United States Solid Waste and EPA530-R-96-017
Environmental Protection t Emergency Response August 1996
Agency -'. . ' (5305W)
vvEPA Solvents Study
. Photocopied on recycled paper that contains at least 20 % post consumer fiber
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SOLVENTS STUDY
** CONTAINS NO CONFIDENTIAL BUSINESS INFORMATION **
August 29, 1996
U.S. Environmental Protection Agency
Office of Solid Waste
Hazardous Waste Identification Division (5304W)
Washington, DC 20460
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Solvents Study
Table of Contents
1.0 Study Background 1
1.1 Legislative and Judicial Background 1
1.1.1 Existing Solvent Listings and the Regulatory Definition of Solvent 1
1.1.2 Summary of EOF Settlement Agreement 2
1.2 Industry Identification Process 2
1.2.1 Research to Identify Potential Uses of Solvents 3
1.2.2 Development of RCRA 3007 Preliminary Questionnaire Mailing List 6
2.0 Representativeness of RCRA 3007 Questionnaire Data to National Data 12
2.1 Solvents Industry Study Methodology 12
2.2 Confidence Level of Solvents Industry Study Results 14
3.0 Data Management and Waste Management Practices 26
3.1 Data Management and Analyses 26
3.2 Identification of Current Waste Management Practices 27
4.0 Discussion of Solvents Study Chemicals 28
4.1 Allyl Chloride 28
4.1.1 Wastes From Use as a Solvent 29
4.1.2 Management Practices 29
4.1.3 Health Data 30
4.2 Aniline 31
4.2.1 Wastes From Use as a Solvent 32
4.2.2 Management Practices 33
4.2.3 Health Data 34
4.3 Diethylamine 34
4.3.1 Wastes From Use as a Solvent 36
4.3.2 Management Practices 37
4.3.3 Health Data 37
4.4 1.4-Dioxane 38
4.4.1 Wastes From Use as a Solvent 41
4.4.2 Management Practices 41
4.4.3 Health Data 43
4.5 Ethylene Oxide 43
4.5.1 Wastes From Use as a Solvent 44
4.5.2 Management Practices 45
4.5.3 Health Data 45
4.6 Bromoform 46
4.6.1 Use as a Solvent 46
4.6.2 Health Data 47
4.7 Vinylidine Chloride 48
4.7.1 Use as a Solvent 48
4.7.2 Health Data 48
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Solvents Study
List of Figures
Figure 1-1 RCRA 3007 Questionnaire Mailing List, by State 9
List of Tables
Table 1-1 Potential Allyl Chloride Users Identified from Chemical Abstracts 3
Table 1-2 Potential Aniline Users Identified from Chemical Abstracts 3
Table 1-3 Potential Bromoform Users Identified from Chemical Abstracts 4
Table 1-4 Potential Diethylamine Identified from Chemical Abstracts 4
Table 1-5 Potential 1,4-Dioxane Users Identified from Chemical Abstracts 4
Table 1-6 Potential Ethylene Oxide Users Identified from Chemical Abstracts 4
Table 1-7 Potential Vinylidene Chloride Users Identified from Chemical Abstracts 4
Table 1-8 Total Reporters and Potential Solvent Use, by Chemical 7
Table 1-9 Number of Facilities Falling Within Potential Solvent Use Quantities Ranges 8
Table 2-1 Cross-Reference of TRI Chemicals with Seven Chemicals of Concern 13
Table 2-2. Total Reporters and Use by Solvent 16
Table 2-3 Solvent Production, Solvent Use, and Survey Results 20
Table 2-4 Solvent Specific Confidence Rationales 21
Table 3-1 Specific Gravities of Solvents 27
Table 4-1 Facilities Using Allyl Chloride in 1993 and Industrial Sector 28
Table 4-2 Use of Allyl Chloride By Industry 29
Table 4-3 Quantity of Allyl Chloride Waste Generated for Each Type Generated 29
Table 4-4 Generation Statistics for Allyl Chloride 30
Table 4-5 Facilities Using Aniline in 193 and Industrial Sector 32
Table 4-6 Use of Aniline By Industry 32
Table 4-7 Quantity of Aniline Waste Generated for Each Type Generated 32
Table 4-8 Generation Statistics for Aniline 33
Table 4-9 Facilities Using Diethylamine in 1993 and Industrial Sector 36
Table 4-10 Use of Diethylamine By Industry 36
Table 4-11 Quantity of Diethylamine Waste Generated for Each Type Generated 37
Table 4-12 Generation Statistics for Diethylamine 37
Table 4-12 Facilities Using 1,4-Dioxane in 1993 and Industrial Sector 39
Table 4-13 Use of 1,4-Dioxane By Industry 41
Table 4-14 Quantity of 1,4-Dioxane Residuals 41
Table 4-15 Generation Statistics for 1,4-Dioxane 42
Table 4-16 Facilities Using Ethylene Oxide in 1993 and Industrial Sector 44
Table 4-17 Use of Ethylene Oxide By Industry 44
Table 4-18 Quantity of Ethylene Oxide Waste Generated for Each Type Generated 45
Table 4-19 Generation Statistics for Ethylene Oxide 45
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Solvents Study
Appendices
Appendix A: Final Memorandum on the Chemical Abstract Search
Appendix B: Instructions from the Toxic Release Inventory Reporting Form R and Instructions
Appendix C: List of industries and chemicals these industries use, by SIC Code.
Appendix D: List of rationale for removing industries from further study as solvent users.
Appendix E: RCRA 3007 Preliminary Survey of Solvent Use
Appendix F: Preliminary Questionnaire Mailing List of 1,497 Facilities.
Appendix G: Preliminary Questionnaire Data for All Responders By SIC Code
Appendix H: RCRA 3007 Survey of Solvent Use
Appendix I: Tables of Waste Generation, Characterization, and Management, by Solvent
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Solvents Study
1.0 Study Background
1.1 Legislative and Judicial Background
1.1.1 Existing Solvent Listings and the Regulatory Definition of Solvent
As part of the Hazardous and Solid Waste Amendments (HSWA) of 1984, EPA was required to
make determinations as to whether certain wastes are hazardous under RCRA. Among these are solvent
wastes. Five hazardous waste listings for solvent wastes have been promulgated to date at
40 CFR §261.31 (a). These are shown below, and the basis for listing these solvents, toxicity (T) or
ignitability (I) is shown in parentheses after the listing description.
D F001: The following spent halogenated solvents used in degreasing: Tetrachloroethylene,
trichloroethylene, methylene chloride, 1,1,1-trichloroethane, carbon tetrachloride, and
chlorinated fluorocarbons; all spent solvent mixtures/blends used in degreasing containing,
before use, a total often percent or more (by volume) of one or more of the above
halogenated solvents or those solvents listed in F002, F004, and F005; and still bottoms
from the recovery of these spent solvents and spent solvent mixtures. (T)
D F002: The following spent halogenated solvents: Tetrachloroethylene, methylene
chloride, trichloroethylene, 1,1,1-trichloroethane, chlorobenzene, 1,1,2-trichloro-
1,2,2-trifluoroethane, ortho-dichlorobenzene, trichlorofluoromethane, and
1,1,2-trichloroethane; all spent solvent mixtures/blends containing, before use, a total of
ten percent or more (by volume) of one or more of the above halogenated solvents or
those listed in F001, F004, or F005; and still bottoms from the recovery of these spent
solvents and spent solvent mixtures. (T)
D F003: The following spent non-halogenated solvents: Xylene, acetone, ethyl acetate,
ethyl benzene, ethyl ether, methyl isobutyl ketone, n-butyl alcohol, cyclohexanone, and
methanol; all spent solvent mixtures/blends containing, before use, only the above spent
non-halogenated solvents; and all spent solvent mixtures/blends containing, before use,
one or more of the above non-halogenated solvents, and, a total often percent or more
(by volume) of one or more of those solvents listed in F001, F002, F004, and F005; and
still bottoms from the recovery of these spent solvents and spent solvent mixtures. (I)
D F004: The following spent non-halogenated solvents: Cresols and cresylic acid, and
nitrobenzene; all spent solvent mixtures/blends containing, before use, a total often
percent or more (by volume) of one or more of the above non-halogenated solvents or
those solvents listed in F001, F002, and F005; and still bottoms from the recovery of these
spent solvents and spent solvent mixtures. (T)
D F005: The following spent non-halogenated solvents: Toluene, methyl ethyl ketone,
carbon disulfide, isobutanol, pyridine, benzene, 2-ethoxyethanol, and 2-nitropropane; all
spent solvent mixtures/blends containing, before use, a total often percent or more (by
volume) of one or more of the above non-halogenated solvents or those solvents listed in
F001, F002, or F004; and still bottoms from the recovery of these spent solvents and spent
solvent mixtures. (I,T)
The existing solvent listings in 40 CFR 261.31 apply to spent solvents that are used for their
"solvent properties," as defined in the December 31, 1985 Federal Register (50 FR 53316). This definition
1
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Solvents Study
of "solvent use" was included in the RCRA §3007 Solvent Use Questionnaire used to obtain information to
support the solvent investigation:
"Solvents are used for their "solvent" properties - to solubilize (dissolve) or mobilize other
constituents. Examples of such solvent use include degreasing, cleaning, and fabric
scouring, use as diluents, extractants, and reaction and synthesis media, and for other
similar uses. This definition is discussed in the listing determination for F001-F005
solvents, 50 FR 53316, December 31,1985. A chemical is not used as a solvent if it is
used only for purposes other than those described above.
1.1.2 Summary of EOF Settlement Agreement
The Environmental Defense Fund (EOF) and EPA entered into a consent decree to resolve most of
the issues raised in a civil action undertaken by the Environmental Defense Fund (EOF v. Browner, Civ. No.
89-0598 (D.D.C.)), in which the Agency agreed, among other things, to a schedule for making a listing
determination and a study on spent solvents. The consent decree was approved by the court on December
9, 1994. As modified, the consent decree provides that the listing determination is scheduled to be
proposed for public comment on or before July 31,1996 and promulgated on or before May 31, 1997. This
listing determination includes the use following spent solvents, still bottoms from the recovery of the
following solvents, and spent solvent mixtures thereof: cumene, phenol, isophorone, acetonitrile, furfural,
epichlorohydrin, methyl chloride, ethylene dibromide, benzyl chloride, p-dichlorobenzene,
2-methoxyethanol, 2-methoxyethanol acetate, 2-ethoxyethanol acetate, and cyclohexanol.
For an additional set of solvents, EPA agreed to conduct a study, in lieu of a listing determination,
and issue a final report. The study is scheduled to be issued by August 30, 1996. This study is to discuss
the wastes associated with the use of the materials as solvents, the toxicity of the wastes, and a description
of the management practices for the wastes. These additional chemicals are: diethylamine, aniline,
ethylene oxide, allyl chloride, 1,4-dioxane, 1,1-dichloroethylene, and bromoform.
1.2 Industry Identification Process
The solvents investigation undertaken to support this study covered spent solvents, still bottoms
from the recovery of spent solvents, and mixtures of spent solvents. Spent solvents are solvents that have
been used and are no longer fit for use without being regenerated, reclaimed, or otherwise processed (50
FR 53316, December 31, 1985). The Agency also investigated the residuals generated by processes that
use the solvents of interest. Residuals include spent solvents, residuals generated during solvent recovery,
and any residuals generated after the solvent has been introduced into the process that might include some
concentration of spent solvent. The solvents under investigation included the seven chemicals for which
EPA must make a listing determination as well as the seven solvent study chemicals that are the subject of
this report.
EPA's solvents investigation did not consider processes where the constituents of interest are used
as raw materials or principally sold as commercial products (i.e., where the constituent is not used for its
solvent properties). This approach is similar to discussions in the December 31, 1985 Federal Register
notice for existing listings, which noted that "...process wastes where solvents were used as reactants or
ingredients in the formulation of commercial chemical products are not covered by the listing." Examples of
the use of solvents as reactants or ingredients are the use of solvents in the manufacture of paints and
coatings. It is important to note, however, that solvents added as a thinner to product paints and coatings
after purchase are being used for their solvent properties and, after use, will meet any applicable spent
solvent listings.
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Solvents Study
1.2.1 Research to Identify Potential Uses of Solvents
As stated above, the solvents investigation is unique in that it focuses on facilities using chemicals
for their solvent properties. Unlike a traditional industry investigation, which would focus on a specific waste
generated in a process unique to one industry, the solvents investigation focussed on the activities of all
users of these solvents. The immediate challenge to the program was the identification of industries using
the chemicals as solvents. To address this challenge, significant background research was conducted on
each chemical to determine its probable solvent uses.
Literature searches were conducted to identify industries using the chemicals as solvents. Initial
sources searched included Chemical Engineering Handbook, the Industrial Solvents Handbook, and the
SRI Chemical Economics Handbook to obtain basic information on production and potential solvent uses.
Chemical Abstracts were searched for a four- to twelve-year period for abstracts on potential uses of each
of the seven chemicals as a solvent. The number of years searched depended on the number of
references available on a specific chemical. Each abstract was reviewed a team of chemists and chemical
engineers to determine whether the use constituted a potential solvent use (as defined by EPA/OSW) and
to relate the use to industries that may employ the solvent in their processes. Chemical Abstracts provided
background on specific solvent uses and were used to determine potential users by Standard Industrial
Classification (SIC) code. These efforts produced a list of SIC codes for industries suspected of using the
chemicals for their solvent properties. The final memorandum on the Chemical Abstract search is included
in Appendix A. The results of the search are summarized in Tables 1-1 through 1-7. Where SIC codes are
followed by a question mark (e.g., 2833? for diethylamine use), the potential use of the chemical by
facilities in these SIC codes is highly questionable based on the Chemical Abstracts. They are included for
completeness.
Table 1-1 Potential Allyl Chloride Users Identified from Chemical Abstracts
2911 Petroleum Refining
Table 1-2 Potential Aniline Users Identified from Chemical Abstracts
2865 Cyclic Organic Crudes and Intermediates, and Organic Dyes and Pigments
2999 Products of Petroleum and Coal. Not Elsewhere Classified
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Solvents Study
Table 1-3 Potential Bromoform Users Identified from Chemical Abstracts
1311 Crude Petroleum and Natural Gas
2899 Chemicals and Chemical Preparations. Not Elsewhere Classified
Table 1-4 Potential Diethylamine Identified from Chemical Abstracts
2611 Pulp Mills
2819 Industrial Inorganic Chemicals, Not Elsewhere Classified
2823 Cellulosic Manmade Fibers
2833? Medicinal Chemicals and Botanical Products
2836 Biological Products, Except Diagnostic Substances
2865 Cyclic Organic Crudes and Intermediates, and Organic Dyes and Pigments
3089 Plastic Products. Not Elsewhere Classified
Table 1-5 Potential 1,4-Dioxane Users Identified from Chemical Abstracts
1311 Crude Petroleum and Natural Gas
2295 Coated Fabrics, Not Rubberized
2611 Pulp Mills
2621 Paper Mills
2679 Converted Paper and Paperboard Products, Not Elsewhere Classified
2752 Commercial Printing
2759 Commercial Printing, Not Elsewhere Classified
2821 Plastics Materials, Synthetic Resins, and Nonvulcanizable Elastomers
2822 Synthetic Rubber (Vulcanizable Elastomers)
2823 Cellulosic Manmade Fibers
2824 Manmade Organic Fibers, Except Cellulosic
2833 Medicinal Chemicals and Botanical Products
2834 Pharmaceutical Preparations
2842 Specialty Cleaning, Polishing, and Santation Preparations
2865 Cyclic Organic Crudes and Intermediates, and Organic Dyes and Pigments
2869 Industrial Organic Chemicals, Not Elsewhere Classified
2879 Pesticides and Agricultural Chemicals, Not Elsewhere Classified
2899 Chemicals and Chemical Preparations, Not Elsewhere Classified
2911 Petroleum Refining
3291 Abrasive Products
Table 1-6 Potential Ethylene Oxide Users Identified from Chemical Abstracts
None One probable solvent use identified over 12 year Chemical Abstracts search could not be linked
to a SIC Code.
Table 1-7 Potential Vinylidene Chloride Users Identified from Chemical Abstracts
None No probable solvent uses were identified over 12 year Chemical Abstracts search.
The Toxic Release Inventory (TRI) database was searched for addresses of facilities reporting
releases of the 7 chemicals. The TRI initially was used to develop a baseline of SIC codes for solvents that
were reported "as otherwise used". This use classification most paralleled EPA's definition of solvent use.
However, some limitations apply. The TRI did not provide complete coverage of the affected industries for
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Solvents Study
a number of reasons. Not all of the 7 solvents under investigation are included in the TRI reporting list;
diethylamine is not on the list of TRI chemicals. The TRI has a reporting threshold of 10,000 pounds.
Facilities using less than that quantity are not required to complete TRI reports (i.e., are not included in the
TRI database) and, therefore, would not have been identified as potentially subject to the solvents listing
determination. Finally, the TRI is limited to facilities in SIC Codes 20-39, which encompass manufacturing
industries. Appendix B to this report contains the instructions from the Toxic Release Inventory Reporting
Form R and Instructions booklet.
Given the TRI limitations, Chemical Abstract SIC codes were cross-referenced with the TRI SIC
codes to develop a final SIC Code list. TRI does not specify that a chemical is used as a solvent, rather, it
notes "as otherwise used" (i.e., as a chemical processing aid, as manufacturing aid, or ancillary or other
use). Where a chemical was reported to the TRI by facilities in a SIC Code group as otherwise used, but
did not correspond to any suspected or known solvent use from Chemical Abstracts research, the SIC
Code was dropped. For example, the TRI indicated that the Leather Tanning and Finishing Industry (SIC
Code 3111) potentially utilized phenol, 2-methoxyethanol, and acetonitrile as solvents. Chemical literature
searches indicated that these chemicals were part of formulations and, therefore, did not meet the solvent
definition. Subsequently, SIC Code 3111 was dropped from further study. Appendix C to this report
presents two lists of industries and chemicals these industries use, by SIC Code. The first list is SIC Codes
potentially affected by the listing determination/study and the second is SIC Codes removed from further
study. Appendix D presents two lists, the first relating industries to solvent uses identified and the second
detailing the rationale for removing industries from further study as solvent users.
By identifying the potential solvent uses of each chemical, it was possible to link uses to specific
industries. Once industries were identified, a final facility address list could be developed. The TRI was the
primary source of facility information for the solvents pre-questionnaire mailing list. In order to ensure the
broadest and most complete list of potentially affected facilities, additional data sources were consulted.
These sources include:
D Trade associations, such as the Pharmaceutical Research and Manufacturers of America, provided
their membership list. EPA also conducted discussions with trade groups representing potentially
affected industries such as the Chemical Manufacturers Association, the Semiconductor
Manufacturers Association, the Chemical Distributor's Association, and the Synthetic Organic
Chemical Manufacturers Association.
D The databases supporting EPA's development of two effluent guidelines were searched for facility
addresses. The effluent guideline databases searched included Pharmaceuticals I and II, and the
Organic Chemicals, Plastics, and Synthetic Fibers.
D The National Air Toxics Inventory of Chemical Hazards (NATICH) was accessed for facility
addresses.
D The address list developed for the RCRA §3007 Questionnaires for petroleum refinery facilities was
used.
D Addresses for pulp and paper mills developed during a study of Subtitle D disposal of pulp and
paper mill sludge was used.
D Addresses for users of solvents were obtained from the Toxic Substances Control Act (TSCA)
Office of Pollution Prevention and Toxics (OPPT) at EPA. These addresses resulted from OPPT's
evaluation of solvents under the Source Reduction Review Project (SRRP).
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Solvents Study
D Addresses were obtained from Dun and Bradstreet (an industrial address book) or the Thomas
Register (a listing of product manufacturers). Industries covered by these sources included rubber
manufacture; paper and paperboard products; printing; selected food-related industries; cement,
concrete, and gypsum manufacture; iron, steel, copper, and aluminum manufacture; electronics
and semiconductors; and medical supply manufacture.
D Finally, facilities that received a RCRA §3007 Chlorinated Aliphatics questionnaire were deleted
from the mailing list because solvents questions were included in the questionnaire mailed to that
industry.
1.2.2 Development of RCRA 3007 Preliminary Questionnaire Mailing List
From these data gathering activities, 1,497 facilities potentially subject to listing determinations
were identified. A copy of the preliminary questionnaire is included in Appendix E to this report. The list of
facilities is included in Appendix F to this report. EPA did not include laboratories in the preliminary
questionnaire mailing. The Agency attempted to obtain laboratory client lists and the identity of firms
purchasing aggregate volumes of solvents from the National Association of Chemical Distributors
members; however, such data were not made available. EPA also worked with the American Chemical
Society (ACS) and their laboratory network to define the universe of affected laboratories. The Agency
presented information on the solvents listing determination and initiated a dialogue with the ACS Task Force
on RCRA and Laboratories at their meeting on May 14, 1994 in Washington, D.C.1 Similar information was
presented at the Twelfth Annual College and University Hazardous Waste Conference on August 8, 1994.2
Based on these discussions, it is believed that nearly all laboratories dispose of the solvents under
investigation as waste rather than recovering them. Further, anecdotal information indicates that the
solvents are managed as hazardous, many because they exhibit the characteristic of ignitability.
Discussions with ACS and the colleges and universities provided a clearer picture of waste management at
universities and further anecdotal information on management of the solvents under investigation.
Of the 1,497 preliminary questionnaires mailed, less than 600 responded that one or more of the
solvents were used at that facility. Further investigations (primarily through telephone calls to verify data)
eliminated additional facilities3. The definition of "solvent" appeared to be unclear to some respondents,
who provided solvents quantities when in fact the compound was part of a formulation or was not used for
its solvent properties. For example, 1,4-dioxane is used as a stabilizer in 1,1,1-trichloroethane which is
already regulated as hazardous waste codes F001 and F002 when used as a solvent. Many facilities
reported 1,4-dioxane use; however, as an additive it is not used for its solvent properties and does not meet
the regulatory definition of solvent provided in Section 1.1.1. Hence, data would reflect use of 1,4-dioxane
as an additive rather than a solvent, and any residuals generated would already be regulated as RCRA
hazardous waste. In addition, a number of facilities did not check the list of solvents carefully and reported
volumes for incorrect compounds, such as those who reported diethylamine use when diethanolamine was
used. Table 1-8 presents data from the RCRA 3007 Preliminary Solvents Use Questionnaire on potential
solvent use in 1992. However, these data include uses reported that subsequently were removed from
consideration (e.g., uses reported by TSDs). The use is considered "potential" because there is no means
lSee Docket for Solvents Listing Determination for Briefing Paper (Docket No. F-96-SLDP).
2lbid.
3Contact sheets documenting these call backs are included in the docket for the Solvents Listing Determination,
Docket No. F-96-SLDP.
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Solvents Study
to determine with complete certainty that the use reported is truly use as a solvent. To the extent possible,
this table reflects totals as revised to eliminate the errors discussed above. Totals shown as greater than
(>) or less than (<) reflect totals that do not include confidential business information. Appendix G presents
detailed non-CBI data for all responders by SIC code. The facilities making claims of confidential business
information (CBI) on their use have been deleted from this list.
The data collected from the Preliminary Solvents Use Questionnaire were limited to the total
volume of solvents used in 1991 and 1992. From the information obtained from the preliminary
questionnaire, EPA proceeded to develop a detailed solvent use survey to collect process, waste
generation, and waste management information, which was under the authority of RCRA Section 3007.
Trade associations also were given the opportunity by EPA to review the draft questionnaire for technical
accuracy and relevance.
Table 1-8 Total Reporters and Potential Solvent Use, by Chemical
(Source: RCRA §3007 Preliminary Questionnaire of Solvent Use)
Solvent
1 ,4-Dioxane
Allyl Chloride
Aniline
Bromoform
Diethylamine
Ethylene Oxide
Vinylidene Chloride
Number of Responders
126
4
58
12
44
24
5
Total 1992 Potential
Solvent Use (kg)
303,614
41
15,243,149
18,254
65,082
<1 00,000
24,531
The RCRA §3007 Questionnaire for Solvents Use was based on a new questionnaire design. In
addition to traditional questions regarding generation of residuals, residual characterization, and waste
management practices, the new format of the questionnaire enabled EPA to collect information on solvent
recovery, comanagement of solvents in recycling units, and waste minimization. In addition, respondents
were asked to identify all other on-site and captive off-site units in which solvent residuals are managed, the
common name and type of unit, the unit's location (on or captive off site), the residual and quantity
managed in 1992, other wastes comanaged in the unit, and the permit status of the unit. Finally, facilities
are asked to report shipments to off-site facilities and treatment used (if known). The questionnaire was
designed to enable EPA to gain a clearer understanding of the residuals generated from the use of the
seven chemicals under investigation, their characterization and management, and the management of
solvent residuals in specific units.
After approval from all participating Agency parties, the draft Solvents Use Questionnaire was field
tested in seven facilities in Pennsylvania, New Jersey, and Texas. The final Solvents Use Questionnaire
was revised in response to comments received during field testing and was then mailed to selected positive
responders to the preliminary questionnaire. A copy of the Questionnaire is included in Appendix H to this
report.
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Solvents Study
Of the corrected positive responses to the preliminary questionnaire, a number included small
users (e.g., 5 ml per year, 1 gallon per year). Because of the complexity of the full RCRA §3007 Solvent
Use Questionnaire, an effort was made to eliminate these very small users of solvents from the mailing list
for the Questionnaire. EPA examined the volume of solvents reported and determined that facilities
reporting the use of less than 1,200 kilograms per year combined of all seven solvents under investigation
could be eliminated from further study. This cutoff corresponds to a monthly use of 100 kilograms or less
of the seven solvents under investigation. Table 1-9 presents the breakdown of the number of facilities
reporting greater than or equal to 1,200 kilograms per year of all seven chemicals, by solvent. For
reference, Table 1-9 also presents the number of facilities reporting use of less than 120 kilograms per
year and 120 to less than 1,200 kilograms of an individual solvent.
In all, 157 facilities were sent a Questionnaire. The list of facilities is presented in Figure 1-1. The
impact of limiting the study population and its potential impact on the estimation of national solvent residual
generation rates is discussed in Section 2.0 of this report.
Table 1-9 Number of Facilities Falling Within Potential Solvent Use Quantities Ranges
(Source: RCRA §3007 Preliminary Questionnaire of Solvent Use)
Solvent
Allyl Chloride
Aniline
Bromoform
Diethylamine
1 ,4-Dioxane
Ethylene Oxide
Vinylidene Chloride
<120kg
4
48
11
37
86
17
4
120-<1200kg
0
5
0
4
16
1
0
D 1200 kg
0
5
1
3
24
6
1
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Solvents Study
Figure 1-1 RCRA 3007 Questionnaire Mailing List, by State
FACILITY NAME
CITY
STATE
M & M CHEMICAL EQUIPMENT CO.
DU PONT MOBILE PLANT
CIBA-GEIGYCORP. MCINTOSH SITE
INTEL CORP. - MAIN CHANDLER CAMPUS
CONTINENTAL CIRCUITS CORP.
OIL AND SOLVENT PROCESS CHEMISTRY
CHIRON CORPORATION
ADVANCED DIELECTRICS INC.
PCA METAL FINISHING INC.
CHEVRON CHEMICAL CO.
CHEVRON USA INC. - RICHMOND REFINERY
UNOCAL SAN FRANCISCO REFINERY
NEC ELECTRONICS INC., ROSEVILLE FACILITY
HEWLETT-PACKARD CO.
VLSI TECHNOLOGY INC.
GENENTECH, INC.
AMGEN, INC.
BACHEM INC.
NCR CORPORATION
HEWLETT-PACKARD CO.
NCR MICROELECTRONICS
BOEHRINGER INGELHEIM PHARMACEUTICALS, INC.
SEAFORD FIBERS PLANT
ZENECA-FAIRFAX SITE
PCR INC.
AT&T MICROELECTRONICS-ORLANDO PLANT
CONTINENTAL CIRCUITS INC.
NORTHERN ENGRAVING CORP.
ABBOTT LABORATORIES
ARMOUR PHARMACEUTICAL COMPANY
ARMSTRONG CONTAINERS INC. METAL DECORATING DIV.
BF GOODRICH CO - HENRY PLANT
ABBOTT LABORATORIES
PFANSTIEHL LABORATORIES
ELI LILLY SCO.
RHONE-POULENC INC.
ELI LILLY SCO.
ELI LILLY SCO.
ELI LILLY & CO. - MC RESEARCH
C.P. RECYCLING
CMC, NAO TRUCK FORT WAYNE ASSEMBLY
ELI LILLY SCO.
INDUSTRIAL FUELS & RESOURCES, INC.
ASHLAND OIL COMPANY CATLETTSBURG REFINERY
COMMONWEALTH ALUMINUM CORP.
EXXON CHEMICAL AMERICAS-BATON ROUGE CHEMICAL PLANT
UNIROYAL CHEMICAL CO. INC.
CITGO PETROLEUM CORP. - LAKE CHARLES COMPLEX
CIBA-GEIGY CORP. - ST GABRIEL PLANT
CWM, INC - LAKE CHARLES FACILITY
ANITEC PRINTING PLATE
ANITEC PRINTING PLATE
ATTALLA AL
AXIS AL
MC INTOSH AL
CHANDLER AZ
PHOENIX AZ
AZUSA CA
EMERYVILLE CA
FREMONT CA
FULLERTON CA
RICHMOND CA
RICHMOND CA
RODEO CA
ROSEVILLE CA
SAN JOSE CA
SAN JOSE CA
SOUTH SAN FRANCISCO CA
THOUSAND OAKS CA
TORRANCE CA
COLORADO SPRINGS CO
FORT COLLINS CO
FORT COLLINS CO
RIDGEFIELD CT
SEAFORD DE
WILMINGTON DE
GAINESVILLE FL
ORLANDO FL
WINTER SPRINGS FL
LANSING IA
ABBOTT PARK IL
BRADLEY IL
FRANKLIN PARK IL
HENRY IL
NORTH CHICAGO IL
WAUKEGAN IL
CLINTON IN
HAMMOND IN
INDIANAPOLIS IN
INDIANAPOLIS IN
INDIANAPOLIS IN
LOGANSPORT IN
ROANOKE IN
SHADELAND IN
SOUTH BEND IN
CATLETTSBURG KY
LEWISPORT KY
BATON ROUGE LA
GEISMAR LA
LAKE CHARLES LA
SAINT GABRIEL LA
SULPHUR LA
HOLYOKE MA
HOLYOKE MA
-------
Solvents Study
Figure 1-1 RCRA 3007 Questionnaire Mailing List, by State (continued)
FACILITY NAME
CITY
STATE
SHIPLEY CO. INC.
AT&T - MERRIMACK VALLEY WORKS
POLAROID CORP. - NORWOOD FACILITY
STAHL USA
POLAROID CORP.
ANALOG DEVICES
KANASCO LTD.
TOTAL PETROLEUM INC.
NORTRU. INC.
PARKE-DAVIS
UPJOHN COMPANY
PONTIAC WEST ASSEMBLY
CMC, TECHNICAL CENTER
WARREN TRUCK ASSEMBLY PLANT
ZEELAND CHEMICAL PRODUCTS
3M HUTCHINSON AVTD AND TMD PLANTS
IBM CORP. - ROCHESTER
3M CENTER
CEMTECH (SELMA PLANT)
SIGMA CHEMICAL CO.
MALLINCKRODT SPECIALTY CHEMICALS CO. - ST LOUIS
PACKAGE PRODUCTS SPECIALTY
DU PONT - FAYETTEVILLE WORKS
BURROUGHS WELLCOME CO.
GLAXO INC.
HADCO CORP.
POLYCLAD LAMINATES INC.
HOECHST CELANESE CORP.
CARTER-WALLACE, INC.
SCIENTIFIC DESIGN CO. INC.
NAPP CHEMICALS INC.
E. R. SQUIBB & SONS
HOFFMANN-LA ROCHE INC.
MOBIL OIL PAULSBORO REFINERY
SUVAR CORP.
BRISTOL-MYERS SQUIBB PHARMACEUTICAL GP
MERCK & CO. INC. - RAHWAY SITE
CIBA-GEIGYCORP., PHARMACEUTICALS DIV.
AMP-AKZO CORP.
PFIZER, INC.
IBM CORP.-ENDICOTT FACILITY
IBM CORP. - EAST FISHKILL FACILITY
AZON CORP.
HADCO CORPORATION - OWEGO DIVISION
LEDERLE LABORATORIES DIVISION
STERLING ORGANICS
KODAK PARK SITE
AYERST LABORATORIES INC.
GE PLASTICS, SELKIRK OPERATION
BRISTOL-MYERS SQUIBB CO.
JOSEPH C. WILSON CENTER FOR TECHNOLOGY, XEROX CORP
HUKILL CHEMICAL CORPORATION
MARLBOROUGH MA
NORTH ANDOVER MA
NORWOOD MA
PEABODY MA
WALTHAM MA
WILMINGTON MA
BALTIMORE MD
ALMA Ml
DETROIT Ml
HOLLAND Ml
KALAMAZOO Ml
PONTIAC Ml
WARREN Ml
WARREN Ml
ZEELAND Ml
HUTCHINSON MN
ROCHESTER MN
SAINT PAUL MN
FESTUS MO
SAINT LOUIS MO
ST. LOUIS MO
CHARLOTTE NC
FAYETTEVILLE NC
GREENVILLE NC
RESEARCH TRIANGLE PARK NC
DERRY NH
FRANKLIN NH
BRANCHBURG TOWNSHIP NJ
CRANBURY NJ
LITTLE FERRY NJ
LODI NJ
NORTH BRUNSWICK NJ
NUTLEY NJ
PAULSBORO NJ
PENNSAUKEN NJ
PRINCETON NJ
RAHWAY NJ
SUMMIT NJ
AQUEBOGUE NY
BROOKLYN NY
ENDICOTT NY
HOPEWELL JUNCTION NY
JOHNSON CITY NY
OWEGO NY
PEARL RIVER NY
RENSSELAER NY
ROCHESTER NY
ROUSES POINT NY
SELKIRK NY
SYRACUSE NY
WEBSTER NY
BEDFORD OH
10
-------
Solvents Study
Figure 1-1 RCRA 3007 Questionnaire Mailing List, by State (continued)
FACILITY NAME
CITY
STATE
CHRYSLER MOTORS TOLEDO ASSEMBLY
CWM RESOURCE RECOVERY, INC.
SUN REFINING & MARKETING CO.
INTEL CORP.
PRAEGITZER INDUSTRIES INC.
FUJITSU MICROELECTRONICS INC., GRESHAM MANUF. DIV.
AT&T MICROELECTRONICS - ALLENTOWN
LONZA INC.
HARRIS SEMICONDUCTOR
MERCK&CO. INC.
CEMTECH
WYETH-AYERST LABORATORIES INC.
BAXTER HEALTHCARE CORP. OF PR
STERLING PHARMACEUTICALS INC.
UPJOHN MANUFACTURING COMPANY
SMITHKLINE BEECHAM PHARMACEUTICALS CO.
SCHERING PLOUGH PRODUCTS
ELI LILLY INDUSTRIES INC.
OCG MICROELECTRONIC MATERIALS
ARKWRIGHTINC.
MOBAY CORP., BUSHY PARK
FUJI PHOTO FILM INC.
DU PONT
TENNESSEE EASTMAN DIVISION
GREAT LAKES CHEMICAL CORP.
AMOCO CHEMICAL CO. - CHOCOLATE BAYOU PLANT
ARGON MEDICAL
ADVANCED MICRO DEVICES INC.
IBM
EXXON
EXXON CHEMICAL AMERICAS - BAYTOWN CHEMICAL PLANT
MOBIL BEAUMONT REFINERY
PHILLIPS 66 CO.
SGS-THOMSON MICROELECTRONICS
LYONDELL PETROCHEMICAL CO.- CHANNELVIEW COMPLEX
GOODYEAR TIRE & RUBBER CO. - BEAUMONT CHEM PLANT
OXY CHEM CORPUS CHRISTI PETROCHEMICALS
TEXAS INSTRUMENTS INC. - EXPRESSWAY SITE
ALCON LABORATORIES, INC.
HITACHI SEMICONDUCTOR AMERICA
VLSI TECHNOLOGY INC.
GIBRALTAR CHEMICAL RESOURCES INC.
NATIONAL SEMICONDUCTOR CORP.
DU PONT
IBM ESSEX JUNCTION VERMONT
BOEING COMMERCIAL AIRPLANE GRP
IMMUNEX CORPORATION
POPE & TALBOT WIS INC.
NORTHERN ENGRAVING CORP., HOLMEN DIV
SHELL CHEMICAL CO., POINT PLEASANT POLYESTER PLANT
RHONE-POULENC AG CO. - INSTITUTE PLANT
TOLEDO
WEST CARROLLTON
TULSA
ALOHA
DALLAS
GRESHAM
ALLENTOWN
CONSHOHOCKEN
MOUNTAINTOP
RIVERSIDE
WAMPUM
WEST CHESTER
ANASCO
BARCELONETA
BARCELONETA
CIDRA
MANATI
MAYAGUEZ
EAST PROVIDENCE
FISKEVILLE
GOOSE CREEK
GREENWOOD
CHATTANOOGA
KINGSPORT
NEWPORT
ALVIN
ATHENS
AUSTIN
AUSTIN
BAYTOWN
BAYTOWN
BEAUMONT
BORGER
CARROLLTON
CHANNELVIEW
CHEEK
CORPUS CHRISTI
DALLAS
FORT WORTH
IRVING
SAN ANTONIO
TYLER
WEST JORDAN
MARTINSVILLE
ESSEX JUNCTION
EVERETT
SEATTLE
EAU CLAIRE
HOLMEN
APPLE GROVE
CHARLESTON
OH
OH
OK
OR
OR
OR
PA
PA
PA
PA
PA
PA
PR
PR
PR
PR
PR
PR
Rl
Rl
SC
SC
TN
TN
TN
TX
TX
TX
TX
TX
TX
TX
TX
TX
TX
TX
TX
TX
TX
TX
TX
TX
UT
VA
VT
WA
WA
Wl
Wl
WV
WV
11
-------
Solvents Study
2.0 Representativeness of RCRA 3007 Questionnaire Data to National Data
This section describes the preliminary conclusions reached about the coverage of facilities
achieved during the solvents industry study for potential listing determinations for residuals generated by the
use of the seven chemicals.
EPA is confident that it identified and surveyed all of the large users of these chemicals as solvents
and high-end generators of solvent residuals. Most of the seven chemicals are used as solvents for very
specific uses by specific industries. Further, most of the seven chemicals included on the lists of chemicals
reported in the Toxic Release Inventory. Thus, as discussed below, EPA is confident that large users were
identified.
EPA did not pursue an industry study methodology based on random sampling; rather, EPA made
a significant effort to identify users of these chemicals as solvents and collect data directly from facilities at
which there was a reason for suspected solvent use for at least one of the seven chemicals under study.
With the probable exception of 1,4-dioxane, solvent uses of these chemicals of concern are relatively
obscure when compared to solvent uses of many F001 - F005 solvents (e.g., methylene chloride and 1,1,1-
trichloroethylene). Therefore, it was possible to identify and survey all facilities that might reasonably be
expected to use significant quantities (i.e., greater than 1,200 kg per year) of these chemicals as solvents.
This industry study does not claim to have identified all facilities that used these seven chemicals as
solvents. However, for most of the seven chemicals of concern, industry study conclusions about the extent
of solvent use were confirmed by taking national production and import/export totals for each of the seven
chemicals and subtracting out:
1) identified nonsolvent uses of these chemicals (identified from other sources such as SRI),
and
2) total solvent use quantities as identified in RCRA §3007 questionnaire.
For most of the seven chemicals of concern, the industry study concluded that solvent usage is
either negligible or limited to a extremely narrow uses by a small number of facilities. The exception to this
conclusion is 1,4-dioxane, which is widely used in laboratories. The specific industry study conclusions
about issues relating to identification of solvent users and support for those conclusions are discussed
below.
2.1 Solvents Industry Study Methodology
Step One: Identification of Industries and Processes Using these Chemicals as Solvents
As described in Section 1.2.1, an extensive literature was undertaken to identify potential uses and
users of the seven chemicals as a solvent as defined by EPA. The primary reference source for this
literature search was Chemical Abstracts, which is discussed below.
Chemical uses identified from Chemical Abstracts may be limited by the following considerations:
(1) solvents uses by many industries may be considered "confidential" and, therefore, not published; (2)
solvent use abstracts may not have been identified in the years surveyed, previous years' abstracts may
have identified additional uses; (3) abstracts were sometimes ambiguous as to the nature of the activity for
the chemical listed (although a conservative approach was taken where ambiguity existed); and (4) solvents
used in a particular study may not have been identified in the abstract and, therefore, solvent use went
undetected. Although use of Chemical Abstracts to identify uses of the solvents being investigated has its
12
-------
Solvents Study
drawbacks, no better supplementary source for solvent use identification exists. Even with the limitations
inherent in Chemical Abstracts, few, if any, solvent uses for the study chemicals were missed using this
extensive literature search.
Step Two: Cross-Referencing of "Target" SIC Code List With Other Data Sources to Identify Specific
Facilities
Once the list of SIC codes was developed, several searches were performed to identify specific
facilities in those industries that might use one of the chemicals under study. The methodology used to
identify specific facilities that might use any of the seven chemicals as solvents is described in Section 1.2.1.
Table 2-1 presents a cross-reference of chemicals reported in TRI (the primary source for facility
addresses) and the seven chemicals of concern.
Table 2-1 Cross-Reference of TRI Chemicals with Seven Chemicals of Concern
TRI chemicals that coincide with
the seven chemicals of interest
Non-TRI chemicals
of the seven chemicals of interest
Allyl Chloride
Aniline
Bromoform
7,4-Dioxane
Ethylene Oxide
Vinylidene Chloride
Diethylamine
The Agency also conducted meetings with members of the National Association of Chemical
Recyclers, however, their membership was not surveyed directly. Rather, some recyclers were identified
through other sources, primarily TRI.
Compilation of RCRA §3007 Preliminary Questionnaire Data
In all, a total of 1,497 preliminary questionnaires were distributed to facilities across the country
using the methodology described above. These preliminary questionnaires requested information on
solvent use quantities only (not solvent residual generation or management, and facilities were not
requested to characterize the solvent use).
Responses to the preliminary questionnaire show that some specific chemicals are used as
solvents for a very limited number of industries in very small quantities while a few chemicals are used in
relatively larger quantities across numerous industries. Of the 1,497 preliminary questionnaires mailed, less
than 273 reported any solvent use of one or more of the seven chemicals.
Follow-up phone calls were made to facilities that reported solvent use for several low-volume
solvent use chemicals (e.g., vinylidene chloride, bromoform) and data corrections were made in the
preliminary questionnaire data set. Information gathered during these follow-up calls revealed that many
facilities over-reported solvent use either from 1) a misapplication of the EPA definition of solvent use, 2)
general ignorance of the precise use of the chemical at the facility and therefore a report of total amount
13
-------
Solvents Study
purchased or used at the facility, or 3) mistaken reading of the chemicals queried (e.g., diethanolamine
mistaken for diethylamine).
It should be noted, however, that follow-up calls were not made to many facilities that reported
solvent use of larger-volume solvents (e.g., 1,4-dioxane). Therefore, based on the results of follow-up
phone calls that were made, it can be assumed that preliminary questionnaire use data do overestimate
solvent use for a portion of the 1,497 facilities surveyed.
Following tabulation of preliminary questionnaire data, all facilities that reported greater than 1,200
kg of solvent use in the preliminary questionnaire for 1992 (157 facilities) were sent "full" RCRA §3007
questionnaires to obtain detailed information on solvent use, solvent residual generation, and management.
Thus, all large-quantity solvent users were captured and were sent a full RCRA §3007 questionnaire if the
facility was sent a preliminary questionnaire.
2.2 Confidence Level of Solvents Industry Study Results
EPA focused its efforts during this industry study on identifying the large quantity users of the seven
chemicals as solvents and potential large quantity generators of these spent solvent wastes (if listed) using
the industry study methodology described above. EPA is confident that the industry study identified and
characterized all large quantity solvent users.
In some cases, significant changes in the reported use of a solvent between the 1992 Preliminary
Questionnaire and the 1993 Questionnaire can be seen. Overall, the preliminary questionnaire totals
included amounts reported by commercial treatment, storage, and disposal (TSD) facilities. In some cases,
such as bromoform and vinylidene chloride, management by a TSD accounts for nearly all reported use.
These amounts are not reflected in the 1993 totals from the full Questionnaire. Prior to mailing the full
RCRA §3007 Questionnaire, EPA attempted to contact all potential recipients of the Questionnaire to
confirm the use of the chemical as a solvent. EPA was only partially successful in reaching all facilities
prior to mailing the full Questionnaire. However, between the telephone calls prior to mailing and
responses to the Questionnaire after the mailing, certain facilities were removed from the mailing list. The
facilities removed either had closed (2 facilities), incorrectly reported chemicals used (2 facilities),
discontinued use of the chemical (17 facilities), or incorrectly reported the chemical as being used as a
solvent (4 facilities).
After review of the full Questionnaire responses, the Agency determined that certain uses did not
meet EPA's definition of solvent use. For example, 34,484 kg of the ethylene reported was actually used as
a sterilant, which does not meet EPA's definiton of solvent use. Nearly all of the aniline reported
(14,920,877 kg of the 14,978,397 kg reported) was used as a raw material that was consumed in the
process. This also does not meet EPA's definition of solvent use. The same is true of diethylamine, where
62,163 kg of the total 64,638 kg reported was actually diethanol amine rather than diethylamine.
Finally, variations in usage are to be expected. In the case of 1,4-dioxane, five facilities reported
higher use in 1992 than in 1993. For other solvents, facilities reported either increases or decreases in use
between 1992 and 1993 that indicate changes in production schedule or product slate. EPA is confident
that all large users of the seven solvents were identified and surveyed as part of the listing determination.
The Agency believes that the solvent use reported in response to the full Questionnaire provides a more
accurate characterization of solvent use patterns than the Preliminary Questionnaire because of the greater
level of detail provided by the respondents. Finally, it is important to recognize that smaller uses of some
solvents were captured through facilities reporting larger uses of other solvents. For example, Unocal,
Rodeo, CA is a significant user of phenol, but also uses a small amount (3.86 kg) of aniline, thus
information on acetonitrile wastes were collected.
14
-------
Solvents Study
Table 2-2 presents the total reported use, by solvent, for each year along with an explanation of the
reasons for the apparent changes in total use. Table 2-3 and Table 2-4 present and discuss the industry
study identification and characterization of large-solvent users for each of the seven target chemicals.
15
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Solvents Study
Table 2-3 Solvent Production, Solvent Use, and Survey Results
Chemical
Allyl Chloride
Aniline
Bromoform
Diethylamine
1 ,4-Dioxane
Ethylene Oxide
Vinylidene
Chloride
Total Chemical
Production
(kg)
313,000,000
560,187,000
Unknown
9,970,000
11,000,000-
14,000,000
2,812,727,200
78,472,000
Production &
Import Data
Year (SRI)
1 990 (capacity)
1994
(imports neg)
Unknown
1990
(no import data)
1985
(estimated)
1989
1995
(no import data)
Quantity Estimated
to be Solvent Use
from SRI (kg)
<31,300,0002
<18,200,0002
None
None
None
None
None
Quantity Identified
as Solvent Use from
1 993 RCRA Survey1
(kg)
12
20
<0.001
44
101,565
4.3
0
1 All quantities exclude amounts reported by TSDs.
2 Represents all "other" uses, which may include solvent use.
19
-------
Solvents Study
Table 2-4 Solvent Specific Confidence Rationales
Allyl Chloride
Chemical
Production
Total (kg)
(import
quantity
unknown)
313,000,000
(SRI, 1990:
U.S. capacity
only)
Quantity
Estimated to be
Solvent Use
from SRI
(kg)
<31,300,0001
Quantity
Identified as
Solvent Use
from 1 993
RCRA
Survey (kg)
12
Comments
D Allyl Chloride is a TRI chemical.
D An estimated 90 percent (281 ,700,000
kg) is used as a chemical in the
production of epichlorohydrin. The
remaining 10 percent is used as a raw
material in the synthesis of allyl
compounds (esters, ethers, and amines)
by substitution of the chlorine and in the
high-temperature chlorination of
propylene.
D Solvent uses could include petroleum
refining and pharmaceutical
applications, however, no evidence of
such current uses are indicated by the
data collected from these industries.
Represents all "other" uses, which may include solvent use.
20
-------
Solvents Study
Aniline
Chemical
Production
Total (kg)
(import
quantity
unknown)
560,187,000
(Mansville,
1994)
Quantity
Estimated to be
Solvent Use
from SRI
(kg)
<18,200,0001
Quantity
Identified as
Solvent Use
from 1 993
RCRA
Survey (kg)
20
Comments
D Aniline is a TRI chemical.
D An estimated 67 percent is used in the
production of MDI and rubber. An
additional 5 percent is used in
agricultural chemicals. Aniline also is a
reactant in the dye industry.
D Potential solvent uses include use in dye
applications and coal liquefaction. Coal
liquefaction facilities reported no aniline
solvent use and dye manufacturers
report aniline as reactant.
Represents all "other" uses, which may include solvent use.
21
-------
Solvents Study
Bromoform
Chemical
Production
Total (kg)
(import
quantity
unknown)
Unknown.
Unavailable
from SRI,
USITC,
Mansville,
and TSCA.
Quantity
Estimated to be
Solvent Use
from SRI
(kg)
None
Quantity
Identified as
Solvent Use
from 1 993
RCRA
Survey (kg)
<0.001
Comments
D Bromoform is a TRI chemical.
D Bromoform is used as a chemical in
organic syntheses and in medicinal
Pharmaceuticals as a sedative.
D Bromoform potentially can be used as a
solvent in mineral separation. No such
use was indicated by the TRI or the
RCRA 3007 Questionnaire responses.
Diethylamine
Chemical
Production
Total (kg)
(import
quantity
unknown)
9,970,000
(USITC,
1990)
Quantity
Estimated to be
Solvent Use
from SRI
(kg)
None
Quantity
Identified as
Solvent Use
from 1 993
RCRA
Survey (kg)
44
Comments
D Diethylamine is not a TRI chemical.
D Non-solvent uses, including production
of N,N-diethylaminoethanol, rubber
processing chemicals, pesticides, and
other chemicals is estimated at
9,305,333 kg.
22
-------
Solvents Study
1,4-Dioxane
Chemical
Production
Total (kg)
(import
quantity
unknown)
11,000,000
to
14,000,000
(SRI, 1985)
Quantity
Estimated to be
Solvent Use
from SRI
(kg)
None
Quantity
Identified as
Solvent Use
from 1 993
RCRA
Survey (kg)
101,565
Comments
D 1 ,4-Dioxane is a TRI chemical.
D The largest use of 1 ,4-dioxane is as a
stabilizer in 1 ,1 ,1-trichloroethane.
D 1 ,4,-Dioxane is used in laboratories as
an alternative to acetonitrile in
chromatography. No attempt was made
to survey laboratories separately.
Ethylene Oxide
Chemical
Production
Total (kg)
2,812,727,200
(SRI)
Quantity
Estimated to
be
Solvent Use
from SRI
(kg)
None
Quantity
Identified as
Solvent Use
from 1 993
RCRA
Survey (kg)
4.3
Comments
D Ethylene oxide is a TRI chemical.
D Ethylene oxide is widely used as a
sterilant in medical applications.
D Ethylene oxide is used as a raw material
in the synthesis of ethylene glycol,
diethylene glycol, triethylene glycol,
polyethylene glycol, and glycol ethers as
well as ethanol amines and non ionic
surface active agents. These uses
account for over 2.8 billion kg (99.6 % of
production and import). An additional 9
million kg is exported.
23
-------
Solvents Study
Vinylidene Chloride
Chemical
Production
Total (kg)
78,472,000
(SRI, 1995)
Quantity
Estimated to
be
Solvent Use
from SRI
(kg)
None
Quantity
Identified as
Solvent Use
from 1 993
RCRA
Survey (kg)
0
Comments
D Vinylidene chloride is a TRI chemical.
D Vinylidene chloride is consumed largely
in the production of polyvinylidene
chloride (PVDC) copolymers. widely
used as a sterilant in medical
applications.
24
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Solvents Study
3.0 Data Management and Waste Management Practices
3.1 Data Management and Analyses
Data from the questionnaire were managed through a linked database system. From the data,
EPA developed spreadsheets detailing residuals as reported by responders for each of the seven
chemicals. Each residual stream reported by responders was evaluated to determine whether the residual
represented a waste or an in-process stream. Residuals that were returned to the process through a
closed loop system were excluded from further analysis.
The Agency completed an enormous task in the data gathering effort. These data helped EPA to
identify the major waste generators. The questionnaire asked for very detailed information on waste
generation, management, and disposal for these chemicals when they are used as solvents. The
questionnaire was sent to larger facilities because 1) only large facilities would be likely to have on-site
treatment, storage, and/or disposal for which questionnaire items would be applicable, and 2) many of the
solvent uses are peculiar to large chemical industries and are not likely to be used in small companies.
Thus, by applying a careful, consistent definition of solvent use and closely examining facilities that use
these chemicals as solvent, the Agency identified where these chemicals are used as solvents, and where
wastes of interest are generated and managed.
Data submitted by TSDRs indicate that the original use of the chemical was unknown. Therefore, it
was not possible to determine whether the residuals managed by TSDRs would be solvent use residuals.
EPA noted that in preliminary questionnaire responses and again in full questionnaire responses, TSDRs
reported the management of greater quantities of some chemicals than were identified by industry
respondents. Generally, EPA believes that this indicates the management of wastes generated from non-
solvent uses. Since separation of wastes from solvent and non-solvent uses was not possible at TSDR
facilities, EPA could not assess management of these wastes with sufficient confidence in the accuracy of
the results. Therefore, the Agency chose not to include residuals reported by TSDR facilities in the
assessment of waste generation and management.
The remaining residuals were deemed to be wastes generated as a result of solvent use. Based
on the quantity of residual generated and the concentration of the solvent in the residual, EPA determined
the loading of the solvent in the residual as
Solvent Residual Quantity x Solvent Concentration = Solvent Loading
All residual quantities were converted to kilograms and all solvent loadings were expressed in
kilograms as well. Where liquid measurements were provided (e.g., liters or gallons), EPA used the
specific gravity of the solvent for conversion of the units. Table 3-1 presents the specific gravities used for
these calculations.
25
-------
Solvents Study
Table 3-1 Specific Gravities of Solvents
Solvent
Allyl Chloride
Aniline
Bromoform
1 ,4-Dioxane
Diethylamine
Ethylene Oxide
Vinylidene Chloride
Specific Gravity (g/cm3)
0.937004
1 .020005
2.894006
1 .032007
1 706008
0.875009
1.2180010
3.2 Identification of Current Waste Management Practices
The current waste management practices were noted, including whether the residual was
managed as hazardous at the time of the Questionnaire. Given the information the Agency has collected
on these solvents, their uses, waste generation, and management, the Agency has a clear picture of the
situation that exists with respect to environmental consequences of current management of these wastes.
The Agency also does not believe management practices for these wastes are likely to change for a
number of reasons: 1) facilities are not likely to abandon investment in capital equipment such as
incinerators, tanks, or wastewater treatment systems, 2) many of these wastes are treated in some ways
because they have value (recycling/reuse and BTU value as fuel), 3) facilities have incentives to try to
recover more solvent, use a different solvent, or eliminate waste based on cost of solvent and reporting
requirements (e.g., TRI), and 4) in the cases where wastes are already hazardous (by characteristic or
mixture with a listed waste), the facilities do not have the option of changing to an unregulated management
practices. In addition, many states have restrictions on management of liquid wastes in land-based facilities
4Shell MSDS, January 1989
5Dupont MSDS, August 1992.
6Rhone Poulenc MSDS, October 1987.
7Ashland 1,4-Dioxane MSDS, August 1992.
8Ashland Diethylamine MSDS, August 1992.
9Shell MSDS, June 1990.
1C'Handbook of Environmental Data on Organic Chemicals, 2nd Edition, 1983.
26
-------
Solvents Study
or the construction of surface impoundments (even non-hazardous ones) that make these options highly
unlikely to occur.
4.0 Discussion of Solvents Study Chemicals
4.1 Allyl Chloride
Ally chloride is produced by high-temperature chlorination of propylene, with dichloropropanes and
dichloropropenes formed as by-products. Allyl chloride is an intermediate to crude epichlorohydrin, which is
used to produce synthetic glycerin or refined to a purer product for synthesis of other products, such as
epoxy resins. Other non-solvent uses include use in the pharmaceutical field as a raw material for the
production of allyl isothiocyanate (synthetic mustard oil), allyl substituted barbiturates (sedatives) and
cyclopropane (anesthetic). Allyl chloride also has been used to prepare allyl esters of starch, which are of
some interest on surface coatings, and in the manufacture of speciality resins for water treatment.11
EPA has identified SIC codes through Chemical Abstracts searches that indicated potential use of
the chemical as a solvent. These potential uses were cross-referenced with TRI data for this chemical
reported to be "otherwise used." A complete description of this methodology is presented in Section 2.0 of
this study. The literature search conducted for this study indicated that allyl chloride can be used in a
solvent mixture for removal of deposits from reservoirs and tanks used for storage of heavy petroleum
products. TRI data indicated that the Chemical and Allied Products industry may utilize allyl chloride for
ancillary purposes. Of three facilities responding to the Preliminary Questionnaire, one confirmed use of
solvent for biological research, and the other two could not confirm solvent use.
The 1993 RCRA 3007 Questionnaire reported allyl chloride use as a solvent by four laboratory
research and development facilities, totaling 12.0 kg. Allyl chloride was reported as having multiple
laboratory uses, including chemicals synthesis by substitution. The use of allyl chloride in a solvent mixture
for the removal of deposits from reservoirs and tanks and its use for ancillary purposes, uses identified in
the literature search, were not confirmed in the 1993 Questionnaire responses.
Table 4-1 presents the facilities reporting use of allyl chloride as a solvent. Table 4-2 presents
solvent use by industry sector.
Table 4-1 Facilities Using Allyl Chloride in 1993 and Industrial Sector
Facility
Eli Lilly & Co., - MC Research
Glaxo Inc.
PCR Inc.
3M Center
Location
Indianapolis, IN
Research Triangle Park, NC
Gainesville, FL
Saint Paul, MN
Industry
Pharmaceuticals
Pharmaceuticals
Industrial Organic Chemicals
Commercial Physical Research
Table 4-2 Use of Allyl Chloride By Industry
11
Shell Chemical Co. MSDS, 1/89.
27
-------
Solvents Study
Industry
Pharmaceuticals
Industrial Organic Chemicals
Commercial Physical Research
Use, kg
3.64
7.26
1.1
4.1.1 Wastes From Use as a Solvent
All of the Wastes generated from the use of allyl chloride as a solvent are small volume,
commingled organic laboratory wastes. Only two wastes of the four reported were larger than 3,000 kg/yr
(with the largest volume wastes at approximately 12,397 kg/yr and 5,000 kg/yr). The remaining waste
quantities were 40.91 kg/yr (with volumes not reported for the remaining waste stream). The total 1993
consumption of allyl chloride reported by each facility ranged from 1.10 kg to 7.26 kg. These low
consumption rates result in total allyl chloride loading quantity of less than 12 kg. Table 4-3 presents the
residuals generated by waste type.
Table 4-3 Quantity of Allyl Chloride Waste Generated for Each Type Generated
Waste Type
Organic Wastes
Spent Solvents
Total Residual Volume
(kg/yr)
17,438
Solvent Loading
(kg/yr)
9.68
4.1.2 Management Practices
Each of the four organic wastes containing allyl chloride generated from its use as a solvent are
managed either by on- or off-site incineration or off-site fuel blending. Most facilities employ on-site
storage. The four wastes represent a total waste volume of approximately 17,438 kg and the allyl chloride
concentration in the waste streams range from 11 ppm to 1%. The overall loadings was low, totaling less
than 12 kg/yr. In all cases the wastes are managed as RCRA hazardous wastes; three of the four wastes
are labeled as D001 (ignitable), one is D002 (corrosive), and the remainder consist of D-codes and several
F-codes. Prior to final disposal or management, three of the spent solvent waste streams are managed in
on-site containers (the fourth being stored off-site). One facility's residual volume and concentration was
not reported. However, through conversations between the Agency and the facility, it was determined that
the waste is managed as hazardous and sent for offsite fuel blending. An assumption was made that the
total amount of allyl chloride used is passed through to the waste loading. Table 4-4 presents the statistics
for the residuals, by management practice.
28
-------
Solvents Study
Table 4-4 Generation Statistics for Allyl Chloride
Management
Practice
Incineration
Fuel Blending
TOTAL
#of
Facilities
3
1
4
#of
Streams
3
1
4
# of Streams
w/Un re ported
Volume
0.00
1
1
Total Volume
(kg)
17,438
NR
17,438
Total Loading
(kg)
2.42
7.26
9.68
4.1.3 Health Data
Allyl chloride (C3H5CI, CAS No. 107-05-1), is a colorless to yellowish brown liquid with a pungent,
unpleasant odor.12 It is extremely flammable, has a low boiling point (45DC), a flash point of- 25DF (by tag
closed cup testing), and vapors that are more dense than air.12 It hydrolyzes in water with a half-life of 44
hours at 35DC.13 Flammable mixtures can be formed at ambient temperatures.12 Upon combustion, allyl
chloride produces hydrogen chloride and/or phosgene and carbon monoxide.12 Allyl chloride is severely
irritating to the eyes, skin, nose, throat, and respiratory tract.14 If inhaled, allyl chloride can produce liver,
kidney, lung, and peripheral nerve damage.14 If ingested, allyl chloride can result in liver and kidney
damage or death.
Based on exposure data, the following exposure limits have been established for allyl chloride. The
OSHA PEL and ACGIH TLV is 1 ppm (3 mg/m3'.15 16 The OSHA and ACGIH STEL limits are 2 ppm.15' 16 The
NIOSH IDLH is 250 ppm, and the threshold odor level is 0.2 pm.15
Toxicity data indicate that acute exposure to allyl chloride can cause unconsciousness, while
chronic exposure can cause cumulative liver and kidney damage.17 The established LD50 for acute
exposure in rats via the oral route is 700 mg/kg and via the inhalation route is 11 gm/m3/2H.18 Allyl chloride
12
Material Safety Data Sheet, Shell Chemical Co., January 27, 1989.
13
Mabey, W., Mill, T., Journal of Chemical Reference Data, 1978, Vol. 7, pp. 383-415.
14
Material Safety Data Sheet, Shell Chemical Co., January 27, 1989. Based upon product testing.
15,
U.S. Department of Health and Human Services. National Institute for Occupational Safety and Health, NIOSH
Pocket Guide to Chemical Hazards. Washington D.C. June 1994.
16,
American Conference of Governmental Industrial Hygienists. 1995-1996 Threshold Limit Values (TLV's) for
Chemical Substances and Physical Agents and Biological Exposure Indices (BEIs). Cincinnati, OH. 1995.
17
TheMerck Index, 11th Edition. Merck and Co., Inc. Rahway, NJ 1989.
18,
U.S. Department of Health and Human Resources. Registry of Toxic Effects of Chemical Substances. National
Toxicology Program, National Library of Medicine, Bethesda, MD. 1996.
29
-------
Solvents Study
is readily absorbed through the skin and is a possible human carcinogen.19 The RfC for allyl chloride is
0.001 mg/m3 based on a No Observable Adverse Effects Limit (NOAEL) of 3.6 mg/m3 for rabbits.20 Due to
the small number of animals involved in the study and poor reporting of results for NOAEL exposure, EPA
has low confidence in the study used as the basis for the RfC.20 Allyl chloride is rated as an EPA Group C
(possible) carcinogen.20 Although no human cancer data were found, animal studies show the potential for
cancer by gavage and skin painting.20 No RfD has been established. Aquatic toxicity has been estimated at
48 ppm for guppies exposed over a 96-hour period in fresh water.19
4.2 Aniline
Seventy-four percent of the aniline produced in the U.S. is consumed as an intermediate in
production of 4,4-Methylenebis(phenylisocyanate) (MDI). Future demand of aniline is expected to be linked
to MDI production, which itself is forecast at a growth rate of 3-5% for 1990-1995.21 EPA has identified SIC
codes through Chemical Abstracts searches that indicated potential use of the chemical as a solvent.
These potential uses were cross-referenced with TRI data for this chemical reported to be "otherwise used."
A complete description of this methodology is presented in Section 2.0 of this study.
Literature searches indicate that aniline can be used as a solvent for conversion of coal to a liquid,
specifically, for low-temperature coal liquefaction in basic nitrogen compounds; thermal dissolution of Fan-
Yagnob coal; and extraction and reaction of coal below 100DC.22 Literature searches indicate that aniline
may be used as a solvent in the dye industry to pretreat polyester fibers. The pretreatment is performed at
a temperature range of 70 to 100DC in order to increase the dyeability of the fiber. It is assumed that only a
portion of the organic solvent used to pretreat the fiber interacts with the fiber and therefore, a spent solvent
would result.23
The 1993 RCRA 3007 Questionnaire reported use of aniline as a solvent by seven facilities totaling
20.38 kg. These facilities include three pharmaceutical manufacturers, one industrial organic chemicals
manufacturer, one petroleum refinery, one office machines manufacturer, and one commercial physical
and biological research facility. All seven facilities use aniline as a solvent for laboratory purposes, such as
acetic acid titration of raw materials, testing properties of hydrocarbon solvents, and as a reaction or
synthesis media for a dye intermediate filtrate. The use of aniline as a solvent for the conversion of coal to
a liquid or in the dye industry to pretreat fibers, as indicated by the literature search, was not confirmed by
the Questionnaire.
Table 4-5 presents the facilities reporting use of aniline as a solvent. Table 4-6 presents the use of
aniline as a solvent by industry.
19Hazardous Chemicals Directory, 1987.
U.S. EPA Integrated Risk Information System (IRIS) on Allyl Chloride. Environmental Criteria and Assessment
Office, Office of Health and Environmental Assessment, Office of Research and Development, Cincinnati, OH. 1993.
SRI Chemical Economics Handbook, 10/91.
22Chemical Abstracts, various dates.
23American Dyestuff Reporter, 3/92.
30
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Solvents Study
Table 4-5 Facilities Using Aniline in 193 and Industrial Sector
Facility Name
Eli Lilly & Co., - MC Research
Merck & Co., Inc.
Glaxo Inc.
Exxon Chemical Americas-
Baytown Chemical
Unocal San Francisco Refinery
Joseph C. Wilson Center for
Technology
3M Center
Location
Indianapolis, IN
Danville, PA
Research Triangle Park, NC
Baytown, TX
Rodeo, CA
Webster, NY
Saint Paul, MN
Industry
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Industrial Organic Chemicals
Petroleum Refining
Office Machines
Commercial Physical and
Biological Research
Table 4-6 Use of Aniline By Industry
Industry
Pharmaceuticals
Industrial Organic Chemicals
Petroleum Refining
Office Machines
Commercial Physical and Biological Research
Use, kg
8.45
0.20
3.86
0.07
7.8
4.2.1 Wastes From Use as a Solvent
All of the wastes generated from the use of aniline as a solvent are small volume commingled
organic laboratory wastes. Only two wastes of the seven reported were larger than 3,000 kg/yr (with the
largest volume waste approximately 12,397 kg/yr and the second highest approximately 5,000 kg/yr). One
facility reported an aniline waste stream of approximately 207 kg/yr, while the remaining estimations were
less than 10 kg/yr. The total 1993 consumption rates result in a total aniline loading quantity of less than 14
kg. One facility did not report their residual volume or concentration. An assumption was made that the
total amount of solvent used is passed through to the waste loading. Table 4-7 presents data on the
generation of aniline residuals, by waste type.
Table 4-7 Quantity of Aniline Waste Generated for Each Type Generated
Waste Type
Organic Wastes
Spent solvents
Total Residual Volume
(kg/yr)
17,614
Solvent Loading
(Kg/yr)
13.84
31
-------
Solvents Study
4.2.2 Management Practices
Each of the seven organic wastes containing aniline generated from its use as a solvent are
managed in one of three ways: 1) stored on-site prior to being incinerated on-or off-site, 2) stored on-site
prior to being sent off-site for fuel blending, or 3) in the case of the aniline stream being treated as "non-
hazardous", treated at an on-site in a tank-based waste water treatment system. The seven wastes
represent total waste volume of approximately 17,614 kg and the aniline concentration ranges from 23 ppm
to 100%. Where high volume waste streams were reported, there were considerably low concentrations of
aniline. Conversely, where low volume waste streams were reported, there were relatively high
concentrations of aniline. Hence, the overall loadings was considerably low, totaling less than 14 kg/yr. In
all but one facility, the wastes are managed as RCRA hazardous wastes: two of the seven wastes are
labeled as D001 (ignitable) only; one is D002 (corrosive) only; one is toxic and ignitable; one is a U-listed
wastes; and one carries various D- and F-codes. Prior to final disposal or management, the spent solvent
wastes are managed in on-site containers or tanks. Table 4-8 presents data on the residuals generated, by
management practice.
Table 4-8 Generation Statistics for Aniline
Management
Practice
Incineration
Fuel Blending
WW-Tanks
TOTAL
#of
Facilities
5
1
1
7
#of
Streams
5
1
1
7
# of Streams
w/Un re ported
Volume
0
0
1
1
Total Volume
(kg)
17,614
0.51
NR
17,614.5
Total Loading
(kg)
9.47
0.51
3.86
13.84
32
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Solvents Study
4.2.3 Health Data
Aniline (C6H7N, CAS No. 62-53-3) is an oily liquid that is colorless when distilled but darkens to red-
brown on exposure to air and light.24 It has a high boiling point (184DC) and a flash point of 169DF (closed
cup).25
Various exposure limits have been established for aniline. The OSHA PEL and ACGIH TLV levels
for inhalation are 5 ppm and 2 ppm, respectively.23 27 The NIOSH IDLH level is 100 ppm. The threshold
odor level is 1 pm.27
Toxicity data indicate that aniline is poisonous by most routes including inhalation and ingestion.
Acute exposure may result in cyanosis and methemoglobinemia.26 Chronic exposure may result in anemia,
anorexia, weight loss, and lesions.28 Via the oral route in rats the LD50 for acute exposure is 250 mg/kg.27
Aniline has a carcinogen slope factor (CSF) of 5.7E-03 mg/kg/day and a health-based limit (HBL) of 6E-03
mg/L.28
Toxicity data indicate that acute exposure to aniline can cause unconsciousness, while chronic
exposure can cause cumulative liver and kidney damage.28 The established LD50 for acute exposure in rats
via the oral route is 250 mg/kg and by inhalation is 250 ppm/4H.29 Aniline is readily absorbed through the
skin and is a possible human carcinogen.29 The RfC for aniline is 0.001 mg/m3 based on spleen toxicity in
rats.30 Due to the small number of animals and single exposure concentration used in one study and the
short duration of a second study, EPA has low confidence in the study used as the basis for the RfC.30
Aniline is rated as an EPA Group B2 (probable) carcinogen.30 Human cancer data are not sufficient to
demonstrate that aniline is a carcinogen, but animal studies show the potential for spleen and body cavity
tumors.30 No RfD has been established. Aquatic toxicity shows that sunfish exposed at 1020 ppm over a 1-
hour period in fresh water were killed.30
4.3 Diethylamine
Fifty percent of diethylamine consumed is used for the production of N,N-Diethylaminoethanol
(DEAE). Diethylene amine based rubber accelerators include various N,N-diethyldithiocarbamate salts
24Solvents Safety Handbook.
25The Merck Index, 11th Edition. Merck and Co., Rahway, NJ. 1989.
26U.S. EPA. Health and Environmental Effects Profile for Aniline. Environmental Criteria and Assessment Office,
Office of Health and Environmental Assessment, Office of Research and Development, Cincinnati, OH. 1985.
27U.S. Department of Health and Human Resources. Registry of Toxic Effects of Chemical Substances. National
Toxicology Program, National Library of Medicine, Bethesda, MD. 1996.
28U.S. Environmental Protection Agency. Integrated Risk Information System. Office of Health and Environmental
Assessment, Office of Research and Development, Cincinnati, OH. 1993.
29Hazardous Chemicals Directory, 1987.
30Solvent Safety Handbook.
33
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Solvents Study
from Uniroyal Chemical, RT Vanderbilt, and ARTEL Chemical. Diethylamine is used to produce N,N-
diethyl-m-toluamide (DEET). Diethylamine is used as a selective solvent for the removal of impurities from
oils, fats, and waxes where its property of hydrating in aqueous solution is utilized.31 Diethylamine mixture is
used as a mobile phase solvent for the optimization of TLC separations of basic drugs and alkaloids.
Diethylamine mixture was used to test the solubility and reactivity of native, mercerized, and regenerative
celluloses, as well as dissolution of cellulose in mixtures of N-methylmorpholine N-oxide. A sulfur
dioxide/diethylamine/dimethyl sulfoxide mixture is used for viscosity measurements of cellulose to
determine the molecular weight of cellulose in wood pulp. Diethylamine mixture is used as a solvent for the
preparation of amorphous cellulose by regeneration of cellulose in its solutions. Diethylamine is used as a
solvent medium for the preparation of the red-blue a-modification of copper phthalocyanine. [The red-blue
pigment is useful for coloring oil varnishes.] A diethylamine mixture is used as a solvent in the reagent to
dissolve iron protoporphyrins in fecal occult blood tests. Diethylamine is used for the cleavage of DMA and
as a medium to study the dropping Hg electrode polarographic behavior of sulfur solutions.32
The 1993 RCRA 3007 Questionnaire reported diethylamine use as a solvent by 12 facilities,
totaling 41.65 kg. All of the facilities indicated that diethylamine was used only in their laboratories. Eight of
these facilities are pharmaceutical laboratories. Three of the pharmaceutical laboratories use diethylamine
in chromatography; one uses it in a quality control lab; one uses the chemical as a solvent for amine
reactions; and the others have multiple laboratory uses of diethylamine. In the industrial organic chemicals
industry, there are two facilities which use the diethylamine for laboratory use. Finally, one laboratory in the
office machines industry and one laboratory in the commercial research industry use diethylamine as a
solvent. Several of the solvent uses identified in the literature search are being used according to the
Questionnaire responses, but at the present time they are only being used on the research/laboratory level.
Table 4-9 presents the facilities reporting the use of diethylamine as a solvent. Table 4-10 presents
the solvent use by industry.
31 Industrial Solvents Handbook, 1991.
Chemical Abstracts, various dates.
34
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Solvents Study
Table 4-9 Facilities Using Diethylamine in 1993 and Industrial Sector
Facility Name
Eli Lilly & Co. - MC Research
Hoffmann - La Roche Inc.
Zeneca - Fairfax Site
Glaxo Inc.
Carter-Wallace, Inc.
Pfizer, Inc.
Ayerst laboratories, Inc.
Alcon Laboratories, Inc.
CIBA-Geigy Corp. Mclntosh Site
PCR Inc.
Xerox
3M Center
Location
Indianapolis, IN
Nutley, NJ
Wilmington, DE
Research Triangle Park, NC
Cranbury, NJ
Brooklyn, NY
Rouses Point, NY
Fort Worth, TX
Mclntosh, AL
Gainesville, FL
Webster, NY
Saint Paul, MN
Industry
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Industrial Organic Chemicals
Industrial Organic Chemicals
Office Machines
Commercial Physical and
Biological Research
Table 4-10 Use of Diethylamine By Industry
Industry
Pharmaceuticals
Industrial Organic Chemicals
Office Machines
Commercial Physical and Biological Research
Use, kg
31.07
7.27
0.02
3.29
4.3.1 Wastes From Use as a Solvent
All of the wastes generated from the use of diethylamine as a solvent are small volume
commingled organic laboratory wastes. Only three wastes of the 13 reported were larger than 3,000 kg/yr
(with the largest volume waste approximately 12,400 kg/yr). All of the remaining waste quantities were less
than 210 kg/yr (with volumes not reported for four waste streams). The total 1993 consumption of
diethylamine reported by each facility ranged from <0.01 kg to 14.12 kg. These low consumption rates
result in a total diethylamine loading quantity of less than 41 kg. Table 4-11 presents data on the
diethylamine residuals generated, by waste type.
Table 4-11 Quantity of Diethylamine Waste Generated for Each Type Generated
35
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Solvents Study
Waste Type
Organic Wastes
Reported Volume
kg/yr
21,285.91
Loading
kg/yr
40.98
4.3.2 Management Practices
Each of the 13 organic wastes containing diethylamine are managed in one of three ways: 1)
incineration on-site or off-site, 2) stored on-site prior to being sent off-site for fuel blending, or 3) burned for
energy recovery. The 13 wastes represent a total waste volume of approximately 21,286 kg and have an
average diethylamine concentration of 543 mg/L. In all cases, the wastes are managed as RCRA
hazardous wastes; six of the thirteen wastes are labeled as D001 (ignitable), one is D002 (corrosive), one is
F003/F005, two are a combination of D001, D018, and F001-F005, and three are unspecified hazardous
wastes. Prior to final disposal or management, the spent solvent wastes are managed in on-site containers
or tanks. Table 4-12 presents statistics for diethylamine residuals, by management practice.
Table 4-12 Generation Statistics for Diethylamine
Management
Practice
Incineration
Fuel Blending
Unspecified
TOTAL
#of
Facilities
7
3
2
12
#of
Streams
8
3
2
13
# of Streams
w/Un re ported
Volume
1
1
2
4
Total Volume
(kg)
21,282
3.90
NR
21,285.90
Total Loading
(kg)
12.25
2.43
19.12
33.80
NR - Not Reported
4.3.3 Health Data
Diethylamine (C^^N, CAS No., 109-89-7) is a colorless liquid with a fishy, ammonia-like odor.33 It
is highly volatile (explosive), has a low boiling point (55.5DC) with vapors more dense than air.35 It is harmful
if ingested or inhaled and can burn eyes and skin.35
Various exposure limits have been established for diethylamine. The OSHA PEL dermal exposure
limit is 25 ppm and the NIOSH IDLH limit is 200 ppm.34 The ACGIH TLV is 5 ppm (15 mg/m3) and the short
term TLV is 15 ppm (45 mg/m3).35
33.
The Merck Index, 11th Edition. Merck and Co., Inc. Rahway, NJ. 1989.
34,
U.S. Department of Health and Human Services. National Institute for Occupational Safety and Health, NIOSH
Pocket Guide to Chemical Hazards. Washington D.C. June 1994.
35
'American Conference of Governmental Industrial Hygienists. 1995-1996 Threshold Limit Values (TLVs) for
Chemical Substances and Physical Agents and Biological Exposure Indices (BEIs). Cincinnati, OH. 1995.
36
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Solvents Study
Toxicity data indicates that diethylamine is a skin and eye irritant; and is moderately toxic by
ingestion, inhalation, and dermal contact.36 Data indicate that acute exposure to diethylamine can cause
eye, skin, mucous membrane, and respiratory tract irritation; diethylamine is corrosive and can severely
damage skin and eyes.38 Chronic exposure can cause tracheitis, bronchitis, preunomitis, and pulmonary
edema.38 Via the oral route in rats the LD50 is 540 mg/kg and the LC50 for exposure via the inhalation route is
4,000 ppm/4H.38 A reference dose (RfD), a carcinogen slope factor (CSF), a health based limit (HBL), or a
maximum contaminant level (MCL) have been established for diethylamine.37 Aquatic toxicity has been
estimated at 85 mg/l for creek chub exposed over a 48-hour period in fresh water.38
4.4 1.4-Dioxane
EPA has identified SIC codes through Chemical Abstracts searches that indicated potential use of
the chemical as a solvent. These potential users were cross-referenced with TRI data for this chemical
reported to be "otherwise used." A complete description of this methodology is presented in Section 2.0 of
this study.
1,4-Dioxane is used as a solvent for extracting animal and vegetable oils and in the formulation of
inks, coatings, and adhesives. In the laboratory, 1,4-dioxane is useful as a cryoscopic solvent for molecular
mass determinations and as a stable reaction medium for diverse reactions.39 1,4-Dioxane is used primarily
as a solvent in such widely used products as paints, varnishes, lacquers, cosmetics, deodorants, cleaning
and detergent preparations, and in scintillating fluids.40 Literature searches also indicated the potential for
use as a solvent in the processing of crude petroleum, petroleum refining, petrochemicals, pulp and paper,
explosives, commercial printing, electroplating/polishing, pesticide and agricultural manufacture, dyes, fiber
manufacture, Pharmaceuticals, adhesives, semiconductors, electronic components, photographic
equipment, magnetic recording media, polymers, plastics, rubber manufacture, and organic and inorganic
chemical manufacture.41
The 1993 RCRA 3007 Questionnaire reported 1,4-dioxane use as a solvent in 27 facilities, totaling
101,577.08 kg. Only one facility in the coated and laminated paper industry indicated the use of 1,4-
dioxane. The chemical was used in the dissolution of polymers to produce a coating. Sixteen
pharmaceutical facilities reported the use of 1,4-dioxane, fourteen of which use the small amounts of the
chemical in laboratory operations such as research and development, quality control of finished goods, and
laboratory experiments. The remaining two facilities use 1,4-dioxane as a medium for crystallization and for
the distillation and dissolution of an intermediate product.
36U.S. Department of Health and Human Resources. Registry of Toxic Effects of Chemical Substances. National
Toxicology Program, National Library of Medicine, Bethesda, MD. 1996.
37U.S. EPA. Integrated Risk Information System (IRIS). Environmental Criteria and Assessment Office, Office of
Health and Environmental Assessment, Office of Research and Development, Cincinnati, OH 1993.
-10
Solvents Safety Handbook.
39Ullman's, 1987.
40Handbook of Environmental Fate and Exposure Data, 1990.
Chemical Abstracts, various dates.
37
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Solvents Study
Three facilities in the organic chemicals industry use 1,4-dioxane. One facility uses small amounts
of 1,4-dioxane in a quality assurance laboratory; one facility uses it for distillation and as a reaction/synthesis
medium; and the third facility uses 1,4-dioxane for chromatography in polyolefin catalyst synthesis. The
largest use of 1,4-dioxane is by a pesticide and agricultural chemical facility. This facility uses the chemical
as a polar reaction medium for a nucleophilic displacement reaction. Both the facility in the chemical
preparations industry and the petroleum refining industry use minimal amounts of 1,4-dioxane. The
chemical preparations facility uses 1,4-dioxane as a reaction medium in the laboratory. The petroleum
refining facility uses it at a concentration of 1% in a cleaning solvent. One facility uses 1,4-dioxane in the
office machines industry for the dissolution of pigment for an interface spray. In the photographic industry,
there are two facilities which use 1,4-dioxane; one facility uses it to dissolve resins and polymers into
solution for film coating; the other facility uses 1,4-dioxane as a photochemical reaction/synthesis medium
as well as for miscellaneous research and development projects. Finally, one facility in the commercial
research industry uses 1,4-dioxane in its laboratories as a solvent in reactions and distillation.
The use of 1,4-dioxane in the processing of explosives, dyes, fiber manufacture, semiconductors,
and rubber manufacture, uses identified in the literature search, were not reported in the 1993
Questionnaire responses.
Table 4-12 presents the facilities reporting the use of 1,4-dioxane as a solvent. Table 4-13
presents the use of solvent, by industry.
Table 4-12 Facilities Using 1,4-Dioxane in 1993 and Industrial Sector
Facility Name
3M Hutchinson AVTD and TMD
Plants
Merck & Co. Inc. - Rahway Site
Abbott Laboratories
Eli Lilly - MC Research
Hoffman-LaRoche, Inc.
Merck and Co., Inc.
Schering Plough Products
Genetech, Inc.
Zeneca - Fairfax Site
Abbott Laboratories
Eli Lilly& Co.
Eli Lilly& Co.
Upjohn Company
Glaxo Inc.
Location
Hutchinson, MN
Rahway, NJ
North Chicago, IL
Indianapolis, IN
Nutley, NJ
Danville, PA
Manati, PR
South San Francisco, CA
Wilmington, DE
Abbott Park, IL
Indianapolis, IN
Shadeland, IN
Kalamazoo, Ml
Research Triangle Park, NC
Industry
Coated and Laminated Paper
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
38
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Solvents Study
Facility Name
Carter-Wallace, Inc.
Pfizer, Inc.
Ayerst laboratories, Inc.
BF Goodrich Co - Henry Plant
Sigma Chemical Co.
Exxon Chemical Americas
Du Pont Mobile Plant
OCG Microelectronic Materials
Mobile Beaumont Refinery
Xerox
Polaroid Corp. - Norwood Facility
Kodak park Site
3M Center
Location
Cranbury, NJ
Brooklyn, NY
Rouses Point, NY
Henry, IL
Saint Louis, MO
Baytown, TX
Axis, AL
East Providence, Rl
Beaumont, TX
Webster, NY
Norwood, MA
Rochester, NY
Saint Paul, MN
Industry
Pharmaceuticals
Pharmaceuticals
Pharmaceuticals
Industrial Organic Chemicals
Industrial Organic Chemicals
Industrial Organic Chemicals
Pesticide/Agricultural Chem.
Chemical Preparations
Petroleum Refining
Office Machines
Photographic
Photographic
Commercial Research
39
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Solvents Study
Table 4-13 Use of 1,4-Dioxane By Industry
Industry
Pesticides and Agricultural Chemicals
Photographic Equipment and Supplies
Pharmaceutical Preparations
Office Machines
Coated and Laminated Paper
Industrial Organic Chemicals
Commercial Physical and Biological Research
Chemicals and Chemical Preparations
Petroleum Refining
Use, kg
53,852.85
20,796.46
15,940.77
5,686.15
3,850.13
1,137.69
88.98
13.60
0.45
4.4.1 Wastes From Use as a Solvent
The wastes generated from the use of 1,4-dioxane as a solvent are organic wastes, waste waters,
and solids. The majority of the waste streams (39 of the 48) are in the form of organic wastes, and they
vary from the smallest volume of 0.1 kg to the largest volume of 297,000 kg. These facilities reported 1993
consumptions of 1,4-dioxane in the range of 0.45 kg to 54,000 kg. Seven of the waste streams are
wastewaters. The wastewater streams range from 356 kg to 206,000,000 kg. The 1993 use of 1,4-dioxane
was between 1 and 54,000 kg for the wastewater streams. Two wastes were reported as solids. The
residual volumes were 12,000 kg and 554,000 kg, and the total 1993 1,4-dioxane consumptions were 3,850
kg for both streams. Table 4-14 presents data on the generation of 1,4-dioxane residuals, by waste type.
Table 4-14 Quantity of 1,4-Dioxane Residuals
Waste Type
Waste waters
Process Waste waters
Scrubber Waters
Filtrates/Condensates
Solids
Organic Waste
Spent Solvents
Precipitates, Filtrates,
Condensates, Distillates
Gases/Vapors
Organic Residues
Reported Volumes
kg/yr
206,211,494
8,182
NR
566,337
66,492
243,108
1,508
305,836
Total Loading
kg/yr
4,728
82
1,112
754
2,522
2,439
473
2,377
4.4.2 Management Practices
40
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Solvents Study
The wastes containing 1,4-dioxane generated from the use of 1,4-dioxane as a solvent are
managed in at least five different ways. The solids and organic wastes are managed in one of three ways:
incinerated on-site or off-site, maintained on-site until they are burned off-site for energy recovery, or
maintained on-site until they are sent off-site for fuel blending. The majority of the solid and organic wastes
are incinerated. In all three cases, the waste streams are managed as RCRA hazardous wastes. There is
one exception where a facility has non-hazardous on-site solids incineration. Seven of the 41 waste
streams are labeled as D001; 18 are labeled as a combination of D001, D002, D018, D022, D028, D035,
D038, F002, F003, F005, U003, U005, U007, and U188; and the remainder are unrecorded or disposed of
by some other means. The wastewater streams are either sent to a POTW for treatment or are biologically
treated on-site in a WWTP prior to being discharged. The wastewater streams are all managed as non-
hazardous wastes and the wastewater treatment systems are tank-based. Table 4-15 presents statistics on
the management of 1,4-dioxane residuals, by management practice.
Table 4-15 Generation Statistics for 1,4-Dioxane
Management
Practice
Incineration
Energy
Recovery
Fuel Blending
WWT-Tanks
POTW
WWT - Surface
Impoundment
Unspecified
Disposal
TOTAL
#of
Facilities
16
2
3
2
1
1
2
27
#of
Streams
24
8
4
2
1
1
2
42
# of Streams
w/Un re ported
Volume
0
0
0
0
1
0
1
2
Total Volume
(kg/yr)
936,098
4,714
243,067
205,917,273
NR
297,804
2.5
207,398,959
Total Loading
(kg/yr)
5,799
241
2,444
4,200
1,112
596
96
14,488
41
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Solvents Study
4.4.3 Health Data
1,4-Dioxane (C4H802, CAS No., 123-91-1) is a colorless, flammable liquid with a faint, pleasant
odor.42 It has a moderate boiling point (101 DC) and a flash point of 5 to 18DC.44 Its vapors are heavier
than air.43
Various exposure limits have been established for 1,4-dioxane. The limit for OSHA PEL is 100 ppm
(360 mg/m3) with an assigned "skin notation" indicating that this chemical has the potential for dermal
absorption.44 The ACGIH TLV for dermal exposure is 25 ppm and 90 mg/m for inhalation.45 The NIOSH
IDLH is 500 ppm.46
Toxicity data indicate that acute exposure to 1,4-dioxane can cause respiratory irritation, headache,
nausea, vomiting, drowsiness, dizziness, and central nervous system depression.46 Chronic exposure can
cause liver and kidney damage in animals.48 The established LD50 for acute exposure in rats via the oral
route is 5,200 mg/kg.47 The LC50 for rats via the inhalation route is 46 gm/m3/2H.481,4-Dioxane is a
probable human carcinogen.48 The carcinogen slope factor (CSF) for 1,4-dioxane is 0.011 mg/kg/day and
the health based limit (HBL) at 10~6 risk level is 0.003 mg/L49 A reference dose (RfD) and a maximum
contaminant level (MCL) have not been established for 1,4-dioxane.51 1,4-Dioxane is rated as an EPA
Group B2 (probable) carcinogen.51 Three epidemiological studies showed no relationship between
exposure to 1,4-dioxane and human cancer.51 Animal studies show the potential for liver and nasal cavity
cancer by ingestion.48
4.5 Ethylene Oxide
A small fraction of ethylene oxide production (less than 0.5 percent) is consumed by a sterilant or
fumigant users. Ethylene oxide is utilized as a sterling agent by various facets of the health care industry for
the sterilization of delicate instruments and heat and moisture sensitive devices. (EPA 49 FR 25734). Such
42The Merck Index, 11th Edition. Merck and Co., Inc., Rahway, NJ. 1989.
SRI Chemical Economics Handbook, 11/91.
44U.S. Department of Health and Human Services. National Institute for Occupational Safety and Health, NIOSH
Pocket Guide to Chemical Hazards. Washington, D.C. June 1994.
American Conference of Governmental Industrial Hygienists. 1995-1996 Threshold Limit Values (TLVs) for
Chemical Substances and Physical Agents and Biological Exposure Indices (BEIs). Cincinnati, OH 1995.
46U.S. Department of Health and Human Resources. Registry of Toxic Effects of Chemical Substances. National
Toxicology Program, National Library of Medicine, Bethesda, MD. 1996.
47Material Safety Data Sheet, BASF. March 14, 1989.
48
National Institute of Environmental Health Science. Reasonably Anticipated to be Carcinogen: 1,4-Dioxane (CAS
No. 123-91-1). ARC/RAC online database.
49
U.S. EPA. Integrated Risk Information System (IRIS). Environmental Criteria and Assessment Office, Office of
Health and Environmental Assessment, Office of Research and Development, Cincinnati, OH, 1993.
42
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Solvents Study
use does not meet EPA's definition of "solvent use." EPA has identified SIC codes through Chemical
Abstracts searches that indicated potential use of the chemical as a solvent. These potential uses were
cross-referenced with TRI data for this chemical reported to be "otherwise used." A complete description of
this methodology is presented in Section 2.0 of this study.
Potential solvent uses identified through literature searches include use as a solvent/catalyst in
catalyst systems subjected to different stages of heat treatments in the skeletal isomerization of
cyclohexane to 1-methylcyclopentene and 3-methylcyclopentene.50
The 1993 RCRA 3007 Questionnaire reported ethylene oxide use as a solvent by three
pharmaceutical research laboratories, totaling 4.29 kg. In these laboratories, ethylene oxide had multiple
small-scale solvent uses, such as a reaction or synthesis medium in oxidation and use as a standard for
gas chromatography. The use of ethylene oxide as a solvent in catalyst systems in the skeletal
isomerization of cyclohexane, a use identified in the literature search, was not reported in the 1993
Questionnaires.
Table 4-16 presents the facilities reporting the use of ethylene oxide as a solvent. Table 4-17
presents the use of ethylene oxide as a solvent by industry.
Table 4-16 Facilities Using Ethylene Oxide in 1993 and Industrial Sector
Facility Name
Eli Lilly & Co. - MC Research
Glaxo Inc.
Carter-Wallace, Inc.
Location
Indianapolis, IN
Research Triangle Park, NC
Cranbury, NJ
Industry
Pharmaceutical
Pharmaceutical
Pharmaceutical
Table 4-17 Use of Ethylene Oxide By Industry
Industry
Pharmaceuticals
Use, kg
4.29
4.5.1 Wastes From Use as a Solvent
Most of the wastes generated from the use of ethylene oxide as a solvent are commingled organic
laboratory wastes. The residual volumes reported range from 210 kg to 12,400 kg. The three waste
volumes each had concentrations of much less than one percent. This resulted in all three loadings being
under 3 kg, totaling 4.3 kg of ethylene oxide. Table 4-18 presents data on the quantity of ethylene oxide
residuals, by waste type.
Table 4-18 Quantity of Ethylene Oxide Waste Generated for Each Type Generated
50
Chemical Abstracts, various dates.
43
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Solvents Study
Waste Type
Organic Waste
Reported Volumes
kg/yr
17,611
Total Loading
kg/yr
4.3
4.5.2 Management Practices
Each of the three organic wastes containing ethylene oxide generated from the use of ethylene
oxide are managed in one of two ways: onsite storage followed by either incineration or fuel blending. The
three wastes represent a total waste volume of 17,611 kg and have concentrations ranging from 11 parts
per million to 0.01 percent. In all cases, the wastes are managed as RCRA hazardous wastes and are
labeled as D001 (ignitable). One of these three is also labeled D018 and F002/F003/F005. Table 4-19
presents statistics for the management of ethylene oxide residuals by management practice.
Table 4-19 Generation Statistics for Ethylene Oxide
Management
Practice
Incineration
Fuel Blending
TOTAL
#of
Facilities
2
1
3
#of
Streams
2
1
3
# of Streams
w/Un re ported
Volume
0
0
0
Total Volume
(kg/yr)
17,397
214
17,611
Total Loading
(kg/yr)
4.3
0.0005
4.3005
4.5.3 Health Data
Ethylene oxide (C2H40, CAS No., 75-21-8) is a colorless gas condensing at low temperatures
(below 12DC) to a mobile liquid, with a ether-like odor.51 Ethylene oxide is a highly reactive molecule with
vapors that are flammable and explosive.52 It hydrolyzes in water with a half-life at 25DC of about 12
days.53 As little as three percent ethylene oxide in air can be flammable.54 Ethylene oxide has a very low
boiling point (10.6DC) with vapors that are heavier than air.54 It may undergo hazardous polymerization
upon contact with highly active catalytic surfaces.54
Based on exposure data the following exposure limits were established for ethylene oxide. The
OSHA PEL limits for TWA and 15 minute excursion are 1 ppm and 5 ppm, respectively.54 The ACGIH TLV
51
The Merck Index, 11th Edition. Merck and Co., Inc. Rahway, NJ. 1989.
52
Material Safety Data Sheet, Shell Chemical Co., June 6, 1990.
53
Mabey, W., Mill, T., Journal of Chemical Reference Data, 1978, Vol. 7, pp. 383-415.
54,
NIOSH Pocket Guide to Chemical Hazards. U.S. Department of Health and Human Services, National Institute
for Occupational Safety and Health. Washington, D.C. June 1994.
44
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Solvents Study
limits for TWA is 1 ppm.55 The ACGIH also reports an odor threshold of 261 ppm for perception and 500 to
700 ppm for recognition.55 The NIOSH IDLH limit is 800 ppm and the threshold odor level is 1 pm.56 The
NIOSH TLV limits for TWA and the ceiling are <0.1 ppm and 5 ppm, respectively.
The toxicity data indicate that ethylene oxide is irritating to the skin, eyes, and mucous membranes
of respiratory tract.56 Toxicity data indicate that acute exposure to ethylene oxide can cause nausea,
vomiting, and death.57 Chronic exposure can cause irritation of eyes, skin, and mucous membranes,
cataracts, and problems in brain function.58 Exposure to ethylene oxide may result in lung, liver, and kidney
damage.58 Via the oral route in rats the LD50 is 72 mg/kg and via the inhalation route, the LC50 is 800
ppm/4H.58 Ethylene oxide is rated as a Group B1 (probable) human carcinogen.59 The carcinogen slope
factor (CSF) is 1.02 mg/kg/day and the health-based limit (HBL) is 3E-05 mg/L.61 A reference dose (RfD)
and a maximum contaminant level (MCL) have not been established for ethylene oxide.61
4.6 Bromoform
Bromoform is reportedly used in separating mixtures of minerals60, as a solvent to selectively
extract rare earth metals (e.g., Cs and Rb), and to separate Ekibastuz coal into fractions (benefication).61
Non-solvent uses of bromoform include use in organic syntheses and in medicinal Pharmaceuticals as a
sedative.62 EPA has identified SIC codes through Chemical Abstracts searches that indicate potential use
of the chemical as a solvent. These potential uses were cross-referenced with TRI data for this chemical
reported as "otherwise used." A complete description of this methodology is presented in Section 2.0 of this
study.
4.6.1 Use as a Solvent
In response to the RCRA 3007 Preliminary Questionnaire, 12 facilities indicated the use of
bromoform as a solvent at their site. These facilities reported a total use of 18,254 kilograms in 1992.
55American Conference of Governmental Industrial Hygienist. 1995-1996 Threshold Limit Values (TLVs) for
Chemical Substances and Physical Agents and Biological Exposure Indices (BEIs). Cincinnati, OH, 1995.
U.S. Department of Health and Human Resources. Registry of Toxic Effects of Chemical Substances. National
Toxicology Program, National Library of Medicine, Bethesda, MD. 1996.
Agency for Toxic Substances and Disease Registry (ATSDR). Toxicological Profile for Ethylene Oxide. U.S.
Public Health Service, U.S. Department of Health and Human Services. 1990.
eg
U.S. Department of Health and Human Resources. Hazardous Substances Data Base. National Toxicology
Program, National Library of Medicine, Bethesda, MD. 1993.
U.S. EPA. Integrated Risk Information System (IRIS). Environmental Criteria and Assessment Office, Office of
Health and Environmental Assessment, Office of Research and Development, Cincinnati, OH, 1993.
60Merck Index, 1989.
61Chemical Abstracts.
Rhone-Poulenc Product Information.
45
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Solvents Study
Nearly all of the "use" was reported by TSD facilities that accepted bromoform for thermal treatment. Two
facilities reported the use of bromoform in the RCRA 3007 Questionnaire of Solvent Use, one of which
erroneously reported its use as a solvent, when in fact it was used as a reactant. The only facility to indicate
the use of bromoform as a solvent used a very small amount, 0.001 liters per year. The facility did not
report any residuals associated with this use due to the very small quantity involved.
4.6.2 Health Data
Bromoform (CHBr3, CAS No., 75-25-2) is a colorless to yellow, very heavy liquid (density = 2.9031),
with a chloroform-like odor.63 It is toxic by inhalation, ingestion, and skin absorption; is irritating to the skin,
eye and respiratory tract.65 It is a lachrymator.65 It is non-flammable, has low reactivity, and has a moderate
boiling point (149DC).65
Based on exposure data the following limits have been established for bromoform. The OSHA
PEL and the ACGIH TLV are 5 mg/m3 (0.5 ppm) and 5.2 mg/m3 (0.5 ppm), respectively and a "skin
notation" has been assigned, which indicates a potential for dermal absorption ,64 65 The NIOSH IDLH limit
is 850 ppm.66
Bromoform is moderately toxic via the oral and subcutaneous routes.66 Acute inhalation of small
amounts causes irritation, provoking the flow of tears and saliva, and reddening of the face.22 Cumulative
exposures cause liver damage and abuse of bromoform can lead to addiction.22 Acute exposure in rats via
the oral route has a LD50 of 1,147 mg/kg and an LC50 via the inhalation route of 45 gm/m3/4H.68 Bromoform
has a reference dose (RfD) of 2E-02 mg/kg/day, a carcinogen slope factor (CSF) of 7.9E-03 mg/kg/day,
and a health-based limit (HBL) limit of 4E-03 mg/L at 10~6 risk level.67 An interim maximum contaminant
level (MCL) of 0.10 mg/L has ben established for total trihalomethanes.69 No RfC has been established.69
According to IRIS, the inhalation unit risk value is 1.1E-06 (ug/m3)"1, and thus, the concentration in
air corresponding to a risk level of 10~6 is 9E-04 mg/m3.69
Toxicity data indicate that acute exposure to bromoform can cause central nervous system
depression, while chronic oral exposure can cause liver, kidney, and central nervous system damage in
animals.68 Bromoform is rated as an EPA Group B2 (probable) carcinogen.69 Although no human cancer
data were found, animal studies show the potential for liver and intestinal cancer by oral exposure.69
63The Merck Index, 11th Edition. Merck and Co., Inc., Rahway, NJ. 1989.
64U.S. Department of Health and Human Services. National Institute for Occupational Safety and Health, NIOSH
Pocket Guide to Chemical Hazards. Washington, D.C. June 1994.
65American Conference of Governmental Industrial Hygienists. 1995-1996 Threshold Limit Values (TLVs) for
Chemical Substances and Physical Agents and Biological Exposure Indices (BEIs). Cincinnati, OH. 1995.
U.S. Department of Health and Human Resources. Registry of Toxic Effects of Chemical Substances. National
Toxicology Program, National Library of Medicine, Bethesda, MD. 1996.
U.S. EPA. Integrated Risk Information System (IRIS) on Vinyliende Chloride. Environmental Criteria and
Assessment Office, Office of Health and Environmental Assessment, Office of Research and Development, Cincinnati,
OH. 1993.
46
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Solvents Study
4.7 Vinylidine Chloride
Vinylidene chloride's major use is as an intermediate in the production of "vinylidene polymer
plastics" such as Saran and Velon. It also is used captively for the production of 1,1,1-trichloroethane. EPA
has identified SIC codes through Chemical Abstracts searches that indicated potential use of the chemical
as a solvent. These potential uses were cross-referenced with TRI data for this chemical reported as
"otherwise used." A complete description of this methodology is presented in Section 2.0 of this study. No
solvent uses have been identified due to its reactivity.
4.7.1 Use as a Solvent
Data from the RCRA 3007 Preliminary Questionnaire indicted that five facilities used a total of
24,532 kilograms of vinylidene chloride as a solvent in 1992, which included 24,529 kg reported by two
TSDs. An additional 3 kg reported by two facilities did not meet EPA's definitions of "solvent use." One
facility used less than 0.03 kg; this use was not continued in 1993. In response to the RCRA 3007
Questionnaire, the only "use" of vinylidene chloride was reported by a TSD facility that accepted vinylidene
chloride for treatment. No other facilities reported the use of vinylidene chloride on the RCRA 3007
Questionnaire.
The use of vinylidene chloride as a solvent appears to be very limited, if it even occurs. It is unlikely
that it has any industrial solvent use, rather it is used for specialty applications in laboratories.
4.7.2 Health Data
Vinylidene chloride (C2H2CI2, CAS No., 75-35-4) is a colorless, mobile liquid with a sweet, slightly
irritating odor resembling that of chloroform.68 It is toxic by ingestion or inhalation and is an eye and skin
irritant.70 It is flammable and may undergo hazardous polymerization with atmospheric oxygen if its inhibitor
has been depleted.70 It has a low boiling point (31.6DC) and a flash point of -15DC.70
Based on exposure data the following limits have been established for vinylidene chloride. The
ACGIH TLV and STEL exposure limits are 5 ppm and 20 ppm, respectively.69 No exposure limits have
been established for the OSHA PEL, NIOSH IDLH, and the threshold odor level.
Toxicity data indicate that the vinylidene chloride is a skin and mucous membrane irritant.70 Toxicity
data indicate that acute exposure to vinylidene chloride can have adverse respiratory and neurological
effects (e.g., central nervous system depression, convulsions, spasms, and unconsciousness).70 Chronic
exposure can cause cumulative live rand kidney damage.72 It has caused liver and kidney injury in
experimental animals and is a narcotic at high concentrations.70 The established LD50 for acute exposure in
rats via the oral route is 200 mg/kg and the LC50 for inhalation in rats is 6,350 ppm/4H.72 Vinylidene chloride
is a possible human carcinogen. Vinylidene chloride has a reference dose (RfD) of 0.009 mg/kg/day, a
carcinogen slope factor (CSF) of 0.6 mg/kg/day, and a health-based limit (HBL) of 6E-05 (corresponding to
6*The Merck Index, 11th Edition, Merck and Co., Inc., Rahway, NJ. 1989.
American Conference of Governmental Industrial Hygienist. 1995-1996 Threshold Limit Values (TLVs) for
Chemical Substances and Physical Agent and Biological Exposure Indices (BEIs). Cincinnati, OH 1995.
70U.S. Department of Health and Human Resources. Registry of Toxic Effects of Chemical Substances. National
Toxicology Program, National Library of Medicine, Bethesda, MD. 1996.
47
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Solvents Study
a risk level of 1E-06)71 and a maximum contaminant level (MCL) of 0.007 mg/L.71 EPA has medium
confidence in the study used as the basis for the RfD.71 Vinylidene chloride is rated as an EPA Group C
(possible) carcinogen.71 Although no relationship between occupational exposure to vinylidene chloride and
human cancer were found, animal studies show the potential for kidney and mammary cancer by
inhalation.71
The concentration in water corresponding to a risk level of 10E-06 as reported by IRIS is 6E-05
mg/l. The inhalation unit risk value is 5E-05 (ug/m3)"1, and thus, the concentration in air corresponding to a
risk level of 10E-06 is 2E-05.71
71U.S. EPA. Integrated Risk Information System (IRIS). Environmental Criteria and Assessment Office, Office of
Health and Environmental Assessment, Office of Research and Development, Cincinnati, OH, 1993.
48
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