volunteers. These results indicate that the undiluted
terpenes are moderate skin irritants and that diluted or
formulated terpenes may not be skin irritants. There is no
information on the dermal irritation of a- and 0-terpinene and
terpinolene. Eye irritation information is not available for any
of the eight terpenes.
No data are available on the dermal sensitization potential
of a- and /3-terpinene and terpinolene. Purified d-limonene, a-
and /3-pinene, anethole, and dipentene did not induce contact
dermatitis in humans. However, the oxidative product of a
contaminant of some formulated terpenes, A-3-carene, is a
sensitizer. In view of the fact that terpenes are expected to be
used in an oxidizing environment, sensitization is a potential
problem with commercially available preparations of terpenes
contaminated with A-3-carene.
Subchronic and chronic toxicity; The subchronic and chronic
oral toxicities of d-limonene have been adequately tested in rats
and mice. The data show that chronic oral exposure to d-limonene
results in a pattern of histopathology specific for the male rat
kidney but that this effect apparently is not significant to
humans (see discussion in carcinogenicity and mutagenicity
section below). In a 2-year feeding study of d-limonene in rats
and mice by the National Toxicology Program, dose-related kidney
toxicity was observed in male rats at both doses (75 and 150
mg/kg/day). The apparent lowest observed adverse-effect level
(LOAEL) for kidney toxicity is 75 mg/kg/day. In a subchronic
toxicity study and in several short-term oral toxicity studies
with d-limonene, similar kidney toxicity was observed in male
rats.
In the 2-year feeding study of d-limonene in mice, signs of
general toxicity, such as body weights 5%-15% lower than those of
vehicle controls, were observed in high-dose females (1,000
mg/kg/day) after week 28. Signs of liver toxicity were seen in
the high-dose males (500 mg/kg/day). Thus, there is an apparent
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no observed adverse-effect level (NOAEL) of 500 mg/kg/day for
general toxicity in female mice and an apparent NOAEL of 250
mg/kg/day for liver toxicity in male mice.
Anethole has been reported to cause liver toxicity in two
subchronic oral toxicity studies in rats. In one study, anethole
was fed to rats for 90 days at doses of 50, 150, 500, or 1,500
mg/kg/day. Liver toxicity in the form of hepatocellular edema
and degeneration was seen at the dose levels >150 mg/kg/day. No
effects were seen at 50 mg/kg/day. Based on the results of this
study, the NOAEL for liver toxicity is 50 mg/kg/day. In the
second study, slight liver toxicity was found in rats fed
anethole at 500 mg/kg/day for 15 weeks, but no effects were seen
in rats fed 125 mg/kg/day of the compound for 1 year.
Carcinoqenicity and mutagenicity; Anethole, the only
terpene of interest with an aromatic configuration, has been
tested in four limited (e.g., duration less than lifetime, only
one species tested, route of exposure not relevant) cancer
bioassays in mice. No tumorigenic responses were found in any of
the available studies. However, there are indications that
anethole is a gene mutagen in prokaryotes when tested with
metabolic activation.
In a 2-year feeding study of d-limonene in rats and mice, a
dose-related incidence of kidney tumors was seen in male rats at
75 and 150 mg/kg/day. This study showed no evidence of
tumorigenicity in female rats or in male and female mice.
The mechanism by which d-limonene induces nephrotoxicity and
kidney tumors in male rats is not fully understood, and the
biological relevance to humans is unclear. However, current data
suggest that d-limonene-induced nephropathy and renal neoplasia
in the male rat occur via excessive accumulation of a-2/i-
globulin, whose synthesis is male rat-specific, in renal tubules.
It has been proposed that male rat kidney tumors should not be
considered as relevant to human risk as other tumors. This is
because concentrations of similar proteins in human urine are
well below those found for a-2/i-globulin in male rats. Given
this situation, it is unlikely that enough protein could
accumulate in the human kidney following exposure to d-limonene
to result in hyaline droplet formation containing this protein.
In addition, these human proteins appear to have low binding
affinity to d-limonene. The Agency is currently addressing this
issue.
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No carcinogenicity or mutagenicity data are available for
any of the other terpenes of interest.
Reproductive and developmental effects; Available
information on the developmental toxicity of these terpenes is
limited to two developmental toxicity studies of d-limonene in
mice and in rabbits. Neither study is adequate for establishing
LOAELs or NOAELs because of the small sample sizes. Furthermore,
only two dose levels were tested in the mouse study, and dosing
did not occur throughout the entire period of organogenesis. In
the mouse study, a very high dose (2,363 mg/kg/day by gavage)
resulted in maternal toxicity, as demonstrated by a significant
reduction in body weight. Exposure to this dose also resulted in
developmental toxicity (pre- and postnatal), as manifested by a
significant increase in the number of fetuses with skeletal
abnormalities, including lumbar ribs, fused ribs, and delayed
ossification of several bones in the paws. No maternal or
developmental toxicity was observed in mice exposed to 591
mg/kg/day.
In the rabbit study, exposure of does to 500 or 1,000
mg/kg/day of d-limonene by gavage resulted in maternal toxicity.
There was a significant reduction in food consumption and body
weight, while exposure to 1000 mg/kg/day also led to death.
There was no indication of maternal toxicity at the lowest dose
tested, 250 mg/kg/day. There also was no significant evidence of
developmental toxicity at any dose level, but it should be noted
that the sample sizes were small.
No reproductive toxicity studies have been conducted on
terpenes. In a 6-month toxicity study in which rats were
administered d-limonene by gavage at 277, 554, or 1,385
mg/kg/day, no effects on reproductive organs were noted.
However, in an earlier 28-day study in which rats were treated by
gavage at 277, 554, 1,385, or 2770 mg/kg, there was a
significant, dose-related reduction in absolute ovarian weight in
rats exposed to >554 mg/kg/day and a significant reduction in
relative ovarian weight after exposure to 2,770 mg/kg/day. The
reasons for this conflicting finding are not known.
Neurotoxicity; The available neurotoxicity studies on a-
pinene and on a pesticide containing d-limonene showed no
compound-related neurotoxic effects. The study on a-pinene was
well designed, executed, and analyzed. A functional
observational battery (FOB) and a neurochemical analysis were
performed. No neurotoxic effects were reported in 40 rats
exposed via inhalation to 200 mg/kg/day (approximately 300 ppm)
of commercial turpentine containing 95% a-pinene for 8 weeks.
A single dermal application to cats of a commercially
available pet flea and tick dip containing 78.2% d-limonene and
unspecified additional chemicals produced several neurotoxic
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signs and symptoms. However, since the neurotoxic effects noted,
such as muscle tremors, ataxia, and hypersalivation, are all
associated with hyperactivity in the cholinergic system, and most
insecticides formulated for use on pets contain small amounts of
cholinesterase inhibitors, it is reasonable to conclude that the
neurotoxic effects observed are associated with a component of
the remaining 21.8% of the mixture, not d-limonene. No data are
available to evaluate the neurotoxic potential of the other
terpenes.
Environmental effects; Analysis of available acute and
chronic toxicity values for freshwater aquatic organisms and
predicted values based on SAR (structure-activity relationship)
analysis indicates that the terpenes present a moderate (1-100
mg/L) to high (<1 mg/L) hazard to aquatic organisms.
Measured acute toxicity values for fish (96-hr LC50) and
daphnids (48-hr LC50) and measured toxicity values for freshwater
green algae (96-hr EC50) are, respectively (in milligrams/liter) ,
0.711, 0.730, NM [not measured] for d-limonene; 38.5, 31.0, and
6.9 for dipentene; 0.280, 1.44, and NM for ot-pinene; 0.502,
1.250, and NM for /3-pinene; 7.69, 6.82, and 4.24 for anethole;
3.15, 1.85, and NM for a-terpinene; and 1.21, 2.55, and NM for
terpinolene. When a chemical was not measured, it was due to the
fact that there was a complete loss of chemical within 24 hr.
Tests were not run with /3-terpinene because the chemical is
commercially unavailable.
Measured chronic toxicity values are available for only two
of the terpenes and they are for freshwater green algae only:
the 96-hr no-effect concentrations are 4.08 mg/1 for dipentene
and 3.09 mg/1 for anethole.
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The chemical structures of the eight terpenes under review
and that of p-cymene, an analogue, are shown below.
d-Limonene
Anethole
Dipentene
(dl-limo-
nene)
a-Ter-
pinene
Terpinole-
ne
/3-Ter-
pinene
a-Pinene
/3-Pinene
p-Cymene
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3. INDUSTRIAL APPLICATIONS AND OCCUPATIONAL EXPOSURE
This section characterizes potential occupational exposures
that may result from the increased manufacture, formulation, and
use of aqueous and terpene-based cleaning formulations as
substitutes for CFC-113 and methyl chloroform in PC board and
metal cleaning. The information presented in this section is
discussed in more detail in the two support documents on
occupational exposure and environmental release (PEI, 90a; PEI,
90b). The following occupational exposures scenarios are
addressed in this section: manufacture of terpenes; formulation
of aqueous and terpene cleaners; and use of aqueous and terpene
cleaners in PC board cleaning, warm immersion cleaning, and cold
immersion cleaning.
Both aqueous and terpene-based cleaners are mixtures,
comprised of components which enhance the cleaning product's
performance in a specific application. The most common aqueous
cleaners generally consist of three components: alkalis or
alkaline salts which provide alkalinity, reduce hardness, and act
as buffering and chelating agents in the cleaning solution;
chemical additives which may provide additional cleaning, surface
modification properties, rust inhibition or water softening
depending on the specific use application; and surfactants which
improve detergency, emulsification, and surface wetting
properties. Terpene cleaners generally consist of: a terpene
which provides a high solvency of greases and oils; chemical
additives, depending on the sensitivity of the materials cleaned
and degree of cleanliness required; and surfactants. Because
there are a number of possible cleaner formulations, for purposes
of this report, four model aqueous cleaner formulations and two
model terpene cleaner formulations were used to screen potential
occupational exposures. These formulations are intended to be
representative of cleaners as a whole. The composition of the
model formulations are described in sections 3.2.1 and 3.3.2.
Occupational exposure assessments require information that
is representative of the variability in the industrial sector
under review, on: the populations exposed; worker activities and
industrial practices leading to exposure; routes of exposure; and
the frequency, duration, and levels of exposure to the chemicals
under review. A comprehensive exposure assessment would relate
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worker activities to exposures measured, and then present the
range and distribution of the monitoring data. In the case of
aqueous and terpene-based cleaners, there were no personal
monitoring data available to characterize potential exposures,
primarily because these cleaners are not currently in extensive
use in these applications. In the absence of any monitoring
data, exposure levels were estimated using techniques frequently
used in EPA occupational exposure analyses.
Both typical and outerbound potential occupational exposures
were estimated. Typical exposures are presented to provide a
sense of what likely or average exposures may potentially be.
EPA has some degree of confidence that potential exposures are
likely to be less than the outerbound levels presented. There is
more uncertainty in the estimates of typical exposures because
typical conditions are more difficult to establish. It should be
noted that the exposure estimates presented do not take into
account the use of personal protective equipment, such as gloves
and respirators, or the use of equipment, such as closed-loop
systems and nitrogen blankets, which may help to reduce exposures
in future uses of aqueous and terpene cleaners.
The routes of occupational exposure assessed for the aqueous
and terpene cleaners were the inhalation and dermal routes. The
major sources of information used to develop this assessment
include:
o Permissible Exposure Limits (PELs) promulgated by the
Occupational Safety and Health Administration (OSHA);
o A database maintained by OSHA which contains records on
1400 chemicals regulated by OSHA and monitored mostly
for enforcement purposes) since 1981;
o Information from National Institute of Occupational
Safety and Health (NIOSH) studies such as Health Hazard
Evaluations and Industry Wide Surveys;
o Information voluntarily submitted to the Agency by
manufacturers and users of aqueous and terpene-based
cleaners during the development and review of this
document.
For solid components of aqueous cleaners, the OSHA PEL for
nuisance dust, 15 mg/m total dust, 8-hour time-weighted average
(TWA), was used to estimate the outerbound inhalation exposure
during formulation and use, if that component does not have a
chemical-specific OSHA PEL. Assuming a breathing rate of 1.25
m/hour and an 8-hour work day, the estimated worker inhalation
exposure to all of the solid constituents during formulation or
use is not expected to exceed 150 mg/day. Concentrations of
chemicals that have PELs are expected to be controlled by their
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chemical-specific PEL rather than by the nuisance dust PEL.
Exposures to individual components may be less than 150 mg/day
when more than one component is present as airborne dust.
Sufficient data are not available to estimate a typical dust
exposure.
For liquid components, two approaches were taken to estimate
levels of exposure: a theoretical modeling approach, and a
surrogate data approach. The modeling approach required an
estimate of source strength, such as the amount of chemical that
might volatilize from a liquid surface. The chemical's airborne
concentration was then estimated considering dilution from mixing
and ventilation in the workplace air. Finally, worker exposure
was estimated based on the chemical concentration, the worker's
breathing rate, and the duration of exposure. Engineering
judgment was used to estimate typical values of model input
variables. The surrogate data approach used actual exposure
monitoring data for a chemical other than the chemical under
review but one used in a similar industrial setting. The
surrogate chemicals used in this exposure assessment were CFC-113
in PC board cleaning and methyl chloroform in metal cleaning.
Workplace concentrations of the surrogate chemical were converted
to concentrations of the chemical under review by taking into
account differences in vapor pressures and use concentrations.
The surrogate data approach does not take into account
differences in work practices and equipment which may change due
to chemical substitution.
Greater reliance is placed on use of the modeling approach
based on past experience with other chemicals where comparisons
with actual data could be made. However, there is uncertainty
with the modelled exposures. This uncertainty originates
predominantly in the assumptions used for model input variable
values. Generally, beyond ventilation of indoor work areas,
controls that might limit exposure were not considered in the
modeling. In addition, the extent to which future differences in
work practices and equipment design will reduce exposures is also
unknown and not considered. The surrogate data approach provides
greater certainty when the only difference in the exposure
scenario is the chemical itself. Because the surrogate chemicals
are not close analogues to the aqueous and terpene substitutes,
there are differences in equipment and work procedures between
the use of the surrogates and the use of aqueous and terpene
cleaners, which add considerable uncertainties to the exposures
estimated from the surrogate data approach. Thus, only the
modeling approach results are presented in this report.
Surrogate data approach exposure estimates range from 2 to 54
percent of modeling approach exposure estimates. A more complete
discussion of the two approaches is presented in the support
documents (PEI, 90a; PEI, 90b).
28
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Dermal exposures were estimated from a model using an
estimate of hand surface area in contact with the substance,
surface concentration of the substance, and concentrations of
specific chemicals in the substance. This model generated
outerbound estimates of the amount of a chemical that might be
available at the skin's surface for dermal absorption.
Sufficient data were not available to estimate a typical dermal
exposure.
3.1 SUMMARY AND CONCLUSIONS
Tables 3-1 and 3-2 summarize the results of this preliminary
assessment which are described in more detail in the following
sections. Monitoring studies of actual worker activities
associated with the use of aqueous and terpene-based cleaners
would reduce uncertainties associated with this exposure
characterization. The monitoring studies could also serve to
show the extent exposures might be lowered through equipment
designs and workplace practices established for these cleaners.
3.2 AQUEOUS CLEANERS
Aqueous solutions have been used in the metal parts cleaning
industry for over twenty years. They have also found acceptance
in maintenance cleaning activities. In the electronics industry,
widespread use of these cleaners has found acceptance only in the
past five years. It is anticipated that aqueous cleaners will
serve as feasible substitutes for CFC-113 and methyl chloroform
in a fraction of all electronics (20 - 35 percent) and metal
cleaning practices (30 to 50 percent). To estimate exposures, it
was assumed that aqueous cleaners will replace CFC-113 and methyl
chloroform in 30 percent of PC board cleaning operations and in
40 percent of metal cleaning operations.
Aqueous cleaners are available in many chemical
formulations, depending on the substrate being cleaned, the type
of surface contaminant, and the degree of cleanliness required.
These formulations can be generic multi-purpose cleaning
solutions or be formulated for the needs of a specific industry.
There are three general types of aqueous cleaning solutions:
alkaline cleaners; acidic cleaners; and solvent emulsion
cleaners, which include terpene cleaners, also discussed in this
report. Since alkaline cleaners are the most likely to serve as
substitutes for CFC-113 and methyl chloroform, they are the focus
of the aqueous formulations discussed in this report.
29
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TABLE 3-1 SUMMARY OF ESTIMATED OCC, ,-JiSAL EXPOSURES TO AQUEOUS CLEANER
Estimated
number of Estimated
sites at number
Outerbound Outerbound
estimated of exposed
inhalation dermal
substitution employees
exposure , exposure
Use rate per site
mg/dayc
-------
150
N/A
PC board
cleaning
730
550
N/A
2300
200
Surfactants Liquid
210
25
Alkaline
salts
Additives
Solid
Liquid
Surfactants Liquid
8
N/A
8
8
N/A
8 Total number of formulation sites for both metal cleaning and electronics cleaning formulations.
b Duration of exposure is a function of worker activities.
c Exposure estimates do not account for personal protective equipment or enhancements to equipment
design which may reduce
exposures.
d Concentrations of chemicals that have PELs, such as sodium hydroxide and borax, are expected to be
controlled by their
chemical-specific PEL rather than by the nuisance dust PEL, and resulting exposures may be lower
than 150 mg/day.
31
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TABLE 3-2 SUMMARY OF ESTIMATED OCCUPATIONAL EXPOSURES TO TERPENE CLEANER CONSTITUENTS
Estimated
number of Estimated
sites at number
Outerbound Outerbound
estimated of exposed
inhalation dermal
substitution employees
exposure , exposure
Use rate per site
mg/dayb mg/dayb
Manufacturing- 35 10
1500 3900
terpenes
Formulation- 10 10
92 3900
metal
150 3900
cleaner
8 3900
8 3900
Formulation- 1 10
.. 720 3900
1 electronics
34 3900
cleaner
Warm 510 7
13 3600
immersion
N/A 550
cleaning
Chemical
category
Terpene
Terpene
Additives
Surfactants
Terpene
Surfactants
Terpene
Additives
Physical
state
Liquid
Liquid
Solid
Liquid
Liquid
Liquid
Liquid
Liquid
Solid
Liquid
Typical
Exposure inhalation
duration, exposure,
hr/daya mg/dayb
<8 600
<4 9
N/A
<1
<1
<4 140
7
<4 3
N/A
<1
32
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Surfactants Liquid
<1
<1
Cold
84
immersion
N/A
cleaning
8
8
PC board
420
cleaning
17
1500
770
3600
550
1100
1500
180
3500
390
4 Terpene
Additives
Surfactants
25 Terpene
Surfactants
Liquid <4
Solid
Liquid
Liquid
Liquid <4
Liquid
17
N/A
2
2
84
3
a Duration of exposure is a function of worker activities.
b Exposure estimates do not account for personal protective equipment or enhancements to equipment
design which may reduce
exposures.
33
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3.2.1 FORMULATION OF AQUEOUS CLEANERS
Formulation refers to the blending of chemicals to result in
a cleaning formulation. Formulation is accomplished using
physical mixing and blending operations. Alkaline-based
cleaners, the most common type of formulation, are produced in
concentrated form as either liquids or powders. These alkaline-
based cleaners are largely comprised of three types of
components: alkalis or alkaline salts, builders, and surfactants.
Typical aqueous formulations for metal and electronics cleaning
are presented in Tables 3-3 and 3-4, respectively. These
formulations provide a basis for occupational exposures and
environmental release estimates presented later in this report.
Table 3-5 presents OSHA PELs for aqueous cleaner constituents for
which exposure limits have been adopted. Concentrations of these
constituents would be expected to be limited to their PELs.
Resulting estimates of exposure to solids in aqueous cleaners,
based on chemical-specific PELs, are not presented in this
report.
There are an estimated 20 companies that produce aqueous
cleaners for metal and electronics cleaning. No information was
available on the average daily throughputs for these facilities;
however, sufficient production capacity seems to exist to meet
potential increases in demand.
These formulators are believed to employ from 10 to 33
employees per site, with an average of 20 total employees. It is
expected that less than 10 employees would be directly exposed
during aqueous formulation at a typical facility. Potential
points of worker exposure include: raw materials handling;
activities at the blending tanks; and product packaging. Workers
may be exposed during 250 days per year.
Rubber gloves are probably used by workers formulating the
cleaners. Information on the use of other forms of personal
protective equipment was not available. General ventilation is
the only engineering control believed to be typically used in
formulating facilities.
Inhalation and dermal exposure estimates, summarized in
Table 3.1, were determined from the models described in the
introduction to section 3. Open-top mixing vessels were assumed
for estimating inhalation exposures to liquid constituents of
metal cleaning formulations. Closed mixing vessels were assumed
for estimating exposures to liquid constituents of electronics
cleaning formulations. Inhalation exposures to surfactants are
estimated to be 4 mg/day in the typical case, 21 mg/day
outerbound. Outerbound dermal exposures are estimated to be
18,000 mg/day for alkaline salts and additives, the solid
components, and 3,900 mg/day for surfactants, the liquid
components available for absorption.
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TABLE 3-3 TYPICAL AQUEOUS METAL CLEANING FORMULATIONS
Weight percentage
Chemical CAS Number in formulation
Formulation 1; Powder Alkaline Metal Cleaner
Sodium carbonate 497-19-8 45
Trisodium phosphate 7601-54-9 15
Sodium tripolyphosphate 7758-29-4 20
Borax 1303-96-4 17
Linear alkyl aryl sulfonate8 - 2
Anionic surfactant - 1
100
Formulation 2; Licfuid Alkaline Metal Cleaner
Water 7732-18-5 30
Sodium metasilicate 6834-92-0 33
Sodium hydroxide 1310-73-2 7
Tetrasodium pyrophosphate 7722-88-5 5
Trisodium phosphate 7601-54-9 22
Alkyl aryl sulfonajte 25155-30-0 2
Anionic surfactant - 1
100
Formulation 3: Non-phosphated Alkaline Aluminum Cleaner
Sodium carbonate 497-19-8 55
Sodium metasilicate 6834-92-0 35
EDTA 60-00-4 4
Linear alkyl aryl sulfonate 25155-30-0 3
Anionic surfactant - 3
100
0 An example of a linear alkyl aryl sulfonate is sodium
dodecylbenzene sulfonate, CAS Number 25155-30-0.
Typical anionic surfactants include ethoxylated octyl phenol
and ethoxylated nonyl phenol.
Sources: Bennett, 75; Kirk-Othmer, 83; Pappalardo, 85; Pettit,
89d.
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TABLE 3-4 TYPICAL AQUEOUS ELECTRONICS CLEANING FORMULATION
" ~" Weight percentage
Chemical CAS Number in formulation
Formulation 4; Alkaline Electronics Cleaner
Monoethanolamine 141-43-5 60
Diethylene glycol
monobutyl ether 112-34-5 35
Anionic surfactant8 - 5
100
" Typical anionic surfactants include ethoxylated octyl phenol
and ethoxylated nonyl phenol.
Sources: Bennett, 75; Kirk-Othmer, 83; Pappalardo, 85; Pettit,
89d.
TABLE 3-5 AQUEOUS CLEANER CONSTITUENTS FOR WHICH EXPOSURE
LIMITS HAVE BEEN ADOPTED
Chemical OSHA, PEL ACGIH, TLV
Sodium hydroxide 2 mg/m , ceiling 2 mg/m , ceiling
2-Butoxyethanol 120 mg/m3, TWAb'c 121 mg/m3, TWA with
"skin" notation
10 mg/m3, TWA 5
tetraborate)
lene glycol
methyl ether "skin" notation
etrasodium
pyrophosphate
Borax (sodium 10 mg/m3, TWA 5 mg/m3, TWA
Dipropylene glycol 600 mg/m , TWA 606 mg/m , TWA with
"skin"
Tetrasodium 5 mg/m , TWA 5 mg/m , TWA
Monoethanolamine 8 mg/m3, TWAd 7.5 mg/m3, TWA
0 The OSHA final limit, effective December 30,1992,is 2 mg/m3,
ceiling. The transitional limit, in effect until December 30,
1992, is 2 mg/m , TWA.
TWA = time-weighted average.
c Transitional limit is 240 mg/m .
There is no transitional limit.
Source: ACGIH, 89.
36
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3.2.2 PC BOARD CLEANING WITH AQUEOUS CLEANERS
Methyl chloroform and CFC-113 are the predominant solvents
used in the electronics industry today. However, aqueous
cleaning is an accepted method of defluxing PC boards in some
applications. Although DOD standards do not currently allow for
the use of terpene cleaners in PC board manufacture for military
use, revision of those standards is underway. It is expected
that the new specifications will discourage use of CFCs and other
ozone-depleting chemicals and will allow any method of cleaning
that satisfies certain cleaning performance criteria. There are
four general types of aqueous cleaning equipment used to remove
fluxes from PC boards: mechanical brushing; low-throughput batch;
high-throughput batch; and in-line conveyorized.
There are an estimated 705 PC board manufacturers in the
U.S. using 5,000 to 7,000 cleaning units. Based on a 30 percent
conversion to aqueous cleaners, 210 sites may substitute aqueous
cleaners for methyl chloroform and CFC-113. At each of these
sites, an average of 24 workers could potentially be exposed
based on estimates of 3 workers per cleaning unit and 8 units per
site.
Workers can be exposed to aqueous cleaners in PC board
cleaning during transfer of the cleaner to the cleaning bath and,
to a much lesser extent, from handling the PC boards after the
boards have been rinsed with water. Workers may be exposed
during 250 days per year. Handling of the PC boards during
cleaning and draining of dirty cleaner and rinse water is usually
an automated, closed process with most unit designs. Gloves are
typically used when handling the cleaned PC boards.
Inhalation and dermal exposure estimates, summarized in
Table 3.1, were determined from the models described in the
introduction to section 3. Enclosed heated immersion baths were
assumed for estimating inhalation exposures to liquid
constituents of the aqueous PC board cleaners. Typical and
outerbound inhalation exposures to all constituents were
estimated to be less than 1 mg/day. Outerbound dermal exposures
were estimated to be 2,300 mg/day for additives and 200 mg/day
for surfactants available for absorption.
3.2.3 WARM IMMERSION CLEANING WITH AQUEOUS CLEANERS
Aqueous cleaning has found wide usage in the manufacturing
sector as an alternative to open-top vapor degreasing for
cleaning metal parts. Cleaning is accomplished by using heated
solutions in immersion tanks or by spraying. Finishing steps
include rinsing, drying, and wastewater disposal. Systems may be
batch, which often require more manual handling of parts, or in-
line, which are used when higher throughput is needed.
37
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An estimated 9,070 open-top vapor degreasers operate in the
U.S., of which 5,106 use methyl chloroform or CFC-113. It was
assumed that there would be up to a 40 percent conversion to
aqueous cleaners, thus resulting in an estimated 2,000 sites
which may substitute aqueous cleaners for methyl chloroform and
CFC-113. The number of workers exposed to aqueous cleaners per
degreaser was assumed to be seven, the same as for open-top vapor
degreasers.
Worker exposure to aqueous cleaners in warm immersion
systems may occur during transfer of the cleaner to the cleaning
bath, handling of the parts during the cleaning operation,
handling of the cleaned parts, and disposal of the dirty cleaning
solution. Workers may be exposed during 250 days per year.
The use of dermal protection is currently recommended by
aqueous cleaner formulators and is probably employed by many
aqueous cleaner users.
Inhalation and dermal exposure estimates, summarized in
Table 3.1, were determined from the models described above.
Open-top warm immersion baths were assumed for estimating
inhalation exposure to liquid constituents of the aqueous metal
cleaners. Outerbound inhalation exposures to alkaline salts and
additives when handled as solids during warm immersion cleaning
were estimated to be 150 mg/day based on the OSHA PEL for
nuisance dust. Typical and outerbound inhalation exposures to
surfactants were estimated to be less than 1 mg/day. Outerbound
dermal exposures were estimated to be 10,000 mg/day for alkaline
salts and 730 mg/day for additives, the solid components, and 550
mg/day for surfactants, the liquid components available for
absorption.
3.2.4 MAINTENANCE COLD CLEANING WITH AQUEOUS CLEANERS
Cold batch immersion systems dominate as a method of metal
cleaning in various industrial/manufacturing settings and service
settings such as automotive garages and repair shops. These
cleaning operations can include spraying, flushing, brushing, and
immersion. Drying will also be necessary if remaining water
could cause rust to form.
An estimated 9,740 cold degreasers operate in the U.S., of
which 7,689 use methyl chloroform or CFC-113. Assuming up to 40
percent conversion to aqueous cleaners, 3,100 sites may
substitute aqueous cleaners for methyl chloroform and CFC-113
units.
The number of workers potentially exposed per unit is the
same as for cold cleaners using chlorinated solvents, or four
workers.
38
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Workers can be exposed to aqueous cleaners in cold cleaning
during: transfer of the cleaner to the cleaning bath; handling of
parts during the cleaning operation; handling of the cleaned
parts; and disposal of the dirty cleaning solution. Workers may
be exposed during 250 days per year.
The use of dermal protection is currently recommended by
aqueous cleaner formulators and is probably employed by many
aqueous cleaner users.
Inhalation and dermal exposure estimates, summarized in
Table 3.1, were determined from the models described above.
Open-top cold aqueous baths were assumed for estimating
inhalation exposures to liquid constituents of the aqueous metal
cleaners. Outerbound inhalation exposures to alkaline salts and
additives when handled as solids during cold cleaning were
estimated to be 150 mg/day based on the OSHA PEL for nuisance
dust. Typical and outerbound inhalation exposures to surfactants
were estimated to be less than 1 mg/day. Outerbound dermal
exposures were estimated to be 10,000 mg/day for alkaline salts
and 730 mg/day for additives, the solid components, and 550
mg/day for surfactants, the liquid components available for
absorption.
3.3 TERPENE CLEANING
Terpenes are a class of natural products commonly found in
the odorous components of plants. Recently, the demand for
certain terpenes has risen as a result of their increased use in
cleaning applications. Of the many terpenes available for use in
industrial applications, monoterpenes, those terpenes which
contain ten carbon atoms, offer the best potential for increased
use in metal and electronics cleaning.
Current consumption of terpenes is estimated to range from
about 157 to 193 million kilograms (about 125 to 161 million
kilograms are derived from pine; 32 million kilograms are derived
from citrus fruits). Assuming terpene-based cleaner substitution
for current methyl chloroform and CFC-113 usage of up to 25
percent in PC board cleaning and up to 10 percent in metal
cleaning, incremental terpene demand could be up to 1.8 million
kilograms per year.
3.3.1 MANUFACTURE OF TERPENES
Most terpenes are obtained from the distillation or
extraction of citrus oils and wood turpentine. Citrus oils are
obtained most commonly from the distillation of discarded orange
and lemon pulp and peels. Turpentines are obtained from
extraction or distillation of stumps and resinous wood wastes and
from the wood-cooking step of the kraft pulping process.
39
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There are an estimated 30 to 35 manufacturers of d-limonene
and four major manufacturers of other terpenes. Florida's
production of d-limonene is approximately 6.8 million kg (15
million Ib) per year. Production of a- and B-pinene was 71
million kg (156 million Ib) in 1987. Estimates of production
quantities of other terpenes were not found.
One terpene manufacturer/formulator reported that they had
35 total employees. Less than 10 employees would be expected to
be exposed to terpenes during manufacture at a site. This
estimate was extrapolated to all terpene manufacturers.
During terpene manufacture, workers may be exposed to
terpenes during: production operations; quality control sampling;
tank truck and drum filling; packaging of product; and
maintenance activities. Sampling and product loadout operations
have the highest potential for exposure. Workers may be exposed
from 26 to 250 days per year.
One manufacturer stated that their workers use "solvent-
resisting" gloves and safety glasses where exposure is likely.
Exposures to terpene concentrations greater than 100 ppm (556
mg/m ) may be very irritating, so it is likely that air
concentrations would be controlled to below this level. It may
be noted that estimated workplace concentrations in this
assessment do not exceed 50 ppm during manufacture of terpenes or
during formulation or use of terpene cleaners.
No monitoring data were found for worker exposure to
terpenes during manufacture. Inhalation and dermal exposure
estimates, summarized in Table 3.2, were determined from the
models described in the introduction to section 3. Inhalation
exposures to terpenes at manufacturing sites for drumming of
terpenes were estimated to be 600 mg/day typically, and 1500
mg/day outerbound. Outerbound dermal exposures were estimated to
be 3900 mg/day terpenes available for absorption.
3.3.2 FORMULATION OF TERPENE CLEANERS
Formulation of terpene cleaners involves mechanical blending
of raw materials. Typical formulations consist of the terpene, a
surfactant, and may include other performance enhancers.
Formulation is done on a batch basis, usually in closed mixing
vessels, but open tanks may be used. Loading of large-quantity
components to the mixer may be manual or automated. Typical
formulations for metal and electronics cleaning are presented in
Table 3-6. These formulations provide a basis for occupational
exposures and environmental release estimates in this assessment.
It may be noted that d-limonene is the only terpene used as a
basis for exposure and release estimates because d-limonene is
believed to have the highest potential to be commercialized.
40
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Future assessments may better address other terpene mixtures
which may be developed for these cleaning operations.
TABLE 3-6 TYPICAL TERPENE-BASED CLEANERS
Percent in
Chemical8 CAS Number formulation
Formulation 1: Electronics Cleaner
d-Limonene 5989-27-5 90
Anionic surfactant 10
Formulation 2; Metal Cleaner
Water 7732-18-5 60
d-Limonene 5989-27-5 20
Diethanolamine 111-42-2 3
Sodium xylene sulfonate 1300-72-7 3
Dipropylene glycol
methyl ether 34590-94-8 6
Anionic surfactant 8
All pure chemicals are liquids except diethanolamine and sodium
xylene sulfonate.
Sources: Hayes, 88; Barnett, 89; Pettit, 89
There are an estimated 100 formulators of terpene cleaners
in the U.S. Of these, 10 are formulators of terpene metal
cleaners, and one formulates terpene electronic cleaners. One
terpene manufacturer/formulator reported that they had 35 total
employees. Less than 10 employees would be expected to be
exposed to terpenes during formulation at a site, and this
estimate was extrapolated to all terpene formulators.
During formulation, workers may be exposed to terpenes and
other formulation components during raw material unloading,
transferring, weighing, blending, sampling, product packaging,
and maintenance. Workers may be exposed during 250 days per
year.
Because terpenes remove skin oils, it is likely that terpene
cleaner formulators will wear impervious gloves when contact is
likely.
Inhalation and dermal exposure estimates, summarized in
Table 3.2, were determined from the models described in the
introduction to section 3. Closed tanks were assumed in
estimating inhalation exposure during terpene electronics cleaner
formulation. For terpene metal cleaning formulation, the closed
41
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tank assumption was used to estimate typical exposure, and an
outerbound estimate of exposure was made assuming the use of open
tanks. Inhalation exposure during the formulation of the metal
cleaner was estimated to typically be 9 mg/day terpene with an
outerbound estimate of 92 mg/day terpene. For other liquid
constituents, inhalation exposures were estimated to be less than
1 mg/day typically and up to 8 mg/day as an outerbound.
Outerbound inhalation exposure to the single solid constituent,
diethanolamine, was estimated to be 150 mg/day based on the OSHA
PEL for diethanolamine (DEA). DBA is the only solid constituent
of terpene cleaners with a chemical-specific OSHA PEL; this PEL
happens be identical to the OSHA PEL for nuisance dust. For
formulation of the electronics cleaner, typical inhalation
exposures were estimated to be 140 mg/day terpene and 7 mg/day
surfactant, with outerbound estimates of 720 mg/day terpene and
34 mg/day surfactant. Outerbound dermal exposures to any
constituent during formulation are estimated to be 3,900 mg/day
available for absorption.
3.3.3 PC BOARD CLEANING WITH TERPENE CLEANERS
Methyl chloroform and CFC-113 are the predominant solvents
used in the electronics industry today. Although DOD standards
do not currently allow for the use of terpene cleaners in PC
board manufacture for military use, revision of those standards
is underway. It is expected that the new specifications will
discourage use of CFCs and other ozone-depleting chemicals and
will allow any method of cleaning that satisfies certain cleaning
performance criteria. Most new terpene cleaning units are in-
line conveyorized, although some batch units are in use.
There are an estimated 705 PC board manufacturers in the
U.S. using 5,000 to 7,000 degreasers. Based on a 25 percent
conversion to terpene cleaners, 176 sites would substitute
terpene cleaners for methyl chloroform and CFC-113. These PC
board manufacturers would average 12 exposed workers per site
based on 3 workers per cleaning unit and 4 units per site.
Workers can be exposed to terpene cleaners in PC board
cleaning during transfer of the cleaner to the cleaning bath and,
to a much lesser extent, from the PC boards after the boards have
been rinsed with water. Handling of the PC boards during
cleaning and draining of dirty cleaner and rinse water is usually
an automated, closed process. Workers may be exposed during 250
days per year.
Because terpenes remove skin oils, it is likely that terpene
cleaner users wear impervious gloves when contact is likely. It
is a common practice to wear gloves when handling PC boards that
have been cleaned.
42
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Inhalation and dermal exposure estimates, summarized in
Table 3.2, were determined from the models described earlier.
Enclosed conveyorized PC board cleaning units were assumed for
estimating inhalation exposures to liquid constituents of terpene
cleaners. Typical inhalation exposures during PC board cleaning
were estimated to be 84 mg/day terpene and 3 mg/day surfactant,
and outerbound inhalation exposures were estimated to be 420
mg/day terpene and 17 mg/day surfactant. Outerbound dermal
exposures were estimated to be 3,500 mg/day terpene and 390
mg/day surfactant available for absorption.
3.3.4 WARM IMMERSION CLEANING WITH TERPENE CLEANERS
Terpene cleaning may be used as an alternative to open-top
vapor degreasing for cleaning metal parts in various industrial
settings. Warm immersion terpene cleaning is accomplished by
using heated solutions in immersion tanks or by spraying.
Finishing steps include rinsing, drying, and wastewater disposal.
Systems may be batch, which often require more manual handling of
parts, or in-line, which are used when higher throughput is
needed.
An estimated 9,070 open-top vapor degreasers operate in the
U.S., of which 5,106 use methyl chloroform or CFC-113. At 10
percent conversion to terpene cleaners, 510 sites will substitute
terpene cleaners for methyl chloroform and CFC-113. The number
of workers exposed to terpene cleaners per degreaser was assumed
to be seven, the same as for open-top vapor degreasers.
Worker exposure to terpene cleaners in warm immersion
systems may occur during transfer of the cleaner to the cleaning
bath, handling of the parts during the cleaning operation,
handling of the cleaned parts, and disposal of the dirty cleaning
solution. Workers may be exposed during 250 days per year.
Because terpenes remove skin oils, it is likely that terpene
cleaner users wear impervious gloves when contact is likely.
Inhalation and dermal exposure estimates, summarized in
Table 3.2, were determined from the models described earlier.
Enclosed warm immersion degreasing units were assumed for
estimating inhalation exposures to liquid constituents of terpene
cleaners. Typical inhalation exposures are estimated to be 3
mg/day terpene and less than 1 mg/day for additives and
surfactants. Outerbound inhalation exposures are estimated to be
13 mg/day terpene and less than 1 mg/day for additives and
surfactants. Outerbound dermal exposures are estimated to be
3,600 mg/day terpene, 550 mg/day solid additives, 1,100 mg/day
liquid additives, and 1,500 mg/day surfactant available for
absorption.
43
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3.3.5 MAINTENANCE COLD CLEANING WITH TERPENE CLEANERS
Cold batch immersion systems dominate as a method of metal
cleaning in industrial/manufacturing settings and service
settings such as automotive garages and repair shops. These
cleaning operations can include spraying, flushing, brushing, and
immersion. Drying may also be necessary if remaining water could
cause rust to form.
An estimated 9,740 cold degreasers operate in the U.S., of
which 7,689 use methyl chloroform or CFC-113. At 10 percent
conversion to terpene cleaners, 770 sites will substitute terpene
cleaners for methyl chloroform and CFC-113. The number of workers
potentially exposed per unit is the same as for cold cleaners
using chlorinated solvents, or four workers.
Workers can be exposed to terpene cleaners in cold cleaning
during transfer of the cleaner to the cleaning bath, handling of
parts during the cleaning operation, handling of the cleaned
parts, and disposal of the dirty cleaning solution. Workers may
be exposed during 250 days per year.
Because terpenes remove skin oils, it is likely that terpene
cleaner users wear impervious gloves when contact is likely.
Inhalation and dermal exposure estimates, summarized in
Table 3.2, were determined from the models described in the
introduction to section 3. Open-top cold immersion baths were
assumed for estimating inhalation exposures to liquid
constituents of terpene cleaners. Typical inhalation exposures
are estimated to be 17 mg/day terpene, and 2 mg/day for both
additives and surfactants. Outerbound inhalation exposures are
estimated to be 84 mg/day terpene and 8 mg/day for both additives
and surfactants. Outerbound dermal exposures are estimated to be
up to 3,600 mg/day terpene, 550 mg/day solid additives, 1,100
mg/day liquid additives, and 1,500 mg/day surfactant available
for absorption.
44
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4. ENVIRONMENTAL RELEASE, FATE, AND EXPOSURE
This section analyzes the likely environmental releases and
impacts that may be associated with a conversion from CFC-113 and
methyl chloroform to aqueous or terpene cleaners. The section
begins by estimating the quantity of chemicals likely to be
released at each site where the cleaners are manufactured,
formulated, or used, and the number of potential release sites.
These releases assume both uncontrolled releases and releases
using control technologies (Section 4.1).
Section 4.2 summarizes the likely fate of aqueous and
terpene cleaners in the environment, based on their physical and
chemical properties. Section 4.3 presents the results of
exposure analyses conducted by EPA which estimate the
concentrations of aqueous and terpene cleaners in the aquatic
environment. Details on the assumptions and calculations used in
this chapter are available in EPA's environmental exposure
support document.
4.1 RELEASES
4.1.1 AQUEOUS CLEANERS
The major environmental impact from converting existing
cleaning operations to aqueous-based systems is the potential
increased discharge to wastewater. The water release estimates
presented in this section represent release to treatment,
receiving stream, or sewer in the absence of pollution prevention
techniques or recycling systems. Closed loop-cleaning systems or
systems that substantially recycle aqueous cleaning solutions
have been developed and may be employed^ These types of systems
may have water releases that are significantly less than the
estimates presented in this assessment.
Releases to water are calculated using mass balance by
estimating total consumption and subtracting releases to all
other media. In the case of recycling and treatment of the
water, some of the filter or sludge waste would require solid
waste disposal.
45
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Wastewater discharged from an aqueous system contains both
the material cleaned from the parts and the chemicals contained
in the cleaning formulation. The release of constituents in the
cleaners is mitigated somewhat if the water release is treated;
however, even after treatment large quantities may still be
released to sewers or receiving streams. This report does not
attempt to address the constituent releases and assumes existing
regulations will control the concentration of these constituents
in the waste stream.
Table 4-1 summarizes the release of aqueous cleaner
constituents to water; Table 4-2 presents the releases of aqueous
cleaners to air. Releases to air are expected to be low for
aqueous cleaners due to the low vapor pressures of the
constituents. For air releases, a model was used to predict
vapor generation rates upon which release estimates were based.
These calculations provide an upper bound release scenario.
TABLE 4-1 ESTIMATED AQUEOUS CLEANER RELEASES TO WATER8
Warm Immersion Cold Immersion PC Board
Chemical Cleaning Cleaning Cleaning Total
Sodium carbonate 47
Sodium metasilicate 32
Sodium hydroxide 4
Sodium tripolyphosphate 9
Trisodium phosphate 17
367
250
26
74
135
0
0
0
0
0
414
282
29
83
152
Tetrasodium
pyrophospate
Borax
EDTA
Surfactants
Ethanolamines
DGBE
2
8
2
5
0
0
19
62
15
43
0
0
0
0
0
30
360
210
21
70
17
78
360
210
Based on typical formulation and once-through use without
treatment; estimates presented in 1000 kg/yr.
Number of aqueous cleaner sites:
Formulation: 20 PC board cleaning: 212
Warm immersion: 2042 Cold immersion: 3076
46
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TABLE 4-2 ESTIMATED AQUEOUS CLEANER RELEASE TO AIR8
Cateaorv
Alkalies/Salts
Additives
Surfactants
Chemical
Sodium carbonate
Sodium metasilicate
Sodium hydroxide
Sodium tripolyphosphate
Tetrasodium pyrophosphate
Borax
EDTA
Ethanol amines
DGBE
Alkyl aryl sulfonate
Anionic Surfactants
Total . ka/yr
0
0
0
0
0
0
0
50
2
<790
<440
Based on typical formulation; released during formulation,
transfer, and use.
4.1.2 TERPENE CLEANERS
Similar to aqueous cleaners, the most significant releases
to the environment resulting from increased terpene cleaner use
are expected to be the releases to wastewater—as much as 0.6
million kg of terpenes to wastewater per year without the use of
on-site control technologies.
Terpene releases to water represent the release to
treatment, stream, or sewer and do not estimate the efficiency of
wastewater treatment. However, due to concerns for biological
oxygen demand (BOD) and chemical oxygen demand (COD) from
terpenes, terpene wastestreams may require pretreatment before
discharge to a wastewater treatment plant or stream. The
consideration of wastewater treatment is discussed in section
4.2.2. The releases to water of terpenes and the other
constituents of the cleaning solution can be mitigated by recycle
and reuse of the cleaner using filtration and other means to
remove contaminants from the cleaner. Closed loop-cleaning
systems or systems that substantially recycle terpene cleaning
solutions have been developed and may be employed. These types
of systems may have water releases that are significantly less
than the estimates presented in this assessment. The BOD and COD
of terpenes may also limit the release to wastewater treatment
and/or streams. This will usually result in the disposal of
removed wastes by landfill or incineration. Water release
estimates were made based upon total terpene usage, number of
sites, and days of operation per year.
Terpene releases to air were estimated using a vapor
generation rate model for evaporation losses and volume
47
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displacement for transfer losses. Table 4-3 summarizes the
release of terpenes to water. Table 4-4 presents the release of
terpenes to the air.
4.1.3 DATA NEEDS
Amounts of solid and hazardous wastes generated by aqueous
and terpene cleaners, and the composition of those wastes, were
not addressed in detail in this assessment. Solid waste data
from users of aqueous and terpene cleaners would be useful
supplements to the data in this assessment. Additionally, actual
data on releases to all media from operating facilities would be
useful to improve on the estimates in this assessment.
4.2 ENVIRONMENTAL FATE AND TRANSPORT
This section describes the fate of various compounds of
aqueous and terpene cleaning formulations following release into
aquatic environments. It is based on readily available
information obtained from the published literature and from EPA
files. Several of the compounds have limited data bases
available to assess their fate in the environment. In these
cases, estimates are based on known physical and chemical
properties and by the behavior of similar chemicals.
4.2.1 AQUEOUS CLEANERS
A brief description of the environmental fate is provided
here. The environmental fate of the aqueous cleaner constituents
in aquatic systems is similar for many of the potential compounds
of the cleaning formulations.
ALKALIS, SILICATES, AND BORATES
These compounds are very soluble in water and tend to freely
dissociate in aqueous systems under environmental conditions.
Once the salt has dissolved, the dissociated ions produced may
participate in several reactions described in the technical
support document for this section. Therefore, the fate of and
transformations of the individual dissociated ions, rather than
the compounds, must also be investigated.
As an example, with an alkali such as ammonium hydroxide,
the ammonium ion will form an equilibrium in water with the
ammonium hydroxide parent compound (Morel, 83) . Ammonium (NH4+)
is a usable form of nitrogen by plants and is not considered a
pollutant at concentrations within the assimilative capacity of
the system (Morel, 83). However, ammonium can undergo oxidation
to form nitrate and nitrite through nitrification.
48
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TABLE 4-3 ESTIMATED TOTAL TERPENE RELEASE TO WATER
#
Operation Sites
Manufacture
Formulation
PC board cleaning
Cold immersion
Warm immersion
35
11
176
769
511
Sites using
million kg/yr
0"
Oc
0.06
0.1
0.2
no treatment"*
kg/site/day
0"
Oc
6.5
3.0
6.5
Sites usina crravitv
million kg/yr
0"
Oc
0.05
0.09
0.1
separation**
kg/ site/day0
0"
Oc
1.3
0.6
1.3
fa Based on 80% of sites using gravity separation and 20% using no treatment.
Based on 250 operating days for formulation and use, and 350 for manufacture.
c Negligible quantities are released.
49
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TABLE 4-4 ESTIMATED TOTAL TERPENE RELEASE TO AIR
Operation
*
Sites
Release
from
operations
(kg/yr)
Release from
gravity
separation
(kg/yr)
Per site
release from
operations
(kg/ site/day)
Per site release
from gravity
separation
(kg/ site/day)
Manufacture 35
Electronic
formulation 1
Metal
formulation 10
PC board
cleaning 176
Cold immersion 769
Warm immersion 511
3,750
35
280
35,000
32,000
6,100
na
na
na
91,000
180,000
260,000
0.30
0.14
0.11
0.8
0.17
0.05
na
na
na
5.21
2.4'
5.2'
Based on a 25% substitution rate for PC board cleaners and a 10% rate for metal
cleaners.
It is estimated that an equal quantity would be recycled or sent off-site for disposal.
c Release from vacuum distillation, wastewater treatment, spills, and transfer to drum and
tank car.
Release from closed lid formulation represents the typical value.
' Release from evaporation and transfer.
Release from 50% of those sites using gravity separation allowing evaporation of terpene
phase during gravity separation.
50
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PHOSPHATES
Organic and inorganic phosphates are the predominant forms
of phosphorus in the environment. The fully reduced form of
phosphorus, phosphine (PH3) , has been found in polluted springs
and the hypolimnion of lakes and marshes under highly reducing
conditions (Bodek et al, 88).
Orthophosphates and polyphosphates complex with metal ions.
These metal phosphates are poorly soluble (Bodek et al, 88). In
many water environments, complexation with iron (III) and calcium
oxides in the sediment is the primary sink for phosphates. There
the phosphates will remain unless the sediment becomes anaerobic,
resulting in conditions which convert insoluble iron phosphates
and calcium phosphates to soluble forms (Bohn, 79).
ETHANOLAMINES
The ethanolamines are highly water soluble (pH dependent).
There is very little loss of the compounds from water as a result
of non-biological degradation (Gannon et al, 78). Biological
degradation in wastewater treatment, ranged from 25-90 percent
depending on the number of ethanol groups. Discharges of high
concentrations of DBA and TEA have resulted in dissolved oxygen
depletion (Gannon et al, 78).
Diethanolamine (DBA) and triethanolamine (TEA) can react
with nitrite to form N-nitrosodiethanolamine (Yordy and
Alexander, 81). This phenomenon has been reported in bench-scale
experiments (Gannon et al, 78), but not in field experiments, to
date.
ETHYLENEDIAMINETETRAACETIC ACID
BDTA and its salts should be biodegradable in aquatic and
terrestrial ecosystems (days to weeks) provided sufficient
organic matter is present to support microbial growth and the
residence time of EDTA is adequate.
SURFACTANTS
Very limited information is available on the environmental
fate of sodium xylene sulfonate, dodecanedioic acid, and sodium
gluconate. Most surfactants, however, are up to 99 percent
biodegradable in water.
51
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DIETHYLENE GLYCOL N-BUTYL ETHER
Based on ah analysis of the properties of DGBE, it is
considered likely to biodegrade in both water and soil
environments, with days to weeks required for ultimate
degradation.
4.2.2 TERPENE-BASED CLEANERS
Limited fate and transport information is available for the
eight terpenes addressed in this report. The physical and
chemical properties may be found in the technical support
documents for this section. With the exception of anethole, the
terpenes exhibit similar properties, both measured and estimated.
Because of this characteristic, the environmental fate of these
compounds is expected to be similar.
AIR
During daylight hours, terpenes will form smog by
photochemical oxidation and ozone by its reaction with hydroxyl
radicals. However, nighttime reactions of terpenes will reduce
the available terpene and nitrate radicals for the daytime
formation of smog and ozone.
WATER
The fate of terpenes in the aqueous environment has been
estimated using physical/chemical properties generated by
AUTOCHEM and QSAR. Volatilization of the terpenes, except for
anethole, is expected to be moderate to high in flowing water and
moderate in systems such as lakes. The EXAMS II model (discussed
later in this section) predicts an 80 percent removal after 36
miles downstream due to volatility from a river. In natural
flowing waters the volatilization half-life is estimated to be
1.2 hours for all the terpenes except anethole (5.7 hours). In
lakes, the estimated half-life of the terpenes is 111 hours
except anethole (156 hours).
All the terpenes should sorb fairly strongly to soil and
sediment (log Koc values >3). Ultimate biodegradation is
expected to require weeks under aerobic conditions and months or
more under anaerobic conditions. Based on the volatility and
sorption of terpenes, migration to groundwater is expected to
occur slowly. The presence of terpenes over time in the
groundwater would be due to their fairly low biodegradability
aerobically and quite low biodegradability anaerobically.
52
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In a wastewater treatment simulation model, all the
terpenes, with the exception of anethole, are expected to be
removed, principally through volatilization, at an overall
efficiency of approximately 90 percent (Clark et al, 89).
In a bench-scale study conducted for EPA by Versar, the
removal rate of dipentene and anethole were investigated in a
simulated biological treatment system (Versar, 90). The results
of the study show that at least 90 percent of the dipentene and
98 percent of the anethole were removed by the bench-scale
activated sludge system. A separate control showed that
dipentene was removed to below the analytical detection limit (at
least 90 percent removal) by air stripping alone. Therefore, the
amounts removed by biodegradation or sorption, if any, could not
be determined. The control also showed that anethole could be
removed to the extent of approximately 90 percent by air
stripping alone. Therefore, in the biologically active system at
least 8 percent of the anethole was removed by biodegradation
and/or sorption onto waste sludge. It is concluded that, for the
purposes of exposure assessment, terpenes should be at least 90
percent removed under typical treatment conditions.
4.3 EXPOSURE ANALYSIS
This section estimates the exposure of humans and aquatic
organisms to aqueous and terpene cleaners released into water
bodies from industrial operations. The exposure estimates are
based on the typical cleaning formulations for metal and
electronics cleaning and the physical and chemical properties.
The release estimates used in these analyses ranged from
releases without control technology or wastewater treatment to
releases with some degree of on-site (gravity separation)
control along with biological (secondary) wastewater treatment.
EPA uses computer models to estimate the concentrations and
impacts of chemicals released into aquatic environments. The
Probabilistic Dilution Model (PDM) estimates the days of
exceedance of the Concentration of Concern (COC) for the 10
percent of those facilities in an industrial group that will have
the worst number of exceedances.
The ambient water concentrations were estimated for the mean
and low flows for the 50th and 10th percentile streams in an
industrial grouping. The concentrations were estimated by a
simple dilution calculation using the chemical loadings in the
various release scenarios. Table 4-9 provides these results.
These numbers can be compared to the COC of 7 ppb.
Human exposure to drinking water and fish ingestion were
estimated using the above stream concentrations. For drinking
53
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water the estimates were based on 2 liters of water consumption
per day. Fish ingestion estimates were based on the
bioconcentratioh factor (BCF) and the ingestion of 16.9 grams of
fish per day. The formulae and results can be found in the
technical support documents for this section. Exams II was used
to estimate the impact various fate processes would have on the
terpene after release into an aquatic environment.
4.3.1 PROBABILISTIC DILUTION MODEL (PDM)
PDM is a computer model developed by EPA to conduct surface
water exposure assessments. PDM estimates the days of exceedance
of the COC for the 10 percent of those facilities in an
industrial group that will have the worst number of exceedances.
PDM analysis was performed for all the terpenes and for
those aqueous cleaners which had release estimates available.
Table 4-5 contains the COCs for the aqueous and terpene cleaners.
All three use scenarios were examined. The operations were
broken down into the following categories, based on Standard
Industrial Classifications (SIC) codes:
electronic components manufacture
metal can manufacture
electroplating
- metal finishing
motor vehicle manufacture
large household appliance and parts manufacture
The average days of exceedance of the 10 percent worst
streams was calculated for each industrial group using the
various release scenarios. The release quantities associated with
wastewater treatment were estimated using a 90 percent
treatability level estimated by EPA using the "Toronto Sewage
Treatment Plant Simulation Model" developed by Clark et al (Clark
et al, 89) and verified by a bench scale treatability study.
AQUEOUS CLEANERS
The COC for the aqueous cleaners was exceeded less than one
day per year except for the following: sodium silicate in all
industry groupings, maximum 10 days; dodecanedioic acid in
Electronic Component Manufacturing, 7 days; and all three
ethanolamines in Electronic Component Manufacturing, 2 days for
MEA, 17 for DBA, 54 for TEA.
54
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TERPENE CLEANERS
d-Limonene was selected as the focus of the terpene analysis
because it is anticipated to be the most likely terpene used in
the formulation of these cleaners. The COC was derived from
measured data on acute toxicity to fish and daphnids. Data on
the toxicity to algae will be available at a later date and may
lower the COG for terpenes.
TABLE 4-5 CONCENTRATIONS OF CONCERN (COC)
FOR THE CONSTITUENTS OF TERPENES AND AQUEOUS CLEANERS
ChemicalCOC(ppb)
Terpenes
a-Pinene 3
6-Pinene 5
d-Limonene 7
Terpinolene 12
a-Terpinene 20
Anethole 70
Dipentene 300°
Aqueous Cleaners
Ammonium hydroxide 8
Potassium hydroxide 800
Sodium hydroxide 400
Borax 300
Sodium silicate 5,000
Sodium metasilicate 100
Sodium carbonate 1,000
Phosphate 0.1
Sodium gluconate 10,000
Dodecanedioic acid (freshwater) 200
(saltwater) 60
DGBE 10,000
EDTA 100
Sodium xylene sulfonate 1,000
Monoethanolamine 90
Diethanolamine 700
Triethanolamine 200
" The COC for dipentene was generated using a commercial grade
product, unlike the other terpenes which were tested using a pure
grade material. The impact, if any, on the measured COC is
unknown.
55
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Analysis of the days of exceedance for terpenes released
untreated into a receiving stream was also performed to estimate
the effects of ho controls. However, due to the BOD and COD of
terpene-based cleaning formulations, it is anticipated that
discharge into a stream untreated may be prohibited under certain
provisions of the Clean Water Act or an approved state NPDES
program. Thus, discharge to a municipal wastewater treatment
plant or use of an on-site control technology is likely.
To estimate the effectiveness of control technologies, the
exceedance of the COC was estimated using gravity separation
prior to release of the terpene to a receiving stream, wastewater
treatment without gravity separation, and gravity separation
followed by wastewater treatment.
Tables 4-6 and 4-7 show a summary of the results of PDM
(the 10 percent worst-case streams) for a COC of 7 ppb (7 ug/L)
under the four release scenarios. The worst-case release of
terpenes to water (no gravity separation or wastewater treatment)
resulted in 212-248 day of exceedance per year. With wastewater
treatment the COC was exceeded 52-178 day per year. When gravity
separation is used prior to discharge the COC is exceeded 101-208
days per year. When both gravity separation and wastewater
treatment are used the exceedance is 9-81 days per year. The
days of exceedance for the remaining terpenes may be found in the
technical support documents for this report.
The level of treatment required to avoid exceeding the COC
20 or more days per year will range from 95 to 99 percent
depending on the industrial category from which the release
originates.
4.3.2 STREAM CONCENTRATIONS
A search of the open literature and the data base STORET did
not find any reference to ambient levels of terpenes in surface
waters. Additional efforts are on-going to ascertain if ambient
levels of terpenes in surface waters exist in other sources.
The stream concentrations were estimated for the mean and
low stream flows for the 50th and 10th percentile stream within
each SIC. Results after wastewater treatment ranged from <1 ppb
to 83 ppb depending on stream flow and industrial grouping. For
release after gravity separation the concentration ranged from <1
ppb to 167 ppb and after both gravity separation and wastewater
treatment the concentration ranged from <1 ppb to 17 ppb. Table
4-8 provides the results for each scenario by SIC code. These
results would indicate that the COC may be exceeded under
certain, but not all, stream flow and release conditions and do
not indicate the frequency at which the COC will be exceeded.
56
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TABLE 4-6 DAYS OF EXCEEDANCE OF THE COG FOR D-LIMONENE
BY SIC CODE AND OPERATION WITHOUT GRAVITY SEPARATION
SIC CodeOperationDays Per Year Exceedance
Percent Treatment
90 0
Motor Vehicle
Manufacture
Cold Immersion Cleaning
Warm Immersion Cleaning
133
178
237
247
Metal Finishing Cold Immersion Cleaning 79 229
Warm Immersion Cleaning 135 246
Large Household Cold Immersion Cleaning 66 222
Appliances and Warm Immersion Cleaning 119 243
Parts Manufacture
Electroplating Cold Immersion Cleaning 66 222
Warm Immersion Cleaning 121 243
Metal Can Cold Immersion Cleaning 52 212
Manufacture Warm Immersion Cleaning 108 240
Electronic PC Board Cleaning, etc 139 248
Component
57
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TABLE 4-7 DAYS OF EXCEEDANCE OF THE COC FOR D-LIMONENE*
BY SIC CODE AND OPERATION WITH GRAVITY SEPARATION^
SIC Code
Operation
Days Per Year Exceedance
Percent Treatment
90 0
Motor Vehicle
Manufacture
Metal Finishing
Large Household
Appliances and
Parts Manufacture
Electroplating
Metal Can
Manufacture
Electronic
Component
Manufacture
Cold Immersion Cleaning 42
Warm Immersion Cleaning 81
Cold Immersion Cleaning 14
Warm Immersion Cleaning 35
Cold Immersion Cleaning 9
Warm Immersion Cleaning 26
Cold Immersion Cleaning 9
Warm Immersion Cleaning 27
Cold Immersion Cleaning 3
Warm Immersion Cleaning 15
PC Board Cleaning 40
174
208
129
185
113
172
114
174
101
162
189
COC: 7ppb (7 ug/L) for d-limonene.
Release without gravity separation represents approximately 20
percent of use sites.
For the above stream flow conditions, the treatability of
the terpenes would need to range from 96.5 to 99.2 percent to
avoid exceeding the COC of 7 ppb more than 20 days per year.
58
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TABLE 4-8 STREAM CONCENTRATION (ug/L)
Terpene Cleaners Results after wastewater treatment only. (Results
after gravity separation and WWT). [Results after gravity separation
only].
Flows
%tile Plant Mean Low3
Electronic Component Manuf. 50 0.6(0.1)[1.2] 6.6(1.3)[13.2]
10 5.7(1.1)[11.4] 51.6(10.3)[103]
Warm Immersion Cleaning
Metal Can Manuf. 50 0.2(0.1)[0.5] 3.4(0.7)[6.8]
10 3.1(0.6)[6.2] 61.3(12.3)[123]
Electroplating 50 0.9(0.2)[1.8] 2.1(0.4)[4.3]
10 3.1(0.6)[6.2] 40.1(8.1)[81.3]
Lg. Household Appliance Manuf. 50 0.5(0.1)[1.0] 4.5(0.9)[9.0]
10 4.1(0.8) [8.1] 48.9(9.8) [98.0]
Metal Finishing 50 0.7(0.1)[1.3] 3.8(0.8)[7.6]
10 4.1(0.8)[8.2] 50.8(10.2)[102]
Motor Vehicle Manuf. 50 0.5(0.1)[1.0] 4.3 (0.9)[8.8]
10 6.3'(1.3) [12.7] 83.3(16.7) [167]
Cold Immersion Cleaning
Metal Can Manuf. 50 0.1(0.0)[0.2] 1.6(0.3)[3.1]
10 1.4(0.3)[2.8] 28.3(5.7)[56.6]
Electroplating 50 0.4(0.1)[0.8] 1.0(0.2)[2.0]
10 1.4(0.3)[2.8] 18.8(3.8)[37.5]
Lg. Household Appliances Manuf. 50 0.2(0.0)[0.4] 2.1(0.4)[4.1]
10 1.9(0.4)[3.8] 22.6(4.5)[45.1]
Metal Finishing 50 0.3(0.1) [0.6] 1.7(0.4) [3.5]
10 1.9(0.4)[3.8] 23.4(4.7)[46.9]
Motor Vehicle Manuf. 50 0.2(0.1)[0.5] 2.0(0.4)[4.1]
10 2.9(0.6)[5.8] 38.5(7.7)[76.9]
alow flow is the 7Q10 flow.
59
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4.3.3 EXPOSURE ANALYSIS MODELING SYSTEM (EXAMS II)
In an attempt to quantify the loss of terpenes due to the various
fate processes after release to an aquatic system (river) , EXAMS II wai,
performed. EXAMS II estimates the change in the surface water
concentration after accounting for fate and persistence for a selected
stream segment. EXAMS incorporates various fate, transport, and
transformation processes, which include hydrolysis, biodegradation,
photolysis, oxidation, reduction, adsorption, volatilization, and ion
exchange. The change in surface water concentration with distance as a
result of the various fate processes, was estimated at 80 percent after
36 miles (60km).
4.3.4 DRINKING WATER AND FISH INGESTION ESTIMATES
No measured levels of aqueous and terpene compounds in drinking
water and fish were identified in the open literature or EPA files.
Modeled drinking water and fish ingestion estimates indicated maximum
exposures would be approximately 3 mg/yr and 26 mg/yr respectively from
terpenes and approximately 50 mg/yr for drinking water from aqueous
cleaner formulations. As aqueous and terpene cleaner compounds are
substituted for CFCs, measured data would add additional
characterization of the exposure to aquatic and human populations. The
results are summarized in Tables 4-9 and 4-10 for terpenes and aqueous
cleaners, respectively.
60
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TABLE 4-9 HUMAN EXPOSURE TO TERFENE CLEANERS IN DRINKING WATER,
BY OPERATION AFTER TREATMENT
Operation
Ft; Board cleaning
Electronic Component
Manufacture
Warm Immersion Cleaning
Metal Can Manufacture
Electroplating
Large Household
Appliances and Parts
Manufacture
Metal Finishing
Motor Vehicle
Manufacture
Cold Immersion Cleaning
Metal Can Manufacture
Electroplating
Large Household
Appliances and Parts
Manufacture
Metal Finishing
Motor Vehicle
Drinking. Water (mg/yr) „ Fish Ingestion (mg/yr)
50th%tile 10th%tile8 50th%tile 10th%t
0.31
0.11
0.45
0.24
0.33
0.23
0.05
0.21
0.11
0.15
0.11
2.85
1.54
1.54
2.03
2.04
3.16
0.71
0.71
0.94
0.94
1.46
2.53
0.95
3.69
1.99
2.76
1.90
0.44
1.70
0.92
1.28
0.88
23.54
12.72
12.72
16.77
16.88
26.06
5.87
5.87
7.74
7.79
12.03
Manufacture
850%tile indicates that 50% of those facilities within the SIC code will have exposure estimates
lower than those reported. The 10%tile indicates that 90% of those facilities within the SIC
code will have exposure estimates lower than those reported.
61
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TABLE 4-10 HUMAN EXPOSURE TO AQUEOUS CLEANERS IN DRINKING WATER,
BY OPERATION BEFORE TREATMENT
Operation Drinking Water (mg/yr)
50th%tilea I0th%tilea
PC Board Cleaning
Electronic Component Manufacture 5.33 49.56
Warm Immersion Cleaning
Metal Can Manufacture 0.05 0.71
Electroplating 0.21 0.71
Large Household Appliances 0.11 0.94
and Parts Manufacture
Metal Finishing 0.15 0.94
Motor Vehicle Manufacture 0.11 1.46
Cold Immersion Cleaning
Metal Can Manufacture 0.25 3.32
Electroplating 0.96 3.32
Large Household Appliances 0.52 4.38
ans Parts Manufacture
Metal Finishing 0.72 4.40
Motor Vehicle Manufacture 0.50 6.80
850th%tile indicates that 50% of those facilities within a SIC code will
have exposure estimates lower than those reported. The 10th%tile
indicates that 90% of those facilities within the SIC code will have
exposure estimates lower than those reported.
62
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EPA SUPPORT DOCUMENTS
PEI Associates, Inc. 1990. Occupational Exposure, Environmental
Release, and Control Analysis of Aqueous Cleaning Substitutes for
1,1,1-Trichloroethane and CFC-113 for Cleaning of Electronic and
Metal Objects. Prepared under Contract No. 68-D8-0112 for Office
of Toxic Substances, U.S. EPA.
PEI Associates, Inc. 1990. Occupational Exposure, Environmental
Release, and Control Analysis of Terpene Metal Cleaning
Substitutes for 1,1,1-Trichloroethane and CFC-113. Prepared
under Contract No. 68-D8-0112 for Office of Toxic Substances,
U.S. EPA.
U.S. EPA, Office of Toxic Substances, 1990. Fate and Exposure
Assessment of Aqueous and Terpene Cleaning Substitutes for
Chlorofluorocarbons and Chlorinated Solvents.
U.S. EPA, Office of Toxic Substances, 1990. Health and
Environmental Effects of Selected Aqueous Cleaner Chemicals.
U.S. EPA, Office of Toxic Substances, 1990. Terpene Hazard
Assessment.
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