United States
Environmental Protection
Agency
Office of Pollution*
Prevention and Toxics
Washington, DC 20460
EPA 745 J?-99-007
July 1999
EPA Emergency Planning and Community Right-
To-Know Act Section 313 Reporting Guidance
for Semiconductor Manufacturing
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TABLE OF CONTENTS
Page
ACKNOWLEDGMENT vi
OVERVIEW vii
CHAPTER 1 - INTRODUCTION 1-1
1.0 PURPOSE 1-1
1.1 Background on EPCRA Section 313 and PPA Section 6607 1-2
CHAPTER2 - REPORTING REQUIREMENTS 2-1
2.0 PURPOSE 2-1
2.1 Must You Report? - 2-2
2.2 SIC Code Determination 2-4
2.3 Number of Employees 2-6
2.4 Manufacturing, Processing, and Otherwise Use of EPCRA Section 313
Chemicals or Chemical Categories 2-7
2.5 Activity Categories 2-8
2.6 How Do You Report? 2-10
2.7 FormR 2-11
2.8 Alternate Threshold and Form A 2-12
2.9 Trade Secrets 2-13
2.10 Recordkeeping 2-14
CHAPTER 3 - EPCRA SECTION 313 CHEMICAL OR CHEMICAL CATEGORY
ACTIVITY THRESHOLD DETERMINATIONS . 3-1
3:0 PURPOSE ..., - 3-1
3.1 Step 1 - Identify Which EPCRA Section 313 Chemicals or Chemical
Categories are Manufactured (Including Imported), Processed, or Otherwise
Used .. -. 3-1
Qualifiers 3-4
3.2 Step 2. Identify the Activity Category and any Exempt Activities for Each
EPCRA Section 313 Chemical 3-7
3.2.1 Concentration Ranges for Threshold Determination 3-11
3.2.2 Evaluation of Exemptions 3-12
3.2.2.1 De Minimis Exemption 3-13
3.2.2.2 Article Exemption 3-15
3.2,2.3 Facility-Related Exemption ..... .,.-.-/...... . 3-17
Laboratory Exemption 3-17
3.2.2.4 Activity-Related Exemptions 3-17
3.2.3 Additional Guidance on Threshold Calculations for Certain
Activities 3-19
3.2.3.1 Reuse Activities 3-19
3.2.3.2 Remediation Activities 3-20
3.2.3.3 Recycling Activities 3-21
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TABLE OF CONTENTS (Continued)
Page
3.3 Step 3. Calculate the Quantity of Each EPCRA Section 313 Chemical and
Chemical Category and Determine Which Ones Exceed an Activity
Threshold 3_2l
4.0 PURPOSE 4-1
4.1 General Steps for Determining Release and Other Waste Management
Activity Quantities 4-1
4.1.1 Step 1: Prepare a Process Flow Diagram 4-3
4.1.2 Step 2: Identify EPCRA Section 313 Chemicals and Chemical
Categories and Potential Sources of Chemical Release and Other
Waste Management Activities 4-3
4.1.3 Step 3: Identify Release and Other Waste Management Activity
Types , 4.4
4.1.4 Step 4: Determine the Most Appropriate Method(s) to Calculate the
Estimates for Release and Other Waste Management Activity
Quantities 4-16
4.1.4.1 Monitoring Data or Direct Measurement (code M) 4-18
4.1.4.2 Mass Balance (code C) '. 4-19
4.1.4.3 Emission Factors (code E) 4-21
4.1.4.4 Engineering Calculations (code O) 4-23
4.1.4.5 Estimating Release and Other Waste Management
Quantities 4-24
4.2 Process Descriptions (Chemical Activities) 4-29
4.2.1 Photolithography 4-31
4.2.1.1 Step 1: Prepare Process Flow Diagram 4-32
4.2.1.2 Step 2: Identify Potential Sources of Chemical Release and
Other Waste Management Activities 4-33
4.2.1.3 Step 3: Identify Release and Other Waste Management
Activity Types 4-33
4.2.1.4 Step 4: Determine the Most Appropriate Method(s) to
Calculate the Estimates for Release and Other Waste
Management Activity Quantities 4-34
4.2.2 Thin Films 4-36
4.2.2.1 Step 1: Prepare Process Flow Diagram 4-37
4.2.2.2 Step 2: Identify Potential Sources of Chemical Release and
Other Waste Management Activities 4-37
4.2.2.3 Step 3: Identify Release and Other Waste Management
Activity Types 4-38
4.2.2.4 Step 4: Determine the Most Appropriate Method(s) to
Calculate the Estimates for Release and Other jVaste
Management Activity Quantities 4-39
4.2.3 Etching 4-40
4.2.3.1 Step 1: Prepare Process Flow Diagram 4-41
4.2.3.2 Step 2: Identify Potential Sources of Chemical Release and
Other Waste Management Activities 4-41
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TABLE OF CONTENTS (Continued)
Page
Appendix A
Appendix B
Appendix C
Appendix D
Appendix E
Appendix F
INDEX
4.2.3.3 Step 3: Identify Release and Other Waste Management
Activity Types 4-42
4.2.3.4 Step 4: Determine the Most Appropriate Method(s) to
Calculate the Estimates for Release and Other Waste
Management Activity Quantities 4-42
4.2.4 Cleaning ... , 4-43
4.2.4.1 Step 1: Prepare Process Flow Diagram 4-44
4.2.4.2 Step 2: Identify Potential Sources of Chemical Release and
Other Waste Management Activities 4-44
4.2.4.3 Step 3: Identify Release and Other Waste Management
Activity Types 4-45
4.2.4.4 Step 4: Determine the Most Appropriate Method(s) to
Calculate the Estimates for Release and Other Waste
Management Activity Quantities 4-48
4.2.5 Doping 4-48
4.2.5.1 Step 1: Prepare Process Flow Diagram 4-49
4.2.5.2 Step 2: Identify Potential Sources of Chemical Release and
Other Waste Management Activities 4-50
4.2.5.3 Step 3: Identify Release and Other Waste Management
Activity Types 4-50
4.2.5.4 Step 4: Determine the Most Appropriate Method(s) to
Calculate the Estimates for Release and Other Waste
Management Activity Quantities 4-51
4.2.6 Chemical Mechanical Planarization 4-51
4.2.6.1 Step 1: Prepare Process Flow Diagram 4-52
4.2.6.2 Step 2: Identify Potential Sources of Chemical Release and
Other Waste Management Activities 4-52
4.2.6.3 Step 3: Identify Release and Other Waste Management
Activity Types , 4-53
4.2.6.4 Step 4: Determine the Most Appropriate Method(s) to
Calculate the Estimates for Release and Other Waste
Management Activity Quantities 4-53
TRI GUIDANCE RESOURCES
BASIC CALCULATION TECHNIQUES
GUIDANCE FOR REPORTING AQUEOUS AMMONIA
GUIDANCE FOR REPORTING SULFURIC ACID
LIST OF TOXIC CHEMICALS WITHIN THE WATER DISSOCIABLE
NITRATE COMPOUNDS CATEGORY AND GUIDANCE FOR REPORTING
UNIT CONVERSION FACTORS
111
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LIST OF TABLES
Page
2-1 SIC Codes Covered by EPCRA Section 313 Reporting ., 2-4
2-2 EPCRA Section 313 Chemicals and Chemical Categories Commonly Encountered
in Semiconductor Manufacturing 2-8
2-3 Activity Categories .....: 2-9
3-1 Reporting Thresholds 3-8
3-2 Definitions and Examples of Manufacturing Subcategories 3-9
i
3-3 Definitions and Examples of Processing Subcategories ........-, 3-10
3-4 Definitions and Examples of Otherwise Use Subcategories : ..v.-.;.:....... 3-11
3-5 EPCRA Section 313 Reporting Threshold Worksheet 3-24
3-6 Sample EPCRA Section 313 Reporting Threshold Worksheet 3-25
4-1 Summary of Liquid Residue Quantities From Pilot-Scale Experimental Study
(weight percent of drum capacity) 4-9
4-2 Potential Data Sources for Release and Other Waste Management Calculations .... 4-18
4-3 Release and Other Waste Management Quantity Estimation Worksheet 4-25
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LIST OF FIGURES
2-1
4-1
4-2
4-3
4-4
4-5
4-6
4-7
4-8
4-9
Pagf
EPCRA Section 313 Reporting Decision Diagram ..:.....:;..;./.............. 2-3
Release and Other Waste Management Activity Calculation Approach .. .>.....:.... 4-2
Possible Release and Other Waste Management Activity Types fof EPCRA Section
313 Chemicals and Chemical Categories ............... .......'.... 4-5
Overall Process Flow Diagram - Semiconductor Manufacturing ........;.,-...;.; 4-33
Process Flow Diagram for Typical Photolithography Process ...'..,....,..::..., 4^32
Process Flow Diagram for Typical Thin Film Process .;'. i. i.....».:..-..:,:... 4-38
Process Flow Diagram for Typical Etching Process .,;......;......»...... 4-41
Process Flow Diagram for Typical Wafer Cleaning Process ........... ..;.. 4-44
Process Flow Diagram for Typical Doping Process ...... ..... .->»". 4-50
Process Flow Diagram for Typical Chemical Mechanical Planarizatidn (CMP)
Process
4-52
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ACKNOWLEDGMENT
The U.S. EPA wishes to acknowledge the valuable contributions made by the staff and members
of the Semiconductor Industry Association (SIA). Without the insight provided by those in the
industry with actual experience in the fulfilling of the EPCRA Section 313 reporting
requirements, we would not have been able to produce a document which we believe will be of
great assistance to those who must prepare future EPCRA Section 313 reports. Special thanks go
to Mr. Reed Content, Advanced Microdevices, Mr. Don Lassiter, SIA, and Ms. Karen Silberman,
Motorola, for their hard work.
VI
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OVERVIEW
This document supersedes the booklet entitled Title III Section 313 Release
Reporting Guidance, Estimating Chemical Releases From Semiconductor Manufacturing, dated
January 1988. It is intended to assist establishments and facilities designated by Standard
Industrial Classification (SIC) Code 3674 in complying with the Emergency Planning and
Community Right-To-Know Act (EPCRA) Section 313 and Pollution Prevention Act (PPA)
Section 6607 reporting requirements, the preparation of Form R or the alternate certification
statement, Form A. The EPCRA Section 313 program is commonly referred to as the Toxic
Chemical Release Inventory (TRI).
The principal differences in the new document include:
More detailed examples;
New EPCRA Section 313 regulations and guidance developed since 1988;
PPA Section 6607 reporting requirements;
U.S. Environmental Protection Agency's (EPA's) interpretive guidance on
various issues specific to the Semiconductor Manufacturing industry; and
EPCRA Section 313 issues regarding processes not discussed in the earlier
document.
This document is designed to be a supplement to the annual issue of the Toxic
Chemical Release Inventory Reporting Forms and Instructions, (TRIForms and Instructions). It
is organized to provide a step-by-step guide to compliance with EPCRA Section 313 and PPA
Section 6607, starting with how to determine if your facility must report and ending with
guidance for estimating release and other waste management quantities.
Chapter 1 introduces EPCRA Section 313 and PPA Section 6607 reporting and
provides a brief background on Section 313 of EPCRA and Section 6607 of PPA.
Chapter 2 discusses reporting requirements and begins with how to determine
whether your facility must report. This determination is based on your answers to a series of four
questions:
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Is your facility's primary Standard Industrial Classification (SIC) Code on the
EPCRA Section 313 list?
Does your facility employ ten or more full-time employees or the equivalent?
Does your facility manufacture, process, or otherwise use any EPCRA Section
313 chemicals or chemical categories?
Does your facility exceed any of the activity thresholds for an EPCRA Section
313 chemical or chemical category?
If the answer to ANY ONE of the first three questions is "No" you are not
i
required to submit an EPCRA Section 313 report. If you answer "Yes" to ALL four questions,
the next step is to determine what kind of report you must prepare, a Form R or the alternate
certification statement, Form A. Chapter 2 provides detailed information on the requirements for
each kind of report. Chapter 2 concludes with a discussion on how to address trade secrets and
!|
the records that should be kept to support your reporting.
Chapter 3 discusses how to calculate the activity thresholds (manufacture,
process, and otherwise use) for the EPCRA Section 313 chemicals or chemical categories.
Information is provided on how to determine which EPCRA Section 313 chemicals or chemical
categories your facility manufactures, processes, or otherwise uses' and how to calculate the
quantities of each. Detailed information is also provided on the various exemptions:
De minimis exemption;
Article exemption;
Facility-related exemption; and
Activity-related exemptions.
Chapter 3 concludes with a discussion of how to determine which EPCRA
Section 313 chemicals or chemical categories exceed a reporting threshold.
Chapter 4 discusses how to estimate the release and other waste management
amounts for those EPCRA Section 313 chemicals and chemical categories for which you must
prepare a report. The first part of this chapter provides a step-by-step approach designed to
minimize the risk of overlooking an activity involving an EPCRA Section 313 chemical or
chemical category and any potential sources or types of release and other waste management
activities. This procedure consists of:
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Preparation of a detailed process flow diagram;
Identification ofEPCRA Section 313 chemicals and chemical categories and
potential sources of chemical release and other waste management activities;
Identification of the potential types of release and other waste management
activities from each source; and
Determination of the most apprqpriate methods for estimating tlie quantities of
EPCRA Section 313.chemical and chemical category release and'other waste
management activities.
The second part of Chapter 4 is organized around six common activities in the
semiconductor manufacturing industry where EPCRA Section 313 chemicals arid chemical
categories are manufactured, processed, and otherwise used. The commonly used EP/CRA
Section 313 chemicals, process descriptions, reporting thresholds, release anxl other waste
management estimates, and common problems are presented.
This document includes examples and common errors applicable to the
semiconductor manufacturing industry. These are based on information received from
representatives of the Semiconductor Industry Association, on the questions received by the
EPCRA Hotline, and questions identified during voluntary site surveys of facilities that have
filed EPCRA Section 313 reports in the past.
IX
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CHAPTER 1 - INTRODUCTION
1.0
PURPOSE
The purpose of this guidance manual is two-fold. The primary purpose is to assist
Semiconductor Manufacturing facilities in complying with the reporting requirements of
Section 313 of the Emergency Planning and Community Right-to-Know Act of 1986 (EPCRA)
and of Section 6607 of the Pollution Prevention Act of 1990 (PPA). This manual explains the
EPCRA Section 313 reporting requirements and discusses specific release and other waste
management activities encountered at facilities that produce semiconductor chips used in
computers, cellular phones, pagers, calculators, and other electrical devices. Since each plant is
unique, the recommendations presented may have to be modified for your particular facility. The
secondary purpose is to provide information to other interested parties (such as management,
legal professionals, inspectors, consultants, teachers, students, and to general public) about the
processes and the toxic chemicals used in semiconductor manufacturing.
This manual is intended solely for guidance and does not alter any statutory or
regulatory requirements. The document should be used in conjunction with the appropriate
statutes and regulations but does not supersede them. Accordingly, the reader should consult
other applicable documents (for example, the statute, the Code of Federal Regulations (CFR),
relevant preamble language, and the current Toxic Chemical Release Inventory Reporting Forms
and Instructions (TRI Forms and Instructions)).
This document supersedes the 1988 document entitled Title III Section 313
Release Reporting Guidance, Estimating Chemical Releases from Semiconductor
Manufacturing. This new document includes:
More detailed examples;
New EPCRA Section 313 regulations and guidance developed since 1988;
PPA Section 6607 reporting requirements;
U.S. Environmental Protection Agency's (EPA's) interpretive guidance on
various issues specific to the Semiconductor Manufacturing industry; and
1-1
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EPCRA Section 313 issues regarding processes not discussed in the earlier
document.
It is intended to supplement the TRI Forms and Instructions document that is updated and
published annually by U.S. EPA. It is essential that you use the current version of the TRI
Forms and Instructions to determine if (and how) you should report. Changes or modifications
to Toxic Chemical Release Inventory (TRI) reporting requirements are reflected in the annual
TRI Forms and Instructions and should be reviewed before compiling information for the report.
The objectives of this manual are to:
Reduce the level of effort expended by those facilities that prepare an
EPCRA Section 313 report; and
Increase the accuracy and completeness of the data being reported by the
semiconductor manufacturing industry.
U.S. EPA cannot anticipate every potential issue or question that may apply to
your facility. Therefore, this manual attempts to address those issues most prevalent or common
for the semiconductor manufacturing industry. Used in conjunction with the most current TRI
Forms and Instructions and Estimating Releases and Waste Treatment Efficiencies for the Toxic
Chemical Release Inventory Form (1999 version), facilities should be able to provide complete
,|
and accurate information for EPCRA Section 313 reporting. Additional discussions on specific
l I
issues can be found in U.S. EPA's current edition of EPCRA Section 313, Questions and
Answers (the 1998 edition is EPA 745-B-98-004), which is available on the U.S. EPA's TRI
website (http://www.epa.gov/opptintr/tri) or by contacting the EPCRA Hotline at 1-800-424-
9346. In the Washington, DC metropolitan area, call 703-412-9810.
1.1
Background on EPCRA Section 313 and PPA Section 6607
The following overview of EPCRA Section 313 and Section 6607 of the PPA will"
j
provide you with a basic understanding of the objectives and requirements of this program, and
will help you in completing your forms.
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One of the primary goals of EPCRA is to increase the public's knowledge of, and
access to, information on both the presence of toxic chemicals in their communities and on
releases into the environment and other waste management activities of those chemicals.
EPCRA Section 313 requires certain designated businesses (see SIC Code discussion, Chapter 2,
Section 2.2) to submit annual reports (commonly referred to as Form R reports and Form A
reports) on over 600 EPCRA Section 313 chemicals and chemical categories and the amounts
released or otherwise managed as waste, even if there are no releases or other waste management
quantities associated with these chemicals. Throughout this document, whenever EPCRA
Section 313 chemicals are discussed, the discussion includes chemical categories, as appropriate.
Chemicals or chemical categories may be added or deleted from the list. Therefore, before
completing your annual report, be sure to check the most current list included with the TRI
Forms and Instructions when evaluating the chemicals and chemical categories in use at your
facility. Copies of the reporting package can be requested from the EPCRA Hotline, 1-800-424-
9346.
All facilities meeting the EPCRA Section 313 reporting criteria must report the
annual release and other waste management activity quantities (routine and accidental) of
EPCRA Section 313 chemicals and chemical categories to all environmental media. A separate
report is required for each EPCRA Section 313 chemical or chemical category that is
manufactured (including imported), processed, or otherwise used above the reporting threshold.
The reports must be submitted to U.S. EPA and State or Tribal governments, on or before July 1,
for activities in the previous calendar year. The owner/operator of the facility on July 1 is
primarily responsible for the report, even if the owner/operator did not own the facility during the
reporting year. However, property owners with no business interest in the operation of the
facility (for example, owners of an industrial park) are exempt from reporting requirements.
EPCRA also mandates U.S. EPA to establish and maintain a publicly available
database system consisting of the information reported under Section 313 and un4er Section
6607 of the PPA. This database, known as the Toxic Chemical Release Inventory (TRI), can be
accessed through the following sources:
National Library of Medicine (NLM) TOXNET on-line system;
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U.S. EPA Internet site, http://www.epa.gov/opptintr/tri;
Envirdfacts Warehouse Internet site, http://www.epa.gov/enviro/html/tris-
querry-j ava.html;
CD-ROM from the Government Printing Office;
Microfiche in public libraries; and
Magnetic tape and diskettes from the National Technical Information
Service.
Information identified by the submitter as trade secret in accordance with the
regulatory requirements is protected from public release. In addition to being a resource for the
public, TRI data are also used in the research and development of regulations related to EPCRA
Section 313 chemicals and chemical categories.
To reduce the reporting burden for small businesses, U.S. EPA established an
alternate activity threshold of one million pounds manufactured, processed, or otherwise used for
facilities with total annual reportable amounts of 500 pounds or less of the EPCRA Section 313
chemical or chemical category. Provided the facility does not exceed either the reportable
amount or the alternate threshold, the facility may file a certification form (Form A) rather than a
Form R. By filing the Form A, the facility certifies that they do not exceed the reportable
amount of 500 pounds or exceed the alternate threshold of one million pounds.
Note that the annual reportable amount includes the quantity of the EPCRA
Section 313 chemical or chemical category in all production-related waste management
activities, not just releases (see the discussion in Section 2.8 for more detail). Also note that
either a Form A or a Form R, but not both, must be submitted for each EPCRA Section 313
chemical or chemical category above any reporting threshold, even if there are zero release and
other waste management activity quantities.
Violation of EPCRA Section 313 reporting provisions may result in federal civil
penalties of up to $27,500 per day for each violation (61 FR 69360). State enforcement
provisions may also be applicable depending on the state's EPCRA Section 313 reporting
regulations.
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Members of the Semiconductor Industry Association provided input on common
problems specific to the semiconductor manufacturing industry that are encountered by those
completing EPCRA Section 313 reports. U.S. EPA has combined this input with questions
forwarded to the EPCRA Hotline and those identified during voluntary site surveys of facilities
that have filed EPCRA Section 313 reports in the past. Selected issues and guidance addressing
these common problems are presented throughout this document as applicable.
The TRIForms and Instructions and.The 1994 and 1995 Toxic Release Inventory
Data Quality Report, EPA 745-R-98-002, also contains discussions of common problems in
completing the EPCRA Section 313 reports. You are encouraged to read both documents before
filling out the Form R (or Form A) for your facility.
If, after reading this manual, you still have questions about EPCRA Sectioji 313
reporting, please contact the EPCRA Hotline at 1-800-424-9346. Assistance is also available
from the designated EPCRA Section 313 Coordinator in the U.S. EPA regional offipe and the
EPCRA contact in your state (see the TRI Forms and Instructions for a current list of these
contacts). Additional guidance is also available in the resources listed in Appendix A.
1-5
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CHAPTER 2 - REPORTING REQUIREMENTS
2.0
PURPOSE
The purpose of this chapter is to help you determine if you must prepare an
EPCRA Section 313 report(s) and, if so, what kind of a report(s) should be prepared (Form R or
the alternate certification statement, the Form A). This chapter presents the EPCRA Section 313
reporting requirements to help you determine if these requirements apply to your facility. It also
discusses the reporting of trade secrets and the records that must be kept.
To understand the following discussion you must first understand how EPCRA
defines a facility. The term "facility" is defined as, "all buildings, equipment, structures, and
other stationary items which are located on a single site or oil contiguous or adjacent sites and
which are owned or operated by the same person (or by any person which controls, is 'controlled
by, or is under common control with such person). A facility may contain more than one
"establishment" (40 CFR 372.3). An "establishment" is defined as, "an economic unit, generally
at a single physical location, where business is conducted, or services or industrial operations are
performed" (40 CFR 372.3).
U.S. EPA recognizes that for business reasons it may be easier and more
appropriate for multiple establishments at one facility to report separately. However, the
combined quantities of EPCRA Section 313 chemicals and chemical categories manufactured,
processed, or otherwise used in all establishments in that facility must be considered for
threshold determinations. Also, the combined release and other waste management activity
quantities reported singly for each establishment must equal those for the facility as a whole.
Note that if a facility is comprised of more than one establishment, once an
activity threshold is met by the facility, providing the facility meets SIC Code and employee
criteria, release and other waste management activities from all establishments at the facility
must be reported.
2-1
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Example - Multiple Establishments
Your facility has several different establishments, all with SIC Codes covered by EPCRA Section 313. One
establishment used 7,000 pounds of toluene, an EPCRA Section 313 chemical, during the year to clean
equipment. Another establishment purchased and used 4,000 pounds of toluene during the year as a
semiconductor manufacturing aid. Both activities constitute otherwise use of the EPCRA Section 313 chemical
(as presented in Section 2.5 and described in detail in Chapter 3) and the total for the facility exceeded the
10,000-pound otherwise use threshold for the year. Thus, if your facility meets the employee threshold, you
must file either one Form R for that chemical from your facility, or two Form Rs, one from each establishment.
Please note that you may be eligible to file one Form A for the facility but you cannot file a separate Form A for
each establishment.
2.1
Must You Report?
How do you determine if your facility must prepare an EPCRA Section 313
report? Your answers to the following four questions will help you decide (illustrated by
Figure 2-1):
1) Is the primary SIC Code for your facility included in the list covered by
EPCRA Section 313 reporting (see Section 2.2)?
2) Does your facility have 10 or more full-time employees or the equivalent
(see Section 2.3)?
3) Does your facility manufacture (which includes importation), process, or
otherwise use EPCRA Section 313 chemicals or chemical categories (see
Section 2.4)?
4) Does your facility exceed any applicable thresholds of EPCRA Section
313 chemicals or chemical categories (25,000 pounds per year for
manufacturing; 25,000 pounds per year for processing; or 10,000 pounds
per year for otherwise use see Section 2.5)?
If you answered "No" to any of the first three questions, you are not required to
prepare any EPCRA Section 313 reports. If you answered "Yes" to ALL of the first three
questions, you must complete a threshold calculation for each EPCRA Section 313 chemical at
the facility, and submit an EPCRA Section 313 report for each chemical and chemical category
exceeding the applicable threshold.
2-2
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is Your Facility's Primary SIC Code
Included on the EPCRA Section 313 List?
(See Section 2.2)
YES
Does Your Facility Have 10 or More Full-
Time Employees or the Equivalent?
(See Section 2.3)
YES
Does Your Facility Manufacture, Process,
or Otherwise Use Any EPCRA Section 313
Chemicals or Chemical Categories?
(See Section 2.4)
YES
Does Your Facility Exceed Any of the
Thresholds for a Chemical or Chemical
Category (after excluding quantities that are exempt
from threshold calculations)
(See Section 2.5)
NO
NO
NO
STOP
NO EPCRA
SECTION 313 REPORTS
REQUIRED FOR ANY CHEMICALS
OR CHEMICAL CATEGORIES
NO
AN EPCRA SECTION 313
REPORT IS NOT REQUIRED FOR
THIS CHEMICAL OR CHEMICAL
CATEGORY
YES
AN EPCRA SECTION 313 REPORT IS
REQUIRED FOR THIS CHEMICAL OR
CHEMICAL CATEGORY
Is the Amount Manufactured, OR Processed, OR Otherwise Used less than or equal to
1,000,000 pounds AND Is the Reportable Amount less than or equal to 500 Ib/yr
(See Section 2.8)
YES
NO
FORM A OR FORM R
IS REQUIRED FOR THIS CHEMICAL OR
, CHEMICAL CATEGORY
FORM R IS REQUIRED FOR THIS
CHEMICAL OR CHEMICAL
CATEGORY (FORM A CANNOT
BE SUBMITTED)
Figure 2-1. EPCRA Section 313 Reporting Decision Diagram
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2.2
SIC Code Determination
Facilities with the SIC Codes presented in Table 2-1 are covered by the EPCRA
..., ;. r ._. - ,....* , J
Section 313 reporting requirements.
Table 2-1
' -\:'K-\\::.: ;
SIC; Codes Covered by EPCRA Section 313 Reporting
»"!!!|l"'l
SIC Code Major Groups
SIC Codes
10
12
20 through 39
49 11, 4931, and 4939
4953 ....
5169
5171
7389
Industry
Metal Mining
Coal Mining
Manufacturing
Electric and Other Services and
Combination Utilities
Refuse Systems
Chemicals and Allied Products
Petroleum Bulk Stations and Terminals
Business Services
Qualifiers
Except SIC Codes 1011, 1081, and 1094
Except SIC Code 1241
None
Limited to facilities that combust coal
and/or oil for the purpose of generating
electricity for distribution in commerce
Limited to facilities regulated under
RCRA Subtitle C
None
None
Limited to facilities primarily engaged in
solvent recovery services on a contract or
fee basis
Most semiconductor manufacturing industry facilities fall under SIC Code 3674
, , ; ill T'll .'.,'. ||
(Semiconductors and Related Devices) and are required to prepare a report (or reports) if they
meet the employee and chemical activity thresholds. However, you should determine the SIC
Code(s) for your facility based on the activities on site. For assistance in determining which SIC
Code best suits your facility refer to Standard Industrial Classification Manual, 1987 published
by the Office of Management and Budget.
Note that auxiliary facilities can assume the SIC Code of another covered
: ,<;:..! iiii; "'";$"*.£',*', t'l, .
iilNpJ^ill jp''» ^ 'nil,
lhl Illlll IIIJ, 1 ill , "!' ,iil!' ill V"
"'i::,iiiiiiiiiiiiiiiiiii,,,ilHii iiiiiii,'!r"iiir" j.ii:,,"!!!,, ,
2-4
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engaged in performing support services for another covered establishment or multiple
establishments of a covered facility, and are in a different physical location from the primary
facility. In addition, auxiliary facilities perform an integral role in the primary facility's
activities. In general, the auxiliary facility's basic administrative services (e.g., paperwork,
payroll, employment) are performed by the primary facility. If an auxiliary facility's primary
function is to support/service a facility with a covered SIC Code, the auxiliary facility assumes
the covered SIC Code as its primary SIC Code and therefore is covered'by the EPCRA Section
313 reporting requirements. However, if the SIC Code for the primary facility is not covered by
EPCRA Section 313, then neither the primary nor the auxiliary facility is required to submit a
a-
report.
If your facility has more than one SIC Code (i.e., several establishments with
different SIC Codes are owned or operated by the same entity and are located at your facility),
you are subject to reporting requirements if:
All the establishments have SIC Codes covered by EPCRA Section 313;
OR '',"- ',:,"-
The total value of the products shipped or services provided at
establishments with covered SIC Codes is greater than 50% of the value of
the entire facility's products and services; OR
Any one of the establishments with a covered SIC Code ships and/or
produces products or provides services whose value exceeds the value of
services provided, products produced, and/or shipped by any other
establishment within the facility.
A pilot plant within a covered SIC Code is considered a covered facility and is
subject to reporting, provided it meets the employee and activity criteria (note that pilot plants
are not eligible for the laboratory exemption, which is discussed in Chapter 3\ Warehouses on
the same site as facilities in a covered SIC Code are also subject to reporting. Likewise,
warehouses that qualify as auxiliary facilities of covered facilities also must report, provided all
applicable thresholds are met.
While you are currently required to determine your facility's reporting eligibility
based on the SIC code system described above, it is important to be aware that the SIC code
system will be replaced by a new system in the future. On April 9, 1997 (62 FR 17287), the
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Office of Management and Budget promulgated the North American Industrial Classification
System (NAICS). NAICS is a new economic classification system that replaces the SIC code
system as a means of classifying economic activities for economic forecasting and statistical
purposes. The transition to the new NAICS may require statutory and/or regulatory actions. As
a result, the SIC code system is still required to be used as the mechanism to determine your
facility's reporting eligibility. EPA will issue notice in the Federal Register to inform you and
other EPCRA Section 313 facilities of its plans to adopt the NAICS and how facilities should
make their NAICS code determination.
2.3
Number nf Employees
Jl
If your facility meets SIC Code and activity threshold criteria, you are required to
prepare an EPCRA Section 313 report if your facility has 10 or more full-time employees or the
equivalent. A full-time employee equivalent is defined as a work year of 2,000 hours. If your
facility's employees aggregate 20,000 or more hours in a calendar year, you meet the 10 or more
employee criterion.
The following should be included in your employee calculations:
Owners;
Operations/manufacturing staff;
Clerical staff;
Temporary employees;
Sales personnel;
Truck drivers (employed by the facility);
Other non-manufacturing or off-site facility employees directly supporting
the facility;
Paid vacation and sick leave; and
Contractor employees (maintenance, construction, etc. but excluding
contracted truck drivers).
In general, if an individual is employed or hired to work at the facility, all the
hours worked by that individual must be counted in determining if the 20,000-hour criterion has
been met.
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Example - Fmployee Equivalent Calculation
Your facility has six full-time employees working 2,000 hours/year. You also employ two full-time sales people
and a delivery truck driver (employed by the facility) who are assigned to the plant, each working 2,000'
hours/year but predominantly on the road or from their homes. The wastewater treatment plant (on site and
owned by the facility) is operatedby a contractor who spends an average of two hours per day and five days per
week at the plant. Finally, you built an addition to the plant warehouse during the year, using four contractor
personnel who were on site full time for six months (working on average of 1,000 hours each). You would
calculate the number of full-time employee equivalents as follows:
Hours for your nine full-time employees (six plant personnel, two salespeople, and one
: delivery truck driver) are: ,
(9 employees) x (2,000 hours/year) = 18,000 hours/year
Hours for the wastewater treatment plant operator are:
(2 hours/day) x (5 days/week) x (52 weeks/year) = 520 hours/year; and
Hours for the construction: crew are:
(4 contractors) ;*( 1,000 hours) =4,000 hours/year.
Your facility has a total of 22,520 hours for the year, which is above the 20,000 hours/year threshold; therefore,
you meet Ihe employee criterion. ; _^______
2.4
Manufacturing, Processing, and Otherwise Use of EPCRA Section 313
Chemicals or Chemical Categories
If you are in a covered SIC Code and have 10 or more full-time employee
equivalents, you must determine which EPCRA Section 313 chemicals and chemical categories
are manufactured, processed, or otherwise used at your facility. You should prepare a list that
includes all chemicals and chemical categories found in mixtures and trade name products at all
establishments at the facility. This list should then be compared to the CURRENT list of
EPCRA Section 313 chemicals and chemical categories found in the TRI Forms and Instructions
document for that reporting year (also available from the EPCRA Hotline, 1-800-424-9346).
Once you identify the EPCRA Section 313 chemicals and chemical categories at your facility,
you must evaluate the activities involving each chemical and chemical category and determine if
any activity thresholds are met.
Note that chemicals and chemical categories are periodically added, delisted, or
modified. Therefore, it is imperative that you refer to the appropriate reporting year's list. Also,
note that a list of synonyms for EPCRA Section 313 chemicals and chemical categories can be
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found in the U.S. EPA publication Common Synonyms for Chemicals Listed Under Section 313
of the Emergency Planning and Community Right-To-Know Act (EPA 745-R-95-008). Table 2-2
lists the EPCRA Section 313 chemicals and chemical categories most frequently reported for the
semiconductor manufacturing industry and the process in which they are typically used. This list
is not intended to be all inclusive and should only be used as a guide.
Table 2-2
I
EPCRA Section 313 Chemicals and Chemical Categories Commonly
Encountered in Semiconductor Manufacturing
Unit Operation
Photolithography
Thin Films
Cleaning/Etching
Doping
Chemical Mechanical
Planarization
Typteal EPCJRA Section 313 Chemicals
Xylenes, ammonia, N-methyl-2-pyrrolidone, glycol ethers, methyl ethyl ketone,
ethylbenzene, dichloroethylene
Ammonia (silicon nitride film deposition), copper
Ethylene glycol, glycol ethers, methanol, N-methyl-2-pyrrolidone, sulfuric acid aerosols
(spray etching/cleaning), hydrochloric acid aerosols (spray etching/cleaning), hydrogen
fluoride, nitric acid, nitrate compounds, ammonia
Arsenic, antimony, phosphine
Nitrate compounds, copper
2.5
Activity Categories
EPCRA Section 313 defines three activity categories for the listed chemicals and
chemical categories: manufacturing (which includes importing), processing, and otherwise use.
The activity thresholds are 25,000 pounds per year for manufacturing, 25,000 pounds per year for
processing, and 10,000 pounds per year for otherwise use. These thresholds apply to each
chemical and chemical category individually. The quantity of chemicals or chemical categories
stored on site or purchased is not relevant for threshold determinations. Rather, the
determination is based solely on the quantity actually manufactured (including imported),
processed, or otherwise used. Therefore, EPCRA Section 313 chemicals and chemical categories
that are brought on site and stored, but are not incorporated into a product for distribution or not
I
otherwise used on site during the reporting year, are not considered towards any activity
thresholds.
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Expanded definitions with examples of each of the three activities are found in
Chapter 3, Tables 3-2, 3-3, and 3-4. The terms are briefly defined as follows:
Table 2-3
Activity Categories
Activity
Category
Definition
Threshold
(Ib/yr)
Manufacture
To produce, prepare, import, or compound an EPCRA Section 313 chemical or chemical
category. Manufacture also applies to an EPCRA Section 313 chemical or chemical category
that is produced coincidentally during the manufacture, processing, otherwise use, or
disposal of another chemical or mixture of chemicals as a byproduct, and an EPCRA Section
313 chemical or chemical category that remains in that other chemical or mixture of
chemicals as an impurity during the manufacturing, processing, or otherwise use or disposal
of any other chemical substance or mixture. An example would be the production of
ammonia or nitrate compounds in a wastewater treatment system.
25,000
Process
To prepare a listed EPCRA Section 313 chemical or chemical category, or a mixture or trade
name product containing an EPCRA Section 313 chemical or chemical category, for
distribution in commerce (usually the. intentional incorporation of an EPCRA Section 313 '
chemical or chemical category into a product). For example, arsenic may be used as a
dopant, and would have to be reported if you exceeded the reporting threshold. Processing
includes the preparation for sale to your customers (and transferring between facilities within
your company) of a chemical or formulation that you manufacture. For example, if you
manufacture a chemical or product, package it, and then distribute it into commerce, this
chemical has been manufactured AND processed by your facility.
25,000
Otherwise
Use
Generally, use of an EPCRA Section 313 chemical or chemical category that does not fall
under the manufacture or process definitions is classified as otherwise use. An EPCRA
Section 313 chemical or chemical category that is otherwise used is not intentionally
incorporated into a product that is distributed in commerce, but may be used instead as a
manufacturing or processing aid (e.g., catalyst), in waste processing, or as a fuel (including
waste fuel). For example, acids used to clean equipment are classified as otherwise used.
On May 1,1997 U.S. EPA revised the interpretation of otherwise use. The-following new
otherwise use definition becomes effective with the 1998 reporting year (62 FR 23834, May
1,1997):
Otherwise use means "any use of a toxic chemical contained in a mixture or other
trade name product or waste, that is not covered by the terms manufacture or
process. Otherwise use of a toxic chemical does not include disposal, stabilization
(without subsequent distribution in commerce), or treatment for destruction unless:
1) The toxic chemical that was disposed, stabilized, or treated for destruction was
received from off site for the purposes of further waste management; OR
2) The toxic chemical that was disposed, stabilized, or treated for destruction was
manufactured as a result of waste management activities on materials received from
off site for the purposes of further waste management activities."
10,000
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COMMON ERROR - Coincidental Manufacture
The coincidental manufacture of an EPCRA Section 313 chemical, outside the primary product process line but
in direct support of the process, is frequently overlooked. For example, semiconductor manufacturers often use
halogenated organic gases in plasma environments for various cleaning and etching operations. EPCRA Section
313 chemicals may be coincidentally manufactured by the degradation of these compounds. The amount of each
coincidentally manufactured chemical must be included in the manufacturing threshold determination and, if a
threshold is exceeded, any subsequent release and other waste management activity calculations. Typical
EPCRA Section 313 chemicals coincidentally manufactured from these activities include hydrofluoric acid and
aerosol forms of hydrochloric acid.
Relabeling or redistribution of an EPCRA Section 313 chemical where no
repackaging occurs does not constitute manufacturing, processing, or otherwise use of that
!
chemical. This type of activity should not be included in threshold calculations.
Also, note that the threshold determinations for the three activity categories
(manufacturing, processing, and otherwise use) are mutually exclusive. That is, you must
conduct a separate threshold determination for each activity category and if you exceed any
threshold, all release and other waste management activities of that EPCRA Section 313 toxic
chemical or chemical category at the facility must be considered for reporting.
Example - Relabeling
You buy a mixture in small containers which contains an EPCRA Section 313 chemical or chemical category.
When it arrives you put your own label on each container and put the containers in a larger box with several
other items you manufacture, and sell the larger box as a kit. The quantity of the EPCRA Section 313 chemical
or chemical category in the small containers should not be counted toward the processing (because you did not
repackage the toxic chemical) or otherwise use thresholds, nor should it be counted toward the manufacturing
activity threshold unless the small containers were imported. However, you must consider other EPCRA Section
313 chemicals and chemical categories that you manufactured in the kit toward manufacturing and processing
threshold determinations.
2.6
How Do You Report?
You must submit an EPCRA Section 313 report for each EPCRA Section 313
chemical or chemical category that exceeds a threshold for manufacturing, OR processing, OR
otherwise use (providing you meet the employee and SIC Code criteria). Provided you do not
exceed certain alternate activity thresholds and total annual reportable amounts, you may prepare
a Form A (See Section 2.8) rather than a Form R. The TRI Forms and Instructions contain
detailed directions for the preparation and submittal of EPCRA Section 313 reports for each
listed chemical for the reporting year. The TRI Forms and Instructions are sent to all facilities
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that submitted EPCRA Section 313 reports the preceding year. However, if you do not receive a
courtesy copy, you may request copies of the TRI Forms and Instructions from the EPCRA
Hotline (1-800-424-9346).
2.7
FormR
Form R is the more detailed and more common EPCRA Section 313 report. If
you are submitting a Form R, it is essential that you use the TRI Forms and Instructions for the
appropriate reporting year. U.S. EPA encourages the electronic submittal of the Form R, via the
Automated Toxic Chemical Release Inventory Reporting Software (ATRS). Use of the ATRS
will save preparation time in data entry and photocopying and reduce errors via on-line
validation routines and use of pick lists. The ATRS can be found on the Internet at:
http://www.epa.gov/opptintr/atrs
The ATRS is available in both DOS and Windows versions. More information can be found in
the TRI Forms and Instructions and by calling the ATRS User Support Hotline at (703) 816-
4434.
The Form R consists of two parts:
Part I, Facility Identification Information. This part may be photocopied and re-
used for each Form R you submit, except for the signature which must be original
for each submission.
Part II, Chemical Specific Information. You must complete this part separately
for each EPCRA Section 313 chemical or chemical category; it cannot be reused
year to year even if reporting has not changed.
Submission of incomplete EPCRA Section 313 reports may result in issuance of a
Notice of Technical Error (NOTE), Notice of Significant Error (NOSE), or Notice of
Noncompliance (NON). See the current TRI Forms and Instructions for more detailed
information on completing the Form R and submitting the EPCRA Section 313 report.
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2.8
Alternate Threshold and Form A
U.S. EPA developed the Form A, also referred to as the "Certification Statement,"
to reduce the annual reporting burden for facilities with minimal amounts of EPCRA
I
Section 313 chemicals or chemical categories released and otherwise managed as a waste (59 FR
61488, November 1994; applicable beginning reporting year 1994 and beyond). A facility must
meet the following two criteria hi order to submit a Form A:
First, the total annual reportable amount of the EPCRA Section 313
chemical or chemical category cannot exceed 500 pounds per year. The
"reportable amount" is defined as the sum of the on-site amounts released
(including disposal), treated, recycled, and combusted for energy recovery,
combined with the sum of the amounts transferred off site for recycling,
energy recovery, treatment, and/or release (including disposal). This total
corresponds to the total of data elements 8.1 through 8.7 on the 1997
version of the Form R.
Second, the amount of the chemical manufactured, processed, OR
otherwise used cannot exceed one million pounds. It is important to note
that the quantities for each activity are mutually exclusive and must be
evaluated independently. If the quantity for any one of the activities
exceeds 1,000,000 pounds a Form A cannot be used.
Example - Form A Threshold
Providing the combined annual reportable amounts from all activities does not exceed 500 pounds, a facility that
manufactures 900,000 pounds of an EPCRA Section 313 chemical or chemical category and processes
150,000 pounds of the same listed toxic chemical or chemical category is eligible to use the Form A because the
facility did not exceed the one million pound threshold for either activity, even though the total activity usage
exceeds one million pounds.
The Form A Certification Statement must be submitted for each eligible EPCRA
Section 313 chemical or chemical category. The information on the Form A will be included in
the publicly accessible TRI database; however, these data are marked to indicate that they
represent certification statements rather than Form Rs. Note that separate establishments at a
facility cannot submit separate Form As for the same chemical or chemical category; rather, only
one Form A per EPCRA Section 313 chemical or chemical category can be submitted per
facility.
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Like the Form R, Form A requests facility identification information. However,
no release and other waste management estimations to any media are required. You must simply
certify that the total annual reportable amount did not exceed 500 pounds and that amounts
manufactured, processed, or otherwise used did not exceed one million pounds. Once the facility
has completed estimates to justify the submission of a Form A, there is a considerable time
savings in using the Form A, especially in subsequent years, providing activities involving the
chemical or chemical category did not change significantly. It is strongly recommended that you
document your initial rationale and refer to it every year to verify that you have not modified a
part of the process that would invalidate the initial rationale supporting submission of Form A.
2.9
Trade Secrets
If you submit trade secret information, you must prepare two versions of the
substantiation form as prescribed in 40 CFR Part 350 (see 53 FR 28801, July 29, 1988) as well as
two versions of the EPCRA Section 313 report. One set of reports should be "sanitized" (i.e., it
should provide a generic name for the EPCRA Section 313 chemical or chemical category
identity). This version will be made available to the public. The second version, the
"unsanitized" version, should provide the actual identity of the EPCRA Section 313 chemical or
chemical category and have the trade secret claim clearly marked in Part I, Section 2.1 of the
Form R or Form A. The trade secrets provision only applies to the EPCRA Section 313
chemical or chemical category identity. All other parts of the Form R or Form A must be filled
out accordingly.
Individual states may have additional criteria for confidential business
information and the submittal of both sanitized and unsanitized reports for EPCRA Section 313
chemicals and chemical categories. Facilities may jeopardize the trade secret status of an
EPCRA Section 313 chemical or chemical category by submitting an unsanitized version to a
state agency or tribal government that does not require an unsanitized version.
More information on trade secret claims, including contacts for individual state's
submission requirements, can be found in the TRI Forms and Instructions.
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2.10
Recordkeeping
Complete and accurate records are absolutely essential to meaningful compliance
with EPCRA Section 313 reporting requirements. Compiling and maintaining good records will
help you to reduce the effort and cost in preparing future reports, and to document how you
arrived at the reported data in the event of U.S. EPA compliance audits. U.S. EPA requires you
to maintain records substantiating each EPCRA Section 313 report submission for a minimum of
three years. Each facility must keep copies of every EPCRA Section 313 report along with all
supporting documents, calculations, work sheets, and other forms that you used to prepare the
EPCRA Section 313 report. U.S. EPA may request this supporting documentation during a
regulatory audit.
ii
Specifically, U.S. EPA requires the following records be maintained for a period
of three years from the date of the submission of a report (summarized from 40 CFR 372.10):
1) A copy of each EPCRA Section 313 report that is submitted.
2) All supporting materials and documentation used to make the compliance
determination that the facility or establishment is a covered facility.
3) Documentation supporting the report submitted, including:
Claimed allowable exemptions,
Threshold determinations,
Calculations for each quantity reported as being released, either on
or off site, or otherwise managed as waste,
Activity determinations, including dates of manufacturing,
processing, or use,
The basis of all estimates,
Receipts or manifests associated with transfers of each EPCRA
Section 313 chemical or chemical category in waste to off-site
locations, and
Waste treatment methods, treatment efficiencies, ranges of influent
concentrations to treatment, sequential nature of treatment steps,
and operating data to support efficiency claims.
4) For facilities submitting a Form A, all supporting materials used to make
the compliance determination that the facility or establishment is eligible
to submit a Form A, including:
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Data supporting the determination the alternate threshold applies,
Calculations of the annual reportable amounts,
Receipts or manifests associated with the transfer of each EPCRA
Section 313 chemical or chemical category in waste to off-site
locations, and
Waste treatment methods, treatment efficiencies, ranges of influent
concentrations to treatment, sequential nature of treatment steps,
and operating data to support efficiency claims.
Because EPCRA Section 313 reporting does not require additional testing or
monitoring you must determine the best readily available source of information for all estimates.
Some facilities may have detailed monitoring data and off-site transfer records that can be used
for estimates while others may only have purchase and inventory records. Examples of records
that you should keep, if applicable, might include:
Each EPCRA Section 313 report submitted;
EPCRA Section 313 Reporting Threshold Worksheets (sample worksheets
can be found in Chapter 3 of this document as well as in the TRI Forms
and Instructions);
EPCRA Section 313 Reporting Release and Other Waste Management
Quantity Estimation Worksheets (sample worksheets can be found in
Chapter 4 of this document);
Engineering calculations and other notes;
Purchase records from suppliers;
Inventory data;
New Source Performance Standards;
National Pollutant Discharge Elimination System (NPDES)/State Pollutant
Discharge Elimination System (SPDES) permits and monitoring reports;
, EPCRA Section 312, Tier II reports;
Monitoring records;
Air permits;
Flow measurement data;
Resource Conservation Recovery Act (RCRA) hazardous waste
generator's reports;
Pretreatment reports filed with local governments;
Invoices from waste management firms;
Manufacturer's estimates of treatment efficiencies;
Comprehensive Environmental Response, Conservation, and Liability Act
of 1980 (CERCLA) Reportable Quantity (RQ) reports;
RCRA manifests; and
Process flow diagrams (including emissions, releases, and other waste
management activities).
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CHAPTER 3 - EPCRA SECTION 313 CHEMICAL OR CHEMICAL
CATEGORY ACTIVITY THRESHOLD DETERMINATIONS
3.0
PURPOSE
This chapter provides a step-by-step procedure for determining if any EPCRA
Section 313 chemicals or chemical categories exceed a reporting threshold. Threshold
determinations are essentially a three step process:
Step 1) Identify any EPCRA Section 313 chemicals and chemical
categories you manufacture/import, process, or otherwise use.
Step 2) Identify the activity category and any exempt activities for each
EPCRA Section 313 chemical or chemical category.
Step 3) Calculate the quantity of each EPCRA Section 313 chemical or
chemical category and determine which ones exceed an activity
threshold.
3.1
Step 1 - Identify Which EPCRA Section 313 Chemicals or Chemical
Categories are Manufactured (Including Imported), Processed, or Otherwise
Used
Compile lists of all chemicals and mixtures at your facility. For facilities with
many different chemicals and mixtures it is often helpful to prepare two lists: one with the pure
(single ingredient) chemicals (including chemical compounds) and one with the mixtures and
trade name products. On the second list, under the name of each mixture/trade name product,
write the names of all chemicals in that product. Next, compare the chemicals and chemical
categories on both lists to the current EPCRA Section 313 chemicals and chemical categories list
found in the TRI Forms and Instructions (remember that chemicals and chemical categories may
be periodically added and deleted and you should use the current reporting year's instructions).
Highlight the EPCRA Section 313 chemicals and chemical categories that are on your list.
Review the list to be sure each chemical and chemical category is shown by its
correct EPCRA Section 313 name. For example, a common EPCRA Section 313 chemical
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found in the semiconductor manufacturing industry is methyl ethyl ketone. Methyl ethyl ketone
(Chemical Abstracts Service (CAS) Registry No. 78-93-3) has several synonyms including MEK
and 2-butanone. It must be reported on Form R (or Form A), Item 1.2, by its EPCRA Section
313 chemical name, methyl ethyl ketone. Synonyms can be found in the U.S. EPA document
Common Synonyms for Chemicals Listed Under Section 313 of the Emergency Planning and
Community Right-to-Know Act (EPA 745-R-95-008).
The original list of chemicals and chemical categories subject to EPCRA
Section 313 reporting was a combination of chemical lists from New Jersey and Maryland.
Refinements to the list have been made and changes are anticipated to continue. The list can be
modified by U.S. EPA initiative or industry or the public can petition U.S. EPA to modify the
list. When evaluating a chemical or chemical category for addition or deletion from the list, U.S.
EPA must consider the chemical's potential acute human health effects and chronic human
health effects or its adverse environmental effects. U.S. EPA reviews these petitions and initiates
a rulemaking to add or delete the chemical or chemical category from the list, or publishes an
explanation why it denied the petition.
While you must consider every chemical on the EPCRA Section 313 chemical
and chemical category list, you should be aware of the chemicals and chemical categories
J
typically used in the semiconductor manufacturing industry. As a guide, the most frequently
reported EPCRA Section 313 chemicals and chemical categories for reporting year 1995 by
semiconductor manufacturers (SIC Code 3674), and the processes they are typically used in are
listed in Table 2-2.
A computerized spreadsheet may be helpful in developing your facility's chemical
and chemical category list and performing threshold calculations. The spreadsheet could show
the chemical, chemical category, or chemical mixture with corresponding component
concentrations; the yearly quantity manufactured, processed, or otherwise used; and the CAS
Registry number. The spreadsheet could also be designed to identify the total quantity by
activity category (amounts manufactured, processed, and otherwise used) for each EPCRA
Section 313 chemical or chemical category in every mixture, compound, and trade name product.
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An initial investment of time will be required to develop this spreadsheet;
however, the time and effort saved in threshold calculations in subsequent years will be
significant. Such a system will also reduce the potential of inadvertently overlooking EPCRA
Section 313 chemicals or chemical categories present in mixtures purchased from off-site
sources.
To develop the chemical and chemical category list and the associated activity
categories you may want to consult the following:
Material Safety Data Sheets (MSDSs);
Facility purchasing records;
New Source Performance Standards;
Inventory records;
Air and water discharge permits;
Individual manufacturing/operating functions; and
Receipts or manifests associated with the transfer of each EPCRA Section
313 chemical and chemical category in waste to off-site locations.
The following is suggested useful information needed to prepare your EPCRA
Section 313 reports and should be included for each chemical and chemical category on your
spreadsheet:
The mixture name and associated EPCRA Section 313 chemical and
chemical category names;
The associated CAS Registry numbers;
The trade name for mixtures and compounds;
The throughput quantities; and
Whether the chemical or chemical category is manufactured, processed, or
otherwise used at the facility (be sure to include quantities that are
coincidentally manufactured and imported, as appropriate).
MSDSs are one of the best sources of information for the type and composition of
chemicals and chemical categories in mixtures, and for determining whether you have purchased
raw materials that contain EPCRA Section 313 chemicals and chemical categories. As of 1989,
chemical suppliers to facilities in SIC Major Group Codes 20 through 39 are required to notify
customers of any EPCRA Section 313 chemicals and chemical categories present in mixtures or
trade name products distributed to facilities. The notice must be provided to the receiving
3-3
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facility and may be attached or incorporated into that product's MSDS. If no MSDS is required,
the notification must be in a letter that accompanies the first shipment of the product to your
facility each year. This letter must contain the chemical name, CAS Registry number, and the
weight or volume percent (or range) of the EPCRA Section 313 chemical or chemical category in
mixtures or trade name products.
I
Carefully review the entire MSDS. Although new MSDSs must list whether
EPCRA Section 313 chemicals and chemical categories are present, the language and location of
this notification is not currently standardized. Depending on the supplier, this information could
be found in different sections of the MSDS. The most likely sections of an MSDS to provide
information on EPCRA Section 313 chemicals and chemical categories are:
Physical properties/chemical composition section;
Regulatory section;
Hazardous components section;
Labeling section; and
Additional information section.
Also, many EPCRA Section 313 chemicals or chemical categories are present as
impurities in mixtures. These quantities must also be considered in threshold determinations
unless the concentration is below the de minimis value (see Section 3.2.2.1). In some cases, if
the EPCRA Section 313 chemical or chemical category is present below de minimis
concentration, it may be exempt.
Qualifiers
Several chemicals on the EPCRA Section 313 chemical list include qualifiers
related to use or form. Some chemicals are reportable ONLY if manufactured by a specified
process or in a specified activity category. For example, isopropyl alcohol is only reportable if it
is manufactured using the strong acid process and saccharin is reportable only if it is
manufactured. Some other chemicals are only reportable if present in certain forms. For
example, only yellow or white phosphorus is reportable, while black or red phosphorus is not.
3-4
; I
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The qualifiers, associated chemicals and chemical categories, and typical
applicability of these qualifiers and chemicals to the semiconductor manufacturing industry are
presented below. A detailed discussion of the qualifier criteria can be found in the TRI Forms
and Instructions.
Aluminum oxide (fibrous) - Beginning with EPCRA Section 313 reports
for calendar year 1989, aluminum oxide is only subject to threshold
determination release, and other waste management calculations when it is
handled in fibrous forms. U.S. EPA has characterized fibrous aluminum
oxide for purposes of EPCRA Section 313 reporting as a man-made fiber
commonly used in high-temperature insulation applications such as
furnace linings, filtration, gaskets, joints, and seals.
Asbestos (friable) - Asbestos only needs to be considered when it is
handled in the friable form. Friable refers to the physical characteristics of
being able to crumble, pulverize, or reduce to a powder with hand
pressure.
Fume or dust - Three metals (aluminum, vanadium, and zinc) are
qualified with "fume or dust." This definition excludes "wet" forms such
as solutions or slurries, but includes powder, particulate, or gaseous forms
of these metals. For example, use of aluminum metal as a dopant is
therefore not subject to reporting unless the aluminum is in the form of a
fume or dust. However, the entire weight of all aluminum compounds
should be included in the threshold determination for aluminum
compounds regardless of whether the compound is a fume or dust. For
semiconductor applications, aluminum is typically handled in slurry form
and would not be reportable. Keep in mind that if a threshold is exceeded,
only the metal portion of metal compounds is reported in release and other
waste management estimates.
Hydrochloric acid (acid aerosols) - On My 25, 1996, U.S. EPA
promulgated a final rule delisting non-aerosol forms of hydrochloric acid
(CAS Registry No. 7647-01-0) from the EPCRA Section 313 chemical list
(effective for the 1995 reporting year). Therefore, threshold
determinations and release and other waste management estimates now
apply only to the aerosol forms. Under EPCRA Section 313, the term
aerosol covers any generation of airborne acid (including mists, vapors,
gas, or fog) without any particle size limitation. Therefore, any process
that sprays hydrochloric acid "manufactures" hydrochloric acid aerosol.
Manufacturing qualifiers - Two chemicals, saccharin and isopropyl
alcohol, contain qualifiers relating to manufacture. The qualifier for
saccharin means that only manufacturers of the chemical are subject to the
reporting requirement. Isopropyl alcohol (IPA), a commonly used
3-5
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cleaning agent in semiconductor manufacturing operations, contains a
qualifier relating to manufacture. The qualifier for IP A means that only
facilities that manufacture the chemical by the strong acid process are
required to report. Facilities that only process or otherwise use IPA are not
required to report. Thus, a facility that uses IPA as a cleaner does not need
to include the quantities in threshold determination or release and other
waste management calculations.
Nitrate Compounds (water dissociable; reportable only in aqueous
solution) - A nitrate compound is covered by this listing only when in
water and if water dissociable. Although the complete weight of the
nitrate compound must be used for threshold determinations for the nitrate
compounds category, only the nitrate portion of the compound must be
considered for release and other waste management determinations. One
issue recently raised by industry is how to report nitrate compounds in
wastewater and sludge that is applied to farms as a nitrogen source (either
on site or off site). Although during such use nitrate compounds may be
taken up by plants and cycled back into the ecosystem, U.S. EPA
considers the nitrate compounds are managed as waste and should be
reported as being disposed to land (either on site or off site as appropriate).
U.S. EPA has published guidance for these chemicals in List of Toxic
Chemicals Within the Water Dissociable Nitrate Compounds Category
and Guidance for Reporting (EPA 745-R-96-004), which may be found in
Appendix E.
Phosphorus (yellow or white) - Only manufacturing, processing, or
otherwise use of phosphorus in the yellow or white chemical forms require
reporting. Black and red phosphorus are not subject to EPCRA
Section 313 reporting.
Solutions (ammonia, ammonium sulfate, and ammonium nitrate) - On
June 26, 1995, U.S. EPA deleted ammonium sulfate (solution) (CAS
Registry No. 7783-20-2) from the EPCRA Section 313 chemical list and
qualified the listing for ammonia (CAS Registry No. 7664-41-7). The
ammonia listing was modified by adding the following qualifier:
"ammonia (includes anhydrous ammonia and aqueous ammonia from
water dissociable salts and other sources; 10% of total aqueous ammonia
is reportable under this listing)". The deletion of ammonium sulfate
(solution) and the qualification of ammonia are effective as of reporting
year 1994. Therefore, ammonium sulfate is no longer a reportable
chemical under EPCRA Section 313. However, aqueous ammonia that is
formed from the dissociation of ammonium salts (including ammonium
sulfate) in water is reportable as is the aqueous ammonia generated from
the dissociation of ammonium nitrate in water. You must determine the
amount of aqueous ammonia generated from solubilizing these chemicals
and apply it toward the threshold for ammonia. U.S. EPA has published
guidance on reporting for ammonia and ammonium salts in EPCRA
Section 313 Question and Answers, Revised 1997 Version - Appendix A,
3-6
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Directive 8. Additionally, aqueous ammonium nitrate must be included in
threshold determinations and the nitrate portion included for release and
other waste management calculations for the nitrate compounds category.
Refer to Appendix C for further guidance on reporting aqueous ammonia.
Sulfuric acid (acid aerosols) - On June 26, 1995, U.S. EPA promulgated
a final rale delisting non-aerosol forms of sulfuric acid (CAS Registry No.
7664-93-9) from the EPCRA Section 313 chemical list (effective for the
1994 reporting year). Therefore, threshold determinations and release and
other waste management estimates now apply only to the aerosol forms.
Under EPCRA Section 313, the term aerosol covers any generation of
airborne acid (including mists, vapors, gas, or fog) without any particle
size limitation. Therefore, any process that sprays sulfuric acid
"manufactures" sulfuric acid aerosol. Refer to Appendix D for further
guidance on reporting sulfuric acid aerosols.
Other reportable chemicals often used in the semiconductor manufacturing
industry are glycol ethers. The glycol ethers category includes glycol ethers derived from
ethylene glycol, diethylene glycol, and triethylene glycol. It does not include glycol ethers
derived from propylene glycol, dipropylene glycol, or tripropylene glycol. Refer to the EPA
document "Toxics Release Inventory - List of Toxic Chemicals Within the Glycol Ethers
Category" (EPA-745-R-95-006) for a complete discussion, definition, and examples of chemicals
that should be included in the glycol ethers category.
3.2
Step 2. Identify the Activity Category and any Exempt Activities for Each
EPCRA Section 313 Chemical
The next step is to determine the activity category (or categories) and any exempt
activities for each EPCRA Section 313 chemical on your list. Table 3-1 lists the reporting
thresholds for each of these activity categories (Tables 3-2 through 3-4 provide detailed
definitions of subcategories for each activity category). Each threshold must be individually
calculated; they are mutually exclusive and are not additive.
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Table 3-1
Reporting Thresholds
Activity Category
Manufacture (including import)
Process
Otherwise use
Threshold '
25,000 pounds per year
25,000 pounds per year
10,000 pounds per year
Example -Threshold Determination
If your facility manufactures 22,000 pounds of an EPCRA Section 313 chemical or chemical category and you
also otherwise use 8,000 pounds of the same chemical or chemical category, you have not exceeded either
threshold, and an EPCRA Section 313 report for that chemical is not required. However, if your facility
manufactures 28,000 pounds per year of an EPCRA Section 313 chemical or chemical category and otherwise
uses 8,000 pounds of the same chemical or chemical category, you have exceeded the manufacturing threshold
and ALL release and other waste management quantities (except those specifically exempted) of that chemical or
chemical category must be reported on the Form R, including those from the "otherwise used" activity.
COMMON ERROR - Threshold Determination for Recircnlatinn
I
Facilities often incorrectly base threshold calculations on the amount of EPCRA Section 313 chemicals in a
recirculation system rather than the amount actually used in the reporting year. The amount of the EPCRA
Section 313 chemical that is actually manufactured (including the quantity imported), processed, or otherwise
used, not the amount in storage or in the system, should be the amount applied to the threshold determination.
For example, a solvent containing an EPCRA Section 313 chemical is used, recirculated on site, and reused as a
solvent. The amount of EPCRA Section 313 chemical recirculated on site in the on-site recycling process is not
considered in the threshold determination because this is considered a "direct reuse" and is not reportable. Only
the amount of new chemical added to the system should be included in the otherwise used threshold calculation.
However, if you send a solvent containing an EPCRA Section 313 chemical or chemical category off site for
distillation and subsequent recycling, it should be reported as a transfer to an off-site location for recycling (Form
R, Part II, Section 6.2 and 8.5) because the distillation is considered a waste management activity. The amount
of solvent returned to you and subsequently used in the same reporting year must be included in the threshold
determination. If the reporting threshold is exceeded, the total quantity recycled should be reported in Section
8.4, i.e., the amount recycled must be reported in Section 8.4 each time it is recycled.
Each of the activity categories is divided into subcategories. As discussed in the
TRI Forms and Instructions, you are required to designate EACH category and subcategory that
applies to your facility. Detailed definitions, including descriptions of subcategories for each
activity and examples, are presented in Tables 3-2, 3-3, and 3-4.
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Table 3-2
Definitions and Examples of Manufacturing Subcategories
Manufacturing Activity
Subcategory
Definition
Examples in the
Semiconductor
Manufacturing
Industry*
Produced or imported for
on-site use/processing
A chemical or chemical category that is produced or
imported and then further processed or otherwise used at
the same facility.
Sulfuric acid aerosols
are manufactured on
site for etching/cleaning
operations (the acid is
also otherwise used)
Produced or imported for
sale/distribution
A chemical or chemical category that is produced or
imported specifically for sale or distribution outside the
manufacturing facility.
Produced as a byproduct
A chemical or chemical category that is produced
coincidentally during the production, processing, or
otherwise use of another chemical substance or a
mixture and is separated from that substance or mixture.
Toxic chemicals or chemical categories produced and
released as a result of waste treatment or disposal are
also considered byproducts.
Nitrate compounds
produced through the
neutralization of nitric
acid in a wastewater
treatment system
Produced as an impurity
A chemical or chemical category that is produced
coincidentally as a result of the manufacture, processing,
or otherwise use of another chemical and remains
primarily in the mixture or product with that other
chemical.
* More complete discussions of the industry-specific examples can be found in Chapter 4 of this guidance manual.
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Table 3-3
Definitions and Examples of Processing Subcategories
Processing Activity
Subcategory
Definition
Examples in the
Semiconductor
Manufacturing Industry*
Reactant
A natural or synthetic chemical or chemical
category used in chemical reactions for the
manufacture of another chemical substance or
product. Examples include feedstocks, raw
materials, intermediates, and initiators.
Formulation component
A chemical or chemical category that is added to a
product or product mixture prior to further
distribution of the product and acts as a
performance enhancer during use of the product.
Examples include additives, dyes, reaction
diluents, initiators, solvents, inhibitors,
emulsifiers, surfactants, lubricants, flame
retardants, and rheological modifiers.
Arsenic or antimony
compounds used as dopants
Article component
A chemical or chemical category that becomes an
integral component of an article distributed for
industrial, trade, or consumer use.
Lead may be used as solder
or frame for the final chip
assembly
Repackaging only
A chemical or chemical category that is processed
or prepared for distribution in commerce in a
different form, state, or quantity. May include, but
is not limited to, the transfer of material from a
bulk container, such as a tank truck, to smaller
containers such as cans or bottles.
More complete discussions of the industry-specific examples can be found in Chapter 4 of this guidance manual.
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Table 3-4
Definitions and Examples of Otherwise Use Subcategories
Otherwise Use Activity
Subcategory
Definition
Examples in the
Semiconductor
Manufacturing Industry*
Chemical processing aid
A chemical or chemical category that is added to a
reaction mixture to aid in the manufacture or
synthesis of another chemical substance but is not
intended to remain in or become part of the
product or product mixture. Examples include
process solvents, catalysts, inhibitors, initiators,
reaction terminators, and solution buffers.
Chlorine used for water
treatment or etching
Manufacturing aid
A chemical or chemical category that aids the
manufacturing process but does not become part
of the resulting product and is not added to the
reaction mixture during the manufacture or
synthesis of another chemical substance.
Examples include process lubricants,
metalworking fluids, coolants, refrigerants, and
hydraulic fluids.
Ancillary or other use
A chemical or chemical category that is used for
purposes other than aiding chemical processing or
manufacturing. Examples include cleaners,
degreasers, lubricants, fuels (including waste
fuels), and chemicals used for treating wastes.
The majority of the
chemicals reported to TRI
for the semiconductor
industry fall under this
definition, primarily
solvents and acids used for
etching and cleaning
* More complete discussions of the industry-specific examples can be found in Chapter 4 of this guidance manual.
3.2.1
Concentration Ranges for Threshold Determination
You are required to use the best readily available information for all calculations
in EPCRA reporting; however, the exact concentration of an EPCRA Section 313 chemical in a
mixture or trade name product may not be known. The supplier or MSDS may only list ranges,
or upper or lower bound concentrations. U.S. EPA has developed guidance on how to use
information in this situation for threshold determinations.
If the concentration is provided as a lower and upper bound or as a range,
you should use the mid-point in your calculations for the threshold
determination. For example, the MSDS for the trade name product states
methanol is present in a concentration of not less than 20% and not more
than 40%, or it may be stated as present at a concentration between 20 to
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40%. You should use the mid-point value of 30% methanol in your
threshold calculations.
If only the lower bound concentration of the EPCRA Section 313 chemical
or chemical category is specified and the concentration of other
components are given, subtract the other component values from 100%.
The remainder should be considered the upper bound for the EPCRA
Section 313 chemical or chemical category and you should use the given
lower bound to calculate the mid-point as discussed above. For example,
the MSDS states that a solvent contains at least 50% methyl ethyl ketone
and 20% non-hazardous surfactants. Subtracting the non-hazardous
contents from 100% leaves 80% as the upper bound for MEK. The mid-
point between upper (80%) and lower (50%) bounds is 65%, the value you
should use in your threshold calculation.
If only the lower bound is specified and no information on other
components is given assume the upper bound is 100% and calculate the
mid-point as above.
If only the upper bound concentration is provided you must use this value
in your threshold calculation.
Special guidance for concentration ranges that straddle the de minimis value is presented in
Section 3.2.2.1.
3.2.2
Evaluation of Exemptions
When determining thresholds, you can exclude quantities of any EPCRA
;l
Section 313 chemicals and chemical categories that are manufactured, processed, or otherwise
used in exempt activities. Exemptions are divided into four classes:
1. De minimis exemption;
2. Article exemption;
3. Facility-related exemption; and
4. Activity-related exemptions.
COMMON ERROR - Exempt Activities
If an EPCRA Section 313 chemical or chemical category is used in exempt activities, the quantity used in these
activities does not need to be included in your threshold or release and other waste management calculations,
even if the chemical or chemical category is used in a reportable activity elsewhere in the facility.
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3.2.2.1
De Minimis Exemption
If the amount of EPCRA Section 313 chemical(s) or chemical categories present
in a mixture or trade name product processed or otherwise used is below its de minimis
concentration level, that amount is considered to be exempt from threshold determinations and
release and other waste management calculations (note that this exemption does not apply to
manufacturing, except for importation or as an impurity as discussed below). The de minimis
concentration for EPCRA Section 313 chemicals and chemical categories is 1%, except for
Occupational Safety and Health Administration (OSHA)-defined carcinogens, which have a
0.1% de minimis concentration. Note that if a mixture contains more than one member of an
EPCRA Section 313 compound category, the weight percent of all members must be summed. If
the total meets or exceeds the category's de minimis level, the de minimis exemption does not
apply. U.S. EPA has published several detailed questions and answers and a directive in the
current edition of EPCRA Section 313 Questions and Answers (1998 edition is EPA 745-B-98-
004; see Appendix A, Directive #2) that may be helpful if you have additional concerns about the
de minimis exemption. The TRI Forms and Instructions list each EPCRA Section 313 chemical
and compound category with the associated de minimis value.
Example - DeMMmis
Your facility processes a mixture containing 1,1% nifric acid and 6.6% manganese. Use de minimis exemption
would apply to manganese because the concentration r$ below 1%; howeveiv It would act apply toiatric add.
All of the rtitric acid must be included in threshold determinations, aa
-------
to determine quantities applicable to threshold determinations and release and other waste
management calculations when this range straddles the de minimis value. In general, only the
quantity of the processed or otherwise used EPCRA Section 313 chemical or chemical category
whose concentration exceeds the de minimis must be considered. Therefore, U.S. EPA allows
facilities to estimate the quantity below the de minimis and exclude it from further consideration.
The following examples illustrate this point.
Examples - Concentration Ranges Straddling the De Minimis Value
A facility processes 8,000,000 pounds of a mixture containing 0.2 to 1.2% manganese. Manganese is subject to
& 1% de minimis concentration exemption. The amount of mixture subject to reporting is equal to the total
quantity of mixture multiplied by the percentage of the manganese concentration range above the de minimis
concentration. The amount at or above de minimis is calculated as:
(0.012 - 0.009) + (0.012 - 0.002)
Therefore, the amount of the mixture that is subject to threshold determination and release and other waste
management estimates is:
(8,000,000) x ((0.012 - 0.009) * (0.012 - 0.002))
The average concentration of manganese that is not exempt (at or above the de minimis) is:
(0.012+ 0.01)-(2.00)
Therefore, the amount of manganese that is subject to threshold determination and release and other waste
management estimates is:
'(8,000,000) (O.Q12 -O.OOS>)[ 1(0.012 +0.01)
(0.012 - 0.002) || 2.00
= 26,400 Ib manganese (which is above the processing threshold)
In this example, because the facility's information pertaining to manganese was available to one decimal place,
0.9 was used to determine the amount at or above the de minimis concentration. If the information was available
to two decimal places, 0.99 should be used.
The exemption does not apply to EPCRA Section 313 chemicals and chemical
I
categories coincidentally manufactured as byproducts and separated from the product, nor does it
apply to EPCRA Section 313 chemicals and chemical categories coincidentally manufactured as
a result of waste management activities, from either on site or off site. (Under EPCRA Section
313, U.S. EPA does not consider waste to be a mixture.) For example, many facilities treat waste
solvents by incinerating them. If coal is used as the primary fuel source to incinerate these waste
3-14
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solvents, combustion can result in the coincidental manufacture of sulfuric and hydrochloric acid
aerosols and metal compounds. Since the de minimis exemption does not apply to the
coincidental manufacture of EPCRA Section 313 chemicals or chemical categories as a by-
product or in a waste treatment process, the formation of these compounds must be considered
for threshold determinations and release and other waste management calculations.
Once the de minimis level has been equaled or exceeded, the exemption no longer
applies to that process stream, even if the EPCRA Section 313 chemical or chemical category
later falls below the de minimis concentration. All release and other waste management activities
that occur after the de minimis concentration has been equaled or exceeded are subject to
reporting. The facility does not have to report release and other waste management activities that
took place before the de minimis concentration was equaled or exceeded.
3.2.2.2
Article Exemption
An article is defined as a manufactured item that:
Is formed to a specific shape or design during manufacture;
Has end-use functions dependent in whole or in part upon its shape or
design; and
Does not release an EPCRA Section 313 chemical or chemical category
under normal conditions of processing or otherwise use of the item at the
facility.
If you receive a manufactured article from another facility and process or
otherwise use it without changing the shape or design, and your processing or otherwise use does
not result in the release of more than 0.5 pound of the EPCRA Section 313 chemical or chemical
category in a reporting year from all like articles, then the EPCRA Section 313 chemical or
chemical category in that article is exempt from threshold determinations and release and other
waste management reporting.
The shape and design can be changed somewhat during processing and otherwise
use as long as part of the item retains the original dimensions. That is, as a result of processing
or otherwise use, if an item retains its initial thickness or diameter, in whole or in part, then it
3-15
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II
still meets the article definition. If the item's original dimensional characteristics are totally
altered during processing or otherwise use, the item would not meet the definition. As an
example, items that do not meet the definition would be items that are colcl extruded, such as lead
ingots formed into wire or rods. However, cutting a manufactured item into pieces that are
recognizable as the article would not change the exemption status as long as the diameter and the
thickness of the item remain unchanged. For instance, metal wire may be bent and sheet metal
may be cut, punched, stamped, or pressed without losing the article status as long as no change is
made in the diameter of the wire or tubing or the thickness of the sheet and no releases above 0.5
pound per year occur.
i
Any processing or otherwise use of an article that results in a release above 0.5
1
pound per year for each EPCRA Section 313 chemical or chemical category for all like articles
negates the exemption. Cutting, grinding, melting, or other processing of a manufactured item
could result in a release of an EPCRA Section 313 chemical or chemical category during normal
conditions of use and, therefore, could negate the article exemption if the total releases exceed
i
0.5 pound in a year. However, if all of the resulting waste is recycled or reused, either on site or
off site so the release and other waste management of the EPCRA Section 313 chemical or
chemical category does not exceed 0.5 pound, then the article's exemption status is maintained.
Also, if the processing or otherwise use of similar manufactured items results in a total release
and other waste management of less than or equal to 0.5 pound of any individual EPCRA
Section 313 chemical or chemical category to any environmental media in a calendar year, U.S.
EPA will allow this quantity to be rounded to zero and the manufactured items to maintain their
article exemption. The 0.5-pound limit does not apply to each individual article, but applies to
!'" j
the sum of all release and other waste management activities from processing or otherwise use of
i
like articles for each EPCRA Section 313 chemical or chemical category. The current edition of
EPCRA Section 313 Questions and Answers (1998 edition is EPA 745-B-98-004) presents
several specific question and answer discussions pertaining to the article exemption.
3-16
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Example - Article Exemption
If an article, as part of a coating pre-treatment operation, is subjected to an etching process that removes a portion
of an EPCRA Section 313 metal from the surface that is not recycled or reused, this process would constitute a
release and negate the article exemption. For example, a copper plate is cleansed by dipping in a sulfurie acid
solution. Some of the copper reapts with the acid to form copper sulfate and the used cleaning solution is
discharged to a K)TW. This process is considered a release of the copper and, if the release is greater than 0.5
pound ppr year, the plate has Ipst its article exemption. ,
3.2.2.3
Facility-Related Exemption
Laboratory Exemption
EPCRA Section 313 chemicals and chemical categories that are manufactured,
processed, or otherwise used in laboratories under supervision of a technically qualified
individual are exempted from the threshold determination (and subsequent release and other
waste management calculations). This exemption may be applicable hi circumstances such as
laboratory sampling and analysis, research and development, and quality assurance and quality
control activities. It does not include pilot plant scale or specialty chemical production. It also
does not include laboratory support activities. For example, chemicals used to maintain
laboratory equipment are not eligible for the laboratory exemption.
3.2.2.4
Activity-Related Exemptions
Some exemptions apply to the "otherwise use" of a toxic chemical. The specific
quantities of EPCRA Section 313 chemicals used in these activities do not need to be included in
a facility's threshold determination (nor the associated release and other waste management
calculations). The following activities are considered exempt:
EPCRA Section 313 chemicals and chemical categories used in
routine janitorial or facility grounds maintenance. Examples are
bathroom cleaners, fertilizers, and garden pesticides similar in type or
concentration found in consumer products. Materials used to clean process
equipment do not meet this exemption.
Personal use of items. Examples are foods, drugs, cosmetics, and other
personal items including those items within the facility such as in a facility
3-17
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operated cafeteria, store, or infirmary. Office supplies such as correction
fluid are also exempt.
Example -Personal Use Exemption
Ammonia used to clean a cafeteria grill is exempt from threshold determinations and
release and other waste management calculations.
Structural components of the facility. Exemptions apply to EPCRA
Section 313 chemicals and chemical categories present in materials used to
construct, repair, or maintain structural components of a facility. An
example common to all facilities would be the solvents and pigments used
to paint the buildings. Materials used to construct, repair, or maintain
process equipment are not exempt.
i
EPCRA Section 313 chemicals and chemical categories used with
facility motor vehicles. This category includes the use of EPCRA
Section 313 chemicals and chemical categories for the purpose of
maintaining motor vehicles operated by the facility. Common examples
include gasoline, radiator coolant, windshield wiper fluid, brake and
transmission fluid, oils and lubricants, cleaning solutions, and solvents in
paint used to touch up the vehicle. Motor vehicles include cars, trucks,
fbrklifts, locomotives, and aircraft. Note that this exemption applies to the
OTHERWISE USE of EPCRA Section 313 chemical and chemical
categories. The coincidental manufacture of EPCRA Section 313
chemicals and chemical categories resulting from combustion of gasoline
is not exempt and should be considered as part of the manufacturing
threshold.
Example - Motor Vehicle Exemption
Methanol is purchased for use as a processing aid and as a windshield washer anti-
freeze in company vehicles. The amount used for the latter purpose would be
subtracted from me facility total BEFORE the facility total is compared to me activity
threshold. Even if the facility still exceeds the otherwise use threshold, the amount in
the anti-freeze is exempt from release and other waste management reporting.
This exemption does NOT apply to stationary equipment. The use of
lubricants and fuels for stationary process equipment (e.g., pumps and
compressors) and stationary energy sources (e.g., furnaces, boilers,
heaters) are NOT exempt.
3-18
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Example - Process Equipment Chemical Use
Lubricants containing listed EPCRA Section 313 chemicals and chemical categories
used on facility vehicles or 6n-site structural maintenance activities that are not integral
to the prbcessjare exempt activities. However, lubricants used to maintain pumps and
compressors that aid facility process operations are not exempt and the amount of the
EPGRA Section 313 cheinjcal in the lubricant should be applied to the otherwise use
.threshold.-.'... . /- . ''-:'. '".',''.:f .''. '"- ;;-":>;';~.:;''. \._"'.": ;:..;';' ..-.._ ...;':.'"" '."':"-'.
EPCRA Section 313 chemicals and chemical categories in certain air
or water drawn from the environment or municipal sources. Included
are EPCRA Section 313 chemicals and chemical categories present in
process water and non-contact cooling water drawn from the environment
or a municipal source, or chemicals and chemical categories present in air
used either as compressed air or as an oxygen source for combustion.
Tfrrample - Chemicals in Process Water
A facility uses river water for one of its processes. This water contains approximately
100 pounds of an EPCRA Section313 chemical or chemical category. The facility
ultimately returns the water that contains the entire 100 pounds of the EPCRA Section
313 chemical or chemical category to the river. The EPCRA Section 313 chemical or
chemical category in the water can be considered exempt because the EPCRA Section
313 toxic chemical was present as it was drawn from the environment. The facility
does not need to consider the EPCRA Section 313 chemical or chemical category
drawn with river water for threshold determinations or release and other waste
management reporting.
3.2.3
Additional Guidance on Threshold Calculations for Certain Activities
This section covers three specific situations in which the threshold determination
may vary from normal facility operations: reuse, remediation, and recycling activities of EPCRA
Section 313 chemicals and chemical categories.
3.2.3.1
Reuse Activities
Threshold determinations of EPCRA Section 313 chemicals or chemical
categories that are reused at the facility are based only on the amount of the EPCRA Section 313
chemical or chemical category that is added to the system during the year, not the total volume ii
the system. For example, a facility operates a refrigeration unit that contains 15,000 pounds of
anhydrous ammonia at the beginning of the year. The system is charged with 2,000 pounds of
anhydrous ammonia during the year. The facility has therefore otherwise used only 2,000
3-19
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pounds of the EPCRA Section 313 chemical or chemical category and is not required to report
(unless the facility has additional otherwise use activities of ammonia that, when taken together,
" S
exceed the reporting threshold). If, however, the whole refrigeration unit was recharged with
', ' , yi n ;, ]|
15,000 pounds of new or fresh anhydrous ammonia during the year, the facility would exceed the
otherwise use threshold, and be required to report.
3.2.3.2
Remediation Activities
EPCRA Section 313 chemicals and chemical categories undergoing remediation
(e.g., Superfund remediation) are not being manufactured, processed, or otherwise used.
Therefore, they are not included in the activity threshold determinations.
^ ' ' I
However, if you are conducting remediation of an EPCRA Section 313 chemical
': ' : ' I
or chemical category that is also being manufactured, processed, or otherwise used by the facility
above an activity threshold level, you must consider this activity for release and other waste
management calculations. You must report any release or other waste management quantities of
an EPCRA Section 313 chemical or chemical category due to remediation in Part II, Sections 5
through 8, accordingly, of the Form R. Those quantities would also be considered as part of the
" ' I
amount for determining Form A eligibility. EPCRA Section 313 chemicals and chemical
categories used for remediation should be considered toward threshold determinations. If an
EPCRA Section 313 chemical or chemical category exceeds one of the reporting thresholds
elsewhere at the facility, all release and other waste management quantities of that chemical or
chemical category must be reported, including release and other waste management quantities
resulting from remediation.
I
s
Excavation of material already landfilled does not constitute a release or other
waste management activity for EPCRA Section 313 reporting purposes. Routine activities (e.g.,
dredging a lagoon), even if not performed every year, are not considered to be remedial actions
and are always subject to reporting.
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3.2.3.3
Recycling Activities
For on-site recycling and reuse systems, where the same EPCRA Section 313
chemical or chemical category is recycled and reused multiple times, the recycled quantity
should be counted only once for threshold calculations. (Please note that for reporting on-site
waste management activities [Section 8 of Form R] the quantity of the EPCRA Section 313
chemical should be counted every time it exits the recycling unit.) EPCRA Section 313
chemicals and chemical categories recycled off site and returned to the facility should be treated
as newly purchased materials for EPCRA Section 313 threshold determination.
3.3
Step 3. Calculate the Quantity of Each EPCRA Section 313 Chemical and
Chemical Category and Determine Which Ones Exceed an Activity
Threshold
The final step is to determine the quantity and which EPCRA Section 313
chemicals and chemical categories exceed an activity threshold. At this point you should have:
1. Identified each EPCRA Section 313 chemical and chemical category at
your facility.
2. Determined the activity category for each EPCRA Section 313 chemical
and chemical category (manufactured, processed, or otherwise used).
Now, you must sum the usage for each EPCRA Section 313 chemical and
chemical category by activity category, subtract all exempt quantities, and compare the totals to
the applicable thresholds. Each EPCRA Section 313 chemical and chemical category exceeding
any one of the activity thresholds requires the submission of an EPCRA Section 313 report.
Provided you meet certain criteria you may prepare a Form A rather than a Form R (see Section
2.8).
3-21
-------
COMMON ERROR - Assuming a Threshold is Exceeded.
U.S. EPA recently published a report, "The 1994 and 1995 Toxic Release Inventory Data Quality Report," EPA
745-R-98-002, with the site survey results of over 100 facilities to evaluate EPCRA Section 313 reporting
quality. One of the findings of this survey was that facilities that simply assumed that chemical activity
thresholds were exceeded were often in error. This resulted in many of these facilities filing EPCRA Section 313
reports when thresholds were actually not exceeded. Unless the facility has strong grounds to support such an
assumption, the time spent in explicitly calculating the activity threshold is well spent.
COMMON ERROR - What if Your Facility Has No Release and other
Waste Management Quantities of EPCRA Section 313 Chemicals?
If you meet all reporting criteria and exceed any threshold for an EPCRA Section 313 chemical or chemical
category, you must file an EPCRA Section 313 report for that chemical or chemical category, even if you have
zero release and other waste management activities. Exceeding the chemical activity threshold, not the quantity
released and otherwise managed as waste determines whether you must report. Note that if the release and other
waste managed quantity is 500 pounds or less you may be eligible to use the alternate certification statement,
Form A rather than a Form R (see Section 2-8).
To determine if an EPCRA Section 313 chemical or chemical category exceeds a
reporting threshold, you must calculate the annual activity amount of that chemical. Start with
!l ' ' '
the amount of chemical or chemical category at the facility as of January 1, add any amounts
brought on site during the year and the amount manufactured (including imported), and subtract
the amount left in the inventory on December 31. If necessary, adjust the total to account for
li
exempt activities (see Section 3.2.2 for a discussion of exemptions). You should then compare
the result to the appropriate threshold to determine if you are required to submit an EPCRA
Section 313 report for that chemical or chemical category. Keep in mind that the threshold
calculations are independent for each activity category: manufactured, processed, and otherwise
used. If more than one activity category applies, the amount associated with each category is
determined separately.
i
Table 3-5 presents a work sheet that may be helpful when conducting your
ij
threshold determinations. Table 3-6 illustrates an example of how the work sheet can be used for
1
the following example:
3-22
-------
Example - Threshold Worksheet
Assume your facility purchases two mixtures that contain xylene in the applicable reporting year. You purchased
25,000 pounds of Mixture A (which is 50% xylene according to the MSDS) and 110,000 pounds of Mixture B
(which contains 20% xylene). Further, you determine that you process the entire quantity of Mixture A, while
you process only half of Mixture B and otherwise use the other half. You do not qualify for any exempt
' . V. * *" -* "'* * "-' '-"' - v"" > ->'t t "
activities. ' ' ' ^"^ - - , , u; i, i/^,-. rj,:
r "* ar '
In this example, you would have processed a total of 23,500 pounds of xylene (12,500 pounds from activities
associated with Mixture A and 11,000 pounds from activities associated with Mixture B). You would also have
otherwise used a total of 11,000 pounds (all from Mixture B). Therefore, you would not have exceeded the
25,000 pound threshold for processing; however, you would have exceeded the 10,000 pound threshold for
otherwise use and would be required to submit an EPCRA; Section 313 report that includes release and other
waste managed quantities from all activities (including processing). ^____
3-23
-------
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3-25
-------
-------
CHAPTER 4 - ESTIMATING RELEASE AND OTHER WASTE
MANAGEMENT QUANTITIES
4.0
PURPOSE
This chapter is intended to guide the user in developing a systematic approach for
estimating quantities of EPCRA Section 313 chemicals and chemical categories released and
otherwise managed as waste from semiconductor manufacturing operations. Figure 4-1 diagrams
a recommended approach for estimating quantities of reportable EPCRA Section 313 chemicals
or chemical categories.
This chapter also includes common EPCRA Section 313 reporting and
compliance issues as they apply to the semiconductor manufacturing industry. The general
discussion (Section 4.1) is followed by a presentation of specific examples and issues (Section
4.2).
4.1
General Steps for Determining Release and Other Waste Management
Activity Quantities
Release and other waste management activity quantities can be determined by
completing the following four steps, described in detail in the following sections.
Step 1) Prepare a process flow diagram.
Step 2) Identify EPCRA Section 313 chemicals and chemical categories
and potential sources of chemical release and other waste
management activities.
Step 3) Identify release and other waste management activity types.
Step 4) Determine the most appropriate method(s) and calculate the
estimates for release and other waste management activity
quantities.
4-1
-------
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4-2
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For EPCRA Section 313 purposes, "sources" means the streams or units that
generate the release and other waste management activity (such as process vents, container
residue, or spills) and "types" means the environmental media corresponding to elements in
Section 5 through 8 of the 1997 Form R (for example, releases to fugitive air, releases to stack
air, discharges to receiving streams or POTWs, or releases to land).
4.1.1
Step 1: Prepare a Process Flow Diagram
Preparing a process flow diagram will help you to identify potential sources of
EPCRA Section 313 chemicals and chemical categories released and otherwise managed as
waste at your facility. Depending on the complexity of your facility, you may want to diagram
individual processes or operations rather than the entire facility. The diagram should show how
materials flow through the processes and identify material input, generation, and output points.
Looking at each operation separately, you can determine where EPCRA Section 313 chemicals
and chemical categories are used and the medium to which they may be released or otherwise
managed as waste. ,
4.1.2
Step 2: Identify EPCRA Section 313 Chemicals and Chemical Categories
and Potential Sources of Chemical Release and Other Waste Management
Activities
Once a process flow diagram has been developed, you must determine the
potential sources and the EPCRA Section 313 chemicals and chemical categories that may be
released and otherwise managed as waste from each unit operation and process. Remember to
include upsets and routine maintenance activities. Potential sources include:
Accidental spills and releases;
Clean up and housekeeping
practices;
Combustion byproducts;
Container residues;
Fittings;
Flanges;
Process discharge stream;
Process vents
Pumps;
Recycling and energy recovery
byproducts;
Relief valves;
Stock pile losses;
Storage tanks;
Storm water runoff;
Tower stacks;
Transfer operations;
Treatment sludge;
4-3
-------
Volatilization from process or
treatment; and
Waste treatment discharges.
Next, you must identify the EPCRA Section 313 chemicals and chemical
categories that may be released or otherwise managed as waste from each source. A thorough
knowledge of the facility operations and processes is required for this determination. You should
also consider whether any of the EPCRA Section 313 chemicals or chemical categories are
" ii . . !
coincidentally manufactured at your facility. Table 2-2 identifies EPCRA Section 313 chemicals
1 !
and chemical categories typically used in the operations common to semiconductor
manufacturing operations. This table can be used as an aid in identifying which chemicals and
chemical categories are found in your process. The list may not include all the EPCRA Section
j
313 chemicals and chemical categories your facility uses, and it may include many chemicals
and chemical categories that you do not use.
4.1.3
Step 3: Identify Release and Other Waste Management Activity Types
For each identified source of an EPCRA Section 313 chemical or chemical
category, you should examine all possible release and other waste management activity types.
Figure 4-2 schematically represents the possible release and other waste management activity
i
types as they correspond to individual data elements of the Form R. Remember to include both
'i
routine operations and accidents when identifying types. This diagram along with the following
descriptions can be used as a checklist to make sure all possible types of release and other waste
management activities have been considered.
a. Fugitive or Non-Point Air Emissions (Part II, Section 5.1 of Form R)
- Includes all emissions to the air that are not released through stacks,
vents, ducts, pipes, or any confined air stream. Examples include:
Equipment leaks from valves, pump seals, flanges, compressors,
sampling connections, open-ended lines, etc.;
4-4
-------
Point Sources
Fugitive Emissions
EPCRA Section 313 Chemical
or Chemical Category
Operation
Underground Injection
Receiving Stream
Transfer Off Site for Recycling
Transfer Off Site for Energy Recovery
Transfer Off Site for Treatment
Transfer Off Site for Disposal
On-Site Treatment
On-Site Energy Recovery
On-Site Recycling
POTW
Land on site (landfill, land
treatment, surface impoundment)
Figure 4-2. Possible Release and Other Waste Management Activity Types
for EPCRA Section 313 Chemicals and Chemical Categories
Releases from building ventilation systems, such as a roof fan in an
open room;
Evaporative losses from solvent cleaning tanks, surface
impoundments, and spills; and
Emissions from any other fugitive or non-point source.
b. Stack or Point Air Emissions (Part II, Section 5.2 of Form R) -
Includes all emissions to the air that occur through stacks, vents, ducts,
pipes, or any confined air stream, including the emissions from storage
tanks and air pollution control equipment. Air emissions from
semiconductor manufacturing operations are often channeled through air
pollution control devices. These are considered stack emissions. Note
that emissions released from general room air through a ventilation system
are not considered stack or point releases for the purpose of EPCRA
Section 313 reporting unless they are channeled through an air pollution
control device. Instead, they are considered fugitive releases. However,
you should note that for certain state reporting requirements not associated
4-5
-------
e.
with EPCRA Section 313 reporting, some state air quality agencies
consider ventilation systems to be a stack or point source.
Discharges to Receiving Streams or Water Bodies (Part II, Section 5.3
of Form R) - Includes direct wastewater discharges to a receiving stream
or surface water body. Discharges usually occur under a NPDES or
SPDES permit.
'i
;, , ]
Underground Injection On-Site to Class I Wells (Part II, Section 5.4.1
of Form R) and to Class II through V Wells (Part II, Section 5.4.2 of
Form R) - Includes releases into an underground well, at the facility.
These wells may be monitored under an Underground Injection Control
(UIC) Program permit. RCRA Hazardous Waste Generator Reports may
be a good source of information for wastes injected into a Class I well.
Injection rate meters may provide information for all the well classes.
Disposal to Land On-Site (Part II, Section 5.5 of Form R) Includes all
releases to land on-site, both planned (i.e., disposal) and unplanned (i.e.,
accidental release or spill). The four predefined subcategories for
reporting quantities released to land within the boundaries of the facility
are:
(1) Landfill - The landfill may be either a RCRA permitted (Part II,
Section 5.5.1 A) or a non-hazardous waste landfill (Part II, Section
5.5. IB). Both types are included if they are located on site. Leaks
from landfills in the years subsequent to the disposal of the
EPCRA Section 313 chemicals or chemical categories in the
landfill do not need to be reported as a release.
(2) Land treatment/application farming - Land treatment is a
disposal method in which a waste containing an EPCRA Section
313 chemical or chemical category is applied to or incorporated
into soil. Volatilization of an EPCRA Section 313 chemical or
chemical category because of the disposal operation must be
included in the total fugitive air releases and should be excluded
from land treatment/application farming to avoid double counting.
' !.
Sludge and/or aqueous solutions that contain biomass and other
organic materials are often collected and applied to farm land.
This procedure supplies a nitrogen source for plants and supplies
metabolites for microorganisms. U.S. EPA considers this
operation to be land treatment/farming if it occurs on site. If a
facility sends this material off site for the same purpose, it is
considered to be a "transfer to an off-site location, disposal" and
should be reported under Sections 6.2 and 8.1 of the Form R.
4-6
-------
The ultimate disposition of the chemical or chemical category after
application to the land does not change the required reporting. For
example, even if the chemical or chemical category is eventually
bibdegraded by microorganisms or plants, it is not considered
recycled, reused, or treated.
(3) Surface impoundment - A surface impoundment is a natural
topographic depression, man-made excavation, or diked area
formed primarily of earthen materials that is designed to hold an
accumulation of wastes containing free liquids. Examples include:
holding, settling, storage, and elevation pits; ponds; and lagoons.
Quantities of the toxic chemical released to surface impoundments
that aroused merely as part of a wastewater treatment process
generally must not be reported in this section. However, if the
sludge from the surface impoundment contains the EPCRA Section
313 chemical or chemical category, then the EPCRA Section 313
chemicals or chemical pategories in the sludge must be estimated
in this section unless the sludge is removed and subject to another
waste management activity.
(4) Other disposal - Releases to land that do not fit the categories of
landfills, land treatment, or surface impoundment are classified as
other disposal. This disposal may include any spills or leaks of the
EPCRA Section 313 chemical or chemical category to land.
f. Transfers Off Site to a Publicly Owned Treatment Works (POTW)
(Part II, Section 6.1 of Form R) - Includes the amount of EPCRA
Section 313 chemical or chemical category in water transferred to an off-
site POTW. Note that metals and metal compounds transferred to a
POTW must -also be reported in Section 8.1.
g. Transfers to Other Off-Site Locations (Part II, Section 6.2 of Form R)
- Includes all off-site transfers containing the EPCRA Section 313
chemical or chemical category for the purposes of disposal waste
treatment, energy recovery, or recycling. Off-site transfer for disposal
includes underground injection, landfill/surface impoundment, other land
disposal and transfer to a waste broker for disposal. The amount
transferred off site for disposal must also be reported in Section 8.1.
Also reported in Section 6.2 would be any residual EPCRA Section 313
chemicals in "empty" containers transferred off site. U.S. EPA expects
that all containers (bags, totes, drums, tank trucks, etc.) will have a small
amount of residual solids and/or liquid. On-site cleaning of containers
must be considered for EPCRA Section 313 reporting. If the cleaning
occurs with a solvent (organic or aqueous), you must report the disposition
of the waste solvent as appropriate. If the containers are sent off site for
4-7
-------
disposal or reclamation, you should report the EPCRA Section 313
chemical or chemical category in this section.
COMMON ERROR - Shipping Container Residue
Do not overlook residual chemicals or chemical categories in containers, U.S. EPA
recently published The 1994 and 1995 Toxic Release Inventory Data Quality Report,
EPA 745-R-98-002, presenting the site survey results of over 100 facilities to evaluate
EPCRA Section 313 reporting quality. This survey found the largest source of
overlooked release and other waste management activities was from container residue.
So-called "empty" drums may contain an inch or more of liquid after draining and
similarly "empty" bags may contain residues of dust and powder. Even though each
individual drum or bag may only contain a small amount of an EPCRA Section 313
chemical or chemical category, for facilities that receive hundreds or thousands of
drums or bags each year the annual cumulative amount of an EPCRA Section 313
chemical or chemical category can be substantial. The quantities should typically be
reported in Section 6.2 (see Table 4-1 for estimates of liquid drum residual and the
discussion in the text of this section for estimates of residual from solids).
Actual data and a knowledge of the unloading methods at your facility can
be used to estimate the quantity of residual EPCRA Section 313 chemicals
or chemical categories in containers. However, U.S. EPA has developed
guidance to assist facilities if no site-specific information is available.
Table 4-1 provides results from a study of liquid residue quantities left in
drums and tanks when emptied. These results are presented as the mass
percent of the vessel capacity, and are categorized based on unloading
method, vessel material, and bulk fluid material properties such as
viscosity and surface tension. No testing was conducted for residual solids
in this study. If data on site-specific knowledge is available to estimate
the quantity of solid residual in containers it should be considered. If no
data are available, U.S. EPA believes an estimate of 1% residual solid is
reasonable.
4-8
-------
Table 4-1
Summary of Liquid Residue Quantities From
Pilot-Scale Experimental Studya'b
(weight percent of drum capacity)
Unloading
Method
Pumping
Pumping
Pouring
Pouring
Gravity
Drain
Gravity
Drain
Gravity
Drain
Vessel Type
Steel drum
Plastic drum
Bung-top steel
drum
Open-top steel
drum
Slope-bottom
steel tank
Dish-bottom
steel tank
Dish-bottom
glass-lined tank
Value
Range
Mean
Range
Mean
Range
Mean
Range
Mean
Range
Mean
Range
Mean
Range
Mean
Material
Kerosene'
1.93 - 3.08
2.48
1.69-4.08
2.61
0.244 - 0.472
0.404
0.032 - 0.080
0.054
0.020 - 0.039
0.033
0.031-0.042
0.038
0.024 - 0.049
0.040
Water"
1.84 - 2.61
2.29
2.54 - 4.67
3.28
0.266 - 0.458
0.403
0.026 - 0.039
0.034
0.016 - 0.024
0.019
0.033 - 0.034
0.034
0.020 - 0.040
0.033
Motor Oil*
1.97 - 2.23
2.06
1.70 - 3.48
2.30
0.677 - 0.787
0.737
0.328 - 0.368
0.350
0.100-0.121
0.111
0.133-0.191
0.161
0.112-0.134
0.127
Surfactant
Solutionf
3.06
3.06
Not
Available
0.485
0.485
0.089
0.089
0.048
0.048
0.058
0.058
0.040
0.040
"From "Releases During Cleaning of Equipment." Prepared by PEI Associates, Inc., for the U.S. Environmental
Protection Agency, Office of Pesticides and Toxic Substances, Washington DC, Contract No. 68-02-4248. June 30,
1986.
bThe values listed in this table should only be applied to similar vessel types, unloading methods, and bulk fluid
materials. At viscosities greater than 200 centipoise, the residue quantities can rise dramatically and the information
on this table is not applicable.
Tor kerosene, viscosity = 5 centipoise, surface tension = 29.3 dynes/cm2
dFor water, viscosity = 4 centipoise, surface tension = 77.3 dynes/cm2
Tor motor oil, viscosity = 97 centipoise, surface tension = 34.5 dynes/cm2
Tor surfactant solution viscosity = 3 centipoise, surface tension = 31.4 dynes/cm2
4-9
-------
The following example describes how the information in the table can be used to
estimate the quantity of an EPCRA Section 313 chemical or chemical category in
water that was used to clean drums on site.
Example - Container Residue
You have determined that a Form R for an EPCRA Section 313 chemical or chemical category must be
submitted. The facility purchases and uses one thousand 55-gallon steel drums that contain a 10% aqueous
solution of the chemical. Further, it is assumed that the physical properties of the solution are similar to water.
The solution is pumped from the drums directly into a mixing vessel and the "empty" drums are triple-rinsed
with water. The rinse water is indirectly discharged to a POTW and the cleaned drums are sent to a drum
reclaimer.
From Table 4-1, the average drum residue quantity for this scenario is 2.29%. In this example, it can be assumed
that all of the residual solution in the drums was transferred to the rinse water. Therefore, the quantity of the
BPCRA Section 313 chemical transferred to the drum reclaimer should be reported as "zero."
The annual quantity of residual solution that is transferred to the rinse water can be estimated by multiplying the
mean weight percent of residual solution remaining in a pumped steel drum by the total annual weight of solution
ftt the drums. If the density is not known, it may be appropriate to use the density of water (8.34 pounds per
gallon):
(0.0229%) x (55 gal/drum) x (1,000 drums) x (8.34 Ib/gal)
= 10,504 pounds solution
The concentration of the EPCRA Section 313 chemical in the solution is only 10 percent.
(10,504 pounds solution) x (0.1%) = 1,050 pounds EPCRA Section 313 chemical
Therefore, 1,050 pounds of the EPCRA Section 313 chemical are transferred to the POTW and should be
reported in Part n, Sections 6.1 and 8.7 of the 1998 Form R. Because they cannot be destroyed, metals cannot be
reported as being treated, and metals and metal portions of metal compounds should be reported in Part II,
Sections 6.1 and 8.1 of the 1998 FormR.
h. On-Site Waste Treatment (Part II, Section 7A of Form R) - Includes
all on-site waste treatment of EPCRA Section 313 chemjcals or chemical
categories. The information reported in Section 7 A focuses on the
treatment of the entire waste stream, not the specific IJPCRA Section 313
chemical or chemical category. The information includes type of waste
stream (gaseous, aqueous or non-aqueous liquid, or solid); treatment
methods or sequence; influent concentrations of the EPCRA Section 313
chemical or chemical category; treatment efficiency (combined removal
and destruction) of the entire method or sequence; and whether efficiency
data is based on actual operating data. Metals and metal portions of metal
compounds treated in a combustion process are not destroyed but should
still be reported as going through the treatment process, with a treatment
efficiency of zero. Note that only the metal portion of metal compounds
should be reported in the Form R. The following example illustrates how
Section 7A should be completed for on-site treatment of a wastewater
4-10
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stream containing three EPCRA Section 313 chemicals or chemical
categories.
Example - On-Site Waste Treatment
A process at your facility generates a wastewater stream containing an EPCRA Section 313 chemical (chemical
A). A secondprocess generates a wastewaterstreamcontaining two EPCRA Section 313 chemicals, ametal
(chemical B) and a mineral acid (chemical C). Thresholds for all three chemicals have been exceeded and you
are in the process of completing separate FormRs for each chemical.
Both wastewater streams are combined and sent to an 6n-site wastewater treatment system before being released
to a POTW. This system consists of an oil/water separator that removes 99% of chemical A; a neutralization
tank in which the pH is adjusted to 7.5, thereby destroying 100% of the mineral acid (chemical C);,and a settling
tank where95% of the metal (chemical B) is removed from the water (and eventually land rilled off site).
Section 7A shouldI be Completed slightly differently when you file the Form R for each of the chemicals or
chemical categories, The table accompanying this example shows how Section 7A should be completed for each
chemical or chemical category. First^ on each Form R you should identify the type of waste stream in Section
.7A.la as wastewater (aqueous waste, code W). Next, on each Form R you should list the code for each of the
treatment steps mat is applied to the entire waste stream, regardless of whether the operation affects the chemical
or chemical category for which you are completing the Form R (for imtance, me first ifour blocks of Section ;
7A.lb of all three Form Rs should show: P19 (liquid phase; separation), Cll (neutralization), PI 1
(setfling/clarification), and N/A (to signify ;the end of the treatment system). Note that Section 7A.lb is the only
section of the FormR that is not chemical or chemical category specific. It applies to the entire waste stream
being treated. Section 7A.lc of eachjFormR should show the concentration of the specific chemical or chemical
category in the influent to the first step of the process (oil/water separation). For this example, assume chemicals
or chemical categories A, B, andCare att present at concentrations greater than 1 percent; Therefore, code "1"
should be entered. Section 7A.ld is also chemical specific. It applies to the efficiency, of the entire system in
destroying and/or removing the chemical or chemical category for which you are preparing the Form R you are
currently completing. You should enter 99% when-filing for chemical A, 95% for chemical B, and 100% for
chemical C. Finally, you should report whether the influent concentration and efficiency estimates are based on
operating data for each chemical or chemical category, as appropriate. .- '
Chemical A
7A.la
;7Allb I 1. PI 9 2. Cll
3. _PJLL_ 4. WA 5. ____.
6. 7. 8. .
7A;lc
7A.ld
99 %
7A.le
Yes
No
Chemical B
7A.la
7A.lb
3. PH
6.
1. P19
4. .N/A
7. _..
2. C11
5.
8.
7A.lc
7A.ld
95 %
7A.le
Yes
No
Chemical C
7A.la
7A.lb I 1. P19 2. Cll
3. PIT 4. N/A 5.
6. 7. . 8.
7A.lc
7A.ld
100 %
7A.le
Yes
No
4-11
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Note that the quantity removed and/or destroyed is not reported in Section 7 and that the efficiency reported in
Section 7A.ld refers to the amount of EPCRA Section 313 chemical or chemical category destroyed and/or
removed from the applicable waste stream. The amount actually destroyed should be reported in Section 8.6
(quantity treated on site). For example, when completing the Form R for chemical B you should report "0"
pounds in Section 8.6 because the metal has been removed from the wastewater stream, but not actually
destroyed. The quantity of .chemical B that is ultimately land filled off site should be reported in Section 6.2 and
8.1. However, when completing the Form R for chemical C you should report the entire quantity in Section 8.6
because raising the pH to 7.5 will completely destroy the mineral acid.
On-Site Energy Recovery (Part II, Section 7B of Form R) - Includes all
on-site energy recovery of reported EPCRA Section 313 chemicals and
chemical categories. U.S. EPA's view is that EPCRA Section 313
chemicals or chemical categories that do not contribute significant heat
energy during combustion processes should not be considered for energy
recovery. Therefore, only EPCRA Section 313 chemicals or chemical
categories with a significant heating value that are combusted in an energy
recovery unit, such as an industrial furnace, kiln, or boiler can be reported
for energy recovery. If an EPCRA Section 313 chemical or chemical
category is incinerated on site but does not significantly contribute energy
to the process (e.g., chlorofluorocarbons (CFCs)), it must be considered
on-site waste treatment (see 4.1.3, h. above). Metals and metal portions of
metal compounds will never be combusted for energy recovery. Note that
only the metal portion of metal compounds should be reported in the Form
R.
||
On-Site Recycling (Part II, Section 7C of Form R) - Includes all on-site
recycling methods used on EPCRA Section 313 chemicals or chemical
categories.
Source Reduction and Recycling Activities (Part II, Section 8 of Form
R)1 - Provide information about source reduction and recycling activities
related to the EPCRA Section 313 chemical or chemical category for
which release and other waste management activities are being reported.
Section 8 uses some data collected to complete Part II, Sections 5 through
7. For this reason, Section 8 should be completed last. The relationship
between Sections 5, 6, and 8.8 to Sections 8.1, 8.3, 8.5, and 8.7 are
provided in equation forms below.
(1) Quantity Released (Part II, Section 8.1 of Form R) - The
quantity reported in Section 8.1 is the quantity reported in all of
Section 5 plus the quantity of metals and metal compounds
reported as discharged off site to POTWs hi Section 6.1 plus the
quantity reported as sent off site for disposal in Section 6.2 minus
'The Subsection 8,1 through 8.8 designations are for the 1997 Form R. Please refer to the current reporting year
TRI Forms and Instructions for any changes.
4-12
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the quantity reported in Section 8.8 that was released on site or sent
off site for disposal:
§8.1 = §5 + §6.1 (metals and metal compounds) + §6.2 (disposal) -
§8.8 (on-site release or off-site disposal only)
(2) Quantity Used for Energy Recovery On-Site (Part II,
Section 8.2 of Form R) - Estimate the quantity of the EPCRA
Section 313 chemical or chemical category in wastes combusted
for energy recovery on site. This estimate should be the quantity
of the chemical or chemical category combusted in the process for
which codes were reported in Section 7B. Test data from trial
burns or other monitoring data may be used to estimate the
quantity of the EPCRA Section 313 chemical or chemical category
combusted for energy recovery purposes. If monitoring data are
not available, vendor specifications regarding combustion
efficiency may be used as they relate to the EPCRA Section 313
chemical or chemical category. A quantity must be reported in
Section 8.2 when a method of on-site energy recovery is reported
in Section 7B and vice versa.
Two conditions need to be met to report the combustion of an
EPCRA Section 313 chemical or chemical category in waste as
energy recovery: the chemical or chemical category (1) must have
a significant heating value and (2) must be combusted in an energy
recovery unit, such as a waste heat boiler, an industrial furnace, or
a kiln. If an EPCRA Section 31-3 chemical or chemical category
that does not have a significant heating value (except metals and
metal compounds) is combusted for energy recovery on site, it
must be considered on-site waste treatment (see 4.1.3.h). Metals
and metal compounds in a waste that are combusted on site will
never be combusted for energy recovery and are considered to be
disposed. Note that "NA" should be reported for EPCRA Section
313 chemicals or chemical categories that do not have a significant
heating value. This includes metals, metal portions of metal
compounds, halogens, hydrochlorofluorocarbons (HCFCs), and
CFCs.
(3) Quantity Used for Energy Recovery Off-Site (Part II, Section
8.3 of Form R) - The quantity reported in Section 8.3 is the
quantity reported in Section 6.2 for which energy recovery codes
are reported. If a quantity is reported in Section 8.8, subtract any
associated off-site transfers for energy recovery:
§8.3 =§6.2 (energy recovery) -§8.8 (off-site energy recovery)
4-13
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Two conditions need.to be met to report the combustion of an
EPCRA Section 313 chemical or chemical category in waste as
energy recovery: the chemical (1) must have a significant heating
value and (2) must be combusted in an energy recovery unit, such
as a waste heat boiler, an industrial furnace, or a kiln. If an
EPCRA Section 313 chemical or chemical category that does not
have a significant heating value (except metals and metal
compounds) is sent off site for energy recovery, it must be
considered off-site waste treatment (see 4.1.3.g). Metals and metal
compounds sent off site for combustion in energy recovery units
must be considered as sent off site for disposal because typically
they will ultimately be disposed. Metals and metal portions of
metal compounds will never be treated or combusted for energy
recovery. Note that only the metal portion of metal compounds
should be reported in the Form R. Also note that "NA" should be
reported for EPCRA Section 313 chemicals or chemical categories
that do not have a significant heating value. This includes metals,
metal portions of metal compounds, halogens, HCFCs, and CFCs.
(4) Quantity Recycled On-Site (Part II, Section 8.4 of Form R) -
Estimate the quantity of the EPCRA Section 313 chemical or
chemical category recycled in wastes on site. This estimate should
be the quantity of the chemical or chemical category recycled in
the process for which codes were reported in Section 1C. A
quantity should be reported in Section 8.4 when a method of on-
site recycling is reported in Section 7C and vice versa. To estimate
this quantity, you should determine if operating data exist that
indicate a recovery efficiency and use that efficiency value
combined with throughput data to calculate an estimate. If
operating data are unavailable, vendor specifications may be
appropriate.
ij '
(5) Quantity Recycled Off-Site (Part II, Section 8.5 of Form R) -
The quantity reported in Section 8.5 must be the same as the
quantity reported in Section 6.2 for which recycling codes are
reported. If a quantity is reported in Section 8.8, subtract any
associated off-site transfers for recycling:
, . l ' ': (: .
§8.5 = § 6.2 (recycling) - § 8.8 (off-site recycling)
(6) Quantity Treated On-Site (Part II, Section 8.6 of Form R) -
Waste treatment in Section 8 is limited to the Destruction or
chemical conversion of the EPCRA Section 313 chemical or
chemical category in wastes. The quantities reported in Section
8.6 will be those that have undergone processes that are a subset of
the processes for which codes were reported in Section 7A, where
treatment includes physical removal from a waste stream. To
4-14
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estimate the quantity treated, you should determine if operating
data exist that indicate a treatment efficiency (e.g., destruction or
chemical conversion of the EPCRA Section 313 chemical or
chemical category) and use that efficiency value combined with
throughput data to calculate an estimate. Because metals cannot be
destroyed or chemically converted into something other than the
metal or metal compound, metals cannot be reported as being
treated in Section 8.6. Note that conversion of a metal from, one
oxidation state to another (e.g., Cr(VI) to Cr(III)) is not considered
treatment for Section 8.6. If operating data are unavailable,
available vendor specifications may be appropriate. Section 7A
must be completed if a quantity is entered in Section 8.6.
(7) Quantity Treated Off-Site (Part II, Section 8.7 of Form R) -
The quantity reported in Section 8.7 must be the same as the
quantity reported in. Section 6.2 for which treatment codes are
reported plus quantities sent to a POTW as reported in Section 6.1,
except for metals and metal compounds. If a quantity is reported
in Section 8.8, subtract any associated off-site transfers for
treatment:
§8.7 = §6.1 (except metals and metal compounds) + §6.2
(treatment) - §8.8 (off-site treatment)
Because metals cannot be destroyed or chemically converted into
something other than the metal or metal compound, metals cannot
be reported as treated in Section 8.7. Quantities of metals reported
in Section 6.1 and 6.2 should be reported in Section 8.1 (Quantity
Released) unless the facility has knowledge that the metal is being
recovered.
(8) Quantity Released to the Environment as a Result of Remedial
Actions, Catastrophic Events, or One-Time Events Not
Associated with Production Processes (Part II, Section 8.8 of
Form R) - The purpose of this section is to separate quantities
recycled off site, used for energy recovery off site, treated off site,
or released (including disposed) that are associated with normal or
routine production from those quantities that are not. The quantity
reported in Section 8.8 is the quantity of the EPCRA Section 313
chemical or chemical category released directly into the
environment or sent off site for recycling, energy recovery,
treatment, or disposal during the reporting year because of any of
the following events:
Remedial actions;
Catastrophic events such as earthquakes, fires, or floods; or
4-15
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=1;
One-time events not associated with normal or routine
production processes.
..',,'' i
The quantity reported in Section 8.8 should not be included with
quantities reported in Part II, Sections 8.1 through 8.7 of Form R,
but should be included in Part II, Sections 5 and 6 of Form R as
appropriate.
Spills that occur as a routine part of production operations and
could be reduced or eliminated by unproved handling, loading, or
unloading procedures are included in the quantities reported in
Section 8.1 through 8.7 as appropriate. This includes small
drippings and spills that often occur during transfer operations and
loading/unloading operations.
On-site releases and off-site transfers for further waste
management from remediation of an EPCRA Section 313 chemical
or chemical category or an unpreventable accident unrelated to
production (such as a hurricane) are reportable in Section 8.8.
' , i
On-site treatment, energy recovery, or recycling of EPCRA Section
313 chemicals or chemical categories in wastes generated as a
result of remedial actions, catastrophic events, or one-time events
not associated with production processes are not reported in Part n,
Section 8.8 nor Sections 8.1 through 8.7 of Form R.
COMMON ERROR - Douhle Counting
Release and other waste management activities should not be inadvertently "double counted." A single
wastewater discharge should not be listed as both a release to water (on site) and a discharge to POTW (off site).
Similarly, a release to land should not be listed as both a release to land (on site) and a transfer to an off-site
landfill if the sludge from a surface impoundment is ultimately shipped off site. Estimates of release and other
waste management activities should be prepared for Sections 5 through 7 of the Form R. For the most part,
Section 8 relies on the data collected to complete these previous sections. Therefore, Section 8 should be
completed last. However, the data elements of Section 8 (8.1 through 8.7) are mutually exclusive and care
should be taken to avoid double counting.
4.1.4
Step 4: Determine the Most Appropriate Method(s) to Calculate the
Estimates for Release and Other Waste Management Activity Quantities
After you have identified all of the potential sources for release and other waste
management activity types, you must estimate the quantities of each EPCRA Section 313
chemical and chemical category released and otherwise managed as waste. U.S. EPA has
4-16
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identified four basic methods that may be used to develop estimates (each estimate has been
assigned a code that must be identified when reporting). The methods and corresponding codes
are:
Monitoring Data or Direct Measurement (M);
Mass Balance (C);
Emission Factors (E); and,
Engineering Calculations (O).
Descriptions of these techniques are provided in the U.S. EPA publication,
Estimating Releases and Waste Treatment Efficiencies for the Toxic Chemical Release Inventory
Forms (1999 edition). They are also briefly described below. A more detailed discussion
including examples of selected calculation techniques is presented in Appendix B. U.S. EPA
does not require you to conduct additional sampling or testing for EPCRA Section 313 reporting;
however, you are required to use the best readily available information to determine the method
that will result in the most accurate estimate. For example, it may not be appropriate to use
emission factors or engineering calculations if more accurate data, such as stack testing results,
are available. You are required to identify the primary method used for each estimation.
Many potential sources of data exist for these (and other) methods of developing
estimates. Table 4-2 presents potential data sources and the estimation methodology in which
they are most likely to be used. Based on site-specific knowledge and potential data sources
available, you should be able to determine the best method for calculating each release and other
waste management activity quantity.
Once all potential release and other waste management activity sources, types,
and estimation methods have been determined, an estimate for each EPCRA Section 313
chemical and chemical category can be developed corresponding to the elements on Form R.
4-17
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Table 4-2
Potential Data Sources for Release and Other Waste Management
Calculations
DATA SOURCES
Monitoring Data
Air permits
Continuous emission monitoring
Effluent limitations
Hazardous waste analysis
Industrial hygiene monitoring data
New Source Performance Standards
NPDES permits
Outfall monitoring data
pH for acids and bases
POTW pretreatment standards
RCRA permit
Stack monitoring data
Emission Factors
Mass Balance
Air emissions inventory
Hazardous material inventory
Hazardous waste manifests
MSDSs
Pollution prevention reports
Spill event records
Supply records
AP-42 chemical specific emission factors
Facility or trade association derived chemical-
ppecific emission factors
Engineering Calculations
Facility non-chemical specific emission factors.
Henry's Law
Raoult's Law
SOCMI* or trade association non-chemical
specific emission factors
Solubilities
Volatilization rates
* Synthetic Organic Chemicals Manufacturing Industry
4.1.4.1
Monitoring Data or Direct Measurement (code M)
Using monitoring data or direct measurements is usually the best method for
!, ii '.',' !
developing chemical release and other waste management activity quantity estimates. Your
>'. : ' ' ' I I
facility may be required to perform monitoring under provisions of the Clean Air Act (CAA),
. - ..!'.
Clean Water Act (CWA), RCRA, or other regulations. If so, data should be available for
developing estimates. Data may have also been collected for your facility through an
occupational health and safety assessment. If only a small amount of direct measurement data
are available or if you believe the monitoring data are not representative, you must decide if
another estimation method would give a more accurate result.
4-18
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, Example - Monitoring Data
Data from the on-site wastewater treatment facility indicate that the annual average concentration of copper in
the discharge is 2 mg/L. The wastewater treatment facility processed 1.5 million gallons of water in 1997. The
treated wastewater is discharged to an off-site POTW. The amount of copper transferred off site to the POTW
(for Section 6.1 of the Form R) is estimated as follows: ' , ^ -
" , > t"f
Amount of copper transferred ^ - , ~ s , _
= (2 mgn.) x { 1 1 x ( 5?I x J ± j x (1,500,000 gal/yr)
t { 1,000 mgj {453.59 gj {0.2642 galj
= 251b/yr
ERROR - Treatptent Efficiencies
Vendor data on treatment efficiencies ojften represent ideal operating conditions. You should adjust such data to
account for downtime and process Upsets during the year that wouldf result in lower efficiencies. Remember that
efficiencies reported by vendors are often general and may not apply to specific chemicals. For example, an
incinerator or flare may be 99.99% efficient in destroying certain organic chemicals, but will have a 0%
efficiency in destroying metals. ' , t "*__ \
4J.4.2
Mass Balance (code C)
A mass balance involves determining the amount of an EPCRA Section 313
chemical or chemical category entering and leaving an operation. The mass balance is written as
follows:
where:
Input + Generation = Output + Consumption
Input refers to the materials (chemicals) entering an operation. For
example, chlorine added to process water as a disinfectant would be
considered an input to the water treatment operation.
Generation identifies those chemicals created during an operation
(manufactured, including coincidental manufacturing). For example,
when nitrogen sources are used in biological wastewater treatment
systems, additional ammonia may be coincidentally manufactured.
4-19
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Output refers to the materials (chemicals) leaving an operation by various
avenues. Output (avenues) may include on-site release and other on-site
waste management activities; transfers off site for recycling, energy
recovery, treatment, storage, or disposal; or the amount of chemical that
leaves with the final product. For example, solvents used to clean wafers
between different processes may leave the operation through air emissions
or as liquid hazardous waste.
i
: i
Consumption refers to the amount of chemical converted to another
substance during the operation (i.e., reacted). For example, nitric acid
would be consumed by a neutralization during wastewater treatment.
mass balance technique may be used for manufactured, processed, or
; ; l I , " ' '' , !-;,;'1 I" ' ' ''
otherwise used chemicals. It is typically most useful for otherwise used chemicals that do not
,;; I'il : ' ' '," '. I '
become part of the final product, such as catalysts, solvents, acids, and bases. For large input and
!,":!' ' ' " ; , J " " " . : : ' '' ' i ' '"I "''
outputs, a mass balance may not be the best estimation method, because slight uncertainties hi
1'"'"' :i:'!i'!l1' ' ' ' ' " ' "I
mass calculations can yield significant errors in the release and other waste management
estimates.
Example - Mass Balance
^ f f ^ W1.VV 1 *
A facility otherwise uses a volatile EFCRA, Section 313 chemical as aiefrigefant «id adds 20,000 pouads to the
refrigeration system (to make up for system losses). The chemical is released to the air from relief vents, during"
system filling operation* an<| from kates jn valves and fl«tag$. Purtog system maJttfe»a#ee, the lines are Wed
directly into water and the system is vented to flieair. Monitoring data of the wastewater^, iiKlttdfag chemical
concentrations and wastewater throughput, Indicate that 1,200 pounds oi'the chemical were discharged to the
wastewater. The remaining losses are assumed to be fugitive air releases and are'estiiaated as follows:
. - -,'/" ,'f
Fugitive air releases of the BPCRASeefion 31$ chemical: '" -
* Amount input (Ib/yr) - Amount released to wastewater (ib/yr)
- 20,000 Ibyyr - 1,200 Ib/yr
^18,800 Ib/yr
4-20
,1
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COMMON ERROR - Mass Balances for Otherwise Used Chemicals
Facilities often do not account for tie entire quantity of EPCRA Section 313 chemicals or chemical categories
that are otherwise used. Many EPCRA Section 313 chemicals and chemical categories in the semiconductor
manufacturing industry are classified as otherwise used. Such chemicals and chemical categories rarely leave the
facility with the product. In these instances, all throughput may be lost during processing through on-site
releases to air, water, or land, or it may be shipped off site for further waste management activities. Thus, the
entirejthroughput is often reportable on Form R as release and other waste management activities to various
media. Be sure to consider the entire throughput in these circumstances and partition it as appropriate. A mass
balance may be the best starting point to estimate the release and other waste management quantities.
4.1.4.3
Emission Factors (code E)
An emission factor is a representative value that attempts to relate the quantity of
a chemical or chemical category released with an associated activity. These factors are usually
expressed as the weight of chemical or chemical category released divided by a unit weight,
volume, distance, or duration of the activity releasing the chemical (e.g., pounds of chemical
released per pounds of product produced). Emission factors, commonly used to estimate air
emissions, have been developed for many different industries and activities. You should
carefully evaluate the source of the emission factor and the conditions for its use to determine if
it is applicable to the situation at your facility.
The most widely known and used source for emission factors is U.S. EPA's
publication Compilation of Air Pollutant Emission Factors (AP-42). Volume I of AP-42
contains information on over 200 stationary source categories, including process descriptions and
potential sources of air emissions from these processes. Methodologies for estimating the
quantity of air pollutant emissions from these sources are presented as Emission Factors. For
EPCRA Section 313 purposes only CHEMICAL-SPECIFIC emission factors can be reported as
Code "E" - Emission Factor in Part II, Section 5, Column B, Basis for estimate, of the Form R.
AP-42 contains emission factors for individual chemicals and for the chemical group Volatile
Organic Compounds (VOCs). The VOC emission factors are NOT chemical specific and when
used must be reported in Column B as Code "O" - Engineering Calculations. Each chapter in
Volume I covers a major industry or source category.
4-21
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'
AP:42 can be accessed at the following Internet site:
" ii ' ' ''..'' '
» http://www.epa.gov/ttn/chief/ap42.html.
.!, ^ '. ': , , ! I ; ' '!
'! ':; .. ; ': ' . *." !' , :
In an effort to provide current emissions data in an easy-to-access format, U.S.
EiPA has prepared a CD-ROM entitled Air CHIEF (Air ClearingHouse for Inventories and
i'J'i! ' !')' , ' . ' ' 'i ,'..' '"$ "i ' ' " ' ': ' ,i!;':,i'! i ' ,. " '
Emission Factprs). The Air CHIEF CD-ROM is updated annually and is available from the
Government Printing Office and can be ordered from their Web site. In addition to AP-42, the
'"''i'1 , . 'i V :i, III ^ ' .,:..! ii r
Air CHIEF CD-ROM contains the Factor Information Retrieval (FIRE) data system, a database
management system containing U.S. EPA's recommended estimation factors'for criteria and
". " i,-!1'1' ''"ii! " ' ' ' ' '''. 3'' ' 't1 ' :
hazardpus air pollutants. The CD-ROM also contains installable copies of software programs for
air emission estimation models such as "TANKS" for VOC emission from storage tanks;
"WATERS" for air emissions from wastewater systems; and "CHEMDAT8" for VOC emissions
from Treatment, Storage, and Disposal Facility (TSDF) processes. Additional information on
Air CHIEF and the CD-ROM is available at:
http://www.epa.gov/ttn/chief/airchief.html.
Your facility may have developed emission factors for fugitive or stack emissions
from process or control device exhaust vents based on stack tests for various air permits. Be sure
to consider these emission factors if appropriate. However, if such factors are used, they are
li '': , , ' ' t; I;
considered "engineering judgement" for the purposes of EPCRA Section 313 reporting.
4-22
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F.Yarnple - Kmissinn Factors
Emission factors have been developed for air releases of fuel constituents and combustion products from boiler
operations. AP-42 lists a range of formaldehyde emission factors when No. 6 fuel oil is consumed:
0.024 to 0.061 Ib formaldehyde generated/103 gal No. 6 fuel oil fired.
A facility operating a boiler using No. 6 fuel oil could use the above emission factor to determine the amount of
formaldehyde generated and subsequently released to1 the air. If 1,000,000 gallons of No. 6 fuel oil is u£ed
during a reporting year, the amount of formaldehyde generated would be between:
1 i %. f a s
(0.024 lb/10rgal) x (1,000,000 gal) and (0.061 lb/103 gal) x (1,000,000 gal) " " "'
= 24 and 61 Ib of rbrmaldehyde
> , ' * £ -., - ',"" f -<'.. "i
NOTE: No. 6 fuel oil contains other EPCRA Section 313 chemicals and chemical categories and EPCRA
Section 313 chemicals and chernica| categories may also be coincidentallymanuiactared during combustion. All
should be considered for EP^|RA Section J13 reporting.
4.1.4.4
Engineering Calculations (code O)
Engineering calculations are assumptions and/or judgements used to estimate
quantities of EPCRA Section 313 chemicals and chemical categories released or otherwise
managed as waste. The quantities are estimated by using physical and chemical properties and
relationships (e.g., Ideal Gas law, Raoult's law) or by modifying an emission factor to reflect the
chemical properties of the chemical in question. Engineering calculations rely on the process
parameters; you must have a thorough knowledge of your facility Operations to complete these
calculations.
Engineering calculations can also include computer models. Several computer
models are available for estimating emissions from landfills, storage tanks, wastewater treatment,
water treatment, and other processes.
Non-chemical-specific emission factors, Synthetic Organic Chemicals
Manufacturing Industry (SOCMT) emission factors, industry-determined emission factors for
processes or equipment, and site-specific emission factors also can be used, but must be
classified as "engineering calculations" for EPCRA Section 313 reporting.
4-23
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1
Example - Engineering Calculations
Stack monitoring data are available for xylene but you are required to report for toluene. Toluene is used in the
same application as xylene at your facility and the concentrations of the chemicals in the liquid feedstock are
approximately the same. Xylene and toluene are both used as wafer cleaning agents at a semiconductor
manufacturing facility. You can estimate the emissions of toluene by adjusting the monitoring data of xylene by
a ratio of the vapor pressure for xylene to toluene. This example is an engineering calculation based on physical
properties and process operation information:
From facility stack monitoring data, an estimated 200 Ib of xylene are released as air emissions during the
reporting year. Toluene is also present in the air emissions, but not monitored. The stack operates at
approximately 20°C. Based on literature data, the vapor pressures at 20°C for toluene is 22 millimeters of
mercury (mmHg) and for xylene is 6 mmHg. Using a ratio of the vapor pressures, the amount of toluene
released as air emissions from the stack can be calculated:
X Ib/yr toluene =
200 Ib/yr xylene
X Ib/yr toluene =
22 mmHg (vapor pressure of toluene)
6 mmHg (vapor pressure of xylene)
(200 Ib/yr xylene) x (22 mmHg toluene)
(6 mmHg xylene)
Completing me calculation, the facility determines that 730 Ib of toluene were released as stack air emissions
during the reporting year.
Estimating Release and Other Waste Management Quantities
4.1.4.5
Once all sources, types, and appropriate estimation methodologies have been
^i : :' '.J' , '.; :.. ; - ; ,. :, , ' |; ' ', .. i, '
identified, you can estimate the release and other waste management activity quantities for each
. .' ' :: "if "I , -. ': '. "' ' . ...','. . h"! I .
element of the Form R. The recommended approach is that you estimate amounts from all
sources at your facility to each type as identified by the elements of Form R. Table 4-3 presents
a work sheet that may be helpful in compiling this information.
If you prepare a Form R, you must also enter on-site treatment information in
Section 7A, including the code for each treatment method used, the destruction and removal
efficiency for the EPCRA Section 313 chemical or chemical category in the treated waste stream,
and the concentration of the EPCRA Section 313 chemical or chemical category in the influent to
n . j . I .,..'.,.
treatment. You should report treatment methods that do not actually destroy or remove the
": lit "V ' ; '.<'. I I.
chemical or chemical category by entering "zero (0)" for removal efficiency. Similarly, on-site
' ' f!» .;' .' ' ' - . ' J" ' ' 1 .,, , i
energy recovery methods and on-site recycling methods must be reported in Sections 7B and 1C,
respectively.
4-24
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Table 4-3
Release and Other
Waste Management Quantity Estimation Worksheet
Facility Name:
EPCRA Section 313 Chemical or Chemical Category:
CAS Registry Number:
Reporting Year: ,
Date Worksheet Prepared:
Prepared by:
ON SITE " " * * "'"'",. -s<-*~-,^. --" r-v^T
Release or Otber Waste Management Activity Type
Amount
0b)
Basis of
Estimate
Form R Element*
(1998 version)
FUGITIVE AIR
Equipment Leaks
Process Areas
Evaporative Losses, Spills, Surface Impoundments
Total =
5.1 and 8. lor 8.8
5.1 and 8. lor 8.8
5.1 and 8. lor 8.8
5.1 and 8.1 or 8.8
STACK AIR
Process Vents
Storage Tanks
Control Device Stacks
Other
Total =
5.2 and 8. lor 8.8
5.2 and 8.1 or 8.8
5.2 and 8.1 or 8.8
5.2 and 8. lor 8.8
5.2 and 8.1 or 8.8
RECEIVING STREAM/WATER BODY DISCHARGE
Stormwater Discharge
On-Site Treatment Plant Discharge
Total =
5.3 and 8.1 or 8.8
5.3 and 8.1 or 8.8
5.3 and 8. lor 8.8
ON-SITE UNDERGROUND INJECTION
Underground Injection to Class I Wells
Underground Injection to Class n - V Wells
Total =
5.4 and 8. lor 8.8
5.4 and 8. lor 8.8
5.4 and 8. lor 8.8
*Entries for Section 8.8 only if release is result of remedial action, catastrophic event, or one-time event not
associated with production process.
4-25
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'"IS! '"!! 'SPWIliP Illllll1 " Mi'fir 'l:1,"!1
Table 4-3 (Continued)
ON SITE
Release or Other Waste Management Activity Type
Amount
(Ib)
Basis of
Estimate
Form R Element*
1 (1998 version)
ON-SITELAND
RCRA Subtitle C Landfill
Other Landfill
Land Treatment/Application Fanning
Surface Impoundment
Other Disposal
Total =
ON-SITE ENERGY RECOVERY
Industrial Kiln
Industrial Furnace
Industrial Boiler
Other Energy Recovery Methods
Total =
ON-SITE RECYCLING
Solvents/Organics Recovery
Me.tals Recovery
Acid Regeneration
Other Reuse or Recovery
Total =
ON-SITE TREATMENT
Air Emissions Treatment
Biological Treatment
Chemical Treatment
Incineration/Thermal Treatment
Physical Treatment
Solidification/Stabilization
Total =
5.5 and 8.1 or 8.8
5.5 and 8.1 or 8.8
5.5 and 8.1, or 8.8
5.5 and 8.1 or 8.8
5.5 and 8. lor 8.8
5.5 and 8.1 or 8.8
8.2
8.2
8.2
8.2
8.2
8.4
8.4
8.4
8.4
8.4
8.6
8.6
8.6
8.6
8.6
8.6
8.6
;' ' ; ' i , ..';'' ,' ; ;. '
'""' ' " ;','''
*Entries for Section 8.8 only if release is result of remedial action, catastrophic event, or one-time event not
associated with, production process.
!:i '.;! , ;' ' 4-26 ' ' !
-------
Table 4-3 (Continued)
OFF SITE
Release or Other Waste Management
Activity Type
Amount
(lb)
Basis of
Estimate
Form R Element*
(1998 version)
Off-Site Location
(name)
OFF-SITE DISPOSAL
Solidification/Stabilization (metals and
metal compounds only)
Amount of metal and metal compounds to
POTW
Wastewater Treatment (excluding
POTWs) metals and metal compounds
only
Underground Injection
Landfill/Surface Impoundment
Land Treatment
Other Land Disposal
Other Off-Site Management
Total =
6.2 and 8.1 or 8.8
6.1 and 8.1 or 8.8
6.2 and 8.1 or 8.8
6.2 and 8.1 or 8.8
6.2 and 8. lor 8.8
6.2 and 8.1 or 8. 8
6.2 and 8.1 or 8.8
6.2 and 8. lor 8.8
6.2 and 8.1 or 8.8
OTHER AMOUNTS SENT OFF SITE
Amounts sent for storage
Amounts sent for unknown waste
management practice
Total =
6.2 and 8. lor 8.8
6.2 and 8. lor 8.8
6.2 and 8.1 or 8.8
OFF-SITE TREATMENT
Solidification/Stabilization
Incineration/Thermal Treatment
Incineration/Insignificant Fuel Value
Wastewater Treatment (to POTW
excluding metals and metal compounds)
Wastewater Treatment (excluding POTW
and metal and metal compounds)
Sent to Waste Treatment Broker
Total =
6.2 and 8.7 or 8.8
6.2 and 8.7 or 8.8
6.2 and 8.7 or 8.8
6.1 and 8.7 or 8.8
6.2 and 8.7 or 8.8
6.2 and 8.7 or 8.8
6.2 and 8.7 or 8.8
*Entries for Section 8.8 only if release is result of remedial action, catastrophic event, or one-time event not
associated with production process.
4-27
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I! i
Table 4-3 (Continued)
OFFSITE , ' ' ; : . "-- ." ' '
Release or Other Waste Management
Activity Type
Amount
(lb)
Basis of
Estimate
Form R Element*
(1998 version) ,
Off-Site Location
(name)
OFF-SITE ENERGY RECOVERY
Off-Site Energy Recovery
Sent to Energy Recovery Broker
Total =
OFF-SITE RECYCLING
Solvents/Organics Recovery
Metals Recovery
Other Reuse or Recovery
Acid Regeneration
Sent to Recycling Waste Broker
Total =
6.2 and 8.3 or 8.8
6.2 and 8.3 or 8.8
6.2 and 8.3 or 8.8
6.2 and 8.5 or 8.8
6.2 and 8.5 or 8.8
6.2 and 8.5 or 8.8
6.2 and 8.5 or 8.8
6.2 and 8.5 or 8.8
6.2 and 8.5 or 8.8
*Entries for Section 8.8 only if release is result of remedial action, catastrophic event, or one-time event not
associated with production process.
4-28
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4.2
Process Descriptions (Chemical Activities)
A semiconductor is a material that has an electrical conductivity between that of a
conductor and an insulator; its electrical characteristics can be manipulated to behave like either
depending on how it is processed. Silicon has traditionally been the substrate used to
manufacture semiconductors; recently other materials such as gallium arsenide (GaAs) and
indium phosphide (InP) have been used as a substrate material.
The semiconductor manufacturing process is continually evolving. The variety of
distinct processing steps involved results in a range of processes that may occur at a single plant.
Process designs are not uniform from plant to plant. An average semiconductor manufacturing
process consists of hundreds of process steps, of which a significant percentage may be potential
sources of EPCRA Section 313 chemicals. Many of the manufacturing steps are repeated several
times during the production process. For these reasons, this document will discuss general
manufacturing steps and does not attempt to describe a specific type of plant.
A clean environment is essential to the manufacture of semiconductors; thus
cleaning operations precede and follow many of the manufacturing process steps. Wet
processing, during which semiconductor devices are repeatedly immersed in or sprayed with
solutions is commonly used to minimize the risk of contamination. Wet processes are the
primary source of EPCRA Section 313 chemicals found in semiconductor manufacturing.
The primary component of a semiconductor is the semiconductor wafer, or chip.
The manufacture of a semiconductor chip involves six basic processes (see Figure 4-3):
1. Photolithography
2. Thin Films
3. Etching
4. Cleaning
5. Doping
6. Chemical Mechanical Planarization
4-29
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Chemical
Mechanical
Planarization
Figure 4-3. Overall Process Flow Diagram - Semiconductor Manufacturing
A single wafer may undergo one or more of these operations multiple times before processing is
complete.
4-30 !
-------
Through the use of these physical and chemical processes, hundreds of thousands
of miniature transistors are created on the wafer. The result is the formation of integrated circuits
on silicon wafers that, when cut into single "chips," can be packaged and marketed as separate
electronic components to be used in various applications.
The following sections discuss each of the processing steps identified above and
describe how to estimate release and other waste management activity quantities for each. It
should be noted that many of the chemicals used in semiconductor manufacturing are used in
more than one process, and some of the chemicals are used as a raw material as well as
coincidentally manufactured through the use of other chemicals. For example, hydrochloric acid
aerosols are used in wet etching processes and are also coincidentally manufactured in small
quantities during dry etching, where free chlorine from chlorinated organics may react with a
hydrogen carrier to produce hydrochloric acid aerosols. Also, regardless of which process a
chemical is used in, acid/base streams are commonly treated in an on-site wastewater treatment
plant and waste solvents are typically collected and sent off site for further waste management
activities (such as recycling or energy recovery).
4.2.1
Photolithography
Photolithography is used in semiconductor manufacturing to form surface patterns
on the wafer. These patterns will in turn allow various materials to be deposited on or removed
from selected, precise locations. In this process a viscous, solvent-based, light-sensitive
photoresist is applied to the wafer on a spin track. On the spin track a fixed amount of
photoresist is metered onto the wafer, which is then spun at high speed on a rotating element to
coat the wafer surface uniformly.
After a "soft bake" to remove most of the carrier solvent, a pattern is introduced
into the resist by exposing predefined areas of the wafer to light, lasers, electron beams, or by
other means. A template mask, which is a glass plate containing an image of the desired circuit
may be used to introduce the pattern. Depending on the photoresist system, a developer solution
is applied to dissolve some of the photoresist, yielding a stencil for further processing. Materials
4-31
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may be added or removed from the unmasked areas, giving a printed circuit.
photolithography steps required depends on the type of integrated circuit.
The number of
After the subsequent processing steps, residual photoresist is removed by using
wfet stripping (solvent or acid) or plasma gas stripping.
I fi , . ., ,
As is the case with most of the EPCRA Section 313 chemicals used in the
semiconductor manufacturing industry, photoresist solvents, strippers, and developers should be
considered as otherwise used and are subject to the 10,000 pound per year reporting threshold.
COMMON ERROR - Solvent Reporting
Spin tracks used to apply photoresist may use automatic cleaning where solvent, typically isopropyl alcohol,
acetone, or propylene glycol methyl ether acetate (PGMEA, CAS 108-65-6), is dispensed onto the spin track to
prevent photoresist buildup. In this instance none of these chemicals would be reportable under EPCRA Section
313 reporting guidelines. Isopropyl alcohol is reportable only if it is manufactured by the strong acid process,
acetone is not an EPCRA Section 313 chemical, and PGMEA does not fall into the "Certain Glycol Ethers"
category.
4.2.1.1
Step 1: Prepare Process Flow Diagram
. .
A site-specific process flow diagram should be prepared to help identify all
; ' ' '' ' i '
potential sources and types of chemical releases and waste management activities. A typical
flow diagram is presented in Figure 4-4. Please note that aqueous wastes and container residue
should be reported as off-site transfer (disposal, recycling, treatment, energy recovery) as
appropriate.
4-32
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Wafer In-
Stack Air
" Fugitive Air Developer Stack Air
t 1 t
Photoresist Photoresist Photoresist ... , n .
Application * Developer Stripping vraicr uul
1 '
Container Residue
i
1
Container Residue
POTW
' i
i '
POTW
4.2.1.2
Aqueous Organic Waste Aqueous Organic Waste
Figure 4-4. Process Flow Diagram for Typical Photolithography Process
Step 2: Identify Potential Sources of Chemical Release and Other Waste
Management Activities
The most common potential sources of EPCRA Section 313 chemicals from
photolithography are photoresist solvents, strippers, and developers. The primary release source
is tool exhaust from the photoresist applicators, developing, and stripping stations; spent solvent,
developer, and stripping solutions collected and sent either to a POTW or an off-site treatment,
disposal, or energy recovery facility; and container residue. Typical EPCRA Section 313
chemicals include N-methyl-2-pyrrolidone, xylenes, glycol ethers, methanol, hydrofluoric acid,
sulfuric acid aerosols, hydrochloric acid aerosols, emylbenzene, and methyl ethyl ketone.
4.2.1.3
Step 3: Identify Release and Other Waste Management Activity Types
Release and other waste management activity types include fugitive and point
source emissions to the air from wet chemical and solvent stations and control equipment
exhaust, and off-site transfers to POTWs and treatment facilities. Vapors from organic solvents
found in the photoresist and organic based (negative) photoresist strippers are typically sent to
on-site treatment unit, usually some type of concentrator (such as a carbon adsorber) followed by
thermal destruction. Typical release and other waste management activity types and typical
EPCRA Section 313 chemicals are:
an
4-33
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1 ' Sfl!
Type of Release and Other Waste
Management Activity
Stack Air
Fugitive Air
Off-Site Transfer From Container Residue
(off-site recycle, energy recovery,
treatment, or disposal)
POTW
Off-Site Transfer
On-Site Treatment
Typical EPCRA Section 313 Chemical
N-methyl-2-pyrrolidone, xylene, glycol ethers,
ethylbenzene, methanol, hydrofluoric acid, sulfuric acid
aerosols, hydrochloric acid aerosols, MEK
N-methyl-2-pyrrolidone, xylene, glycol ethers,
ethylbenzene, methanol, hydrofluoric acid, sulfuric acid
aerosols, hydrochloric acid aerosols, MEK
N-methyl-2-pyrrolidone, xylene, glycol ethers,
ethylbenzene, methanol, hydrofluoric acid, MEK
Glycol ethers, N-methyl-2-pyrrolidone, ethylbenzene,
methanol, hydrofluoric acid, MEK
N-methyl-2-pyrrolidone, Xylene, glycol ethers,
ethylbenzene, methanol, hydrofluoric acid, MEK
N-methyl-2-pyrrolidone, xylene, glycol ethers,
ethylbenzene, methanol, hydrofluoric acid, MEK
4.2.1.4 SteP4: Determine the Most Appropriate Method(s) to Calculate the
Estimates for Release and Other Waste Management Activity Quantities
, , , i
' :< ; i i . ' ' -'
A mass balance approach is usually the most accurate method for determining
release and other waste management activity quantities of EPCRA Section 313 chemicals
typically found in photoresist, developers, and strippers. To completely account for all the
different fates of the chemical in the mass balance equation, other information may be needed,
such as concentration of the chemical in liquid wastes sent off site for further waste management
activities.
'' " i
Wastewater volumes are normally metered or may be estimated based on make-up
.;;, , . .',.. i' : .
quantities required. Wastewater concentrations of EPCRA Section 313 chemicals may already
be monitored in compliance with discharge or pretreatment permit requirements. Flow and
t ,,. .,, i
concentration data can be used to determine the amount of the EPCRA Section 313 chemical
managed in this fashion.
- i
,1 I'M ' < ij
Quantities of EPCRA Section 313 chemicals in "empty" container residues
subject to waste management can be estimated using established residue factors based on the
4-34
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method of cleaning or draining of the container (see Table 4-1 and the corresponding container
residue example).
Example - Photolithography
Over the course of a year, a facility uses 17,000 pounds of glycol ethers as a photoresist solvent. Fumes from the
process are vented to a thermal oxidizer that has been measured as being 95% efficient in removing solvent
emissions from the exhaust stream. You must determine whether a, reporting threshold is exceeded and if so,
estimate the quantities released to the air, the POTW and sent for off site treatment.
Calculation Steps
1. Determine whether the glycol ethers that the facility uses fit the BPCRA 313 "Certain Glycol Ethers"
category.
After comparing the CAS numbers of the glycol ethers used at the facility, you have determined that 11,000
pounds of the total glycol ethers used are included in the EPCRA 313 "Certain Glycol Ethers" category.
The use of glycol ethers is not an incorporative activity so all 11,000 pounds fall into the "otherwise use"
threshold. Since the facility exceeded the "otherwise use" threshold of 10,000 pounds, all releases and other
waste management quantities (except those specifically exempted) of "Certain Glycol Ethers" must be reported
on the Form R.
2. Estimate releases to air, amount treated on-site, amount transferred off-site, and amount transferred to the
P,OTW.
The facility has testing data to show that approximately 20% of the glycol ethers used evaporate from the process
and are entrained in the airstream hoods going into the thermal oxidizer. Based on hazardous waste monitoring
data, it is known that 75% of the glycol ethers used are drained from the process lines into a waste solvent tank.
Waste from the solvent tank is transferred to an off site treatment site. "Hie remaining 5% is sent to a POTW.
Stack Air Releases = 11,000 x 0.2 (portion which evaporates) x 0.05 (to account for the control efficiency) =
110(lb/year)
This value should be reported in Section 5.2 of the Form R and included in the estimate for Section 8.1.
Amount treated on-site = 11,000 x 0.2 x 0.95 = 2,090 (Ib/year)
This value should be reported in Section 8.6 of the Form R and the appropriate control information entered in
Section 7A,
Off-site Transfer = 11,000 x 0.75 = 8250 pounds
This value should be reported in Section 6.2 of the Form R and included in the estimate for Section 8.7.
POTW releases = 11,000 x 0.05 = 550 pounds
This value should be reported in Section 6.1 of the Form R and included in the estimate for Section 8.7.
4-35
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: Bill1 Mil
4.2.2
Thin Films
In thin film deposition, layers of single crystal silicon, polysil
silicon dioxide, and other materials are deposited on the wafer to provide desirable
portions of the device or to serve as masks. Each of these films serves a specifi
device operation:
Single crystal silicon films (also called epitaxial silicon) serve as the substrate in
which the heart of transistors are constructed.
Amorphous silicon films (also called polysilicon) serve as
modern devices. These films are typically heavily doped to
conductive.
icon, silicon nitride,
properties on
c purpose in
gate
electrodes in most
make them very
Silicon nitride films serve as passivation layers that are used primarily as
protective layers after most device processing has occurred; they may also be used
as an etch stop in some cases.
Silicon dioxide films are deposited by using silicon and oxygen precursor
compounds or are oxidized using wet or dry oxidation processes, and are by far
the, most frequently deposited films. Silicon dioxide films act primarily as
dielectric layers, but may also act as masks for subsequent processing.
in .. i
i
, ll'i " . . ' - , i, . |l I , ' ' ", ' »' i, ''.'"
Deposition of these films is frequently performed in a chemical vapor deposition
(CVD) reactor or a high-temperature tube furnace using silicon-containing gases as reactants.
The deposition rate can be further enhanced by striking a plasma to overcome kinetic barriers.
Selected impurity compounds or dopants may be used in the deposition process to alter the
electrical characteristics of the deposited film or layer. Sometimes a chlorine source (chlorine
gas, hydrogen chloride gas, or 1,2-dichloroethylene) is used during oxidation to modify the oxide
characteristics.
Typical EPCRA Section 313 chemicals used in these deposition processes are
: ' ' . ' I
chlorine, anhydrous ammonia (gas) and 1,2-dichloroethylene.
To interconnect electrical devices on an integrated circuit and to provide for
n
external connections, metallic layers are deposited onto the wafer by evaporation, sputtering, or
CVD. Evaporation consists of vaporizing a metal under a vacuum at a very high temperature.
4-36
-------
Sputtering processes (also called physical vapor deposition or PVD) involve bombarding
metallic targets with a plasma gas, which displaces ions from the target and deposits them on the
wafer. CVD of metal is similar to the other deposition processes described above except that the
reactive gas is a metal-containing vapor. Devices may have a single layer or multiple layers of
metal.
Typical EPCRA Section 313 chemicals used in metallization processes are
arsenic, arsine, boron, trifiuoride, diborane, ammonia and compounds of aluminum and copper.
Thin films application is one process used in semiconductor manufacturing in
which EPCRA Section 313 chemicals are actually introduced and intentionally incorporated into
the final product. Therefore they are considered to be processed and are subject to the 25,000
pound per year reporting threshold.
4.2.2.1
Step 1: Prepare Process Flow Diagram
A site-specific process flow diagram should be prepared to help identify all
potential sources and types of chemical releases and waste management activities. A typical
flow diagram is presented in Figure 4-5.
4.2.2.2 Step 2: Identify Potential Sources of Chemical Release and Other Waste
Management Activities
Potential sources of EPCRA Section 313 chemicals from application of thin films
include: ammonia gas used as a nitrogen source in silicon nitride deposition, organics used as
chlorine sources, organics used to clean deposition furnaces, and metals deposited to interconnect
electrical devices. The primary point of release and other waste management quantities is the
thin film deposition tool (furnace or oxidation chamber). Exhaust from these tools is typically
routed to a scrubber which vents to the atmosphere and also result in wastewater generation.
4-37
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4.2.2.3
Step 3: Identify Release and Other Waste Management Activity Types
Common release and other waste management activity types from thin film
deposition processes include point source air, on-site treatment, and off-site disposal. Typical
; , !| I,,,!] , ' i ' '.''' ! J Ki:! ' ' , ""'" I |, ' ,
release and other waste management activity types and typical EPCRA Section 313 chemicals
'.''I ;': I ; i ' ; i , " . ";" ' ' I ' ' :
are: !l ' ' '' :' ' " ' '::' "' "' " '
Type of Release and Other Waste
Management Activity
Stack Air
Fugitive Air
POTW
Solid Waste Disposal
On-Site Treatment
Typical EPCRA Section 313 Chemical
Ammonia, 1,2-dichloroethylene
Ammonia, 1,2-dichloroethylene
Ammonia
Copper
1 ,2-dichloroethylene
ill
1 i
Wafer In-
Ammonia <3as
Exhaust Gas
Chlorine Source
_L
Thin Film
Deposition
T
* Wafer Out
Off-Site Transfer
POTW
Figure 4-5. Process Flow Diagram for Typical Thin Film
Process
4-38
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4.2.2.4 Step 4: Determine the Most Appropriate Method(s) to Calculate the
Estimates for Release and Other Waste Management Activity Quantities
Release and other waste management quantities of EPCRA Section 313 chemicals
used as phlorine sources (and a^so used as a cleaner for furnace interiors) may be calculated using
a mass balance approach or engineering calculations. Determining the amount of ammonia^
releases to the air usually requires some type of stack testing information used in conjunction
with purchase records and effluent monitoring data. It should be noted that ammonia gas is
anhydrous ammonia and 10|3% of the ammonia used in this form should be considered in both
threshold determinations and release calculations. Release and other waste management
quantities of metal-containing solid waste may be estimated using waste profiles (if available) or
purchase records.
Fvaniple - Thin Films
In addition to ammonia used in etching and cleaning, anyhydrous ammonia is also used at the facility in thin film
deposition to deposita layer of silicon nitride during wafer fabrication. Over the course of a year, 17,000 pounds
of ammonia is used in this process. Since ammonia is used in this application in an incorporative activity
(although not all of the nitrogen in the ammonia is actually incorporated), it is considered toward the processing
threshold of 25,000 pounds which is not exceeded for this application. However, as described above, ammonia
is also used as a cleaner, and the threshold is exceeded for feat activity. Therefore, you must also account for the
release and other waste management activities of ammonia from thin film deposition.
It is known that 20 percent of the total ammonia used ends up being deposited on thewafer, with the remainder
beingvented to an on-site treatment"system (scrubber) with a control efficiency of 90 percent.
Point source air emissipns ate then calculated as follows:
Point Source Air Emissions *= 17,000 (Ib/year) x 0.8 (amount not deposited on the wafer) x (1 - control"
efficiency) - " ' >
= 17,OOP Ob/year) x 0.8 x (1 - 0.9)
<= 1,360 (Ib/year).
This value should be reported in Section 5.2 of the Form R and included in the estimate for Section 8.1,
The amount sent to the POTW (effluent from the scrubber) is calculated as follows:
Release to POTW = 17,000 (Ib/year) x 0.8 (amount not deposited on the wafer) x (control efficiency) x 10
percent (adjustment for aqueous ammonia)
= 17,000 (Ib/year) x 0.8 x Ol9 x 0.1
-1,224 (Ib/year) ' - "
This value should be reported in Section 6.1 of the Worm R and included in the estimate for Section 8.7.
It should be noted that the amount sent to me POTW was adjusted to 10% of the total based on the reporting
requirements for aqueous ammonia. "
4-39
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4.2.3
Etching
Etching is used to chemically remove specific unwanted areas
of deposited film so that an underlying material may be exposed, or another material
deposited, in the etched material's place. Etching processes usually occur after
pattern has been applied, so that the etching is accomplished in specific areas.
of silicon substrate
maybe
a photoresist
Etching may be performed using either solutions of acids, bases, or oxidizers (wet
etching), or by using various gases (usually halogenated) in a plasma environment(dry etching).
In dry etching, halogenated gases are excited in a plasma so that they split apart forming reactive
halogen radicals. The halogen radical etches the surface of the wafer. Typical examples of
chemicals used in dry etching are chlorine and 1,1-dichloro-l-fluoroethane.
Dry etching provides a higher resolution than wet etching, generally produces less
undercutting of the wafer substrate, and is more likely to be used as circuit elements become
smaller. In either case, the fluoride ion or radical is almost always introduced if the substrate or
film to be etched contains silicon oxide or silicon nitride. Chloride species are used if only
silicon is to be etched.
Typical examples of chemicals used hi wet etching processes include chlorine,
ethylene glycol, hydrochloric acid aerosols, hydrogen fluoride, nitric acid, phosphoric acid, and
sulfuric acid aerosols.
COMMON ERROR - Acid Aerosol Renortinc
Both hydrochloric acid and sulrurie acid have qualifiers stating that only aerosol fonns of ihe chemicals are
subject to the EPCRA Section 313 reporting retirements, Etching and cleaaiag processes tot spray
hydrochloric and sulfuric acid cteate whatSPCHA Section 313 defines to be "aerosol" forms of these acids* ftt
this case, acid aerosols are both manufactured (subject to the 25,060 pound jper year reporting threshold) as weU
as otherwise used (subjeetto the 10,000 powod per year reportfegtfereshold). If you otherwise a$e these
chemicals or manufacture diem in etching or cleaning processes and exceed either threshold, you must prepare an
EPCRA Section 313 report. See Appendix C for gather guidance on this issue.
4-40
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COMMON ERROR - Nitric Acid and Nitrate Compound Reporting
Do not overlook the coincidental manufacture of nitrate compounds from on-site wastewater treatment of nitric
acid. In the etching process, nitric acid is typically collecte'd and sent to an on-site treatment plant, where it is
neutralized and discharged to a POTW. Nitrate compoundsare coincidentally manufactured during the
neutralizatipn of nitric acid and are subject to the 25,000 pounds per year manufacturing threshold. If the
threshold is exceeded, corresponding releases should be reported as a "Discharge to PQTW" k Section 6.1 (and
also in Section 8il) of the FormR, and not reported under Section 6.2 "Transfers to Other Off-Site Locations,"
Further information on nitric acid neutralization and associated nitrate; compound generation may be found in
Appendix D r List of Toxic Ciemieals Within the Water Dissociable titrate Compounds Category and Guidance
fpr-Reporting. . ..-/i-". ;.-'. \:~ .. . .....'' ' '.'.:, ,.-'.'' ' .-" '. :-' '': "'. '.''' ' ' . -^.'-'":-.
Stack Air
Etchant
Wafer In
I
Fugitive Air
i
Etching
Wafer Out
On-Site POTW
Treatment
Figure 4-6. Process Flow Diagram for Typical Etching
Process
4.2.3.1
Step 1: Prepare Process Flow Diagram
A site-specific process flow diagram should be prepared to help identify all
potential sources and types of chemical releases and waste management activities. A typical
flow diagram is presented in Figure 4-6.
4.2.3.2 Step 2: Identify Potential Sources of Chemical Release and Other Waste
Management Activities .
The most common potential source of EPCRA Section 313 chemicals from
etching is the etchant material itself, usually inorganic acids used in wet etching processes, and
4-41
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certain halogenated organic compounds used in dry etching processes. Acid vapors from the
etching tools are usually vented through a scrubber. In turn, spent scrubber water is usually
rputpd to an on-site treatment plant for neutralization prior to discharge to a receiving stream or
POTW.
4.2.3.3
Step 3: Identify Release and Other Waste Management Activity Types
Release and other waste management activity types include stack air, container
residue, fugitive air, and discharge to a POTW. Most acids used in etching processes should be
reported hi Section 7A and 8.6 for on-site treatment (see "On-Site Waste Treatment" example in
Section 4.1.3). Acids do not need to be reported as off-site transfers or releases if the effluent
from the on-site treatment plant has a pH between 6 and 9. They are considered to be completely
Si, 1; .' ' ' ..jiif: Jti , !'" vH'ii ''"' ;f* : i": . ',"'' ''. :'i'i' ' ; ;. f: :>'£ '/:. .:i*l8 i' .; * ''f'"" " . :. ;1'
ijfeutralized if they are within this pH range. However, release must be accounted for any time
V' '.' '." . Kl :,;i?iii . ' ':'!:' ' :';.' , .-S : , ': '', ' .: !. ' : ;" ' .V":, , ",' :|i . ' "",:' ,.
the effluent pH drops below 6. Also, the neutralization of nitric acid used in etching processes
\|ill result in thecoincidental manufacture of nitrate compounds, which in turn are sent to a
'f-1 !, . ".::n. ; , It ' " , *' '"' > < , . .:'"''. ; ,:!". ; ' " , -fli r . '. ' ' : :
POTW.
Typical release and other waste management activity types and typical EPCRA
Section 313 chemicals used in etching processes are:
Type of Release and Other Waste
Management Activity
Stack Air
Fugitive Air
POTW
On-site Treatment
Typical EPCRA Section 313 Chemical
Hydrochloric acid aerosols, sulfuric acid aerosols, nitric acid
Hydrochloric acid aerosols, sulfuric acid aerosols, nitric acid
Nitrate compounds
Hydrochloric acid aerosols, sulfuric acid aerosols, nitric acid
4.2.3.4 Step 4: Determine the Most Appropriate Method(s) to Calculate the
Estimates for Release and Other Waste Management Activity Quantities
Most of the'inorganic acids used in etching processes will end up in the on-site
wastewater tfeatnient plant and should be reported as "treated on site" if the effluent from the
"',i ' ..'.' "IB" 'I'll! ,;v i "iii ['",: ,;. . ,:;.:..,. ''j..i . ' ' T (-,,,,, if i.'y i, ,"., ft*1 (!',,'. ,|V, , ':!.,'-
plant has a pH between 6 and 9. Smaller amounts will be released from the acid scrubber stacks;
4-42
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stack test results are the best way to determine these quantities. Further information on
estimating releases of mineral acids can be found in the document "Estimating Releases for
Mineral Acid Discharges Using pH Measurements, U.S. Environmental Protection Agency, June
1991."
Example - Etching
Your facility uses 100,000 pounds per year of nitric acid as an etchant. It is sent to an on-site wastewater
treatment plant for neutralization prior to discharge to the local POTW. Nitrate coinpounds are formed as part of
the neutralization process. You are attempting to estimate the releases of nitrate compounds to the POTW. For
this example, assume all nitric acid is converted to nitrates during treatment and that the pH of the treatment plant
effluent never drops below 6.
The neutralization reaction occurring at the wastevyater treatment plant is:
Since the pH never drops below 6, the amount of nitric acid treated on site would equal 100,000 pounds.
Pounds of nitrates produced =: (Pounds of niMc acid sent to treatment) x
y mol NOj/ 1 mol HNOj) x
(1 rnblHNO3l63 lb) x (62 lb/ molNO3)
= (100,000 lb HNOsOx^lmolNOj/mol
HNO3) x (1 molHNO3/63 lb) x
(621bNQ3/mol)
= 98,413 pounds of Nitrate produced at treatment; and sent to the POTW
It should be noted that metal compounds (such as metal nitrates) may be formed during etching processes and
need to be considered in all threshold and release and other waste management activity quantities. _
4.2.4
Cleaning
Wafer cleaning is required to prepare them for each chemical and physical process
to ensure that contaminants on the wafer surfaces do not affect the final integrated circuit's
electrical performance. Before, and sometimes after, wafers are subjected to any specialized
manufacturing processes, they are typically immersed in, or sprayed with, various aqueous
and/or organic solutions. In some cases they are mechanically scrubbed to remove films,
residues, bacteria, or other particles. Fog chambers may also be used for wafer cleaning.
In addition to cleaning of the actual wafer, equipment is also cleaned using
inorganic acids and organic solvents. As discussed in Section 4.2.3, hydrochloric and sulfuric
4-43
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acids are only reportable if used in aerosol form. If these acids are used in wet benches or baths
(such as dip tanks), then they are not reportable.
4.2.4.1
Step 1: Prepare Process Flow Diagram
A site-specific process flow diagram should be prepared to help identify all
potential sources and types of EPCRA Section 313 chemical release and other waste
management activities. A typical flow diagram is presented hi Figure 4-7.
4.2.4.2 Step 2: Identify Potential Sources of Chemical Release and Other Waste
Management Activities
Typical sources of EPCRA Section 313 chemicals from cleaning operations
Would be cleaning station exhaust vents, waste solvents, and container residue (from "empty"
" !' . i!
containers of the cleaning solution).
Wafer In
Cleaner
(Solvents, Acids)
Stack Air
1
Fugitive Air
1
Cleaning
^
Off
Tra
r
-Site
nsfer
Wafer Out
On-Site container
Treatment Resjdue
Figure 4-7. Process Flow Diagram for Typical Wafer
Cleaning Process
4-44
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4.2.4.3
Step 3: Identify Release and Other Waste Management Activity Types
Release and other waste management activity types from this process include
stack and fugitive air emissions; off-site transfer of the spent cleaning solutions; wastewater
discharges (either direct or to aPOTW); and transfers of "empty" shipping containers to off-site
locations.
Typical release and other waste management activities and typical EPCRA
Section 313 chemicals are:
Type of Release and Other Waste
Management Activity
Stack Air
Fugitive Air
On-Site Treatment
Off-Site Transfer From Container
Residue (off-site recycle, energy
recovery, treatment, or disposal)
Typical EPCRA Section 313 Chemical
Hydrofluoric acid, xylene, methanol, toluene, hydrochloric
acid aerosols, sulfuric acid aerosols
Hydrofluoric acid, xylene, methanol, toluene, hydrochloric
acid aerosols, sulfuric acid aerosols
Nitric acid, hydrochloric acid aerosols, sulfuric acid aerosols
Xylene, methanol, toluene
4-45
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^^ iniiiniiiin^iiiiiinniird'iiivii .......... WI
^iii ...... ill'
-------
i - Cleaning
Your facility uses methanol as a cleaner in a wet bath that is operated 5 days a weekr 50 wetejcsjier year, for 8
hours each day. ' ' > ,
You can estimate methanol emissions using mass transfer kinetics and the following equation (from "Estimating
Releases and Waste Treatment Efficiencies for the Toxic Chemical Release and Inventory Form):
W_ =
Mw^ x K x A x P
R x T
where:
K
U
-..'V..' A
p
RVaP'X
T
Given the following data:
Mwx
U
A
T
R
vap,x
Evaporation rate of pollutant X (Ifc/sec)
Molecular weight of pollutant X (Ib/lb-mole)
Gas-phase mass transfer ^coefficient, (ft/sec)
0.00438 x U0-78 x (18/Mwx)w
Wind speed (miles/hr)
Surface area (ft2)
Vapor pressure of pollutant X (psia)
Ideal gas constant (10.73 psia x ft3/°R x lb-mole)
Temperature of bath (°R)
32 Ib methanol/lb-mole
1.7 miles/hr (default value)
1 ft2 (assumed surface area of your bath)
1.91 psia (pure vapor pressure of methanol)
533°R, °R = (9/5) x (°C + 273)
10.73 psia x fr/°R x lb-mole
*j L' j-_/ « -s
!* ~ , * ?,£ ^_
First, calculate the mass transfer coefficient, K:
Then, calculate Wx:
W.
0.00438 x U078 x (18/MwJ173
0.00547 (ft/sec)
Mw_ x K x A x p
R X
= (32 Ib/mole) x (0.00547 ft/sec) x (1 ft2) x (1.91 psia) * (10.73 psia ft3), -
(°Rx lb-mole)- (533 °R)
5.84 x 10-slb/sec
You can then calculate your annual emissions as follows:
Annual Methanol Emissions = Emissions (Ib/sec) x operating schedule
= (5.84 x 10^ Ib/seo) x
'
minute
f «L=fe) * fit]
^ hr ) { day j
yr
= 420 Ib/yr
4-47
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4.2 A A Step 4: Determine the Most Appropriate Method(s) to Calculate the
Estimates for Release and Other Waste Management Activity Quantities
iv " !'- 'II; ' " ;, : ?; . ':;: :; '"'['- . > -. -
Fugitive and point source air emissions of organic solvents from evaporative
i,' ',, ,'! : , i, ,| I",'I1! ,n ' '' i i. ' , LI! iiiijj ''i',, , '', :ii.i|" i, , '' » ''ll | : ,.,', * '.
losses can be estimated using mass balance and engineering calculations. Engineering
calculations can be used to estimate inorganic acid emissions, and may be used in conjunction
with a mass balance approach to estimate quantities treated on site. Because many of the
EPCRA Sectjon 313 chemicals are used in more than one process, many of the release and other
waste management estimation examples presented for other processes may also be applicable
here. ." ' ' " . ' -:
Quantities of EPCRA Section 313 chemicals in "empty" container residues
.." .. '' . I .
subject to waste management can be estimated using established residue factors based on the
ntethocl of cleaning or draining of the container (see Table 4-1 and the corresponding container
;,' ; , ,'" .:,. , ]
residue example).
4.2.5
Doping
Doping is a process in which specific atoms of impurities are introduced into the
silicon substrate to alter the electrical properties of the substrate by acting as charge carriers.
Their concentration and type dictate the electrical characteristics that define the transistor's, and
ultimately, the device's function. Doping is typically accomplished through ion implantation or
diffusion processes.
'"'. " !! : !:. . '" :: '
f
Ion implantation is the most common method used to introduce impurity atoms
! , «!»i , ! fi a. , . ' . ' ' - " " ,!s . - :: ;.. .:, , ' "M" |i . : ; i, '
in|Q the wafer. It provides a more controlled doping mechanism than diffusion. The dopant
111 ' ' i1 '
atoms are first ionized with a medium-to-high-current filament, then accelerated toward the
wafer surface with large magnetic and electrical fields. Precise control of the dopant ion
! r
momentum in this process allows for precise control of the penetration into the silicon substrate.
Because of the high kinetic energy of the ions during bombardment, damage to the substrate's
crystalline structure occurs. To restore the substrate's structure to a satisfactory level, slow
4-48
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heating or "annealing" of the amorphous material in various gaseous atmospheres is
subsequently performed.
Diffusion is a high-temperature process also used to introduce a controlled
amount of a dopant into the silicon substrate. The process occurs in a specially designed tube
furnace where dopants may be introduced in one of two primary ways: dopant gases may be
introduced into the furnace that will diffuse into the exposed areas of the substrate (gaseous
diffusion), or dopant atoms may diffuse into the substrate from a previously deposited dopant
oxide layer in the areas where the two are in contact (nongaseous diffusion). By knowing the
amount of dopant atoms and using a carefully controlled constant temperature, a predictable
solid-state diffusion may be achieved.
Typical EPCRA Section 313 chemicals used in doping processes are arsenic,
arsine, diborane, boron, boron trifluoride and compounds of antimony. As with thin film
deposition, doping is another process where EPCRA Section 313 chemicals are intentionally
introduced into the final product and are thus considered to be processed, and subject to the
25,000 pound per year processing threshold.
4.2.5.1
Step 1: Prepare Process Flow Diagram
A site-specific process flow diagram should be prepared to help identify all
potential sources and types of chemical release and other waste management activities. A typical
flow diagram is presented in Figure 4-8.
4-49
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Dopants
J_
Stack Air
t
Wafer In
Doping
> Wafer Out
POTW
Off-Site
Transfer
Figure 4-8. Process Flow Diagram for Typical Doping
Process
4.2.5.2 Step 2: Identify Potential Sources of Chemical Release and Other Waste
Management Activities
The most common potential source of EPCRA Section 313 chemicals from
doping are the dopants themselves, as well as certain organic compounds which may be used as
v , 7 ' ' ,,, , i , ,' 3, i I, i , ,, , , hl
furnace cleaning gases or chlorine sources. The physical release and other waste management
, ... .' ' .; '& v:J! :. ' !'h, "! : ' .; : '. '''M >. " , .,
activity points are tool and control device exhaust vents, spent cleaning solutions, and solid or
hazardous waste generated as part of the process.
4.2.5.3
Step 3: Identify Release and Other Waste Management Activity Types
Because relatively low quantities of dopant metals are used, they will not exceed
the reporting threshold frequently. However, in certain cases they will and would be expected to
', _ , ,'! ; " ,, ', ' ".:': j| . ' ,,,
be found in trace amounts in wastewater treatment plant effluent and solid waste shipped off site
;,i: ; fid S ; : . , , :( . i; . ; .; ' i
for further waste management activities. "Empty" containers or drums may also contain trace
I
amounts of metals or other dopants.
ii, ' ii
Organic chemicals may be emitted from furnace exhaust and may also be
., ., » i i. ij
collected and sent off site for further waste management activities.
4-50
-------
"Typ* of Release and Other Waste
',.;.,.;' Management Activity .r 'v: ;;;.-;:'
Stack Air
Off-Site Transfer
POTW
; Ty^al iPCRA Section 313 Chemical
1 ,2-dichloroethylene
Arsenic, antimony
Trace amounts of metals
4.2.5.4 Step 4: Determine the Most Appropriate Method(s) to Calculate the
Estimates for Release and Other Waste Management Activity Quantities
Release and other waste management quantities of organic compounds used as
chlorine sources (also used to clean furnace interiors) may be calculated using a material balance
approach or engineering calculations.
Wastewater volumes are normally metered or may be estimated based on make-up
quantities required. Wastewater concentrations of EPCRA Section 313 chemicals may already
be monitored in compliance with discharge or pretreatment permit requirements. Flow and
concentration data can be used to determine the amount of the EPCRA Section 313 chemical
managed in this fashion.
Example - Doping
Your facility uses arsenic as a dopant in a diffusion furnace. After fee process has been completed, the interior
of the furnace is cleaned using an inorganic acid solution and the contaminated wastewater is sent to the on-site
treatment plant. You are trying to calculate releases of arsenic to the local POTW. The following data are
provided:
Arsenic concentration = 0.005 mg/liter ,
Daily average flowrate = 4Q,o6p,000 liters/day
Operating schedule = 260 days/year . '.',, ;
Annual releases of arsenic = (arsenic concentration in wastewater) x (Daily volume of wastewater) x
(days/year) '-...'-.-,.. -..,'' ' .' :':. . .
= (0.005 mg/liter) -x (40,000,000 liters/day) x (1 lb/454,000 mg) x (260 days/yr)
; = 114(lb/year) : : ; _^
4.2.6
Chemical Mechanical Planarization
Chemical mechanical planarization (CMP) is used in semiconductor
manufacturing to remove the top layer of material from the wafer in a controlled manner, leaving
4-51
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a smooth and flat §urface for further processing. This technology is applied in two ways. The
first is to rempve selectively the top part of a nonconducting layer or film to reduce the
:,::, ' , :i;! :-;ii ' i ,: ' , - , ! . :- r : ,
topography on the wafer (also called planarization). The end result is an increase in the process
margin for both deposition and photolithography. The second type of CMP is removal of excess
];
material from the surface of conducting layers (metals). After a blanket pattern, conducting
material is deposited on the underlayer, and the wafer is polished down to the patterned
underlayer. The result is a smooth, flat surface that has conducting material left in the patterned
crevices.
4.2.6.1
Step 1: Prepare Process Flow Diagram
A site-specific process flow diagram should be prepared to
, ":,'',:ii':il!" ' '!,'" "'' , ' ! ' ' ' ''' , ! ,'",'" in
potential sources and types of chemical release and other waste management
flow diagram is presented hi Figure 4-9.
Ferric Nitrate
help identify all
activities. Atypical
1
Wafer In
CMP
-> Wafer Out
4.2,6.2
POTW
(Nitrates)
Figure 4-9. Process Flow Diagram for Typical
Chemical Mechanical Planarization (CMP) Process
Step 2: Identify Potential Sources of Chemical Release and Other Waste
Management Activities
The only notable source of EPCRA Section 313 chemicals from CMP is the
\ : : . , . .. i '
planarization process that typically contains ferric nitrate (Fe(NO3)3). In the CMP process, this
nitrate compound is considered "otherwise used" and is subject to the 10,000 Ib/yr reporting
4-52
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threshold. The primary point of release is the spent slurry containing nitrates, which is typically
sent off-site to a POTW.
4.2.6.3
Step 3: Identify Release and Other Waste Management Activity Types
As mentioned above, discharge to a POTW is the release type expected from
CMP operations. Typical release types and typical EPCRA Section 313 chemicals are:
Type of Release and Other Waste
Management Activity
POTW
Typical EPCRA Section 313 Chemical |
Nitrate compounds, copper |
4.2.6.4 Step 4: Determine the Most Appropriate Method(s) to Calculate the
Estimates for Release and Other Waste Management Activity Quantities
All atypical sources and types should be considered; however, if nitrate
compounds from the use of ferric nitrate are the Only EPCRA Section 313 chemical, the release
calculation is relatively straightforward. If the amount of ferric nitrate used over the course of a
year is known, releases of nitrates to the POTW may be calculated as shown in the following
Example.
', Example - (Chemical Mechanical Planarization
Your facility uses 8,000 pounds per year of ferric nitrate in CMP operations. The spent slurry from these
operations is sent to the local POTW. The reporting threshold for nitrate compounds has already been exceeded
(from other operations at your facility) and you must calculate the transfer of nitrate compounds to the POTW
from this operation.
Transfer to POTW" = (amount of ferric nitrate used)" x (moles of nitrate/mole of ferric nitrate) *
(ratio of the molecular weights of nitrate to ferric nitrate)
-, i ,7-, *^i 8,000 Ib FeCNO3)3 x (3 moles nitrate/mol ferric nitrate) x (62/242)
, , , j-t #. 6,149 IbNO/yr
Further information on estimating releases of nitrate compounds may be found in Appendix E.
4-53
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!" f
it:
-------
Appendix A
TRI GUIDANCE RESOURCES
-------
-------
A.1
Appendix A
TRI GUIDANCE RESOURCES
EPCRA Section 313 RELATED REFERENCES
40 CFR 372, Toxic Chemical Release Reporting; Community Right-to-Know; Final Rule
See 53 FR 4500, February 16, 1988.
Toxic Chemical Release Inventory Reporting Forms and Instructions for the Current Reporting
Year - See also Automated Toxic Chemical Release Inventory Reporting Software (ATRS) under
Section A.2, Internet Sites.
U.S. EPA publishes this document each year to provide current guidance for preparing the Form
R and Form A reports. This document contains the most up-to-date list of chemicals for which
reports are required. It includes a blank Form R and Form A and provides step-by-step
instructions for completing each report. It also has a list of U.S. EPA regional and state contacts
for EPCRA Section 313 reporting. The current version of this document should always be
consulted in preparing the EPCRA Section 313 report.
Common Synonyms for Chemicals Listed Under EPCRA Section 313 of the Emergency
Planning and Community Right-to-Know Act (EPA 745-R-95-008)
This glossary contains chemical names and their synonyms for substances covered by the
reporting requirements of EPCRA Section 313. The glossary was developed to aid in
determining whether a facility manufactures, processes, or uses a chemical subject to EPCRA
Section 313 reporting.
Consolidated List of Chemicals Subject to the Emergency Planning and Community Right-to-
Know Act (EPCRA) and Section 112(r) of the Clean Air Act (as amended^ (EPA 740-R-95-001)
List of chemicals covered by EPCRA Sections 302 and 313, CERCLA Hazardous Substances,
and CAA 112(r). The list contains the chemical name, CAS Registry Number, and reporting
requirement(s) to which the chemical is subject.
The Emergency Planning and Community Right-to-Know Act: EPCRA Section 313 Release
Reporting Requirements, August, 1995 (EPA 745/K-95-052)
This brochure alerts businesses to their reporting obligations under EPCRA Section 313 and
assists in determining whether their facility is required to report. The brochure contains U.S.
EPA Regional contacts, the list of EPCRA Section 313 toxic chemicals and a description of the
Standard Industrial Classification (SIC) codes subject to EPCRA Section 313.
EPCRA Section 313 Questions and Answers: 199R Version. (EPA 745-B-98-004).
Executive Order 12856 - Federal Compliance with Right-to-Know Laws and Pollution
Prevention Requirements: Questions and Answers (EPA 745-R-95-011)
This document assists federal facilities in complying with Executive Order 12856. This
information has been compiled by U.S. EPA from questions received from federal facilities. This
document is intended for the exclusive use of federal facilities in complying with Sections 302,
A-l
-------
1 ill ' ' I ' , . . , , "'. !,,!'.
303, 304, 311, 312, and 313 of the Emergency Planning and Community Right-to-Know Act
(EPCRA) of 1986 and the Pollution Prevention Act of 1990, as directed by the Executive Order.
Supplier Notification Requirements (EPA 560/4-91-006)
This pamphlet assists chemical suppliers who may be subject to the supplier notification
requirements under EPCRA Section 313. The pamphlet explains the supplier notification
requirements, gives examples of situations which require notification, describes the trade secret
provision, and contains a sample notification.
Toxic Chemical Release Inventory - Data Quality Checks to Prevent Common Reporting F.rrnrs
on Form K/FnrmA (EPA 745-R-98-012)
This is a compilation of Notices of Data Change, Significant Error, Noncompliance, or Technical
Ejror. It provides a listing of common errors found on the Form R reports submitted to U.S.
EPA. It also provides a discussion of the types of errors which result in each of the above
Notices as well as a list of Notice of Technical Error codes and descriptions.
;: <:,: '.- /'; ; v.ji" ",
Trade Secrets Rule and Form
See 53 FR 28772,July 29, 1988. This rule implements the trade secrets provision of the EPCRA
(Section 322) and includes a copy of the trade secret substantiation form.
A.2
INFORMATION SOURCES
Most of the materials included as reference in this manual are available from the following
sources:
i, " " ' . V ' . " 1 .'
National Center for Environmental Publications and Information (NCEPI)
P.O. Box 42419
Cincinnati, OH 45242-2419
(800)490-9198
.,:, Fax: (513)489-8695 ' ' ' ^ " ' '"
Internet: hjtp://www. epa.gov/ncepihom/index. html
X & "J! '', ' : ' ' ;; . ;' jj '; ,
Emergency Planning and Community Right-to-Know (EPCRA) Information Hotline
U.S. Environmental Protection Agency
(800) 424-9346 or (703) 412-9810 (for the Washington, D.C. metropolitan area)
TDD: (860)553-7672
Internet Sites
TRI homepage: http://www.epa.gov/opptintr/tri
This site contains information on the Toxic Release inventory and provides links
to a variety of data and documents related to the TRI program.
Automated Toxic Chemical Release Inventory Reporting Software (ATRS):
^ttp://www.epa.gov/opptintr/atrs
Trus site provides access to the automated EPCRA Section 313 reporting forms
for electronic submittal of required data to U.S. EPA.
A-2
-------
Air CHIEF CD-ROM
http://www. epa.gov/ttn/chief/airchief.html
This site provides information on the Air CHIEF CD-ROM, contents, ordering
information, system requirements, and sources for additional information.
Clearinghouse for Inventories and Emission Factors (CHIEF):
http://www.epa.gov/ttn/chief/
This site provides access to the latest information and tools for estimating
emissions of air pollutants and performing emission inventories.
Code of Federal Regulations, 40 CFR: http://www.epa.gov/epacfr40
This site was created by U.S. EPA to expand access to Title 40 - Environmental
Protections of the Code of Federal Regulations.
Compilation of Air Pollutant Emission Factors (AP-42):
http://www.epa.gov/ttn/chief/ap42etc.html
This site provides access to files containing guidance for estimating emissions
from specific sources and emission factors.
Federal Register Notice: http://www.epa.gov/EPA-TRI
This site provides access to all Federal Register notices related to the TRI
program from 1994 to current.
Material Safety Data Sheets (MSDSs):
http://msds.pdc.cornell.edu/issearch/msdssrch.htm
A key word searchable database of 325,000 MSDSs.
TANKS: http://www.epa.gov/ttn/chief/tanks.html
This site contains information on TANKS, a DOS-based computer software
program that computes estimates of VOC emissions from fixed and floating-roof
storage tanks.
WATER8/CHEMDATS: http://www. epa.gov/ttn/chief/software. html#water8
WATERS is an analytical model for estimating compound-specific air emissions
from wastewater collection and treatment systems. CHEMDAT8 is a Lotus 1-2-3
spreadsheet for estimating VOC emissions from TSDF processes.
A-3
-------
National Technicaj Information Service (NTTS)
Ll,S. Department of Commerce
5285 Port Royal Road
Springfield, VA 22161
Call: (800) 553-6847; (703) 487-4650
Fax: (703) 321-85^7
Publication Number PB97-502-587
E-mail: info@ntis.fechvorld.gov
A.3
INDUSTRY-SPECIFIC TECHNTCAT GUTDANrF DQCTJMF1VTS
In 1988 and 1990, U.S. EPA developed a group of individual guidance documents for industries
oi: activities in industries who primarily manufacture, process, or otherwise use EPCRA
Sect!on 313 cliemi9als- See list of industries/activities below. U.S, EPA is currently revising
some of these documents and preparing additional documents. The newer versions will be
available beginning in the Fall of 1998.
Chemical Distribution Facilities, January 1999 (EPA 745-B-99-005)
Coal Mining
.ilitm^ January 1999 (EPA 745-B-99-002)
iii '
B>4 i ' . 'II
Coincidental Manufacture/By-products
Electricity Generating Facilities, January 1999 (EPA 745-B-99-003)
Estimating Releases and Waste Treatment Efficiencies
Food Processors, September 1998 (EPA 745-R-98-011)
1,' ' ",; ' ' !' .
Formulation of Aqueous Solutions, March 1988 (EPA 560-4-88-004F)
Foundry Operations
;<:,, .(i , ' ' ' : . : , ; . i:.
Leather Tanning and Finishing Industry
',' , . * . . , . / i!
Metal Mining Facilities, January 1999 (EPA 745-B-99-001)
1' : ,:! I!
Metal Fabrication and Electroplating Operations
' i
Monofilament Fiber Manufacture
Paper and Paperhoard Production
Petroleum Terminals and Bulk Storage Facilities, January 1999 (EPA 745-B-99-006)
Presswood & Laminated Wood Products Manufacturing
A-4
-------
Printing Industry
KCR A Subtitle C TSD Facilities and Solvent Recovery Facilities. January 1999 (EPA 745-B-99-
004)
Roller, Knife, and Graviire Coating Operations
Rubber and Plastics Manufacturing
Semiconductor Manufacture
Smelting Operations
Spray Application and Klectrodeposition of Organic Coatings. December 1998 (EPA 745-B-99-
014)
Textile Processing Industry
Welding Operations
Wood Preserving Operations
U.S. EPA, Office of Compliance, published a series of documents in 1995 called Sector
Notebooks. These documents provide information of general interest regarding environmental
issues associated with specific industrial sectors. The Document Control Numbers (DCN) range
from EPA/310-R-95-001 through EPA/310-R-95-018.
A.4
CTTFMTCAT -SPFCTFTC OUTDANCE DOCUMENTS
U.S. EPA has also developed a group of guidance documents specific to individual chemicals
and chemical categories. These are presented below.
Emergency Planning and Community RigVit-to-Know RPCRA Section 313: Guidance for
Reporting Aqnenns Ammonia. July 1995 (EPA 745-R-95-012)
Emergency Planning and Community Rigbt-to-Know EPCRA Section 313: List of Toxic
Chemicals within the Chlornphennk Category. November 1995 (EPA 745-B-95-004)
Estimating Releases for Mineral Acid Discharges Using pH Measurements, U.S. Environmental
Protecti on Agency. June 1991.
Guidance for Reporting Siilfnric Add (acid aerosols including mists, vapors, gas, fop, and Other
airborne form* nf any particle size! November 1997 (EPA-745-R-97-007)
Toxic Release Inventory T.ist of Tmdr. Chemicals within the Glycol Ethers Category and
CTniHar.r.p. for Reporting. May 1995 (EPA 745-R-95-006)
A-5
-------
ll
Toxic Release Inventory List of Toxic Chemicals within the Nicotine and Salts Category and
Guidance for Reporting, February 1995 (EPA 745-R-95-004)
TOXIC Release Inventory List of Toxic Chemicals within the Polychlorinated Alkanes Category
arid Guidance for Reporting, February 1995 (EPA 745-R-95-001)
TOXJC Release Inventory List of Toxic of Chemicals within the Polycyclic Aromatic Compound?
Category. February 1995 (EPA 745-R-95-003)
TOXIC Release Inventory List of Toxic Chemicals within the Strychnine and Salts Category and
Guidance for Reporting, February 1995 (EPA 745-R-95-005)
iiiH ' .; j.:;v ".'Jit ii'Sit : ' r' ''}' .: ' . :'': - . , ,;!''-, ,. " ..: >&'' , ' ': 'j .'.' ;,:
Toxic Release Tnventorv List of Toxic of Chemicals within the Water Dissociable Nitrate
Compounds Category and Guidance for Reporting, May, 1996 (EPA 745-R-96-004)
i
Toxics Release Tnventorv - List of Toxic Chemicals Within Ethylenehisdithiocarbamic Acid
y, November 1994, EPA 745-B-94-003.
Toxics Release Tnventorv - Copper Phthalocyanine Compounds Excluded for the Reporting
'
entS 'Under the Copper Compounds Category on the EPCRA Section 313 List, April
1995, EM 745-R-95-007.
Toxics Release Tnventorv - List of Toxic Chemicals Within Warfarin Category. November 1994,
EPA 745-B-94-004.
A.5
OTHER USEFUL REFERENCES
Burgess, W.A. Recognition of Health Hazards in Industry. Harvard School of Public Health.
Boston, Massachusetts, John-Wiley & Sons.
ii
CRC Handbook of Chemistry and Physics. Latest Edition, Robert C. Weast, Editor, CRC Press,
Inp., Florida.
':, ' . ....' ;;1 ";= . . ..".' ' ' .''' .;... ' ! : .".", :.
Kirk Othmer - Encyclopedia of Chemical Technology Latest Edition, John Wiley & Sons, New
York.
Locating and Estimating Air Emissions from Various Sources. Available from: National
Teijinical Infonnalpn Services (NTIS), (703) 487-4650.
f !' -' 'I'fsl'... - , ti^ , -! '! . :' i;'" ., ': !;- .: ! :* , .'
The Merck Index. Latest Edition, Merck & Co., Inc., New Jersey.
I.'1:'" .' ' ' : I:.I'», : . '!.i!!i! ' ' . , ''.*'.
Perry, R.H. and C.H. Chilton, Chemical Engineer's Handbook. Latest Edition^ McGraw-Hill
Book Company, New York.
Sax,.N.I. andRJ. Lewis, Sr., Hawley's Condensed Chemical Dictionary Latest Edition, Van
Nostrand Reinhold Company, New York.
A-6
-------
Appendix B
BASIC CALCULATION TECHNIQUES
-------
-------
Appendix B
BASIC CALCULATION TECHNIQUES
This section will provide the basic techniques needed to use specific types of data or engineering
calculations. Examples are provided for:
(1) Stack monitoring data;
(2) Industrial hygiene data;
(3) Raoult's Law;
(4) Air emission factors;
(5) RCRA hazardous waste analysis data;
(6) NPDES monitoring data.
(1) Stack Monitoring Data
The following is an example of a release calculation using monitoring data.
Example: Stack monitoring data are available for a paint booth. The measured
average concentration of toluene is 0.1 ppmv (dry gas basis). The moisture
content in the stack is typically 10%, and stack conditions are maintained at 80°C
and atmospheric pressure. The stack gas velocity is 8 m/s. The diameter of the
stack is 0.3 m. Calculate the point air release of toluene.
Step 1. Calculate volumetric flow of stack gas stream.
Volumetric flow = (gas velocity) * [(TC) x (internal stack diameter)2/4)]
Volumetric flow = (8.0 m/s) x [(TL) x (0.3 m)2/4] = 0.6 m3/s
Step 2. Correct for moisture content in stack gas stream.
Stack exhausts may contain large amounts of water vapor. The concentration of
the chemical in the exhaust is often presented on a dry basis. For an accurate
release rate, correct the vent gas flow rate for the moisture content by multiplying
by the term (1 - fraction water vapor). The dry gas rate can then by multiplied by
the chemical concentration.
(Note: If the toluene concentration is on a wet gas basis, no correction is
necessary for moisture content.)
B-l
-------
Dry volumetric flow = (Volumetric flow) x (1-fraction water vapor)
*l.
Dry volumetric flow = (0.6 m3/s) x (1-0.10) = 0.5 m3/s
Step 3. Convert ppmv to mg/m3.
l! '
ppmv is defined as one part of a chemical in 106 parts of gas (1.0 mVlO6
"
Use the molar volume of a gas, corrected for stack temperature and
pressure conditions, calculated by the ideal gas law (P V = nRT). Note that
the molar volume of an ideal gas at 237 K and 1 arm is 22.4 L/mole.
"' ';:!!' " ' ' " , , ' ''! ,;: ii ' , '
, ,, , , , ji
Molecular weight of toluene (MW) = 92. 14 g/mole.
i
JR. = the Ideal Gas Constant (0.082057 L - ami per mole-Kelvin)
To calculate the molar volume of stack gas, use the ideal gas equation.
V RT
Molar volume = =
n P
For the example, the stack conditions are 80° C (353 K) and atmospheric pressure
(1 atm).
Molar volume = 0.082057 L~atm x (353 KV(latm)
( mole-iCj '
= 29.0 L/mole
The conversion of ppmv to mg/m3 can now be calculated.
nag l i
2- = (concentration of chemical, ppmv) x 1
m ) \ molar volume of gas
x (MW)
F '!'!.
IK f"'
B-2
-------
Using the example, the concentration of toluene is calculated as follows:
°-lm3 x mole x 92-14 » I x
106m3 I 29.0 L) ( mole )
1,000 mg| _
I g J
Step 4. Calculate air releases.
Air releases are calculated as follows:
Air Release=(volumetric flow, mVs) x (concentration, mg/m3) x (operating time, s/yr)
The paint booth is used 8 hours per day, 5 days per week, 52 weeks per year.
Operating time = 8
hr , . _
x 5
day / I week
= 2,080 hr/yr
Air Release = (0.5 m3/s) x (0.3 mg/m3) x
3,600 s
hr
2.080 hr
Ib
454 g
g
1,000 mg
= 2.5 Ib/yr of toluene
It is important to note that this calculation assumes the measured emissions are
representative of actual emissions at all times; however, this is not always the case. Ideally, a
continuous emissions monitor provides the most representative data.
Also note that monitoring and stack data may have units that are different than
those used in the example. Modify conversion factors and constants to reflect your data when
calculating air releases.
(2)
Industrial Hygiene Data
The following is an example of a release calculation using industrial hygiene data.
Example: Occupational industrial hygiene data shows that workers are exposed
to an average of 0.1 ppmv benzene (wet gas basis). The density of benzene vapor
is 0.2 lb/ft3. The ventilation system exhausts 20,000 acfm of room air at 70°F.
The plant operates 24 hours per day, 330 days per year.
The benzene concentration is on a wet gas basis, therefore a moisture correction
of the ventilation flow rate is not necessary. The industrial hygiene data is
collected at the same ambient conditions as the ventilation system, therefore no
B-3
-------
f"
> ,1!
adjustment for temperature or pressure needs to be performed. A conservative
estimation of benzene fugitive releases could be calculated as follows:
Air Release =
(ventilation flow rate, ftVmin) x (operating time, min/yr) x
(concentration of chemical, ppmv) x (vapor density of chemical, Ib/ft3)
Benzene releases per year would be calculated as follows:
min
20,000 ft3 f 60 min) f 24
-^ I X I ~ \ X
24 hr] x (
day J (
I.
330 day
0.1 ft3 benzene I 0.2 Ib
(3)
day
= 190 Ib/yr of benzene
106 ft3 air }
ft3
Raoult's Law
" . ! i! ' ' ' ' i
The following is an example of a release calculation using Raoult's Law. Raoult's
Law states th^t th^ partial pressure of a compound in the vapor phase over a solution may be
estimated by multiplying its mole fraction in the liquid solution by the vapor pressure of the pure
chemical.
P ~
where:
po
XA.L
XA.G
PA
PT
Vapor pressure of pure liquid chemical A;
Mole fraction of chemical A in solution;
Mole fraction of chemical A in the gas phase;
Partial pressure of chemical A in the gas phase; and
Total pressure.
n
I
Example: A wash tank holds a solution containing 10% by weight of
o-xylene (A) and 90% by weight of toluene (B). The tank is vented to the atmosphere; the
process vent flow rate is estimated as 100 acfhi (2.83m3/min) based on a minimum fresh air
ventilation rate. The molecular weight of o-xylene is 106.17 g/mole and toluene is 92.14 g/mole.
The vapor pressure of o-xylene is 10 mm of Hg (0.19 psia). The total pressure of the system is
14.7 psia (atmospheric conditions). The process tank is in service 250 days/yr. Calculate the air
release of o-xylene,
ii ."" ' " j ,
Step 1: Calculate the mole fraction of o-xylene in the liquid solution.
B-4
-------
X
wt fraction A
MWA
A,L
wt fraction A wt fraction B
MW,
MWT
Where:
XA,L "'"'" =
MW
wt fraction =
. Mole, fraction of chemical A in liquid solution;
Molecular weight of chemical, g/mole; and
Weight fraction of chemical in material.
A,L
0.1
106.17
0.1
0.9
106.17 92.14
where:
X = 0.09
..Step.2: Calculate the mole fraction of o-xylene in the gas phase.
V
AA,G.
XA,LP°
PT
po
PT
Mole fraction of chemical A in gas phase;
Mole fraction of chemical A in liquid solution;
Vapor pressure of pure liquid chemical A, psia; and
Total pressure of system, psia.
X
A,G
o.!9 psia
14.7 psia
= 0.001
Step 3: Calculate releases using Raoult's Law.
B-5
-------
Emissions = (XAG) x (APR) x (t) x (MW
w*(7^1
where:
Emissions =
AFR
;t , ==
MW
MV
Air release of pollutant A, g-A/yr;
Mole fraction of chemical A in gas phase;
Air flow rate of room, m^min;
Operating time of wash tank, min/yr;
Molecular weight of chemical, g/g-mo|e; and
Gas molar volume (22.4 L/mple at standard temperature
and pressure).
If conditions vary from standard temperature and pressure the gas molar volume
' .j, , '"ll nJ'i'd'N' ' ..... « ........ * !i ji ' I' i*. * ii»n* , u, ..... . -, ' " 'li "" * * J|i , ., ..... %, i ...IP* n. n. r 'f\ ........ JFH' ;'7">W ^* in '* ..... »*. up nl -1" . II"' TTi ..... ,'( *' . j t- I, t
can be calculated u^ing the ideal gas law and tank conditions as presented in
''Example 1. " ' ..... ............ ............... ""
Emissions = (0.001) x
[ 2.83m3 J 250 day ] J 24 hr^ J 60 min^f mole } ( 106.17gX
i x x x x x .
mm J V vr ) \ day ) I hr ) I 22.4L/ I mole .
10-3m3,
= 4.8xiQ6g/yr
The emission of o-xylene is calculated as shown below.
* ' . .
Emissions = (4.8 x ].o6 g/yr) x
Ib
454
= 10,570 Ib/yr pf o-xylene
(4)
Air releases for toluene can be calculated in a similar manner,
Air Emission Factor
The following is an example of a release calculation using air emission factors.
Example: An industrial boiler uses 300 gallons per hour of No. 2 fuel oil. The
boiler operates 2,000 hours per year. Calculate emissions of formaldehyde using
the AP-42 emission factors.
AE = (EF) x (AU) x (QT)
B-6
-------
where:
AE
EF
AU
OT
Annual emissions of pollutant, Ib/yr
Emission factor of pollutant, lb/103 gallon of fuel. EF for
formaldehyde for an industrial boiler burning No. 2 fuel'oil is
0.035 to 0.061 lb/103 gallons.
Quantity of fuel used, gal/yr.
Operating time, hr/yr.
Using an emission factor of 0.061 pounds of formaldehyde per gallon of fuel, the
air releases are calculated as follows:
AE =
0.061 Ib
-
103 gal
f 300 gal | v f 2,000 hr ] ,,,
- - = 36-6
, . . . .
formaldehyde
(5)
RCRA Waste Analysis
The following is an example of a calculation using RCRA waste analysis data.
Example: Spent paint wastes were disposed at an off-site waste treatment
facility. The quantity of paint waste shipped was five 55-gallon drums per year.
Analysis of the waste showed 5% cadmium by weight. Estimating the density of
the paint waste to be 9.5 Ib/gallon, the amount of cadmium to pff-site disposal is
calculated as follows:
Amount of cadmium:
(amount of paint waste disposed, gal/yr) x (concentration of cadmium, Ib/lb) x
(density of paint waste, Ib/gal)
\ /
5 drums 1 I 55 gal
yr /
drum
9.5 Ib
gal ,
51b Cd
lOOlb waste.
= 131 Ib/yr of cadmium
(6)
NPDES Data
The following is an example of a calculation using NPDES data.
NPDES permits require periodic monitoring of the effluent stream. In this
example, quarterly samples were taken to be analyzed for silver content. Each sample was an
hourly, flowrate-based composite taken for one day to be representative of the discharge for that
day. The total effluent volume for that day was also recorded. The following data were collected
on each sample day.
B-7
-------
Yearly Quarter
Sample Number
Discharge Flow Rate
(106 gal/Hay)
0.5
0.6
0.4
0.2
Total Silver (|ig/l)
i 10
; 10
6
<3
j,,... i , .,'! Fl ", ' I
To calculate the amount of silver in pounds discharged on each sample day, the
concentration of sjlver in the discharge is multiplied by the discharge flow rate for that day, as
sfiovvn below for the first quarter sample.
Amount of silver = (daily flow rate) x (silver concentration)
First Quarter: f "**} x f _1«_) x f JJ
I L ) \loVgJ U54gJ
3'785L1 °-5 x Ip
gal ) ( day
= 0.04 Ib/day of silver
The amount of silver discharged during each of the other three monitoring events
was similarly determined to be:
0.05 Ib/day; 0.02 Ib/day, and 0.005 Ib/day.
I;: , ' . i '
For the last data point the concentration of silver was reported by the laboratory to
be less than the detection limit of 3 ug/L. For this calculation the detection limit was used to
calculate the daily discharge, a conservative assumption.
The average daily discharge was calculated to be:
1 !'" i , Ji: .1 jl
( 0.04 + 0.05 + 0.02 +0.005 }....
Ib/day = 0.03 Ib/day
V 4 )
The plant operates 350 days/year (plant shuts down for two weeks in July).
;!j ;i > ' . . '; :l!l 'i
The estimated annual discharge of silver is calculated as follows:
i Jh , ' . I
( ':!'! 'i ' , ''. I
Arinual discharge = (350 day/yr) (0.03 Ib/day) = 10.5 Ib of silver/yr
.* i
B-8
-------
Appendix C
GUIDANCE FOR REPORTING AQUEOUS AMMONIA
-------
-------
United States Environmental
Protection.Agency
Office of Pollution
Prevention and Toxics
Washington, DC 20460
July 1995
EPA 745-R-95-012
EMERGENCY PLANNING AND
COMMUNITY RIGHT-TO-KNOW
EPCRA Section 313
Guidance for Reporting Aqueous Ammonia
EPCRA Section 313 of the Emergency Planning and Community Right-to-Know
Act of 1986 (EPCRA) requires certain facilities manufacturing, processing, or otherwise using
listed toxic chemicals to report their environmental releases of such chemicals annually.
Beginning with the 1991 reporting year, such facilities also must report pollution prevention and
recycling data for such chemicals, pursuant to section 6607 of the Pollution Prevention Act, 42
U.S.C. 13106. When enacted, EPCRA Section 313 established an initial list of toxic chemicals
that was comprised of more than 300 chemicals and 20 chemical categories. EPCRA Section
313(d) authorizes EPA to add chemicals to or delete chemicals from the list, and sets forth
criteria for these actions.
CONTENTS
Section 1. Introduction C-2
1.1 Who Must Report C-2
1.2 Thresholds C-2
1.3 Chemical Sources of Aqueous Ammonia C-3
1.4 De Minimis Concentrations C-3
Section 2. Guidance for Reporting Aqueous Ammonia C-4
2.1 Determining Threshold and Release Quantities for Ammonia C-4
2.2 Chemical Sources of Aqueous Ammonia C-5
2.2.1 Reporting Aqueous Ammonia Generated from Anhydrous
Ammonia
in Water C-5
2.2.2 Reporting of Ammonia Generated from the Dissociation of
Ammonium Salts (Other Than Ammonium Nitrate) C-6
2.2.3 Reporting of Aqueous Ammonia Generated from the Dissociation
of Ammonium Nitrate C-7
Section 3. CAS Number and List of Some Chemical Sources of Aqueous Ammonia ... C-10
C-l
-------
Section 1. Introduction
' .:.:, ' " ':. ' ' ' ' .. ! , , "
On June 30, 1995 EPA finalized four actions in response to a petition received in
to delete amrnoniurn sulfate (solution) from the list of toxic chemicals subject to reporting
under EPCRA Section 313 of the Emergency Planning and Community Right-to-Know Act of
1986 (EPCRA), 42 U.S.C. 11001. The four actions taken are summarized as follows: (1)
deleted ammonium sulfate (solution) from the EPCRA Section 313 list of toxic chemicals, (2)
required that threshold and release determinations for aqueous ammonia be based on 10 percent
ofjhe total aqueous ammonia present in aqueous solutions of ammonia, (3) modified the
ammonia listing by adding the following qualifier: ammonia (includes anhydrous ammonia and
aqueous ammonia from water dissociable ammonium salts and other sources: 10 percent of total
,pi ] ' j ,, ; hi: 11 , 'Hi, , " i , ' i r , ,!', wi . ' i H ,i.,',,ii",.,' " i ' 'In < -V
aqueous ammonia is reportable under this listing), and (4) deleted ammonium nitrate (solution)
as a separately listed chemical on the EPCRA Section 313 list of toxic chemicals. All actions are
elective for the 1§94 reporting year for reports due July i, 1995, with the exception of the
deletion of ammonjuni nitrate (solution) as a separately listed chemical, which is effective for the
19?5 reporting year for reports due July 1, 1996. At the time that these actions were finalized,
EPA indicated that the Agency would develop, as appropriate, interpretations and guidance that
the Agency determines are necessary to facilitate accurate reporting for aqueous ammonia. This
document constitutes such guidance for reporting under the ammonia listing.
II
Section 1.1 Who Must Report
' , ;,.; '» . , , ' , I'.
A plant, factory, or other facility is subject to the provisions of EPCRA Section
3l3, if it meets all three of the following criteria:
'. Hi '; .i , " !" . ' " . -i .1. i
» It conducts manufacturing operations (is included in Standard Industrial
Classification (SIC) codes 20 through 39); and
, . , , || .
It has 10 or more full-time employees (or the equivalent 20,000 hours per
year); and
It manufactures, imports, processes, or otherwise uses any of the toxic
chemicals listed on the EPCRA Section 313 list in ampunts greater than
the "threshold" quantities specified below.
,:? '';::i; "' ' '''' : , . ''. ! I'
Section 1.2 Thresholds
:;i ii i ' I i! , " < ;l i ' ' ' ! 1
:" , .'i': i : ;' . ' , ' , . ' r "' ii.." "
Thresholds are specified amounts of toxic chemicals used during the calendar year
that trigger reporting requirements.
If a facility manufactures or imports any of the listed toxic chemicals, the
threshold quantity will be:
iji " , , " ' ' '" '! , ; ' | I !'
25,000 pounds per toxic chemical or category over the calendar year.
C-2
-------
be:
If a facility processes any of the listed toxic chemicals, the threshold quantity will
25,000 pounds per toxic chemical or category over the calendar year.
If a facility otherwise uses any of the listed toxic chemicals (without incorporating
it into any product or producing it at the facility), the threshold quantity is:
10,000 pounds per toxic chemical or category over the calendar year.
Section 1.3 Chemical Sources of Aqueous Ammonia
If a facility manufactures, processes, or otherwise uses anhydrous ammonia or
aqueous ammonia, they must report under the ammonia listing. EPA is providing a table of
Chemical Abstract Service (CAS) numbers and chemical names to aid the regulated community
in determining whether they need to report under the ammonia listing for aqueous ammonia.
This table includes a list of water dissociable ammonium salts which, when placed in water, are a
source of aqueous ammonia. The table contains only commonly used ammonium salts and
therefore is not exhaustive. If a facility manufactures, processes, or otherwise uses aqueous
ammonia, regardless of its source, it must report under the ammonia listing, even if the source of
the aqueous ammonia is not listed in the table provided in this document.
Section 1.4 DeMinimis Concentrations
The ammonia listing is subject to the one percent de minimis concentration. Thus,
solutions containing aqueous ammonia at a concentration in excess of one percent of the 10
percent reportable under this listing should be factored into threshold and release
determinations.
C-3
-------
:;!::
Section 2. Guidance for Reporting Aqueous Ammonia
N^
aittrnonia, Water dissociable ammonium salts means that the ammonium ion dissociates from its
counterfoil when in solution.
, i
Section 2.1 Determining Threshold and Release Quantities for Ammonia
, , . . ..
If a facility manufactures, processes, or otherwise uses anhydrous ammonia, the
quantity applied towards threshold determinations for the ammonia listing is the total quantity of
the anhydrous ammonia manufactured, processed, or otherwise used. The quantity reported
when calculating the amount of ammonia that is released, transferred, or otherwise managed is
the total quantity of anhydrous ammonia released or transferred.
*"' . ' ''J J ''~''lt ,', " ...... ' ..' ' . . .' '..... ..... ',' ",':,:':.: ."".. ..... ', . . , , ,-[i,'. , ' , ', ....... ,.'
If the facility manufactures, processes, or otherwise uses anhydrous ammonia in
quantities that exceed the appropriate threshold and subsequently dissolves some or all of the
anhydrous ammonia in water, then the following applies: 1) threshold determinations are based
OR. 100 percent of the anhydrous ammonia (simply 10 percent of aqueous ammonia); 2) release,
transfer, and other waste management quantities for the aqueous ammonia are calculated as 10
percent of total ammonia; 3) release, transfer, and other waste management quantities for the
anhydrous ammonia are calculated as 100 percent of the anhydrous ammonia.
*J i", 3v '"iiii'l ''' ' .(.. ' 'it £ ' i . ' i" i ' ! '?:' v , I) ,! ' i; ' »! ' l|:'" ' '' I! '!' i . , , ,;, . :
If a facility manufactures, processes, or otherwise uses aqueous ammonia, the
quantity applied toward threshold determinations for the ammonia listing is io percent of the
total quantity of the aqueous ammonia manufactured, processed, or otherwise used. The quantity
reported when calculating the amount of ammonia that is released, transferred, or otherwise
managed is 10 percent of the total quantity of aqueous ammonia released or transferred.
".If .a, facility dissolves a water dissociable ammonium salt in water that facility has
ffiji ' , * ' ' . ' i'H . . 'I I" I i' " .,' ,,'! " , i I M r II , I . , . >
manufactured aqueous ammonia and 10 percent of the total aqueous ammonia manufactured
from these salts is to be included in manufacturing threshold determinations under the ammonia
listing.
nin'ii"! i , ' i'i - ' M i ', : , ,;. i hi,! ' , i, ' ' , jj ':,,
1 '" '" ' " '(
If aqueous ammonia from water dissociable ammonium salts is processed or
otherwise used, then 10 percent of the total aqueous ammonia is to be included in all processing
an3 otherwise use threshold determinations under the ammonia listing.
ExampJeJL: In a calendar year, a facility places 25,000 Ibs of anhydrous ammonia in water for
processing and processes 25,000 Ibs of aqueous ammonia from an ammonium salt. The
facility must include all of the 25,000 Ibs of anhydrous ammonia in the determination of the
processing threshold, but only 10 percent (or 2,500 Ibs) of the aqueous ammonia from the
ammonium salt in the processing threshold determination.
C-4
-------
Total aqueous ammonia is the sum of the two forms of ammonia (un-ionized,
NH3, and ionized, NH4+) present in aqueous solutions. A precise calculation of the weight of
total aqueous ammonia would require determining the ratio of the two forms of ammonia present
using the pH and temperature of the solution. The weight of total aqueous ammonia can be more
easily calculated by assuming that aqueous ammonia is comprised entirely of the NH4+ form or
the NH3 form. For the purpose of determining threshold and release quantities under EPGRA
Section 313, EPA recommends that total aqueous ammonia be calculated in terms of NH3
equivalents (i.e., for determining weights, assume total ammonia is comprised entirely of the
NH3 form). This method is simpler than using pH and temperature data to determine the ratio of
the two forms present and is consistent with the presentation of total ammonia toxicity in a
separate EPA document, Ambient Water Quality Criteria for Ammonia (EPA document #440/5-
85-001, January 1985).
Section 2.2 Chemical Sources of Aqueous Ammonia
Aqueous ammonia may be generated in solution from a variety of sources that
include the release of anhydrous ammonia to water and the dissociation of ammonium salts in
water. Water dissociable ammonium salts are not reportable in their entirety under the ammonia
listing; these salts are reportable to the extent that they dissociate hi water, and only f 0 percent of
the total aqueous ammonia that results when these salts dissociate is reportable. If these salts are
not placed in water, they are not reportable.
If these salts are purchased neat or as solids by a facility, then placed in water by
that facility, the facility is manufacturing aqueous ammonia.
Section 2.2.1 Reporting Aqueous Ammonia Generated from Anhydrous Ammonia in
Water
If the source of aqueous ammonia is anhydrous ammonia in water, total aqueous
ammonia (calculated in terms ofNH3 equivalents) is equal to the quantity of anhydrous ammonia
manufactured, processed, or otherwise used. A hypothetical scenario demonstrating the
calculations involved in reporting aqueous ammonia generated from anhydrous ammonia in
water is given in Example 2.
Example 2: In a calendar year, a facility uses 30,000 pounds of anhydrous ammonia to
neutralize acids in a wastewater stream. The neutralized waste stream (containing aqueous
ammonia from dissociated ammonium salts) is then transferred to a POTW. The quantity to
be applied toward threshold determinations is the total quantity of anhydrous ammonia used in
the waste stream neutralization, or 30,000 pounds. The quantity of ammonia reported as
transferred is 10 percent of the total quantity of aqueous ammonia transferred, or 3,000
pounds. ^
Section 2.2.2 Reporting Aqueous Ammonia Generated from the Dissociation of
Ammonium Salts (Other Than Ammonium Nitrate)
If the source of aqueous ammonia is the dissociation of ammonium salts in water,
total aqueous ammonia (calculated in terms of NH3 equivalents) is calculated from the weight
C-5
-------
percent (wt%) of the NH3 equivalents of the ammonium salt. The NH3 equivalent wt% of an
arSmcihiUm salt is calculated using the following equation:
K ' ; - i if' ]; ": ' 'i'i1 :!':':J| [' ' " " ',, -' .. , ' .? . ( , >M| ; . ... !i . ,, . , t
NH3 equivalent wt% = (NH3 equivalent weight)/(MW ammonium salt) x 100
'M* ' I ' , ' '' 'I" 'In ! i" ' 1 , , , i , , d . i I i i i ," i J i ll i ' ii<
i , , , / , n , , , ,n , ! |1||N ,|, , i jl i , , . ',,,,.,'
If tlie source of aqueous ammonia is a monovalent compound (such as ammonium chloride,
NH4C1, ammonium nitrate, NH4N03, or ammonium bicarbonate (TSfH4HCO3), the NH3 equivalent
weight is equal to the MW of NH3 (17.03 kg/kmol). If divalent compounds are involved (such as
ammonium carbonate, (NH4)2CO3), then the NH3 equivalent weight is equal to the MW of NH3
multiplied by two. Similarly, if triyalent compound are involved, then the Nli3 equivalent
weight is equal to the MW of NH3 multiplied by three.
Example 3:
The NH3 equivalent wt% of ammonium chloride is calculated as follows:
NH3 equivalent wt% = (NH3 equivalent weight)/(MW ammonium chloride) x 100
NH3 equivalent wt% = (17.03)7(53.49) x 100
NH3 equivalent wt% = 31.84%
The NH3 equivalent wt% of ammonium carbonate is calculated as follows:
NH3 equivalent wt% = 2 x (NH3 equivalent weight)/(MW ammonium chloride) x 100
NH3 equivalent wt% = 2 x (17.03)7(96.09) x 100
NH, equivalent wt% = 35.45% ^^_
jo aid the regulated community in reporting under the ammonia listing for
aqueous ammonia, the table of chemical sources of aqueous ammonium provided in Section 3 of
this document includes, in addition to £AS number, chemical name, and molecular weight, the
Nt!3 equivalent wt% of the commonly used, water dissociable ammonium salts listed in this
table. ._' , " ^ ' .. ' . ' ". , 'i. , . '' ' , ,
Example 4: In a calendar year, a facility uses 100,000 pounds of ammonium chloride, NH4C1,
in aqueous solution which is released to wastewater streams, then transferred to a POTW. The
NH3 equivalent wt% of ammonium chloride is 31.84% (taken from Table 1 in Section 3 below
or calculated as in Example 3 above). The total quantity of aqueous ammonia present in
solution is 31.84% of the 100,000 pounds of ammonia chloride used, or 31,840 pounds. The
quantity applied towards threshold determinations for the ammonia listing is 10 percent of the
total quantity of aqueous ammonia present in solution, or 3,184 pounds. The quantity of
ammonia reported as released or transferred is 10 percent of the total quantity of aqueous
ammonia released or transferred, or 3,184 pounds.
C-6
-------
Example 5: In a calendar year, a facility uses 500,000 pounds of ammonium carbonate,
(NH4)2CO3, and 400,000 pounds of ammonium bicarbonate, NH4HCO3, in aqueous solution
which is released to wastewater streams, then transferred to a POTW. The NH3 equivalent
wt% of ammonium carbonate is 35.45%, and the NH3 equivalent wt% of ammonium
bicarbonate is 21.54% (taken from Table 1 in Section 3 below or calculated as in Example 3
above). The quantity of aqueous ammonia present in solution from ammonium carbonate is
35.45% of the 500,000 pounds of ammonia carbonate used, or 177,250 pounds. The quantity
of aqueous ammonia present in solution from ammonium bicarbonate is 21.54% of the
400,000 pounds of ammonia bicarbonate used or 86,160 pounds. The total quantity of
aqueous ammonia present in solution is 263,410 pounds. The quantity applied towards
threshold determinations for the ammonia listing is 10 percent of the total quantity of aqueous
ammonia present in solution, or 26,341 pounds. The quantity of ammonia reported as released
or transferred is 10 percent of the total quantity of aqueous ammonia released or transferred, or
26,341 pounds.
Section 2.2.3 Reporting Aqueous Ammonia Generated from the Dissociation of
Ammonium Nitrate ,
Some sources of aqueous ammonia may be reportable under other EPCRA
Section 313 category listings. Ammonium nitrate (solution) is relevant to reporting under the ;
ammonia listing to the extent that 10 percent of the total aqueous ammonia that results when
ammonium nitrate dissociates is reported when determining thresholds and calculating releases. ;
However, under the nitrate compound category listing, ammonium nitrate (and other mixed salts '..
containing ammonium and nitrate) must be reported in its entirety. When reporting ammonium
nitrate under this category listing, the total nitrate compound, including both the nitrate ion
portion and the ammonium counterion, is included when determining threshold quantities.
However, only the nitrate ion portion is included when determining the amount of ammonium
nitrate that is released, transferred, or otherwise managed in wastes. The calculations involved in
determining threshold and release quantities for reporting under the nitrate compound category
listing are described in a separate directive, List of Toxic Chemicals within the Water Dissociable^
Nitrate Compounds Category and Guidance for Reporting (EPA document #745-R-95-002,
February 1995). Note: reporting ammonium nitrate under the ammonia listing and nitrate ;
compounds category listing is effective for the 1995 reporting year for reports due July 1, 1996.
C-7
-------
:P
!" i','
i!"
3 .
Hi-
If
Example fi: In a calendar year, a facility uses 1,250,000 pounds of ammonium nitrate,
NH4NO35 in aqueous solution which is released to wastewater streams, then transferred to a
POTW. The NH3 equivalent wt% of ammonium nitrate is 21.28% (taken from Table 1 in
Section 3 below or calculated as hi Example 3 above). The total quantity of aqueous ammonia
present in solution is 21.28% of the 1,250,000 pounds of ammonia chloride used, or 266,000
pounds. The quantity applied towards threshold determinations for the ammonia listing is 10
percent of the total quantity of aqueous ammonia present in solution, or 26,600 pounds. The
quantity of ammonia reported as released or transferred is 10 percent of the total quantity of
aqueous ammonia released or transferred, or 26,600 pounds. For determining thresholds and
calculating releases under the nitrate compound category listing, see the separate directive, List
of Toxic Chemicals within the Water Dissociable Nitrate Compounds Category and Guidance
for Reporting (EPA document #745-R-95-002, February, 1995).
C-8
-------
Example 7: In a calendar year, a facility transfers 100,000 pounds of nitric acid (HNO3) to an
on-site treatment facility. The nitric acid is neutralized with anhydrous ammonia, and
treatment efficiency is 95 percent (the nitrate compound formed as a result of the treatment is
ammonium nitrate, NH4NO3). The neutralized waste stream (containing aqueous ammonia
from dissociated ammonium nitrate) is then transferred to a POTW. The quantity of nitric acid
neutralized is 95 percent of 100,000 pounds or 95,000 pounds. The quantity of nitric acid
neutralized is converted first to kilograms then to kilomoles using the following equations:
Kilograms HNO3 neutralized = (Ibs HNO3 neutralized) x (0.4536 kg/lb)
Kilomoles HNO3 neutralized = (kg HNO3) * (MW of HNO3 in kg/kmol)
Substituting the appropriate values into the above equations yields:
Kilograms HNO3 neutralized = 95,000 Ibs x 0.4536 kg/lb = 43,092 kg
Kilomoles HNO3 neutralized = 43,092 kg * 63.01 kg/kmol = 683.9 kmol
The quantity of anhydrous ammonia used in kilomoles in the acid neutralization and the
quantity of ammonium nitrate generated in kilomoles from the neutralization are equal to the
quantity of nitric acid neutralized (683.9 kmol). The quantity of anhydrous ammonia used in
kilograms and pounds in the acid neutralization is calculated as follows:
Kilograms NH3 used = (kmol NH3) x (MW of NH3 in kg/kmol)
Pounds NH3 used = (kg NH3) x (2.205 Ibs/kg)
Substituting the appropriate values into the above equation yields:
Kilograms NH3 used = (683.9 kmol) x (17.03 kg/kmol) = 11,647 kmol
Pounds NH3 used = (11,647 NH3) x (2,205 Ibs/kg) = 25,682 pounds
The quantity reported applied towards threshold determinations for the ammonia listing is the
total quantity of anhydrous ammonia used in the acid neutralization, or 25,682 pounds. The
quantity of ammonia reported as released or transferred is 10 percent of the total quantity of
aqueous ammonia released or transferred, or 2,568 pounds. For determining thresholds and
calculating releases under the nitrate compound category listing, see the separate directive, List
of Toxic Chemicals within the Water Dissociable Nitrate Compounds Category and Guidance
cor Reporting (EPA document #745-R-95-002, February 1995).
C-9
-------
Section 3. CAS Number and List of Some Chemical Sources of Aqueous Ammonia
' ' '' ";|:i ' '<'' '" '" - ' !' ' ' ''" -
. :')!!' t
it ...... i;
. .
EPA is providing the following table of CAS numbers and chemical names to aid
the regulated community in determining whether they need to report under the ammonia listing
fo,r aqueous ammonia. If a facility manufactures, processes, or otherwise uses, in aqueous
solution, a chemical which is listed below, they must report 10 percent of the total aqueous
ammonia that is the result of the dissociation of this chemical. However, this list is not
exhaustive. If a facility manufactures, processes, or otherwise uses, in aqueous solution, a water
dissociable ammonium compound, they must report 10 percent of the total aqueous ammonia
that is the result of the dissociation of the compound, even if the compound does not appear in
the following table.
I' ';;" ' ;;; ..... ."; Table C-l ^ '' ^ !' i " ^ ^ '''
Listing by CAS Number and Molecular Weight of
Some Chemical Sources of Aqueous Ammonia
Chemical Name
Ammonium acetate
Ammonium aluminum sulfate
(Ammonium aluminum disulfate)
Ammonium antimony fluoride
(Diammonium pentafluoroantimonate)
Ammonium arsenate
(Ammonium arsenate, hydrogen)
(Ammonium arsenate, dihydrogen)
Ammonium arsenate
(Diammonium arsenate)
(Diammonium arsenate, hydrogen)
(Diammonium arsenate, monohydrogen)
Ammonium arsenite
Ammonium azide
Ammonium benzenesulfonate
Ammonium benzoate
Ammonium bromate
Ammonium bromide
Ammonium cadmium chloride
(Ammonium cadmium trichloride)
Ammonium carbamate
Ammonium carbonate carbamate
Ammonium carbonate
(Diammonium carbonate)
Molecular
Weight*
77.08
237.14
252.82
158.97
176.00
124.96
60.06
175.20
139.15
145.94
97.94
236.81
78.07
157.13
96.09
NH3
Equivalent
Wt%
22.09
7.181
13.47
10.71
19.35
13.63
28.35
9.720
12.24
11.67
17.39
7.191
21.81
21.68
35.45
CAS Number
631-61-8
7784-25-0
32516-50-0
13462-93-6
7784-44-3
13462-94-7
12164-94-2
19402-64-3
1863-63-4
13843-59-9
12124-97-9
18532-52-0
1111-78-0
8000-73-5
506-87-3
C-10
-------
Table C-l (Continued)
Chemical Name
Ammonium carbonate, hydrogen
(Ammonium bicarbonate)
Ammonium cerium nitrate
(Ammonium hexanitratocerate)
(Ammonium hexanitratocerate (IV))
(Diammonium cerium hexanitrate)
Ammonium cerous nitrate
(Ammonium cerous nitrate, tetrahydrate)
Ammonium chlorate
Ammonium perchlorate
Ammonium chloride
Ammonium chromate
(Ammonium chromate (VI))
(Diammonium chromate)
Ammonium chromate
(Ammonium dichromate)
(Ammonium dichromate (VI))
(Ammonium bichromate)
(Diammonium dichromate)
Ammonium chromium sulfate
(Ammonium chromic sulfate)
Ammonium citrate
(Ammonium citrate, monohydrogen)
(Ammonium citrate, dibasic)
(Diammonium. citrate)
(Diammonium citrate, hydrogen)
Ammonium citrate
(Ammonium citrate, tribasic)
(Triammonium citrate)
Ammonium cobalt sulfate
(Ammonium cobaltous sulfate)
Ammonium cupric chloride
(Ammonium chlorocuprate (II))
(Diammonium copper tetrachloride)
(Diammonium tetrachlorocuprate)
Ammonium cyanate
(Ammonium isocyanate)
Ammonium cyanide
Ammonium cyanoaurate, monohydrate
(Ammonium tetracyanoaurate, monohydrate)
Molecular
Weight*
79.06
548.23
486.22
101.49
117.49
53.49
152.07
.'
252.06
265.17
226.19
243.22
289.14
241.43
60.06
44.06
319.07
NH3
Equivalent
Wt%
21.54
6.213
7.005
16.78
14.49
31.84
22,40
13.51
6.422
15.06
21.01
11.78
14.11
28.35 .
38.65
5.337
CAS Number
1066-33-7
16774-21-3
13083-04-0
10192-29-7
7790-98-9
12125-02-9
7788-98-9
7789-09-5
13548r43-l
3012-65-5
3458-72-8
13596-46-8
15610-76-1
22981-32^4
122U-52-8
14323-26-3
C-ll
-------
Table C-l (Continued)
Chemical Name
Ammonium cyanoaurate
(Ammonium dicyanoaurate)
Ammonium ferricyanide
(Ammonium hexacyanoferrate (HI))
(Triammonium hexacyanoferrate)
Ammonium ferrocyanide
(Ammonium hexacyanoferrate (II))
(Tetraammonium ferrocyanide)
(Tetraammonium hexacyanoferrate)
Ammonium fluoride
Ammonium fluoride
(Ammonium difluoride)
(Ammonium bifluoride)
(Ammonium fluoride, hydrogen)
(Ammonium difluoride, hydrogen)
(Ammonium bifluoride, hydrogen)
Ammonium ftuoroborate
(Ammonium tetrafluoroborate)
Ammonium fluorogermanate (TV)
(Ammonium hexafluorogermanate (TV))
(Diammonium hexafluorogermanate)
Ammonium fluorophosphate
(Ammonium hexafluorophosphate)
Ammonium fluorosulfate
(Ammonium fluorosulfonate)
Ammonium formate
Ammonium gallium sulfate
Ammonium hydroxide
Ammonium iodide
Ammonium iridium chloride
(Ammonium chloroiridate (III))
(Ammonium hexachloroiridate)
(Triammonium hexachloroiridate)
Ammonium iron sulfate
(Ammonium ferric sulfate)
(Ammonium iron disulfate)
Ammonium iron sulfate
(Ammonium ferrous sulfate)
(Diammonium iron disulfate)
(Diammonium ferrous disulfate)
Molecular
Weight*
267.04
266.07
284.11
37.04
57.04
104.84
222.66
163.00
117.10
63.06
282.90
35.05
144.94
459.05
269.02
286.05
NH3
Equivalent
Wt%
6.377
19.20
23.98
45.98
29.86
16.24
15.30
10.45
14.54
27.01
6.020
48.59
11.75
11.13
6.330
11.91
CAS Number
31096-40-9
14221-48-8
14481-29-9
12125-01-8
1341-49-7
13826-83-0
16962-47-3
16941-11-0
13446-08-7
540-69-2
15335-98-5
1336-21-6
12027-06-4
15752-05-3
10138-04-2
10045-89-3
C-12
-------
Table C-l (Continued)
Chemical Name
Ammonium lactate
(Ammonium 2-hydroxypropionate)
Ammonium laurate
(Ammonium dodecanoate)
Ammonium magnesium sulfate
Ammonium malate
Ammonium malate, hydrogen
(Ammonium bimalate)
Ammonium molybdate
(Piammonium molybdate)
Ammonium molybdate
(Ammonium heptamolybdate)
(Ammonium molybdate, hydrate)
(Ammonium molybdate, tetrahydrate)
(Ammonium ^aramolybdate, tetrahydrate)
Ammonium nickel chloride, hexahydrate
Ammonium nickel sulfate
(Ammonium nickel sulfate, hexahydrate)
(Ammonium nickel disulfate, hexahydrate)
(Diammonium nickel disulfate, hexahydrate)
Ammonium nitrate
Ammonium nitrate sulfate
Ammonium nitrite
Ammonium oleate
Ammonium oxalate
Ammonium palladium chloride
(Ammonium chloropalladate (II))
(Ammonium tetrachloropalladte (II))
(Diammonium tetrachloropalladate)
Ammonium phosphate
(Ammonium orthophosphate)
Ammonium phosphate
(Ammonium biphosphate)
(Ammonium phosphate, hydrogen)
(Ammonium phosphate, dihydrogen)
(Ammonium orthophosphate, dihydrogen)
(Ammonium phosphate, monobasic)
Molecular
Weight*
107.11
217.35
252.50
168.15
151.12
196.01
1,163.8
183.09
286.88
80.04
212.18
64.04
299.50
124.10
284.31
149.09
115.03
NH3
Equivalent
Wt%
15.90
7.835
13.49
20.26
11.27
17.38
8.780
9.301
11.87
21.28
24.08
26.59
5.686
27.45
11.98
34.27
14.80
CAS Number
515-98-0
. 2437-23-2
14727-95-8
6283-27-8
5972-71-4
13106-76-8
12054-85-2
16122-03-5
7785-20-8
6484-52-2
12436-94-1
13446-48-5
544-60-5
1113-38-8
13820-40-1
10124-31-9
7722-76-1
C-13
-------
Table C-l (Continued)
Chemical Name
Ammonium phosphate
(Ammonium phosphate, hydrogen)
(Ammonium orthophosphate, monohydrogen)
(Ammonium phosphate, dibasic)
(Ammonium orthophosphate, dibasic)
(Diammonium phosphate)
(Diammonium orthophosphate)
(Diammonium phosphate, hydrogen)
(Diammonium phosphate, monohydrogen)
(Diammonium orthophosphate, hydrogen)
Ammonium jxhosphinate
(Ammonium hypophosphite)
Ammonium phosphite
(Ammonium biphosphite)
(Ammonium phosphite, dihydrogen)
Ammonium picramate
Ammonium propionate
Ammonium rhodium chloride
(Ammonium chlororhodate (HI))
(Ammonium hexachlororhodate (III))
(Triammonium rhodium hexachloride)
(Triammonium hexachlororhodate)
Ammonium salicylate
(Ammomum 2-hydroxybenzoate)
Ammonium selenide
Ammonium sih'con fluoride
(Ammonium fluorosilicate)
(Ammonium hexafluorosih'cate)
(Diammonium silicon hexafluoride)
(Diammonium fluorosilicate)
(Diammonium hexafluorosilicate)
Ammonium stearate
(Ammonium octadecanoate)
Ammonium succinate
(Diammonium succinate)
Ammonium sulfamate
(Ammonium amidosulfate)
(Ammonium amidosulfonate)
Ammonium sulfate
(Diammonium sulfate)
Molecular
Weight*
132.06
83.03
99.03
216.15
91.11
369.74
155.15
115.04
178.15
301.51
152.15
114.12
132.13
NHs
Equivalent
Wt%
25.79
20.51
17.20
7.879
18.69
13.82
10.98
29.61
19.12
5.648
22.39
14.92
25.78
CAS Number
7783-28-0
7803-65-8
13446-12-3
1134-85-6
17496-08-1
15336-18-2
528-94-9
66455-76-3
16919-19-0
1002-89-7
2226-88-2
7773-06-0
7783-20-2
C-14
iiliiiik ..... .dili
........ lui ;
!iil^ : ............ iUli
;,:i i|. ,'
m,
-------
Table C-l (Continued)
' ' - '." ' .""'-'. ' - J',
Chemical Name
Ammonium sulfate
(Ammonium bisulfate)
(Ammonium sulfate, hydrogen)
(Ammonium sulfate, monohydrogen)
Ammonium persalfate
(Ammonium peroxysulfate)
(Ammonium peroxydisulfate)
(Diammonium persulfate)
(Diammonium peroxydifiilsite)
Ammonium sulfide
(Ammonium bisulfide)
(Ammonium sulfide, hydrogen)
Ammonium sulfide
(Ammonium monosulfide)
(Diammonium sulfide)
Ammonium sulfide
(Diammonium pentasulfide)
Ammonium sulfite, monohydrate
(Diammonium sulfite, monohydrate)
Ammonium sulfite
(Ammonium bisulfite)
(Ammonium sulfite, hydrogen)
Ammonium tetrachloroaurate (III), hydrate
Ammonium thiocarbamate
Ammonium thiocarbonate
(Diammonium trithiocarbonate)
Ammonium thiocyanate
(Ammonium isothiocyanate)
(Ammonium sulfocyanate)
(Ammonium rhodanate)
(Rhodanid)
Ammonium dithionate
Ammonium thiosulfate
(Ammonium hyposulfite)
(Diammonium thiosulfate)
Ammonium tin bromide
(Ammonium bromostannate (IV))
(Ammonium hexabromostannate (IV))
(Diammonium hexabromostannate)
Molecular
Weight*
115.10
228.19
51.11
68.14
196.39
116.13
99.10
356.82
94.13
144.27
76.12
196.19
148.20
634.19
: NH3
Equivalent
Wt%
14.80
14.93
33.32
49.99
17.34
29.33
17.18
4.772
18.09
23.61
22.37
17.36
22.98
5.371
CAS Number
7803-63-6
7727-54-0
12124-99-1
12135-76-1
12135-77-2
7783-11-1
10192-30-0
13874-04-9
16687-42-6
13453-08-2
1762-95-4
60816-52-6
7783-18-8
16925-34-1
C-15
-------
. .niillKllil ' ."Mill ' ! J'1'
Table C-l (Continued)
Chemical Name
Ammonium tin chloride
(Ammonium chlorostannate (IV))
(Ammonium hexachlorostannate (TV))
(Diammonium tin hexachloride)
(Diammonium hexachlorostannate)
Ammonium titanium fluoride
(Ammonium fluorotitanate (IV))
(Ammonium hexafluorotitanate (IV))
(Oiammonium titanium hexafluoride)
(Diammonium hexafluorotitanate)
Ammonium titanium oxalate, monohydrate
(Diammonium dioxalatooxotitanate, monohydrate)
Ammonium tungstate
(Ammonium tungstate (VI))
(Ammonium /wzratungstate)
(Hexaammonium tungstate)
Ammonium tungstate
(Ammonium tungstate (VI))
(Ammonium paratungstate)
(Decaammonium tungstate)
Ammonium valerate
(Ammonium pentoate)
Ammonium zinc chloride
(Ammonium chlorozincate)
(Ammonium tetrachlorozincate)
(Diammonium tetrachlorozincate)
Molecular
Weight*
367.48
197.95
276.00
1,779.2
3,058.6
119.16
243.27
NH3
Equivalent
Wt%
9.269
17.21
12.34
5.743
5.568
14.29
14.00
CAS Number
16960-53-5
16962-40-6
10580-03-7
12028-06-7
11120-25-5
42739-38-8
14639-97-5
*For hydrated compounds, e.g., ammonium sulfite, monohydrate, the molecular weight excludes the weight of the hydrate
portion.
; *
C-16
-------
Appendix D
GUIDANCE FOR REPORTING SULFURIC ACID
-------
Si1
-------
United States
Environmental Protection
Agency
Office of Pollution
Prevention and Toxics
Washington, DC 20460
EPA 745-R-97-007
November 1997
Updated March 3, 1998
EMERGENCY PLANNING AND
COMMUNITY RIGHT-TO-KNOW
EPCRA Section 313
Guidance for Reporting Sulfuric Acid (acid aerosols including mists,
vapors, gas, fog, and other airborne forms of any particle size)
Section 313 of the Emergency Planning and Community Right-to-Know Act of 1986
(EPCRA) requires certain facilities manufacturing, processing, or otherwise using listed toxic
chemicals to report their environmental releases of such chemicals annually. Beginning with the
1991 reporting year, such facilities also must report pollution prevention and recycling data for
such chemicals, pursuant to section 6607 of the Pollution Prevention Act, 42 U.S.C. 13106.
When enacted, EPCRA Section 313 established an initial list of toxic chemicals that was
comprised of more than 300 chemicals and 20 chemical categories. EPCRA section 313(d)
authorizes EPA to add chemicals to or delete chemicals from the list, and sets forth criteria for
these actions.
CONTENTS
Section 1.0 Introduction D-3
1.1 Who Must Report D-3
1.2 Thresholds D-4
1.3 What Constitutes Aerosol Forms of Sulfuric Acid and Their
Manufacture, Processing, or Otherwise Use D-4
Section 2.0 Guidance on Sulfuric Acid Aerosols For Certain Specific
Activities That Generate Aerosols Forms D-5
2.1 Sulfuric Acid Aersosols Generated in Acid Reuse Systems . . D-5
2.2 Sulfuric Acid Aerosols Removed By Scrubbers D-6
2.3 Sulfuric Acid Aerosols Generated In Storage Tanks D-6
Section 3.0 Sulfuric Acid and Its Formation in Air D-6
3.1 Industrial Sources of Sulfuric Acid Aerosols D-7
3.l!l Pulp and Paper Mills D-9
3.1.2 Acid Aerosols From Sulfuric Acid Manufacture D-10
3.1.3 Smelters D-13
3.1.4 Petroleum Refining D-13
D-l
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3.1.5
References
Appendix 1
Sulfuric Acid Aerosol Formation In Stackes From
3.1.6
3.1.7
4.0
JS
1
CombustionPProcesses
Coal Combustion
Fuel Oil Combustion
Measurement Methods
.... D-13
D-15
D-15
D-16
D-16
D-19
I
D-2
hili'iiif'il'ili ' .li'iilJili1,.,, I, ,!,!,',,|,:
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Section 1.0. Introduction
On June 30, 1995 (60 FR 34182), EPA modified the listing for sulfuric acid (Chemical
Abstracts Service Number 7664-93-9) on the list of toxic chemicals subject to the reporting
requirements under section 313 of the Emergency Planning and Community Right-to-Know Act
of 1986 (EPCRA) (5). EPA modified the listing by deleting non-aerosol forms of sulfuric acid
from the section 313 list based on the conclusion that they cannot reasonably be anticipated to
cause adverse effects on human health or the environment. EPA added a modifier to the listing
for sulfuric acid to exclude the non-aerosol forms. The listing now reads "Sulfuric acid (acid
aerosols including mists, vapors, gas, fog, and other airborne forms of any particle size)."
Therefore, beginning with the 1994 reporting year, facilities are no longer required to include
non-aerosol forms of sulfuric acid in threshold and release determinations. In this document we
will use the term "sulfuric acid aerosols" to indicate airborne forms of sulfuric acid as listed in
section 313 of EPCRA.
The purpose of this document is to assist facilities in determining the sources and
amounts of sulfuric acid aerosols that are to be included in threshold and release determinations
under EPCRA section 313. This document is not meant to be exhaustive, but rather provide some
guidance to help facilities in their determination of threshold and release quantities. Threshold
and release determinations for sulfuric acid aerosols are highly dependent on site specific
conditions and equipment. Therefore, this document can only provide general information
concerning the possible formation and release of sulfuric acid aerosols.
Section 1.1. Who Must Report
A plant, factory, or other facility is subj ect to the provisions of EPCRA section 313, if it
meets all three of the following criteria:
It is included in the primary Standard Industrial Classification (SIC) codes 20 through 39
and beginning January 1, 1998, it is in one of the following industries: Metal Mining,
SIC code 10 (except SIC codes 1011, 1081, and 1094); Coal Mining, SIC code 12 (except
SIC code 1241); Electric Utilities, SIC codes 4911, 4931, or 4939 (each limited to
facilities that combust coal and/or oil for the purpose of generating power for distribution
in commerce); Commercial Hazardous Waste Treatment, SIC code 4953 (limited to
facilities regulated under the Resource Conservation and Recovery Act, subtitle C, 42
U.S.C. section 6921 etseq.); Chemicals and Allied Products-Wholesale, SIC code 5169;
Petroleum Bulk Terminals and Plants, SIC code 5171; and, Solvent Recovery Services,
SIC code 7389 (limited to facilities primarily engaged in solvent recovery services on a
contract or fee basis); and
It has 10 or more full-time employees (or the equivalent of 20,000 hours per year); and
It manufactures (includes imports), processes or otherwise uses any of the toxic
chemicals listed on the EPCRA section 313 list in amounts greater than the threshold
quantities specified below.
D-3
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i
i ii
In addition, pursuant to Executive Order 12856 entitled "Federal Compliance with Right-
to-Know Laws and Pollutant Prevention Requirements," federal facilities are required to comply
^ith the reporting requirements of EPCRA Section 313 beginning with calendar year 1994. This
requirement is mandated regardless of the facility's SIC code.
!,!j, ' , ,1 I , ;|l '"Ij I , ; ., ;', II
Section 1.2. Thresholds
';; i, I ''"itl! II " : " '; " ]' ......
X ' I ', , llf ..jr| . ' i||. ,. ' . , ... .. i 1 i ' ,y: ' i "' I. . ,
Thresholds are specified amounts of toxic chemicals manufactured, processed, or
otherwise used during the calendar year that trigger reporting requirements. Reporting is required
for sulfuric acid aerosols if the following thresholds are exceeded.
h ' ;' til ' I . ' , : , .. '<. ' . I ' ' :
* If a facility manufactures or imports 25,000 pounds of sulfuric acid aerosols over the
calendar year.
'! i ii i , i.., '.. " v, / T .; '
* If a facility processes 25,000 pounds of sulfuric acid aerosols over the calendar year.
. iill < !!IJ . . ,; ! ... ' ' j
If a facility otherwise uses 10,000 pounds of sulfuric acid aerosols over the calendar year.
'ii ' ., ."i! i ill , , ' I.-; ' . >,,"(. . 1 ,
The quantities of sulfuric acid aerosols included in threshold determinations are not
limited to the amounts of sulfuric acid aerosols released to the environment. All sulfuric acid
aerosols manufactured, processed, or otherwise used are to be counted toward threshold
determinations. This includes any amount of sulfuric acid aerosols that may be generated in
closed systems or that are generated in stacks prior to or after being treated by scrubbers.
Section 1.3. What Constitutes Aerosol Forms of Sulfuric Acid and Their Manufacture,
Processing, or Otherwise Use
For the purposes of the reporting requirements under EPCRA section 313, sulfuric acid
a|jfoSOjs include iflists, vapors, gas, fog, and other airborne forms of any particle size. Note that
there is no size limit for particles that must be included under the EPCRA section 313 sulfuric
acid aerosols listing. Although the qualifier includes the terms mists, vapors, gas, and fog these
term? are not specifically defined for EPCRA section 313 since the last part of the qualifier
"p.ther airborn^e forms of any particle size" makes it clear that any airborne form is covered by the
li§ting. The specific terms mists, vapors, gas, and fog are included to make.it clear that sulfuric
aqjd that is identified as being in one of these forms would be covered by the sulfuric acid
aerosols listing.
'i1 : ' '» '! i1 " I! , . . - i, ' II ,:
: .. , .
If sulfuric acid is present in the form of a gas, fog, vapor, or mist or any other airborne
fqrrnthen sulfuric acid is considered to be in the aerosol form and is covered by the EPCRA
section 313 sujfuric acid aerosols listing. Solutions of sulfuric acid which do not become
airborne are not covered by the EPCRA section 313 sulfuric acid aerosols listing but such
solutions may generate sulfuric acid aerosols during their manufacture, processing or otherwise
u§e. In general, sulfuric acid aerosols are manufactured any time a solution of sulfuric acid is
made to become airborne such as when it is sprayed or distilled. If the generation of sulfuric acid
aejOsols through spraying or other means is intentional (i.e., it is intended that the sulfuric acid
aerosol be generated for a particular use activity) then, in addition to manufacturing the sulfuric
acjd aerosol, such aerosols are also being otherwise used. Thus, spraying of sulfuric acid aerosols
it:
.si
D-4
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on to an item for cleaning, etching, or other purposes constitutes the manufacture and otherwise
use of sulfuric acid aerosols. If sulfuric acid aerosols are used in a process in which any part of
the sulfuric acid becomes incorporated into a product which is then distributed in commerce
then, under EPCRA section 313, the sulfuric acid aerosols are considered to have been processed.
Section 2.0. Guidance On Sulfuric Acid Aerosols For Certain Specific Activities That
Generate Aerosols Forms
EPA has provided the following guidance for specific activities that generated sulfuric
acid aerosols. The guidance in sections 2.1,2.2, and 2.3 is intended to apply only to the specific
situations discussed in these sections. If you are not sure whether this guidance applies to the
situation at your facility, then EPA should be consulted before using this guidance.
Section 2.1. Sulfuric Acid Aerosols Generated In Acid Reuse Systems
When solutions of sulfuric acid are aerosolized the "manufacture" of a listed chemical
(sulfuric acid aerosols) has occurred. This is a result of the qualifier to the sulfuric acid listing,
which excludes non-aerosol forms and limits the reporting to aerosol forms only. The addition of
the acid aerosol qualifier has an impact on certain processes that, prior to the addition of the
qualifier, would not have been considered to be "manufacturing" a listed chemical. Acid reuse
systems that use aqueous solutions of sulfuric acid to generate acid aerosols, use the acid
aerosols, condense them back into solution, and then reuse the acid solution again and again are
impacted by the addition of the acid aerosol qualifier. In such processes, the continuous reuse of
the acid solutions generates very large quantities of acid aerosols that technically should be
counted towards the "manufacture" [the generation of the acid aerosol is the "manufacture" of
sulfuric acid (acid aerosol)] and "otherwise use" thresholds. This may result in many facilities
greatly exceeding the "manufacture" and "otherwise use" reporting thresholds that, prior to the
addition of the qualifier, would not have exceeded thresholds.
While it is technically correct to apply all of the quantities of acid aerosols generated in
such systems towards the "manufacture" and "otherwise use" reporting thresholds, EPA did not
intend to increase the reporting burden as a result of addition of the sulfuric acid aerosol
qualifier. In addition, under EPA's general approach to reuse systems, a toxic chemical is not
counted toward thresholds each time it is reused but only once per reporting period, and that
approach would apply to sulfuric acid reuse systems were it not for the aerosol qualifier.
Therefore, EPA is providing the following guidance to reduce the reporting burden for facilities
that operate such processes and to bring the treatment of such systems into alignment with EPA's
general approach to reuse.
Rather than having facilities count all quantities of acid aerosol generated in such systems
towards the "manufacture" and "otherwise use" thresholds, EPA will allow facilities to apply the
total volume of acid in these systems only once to these thresholds. For example, if an acid reuse
system starts the year with 2000 pounds of acid and 500 pounds is added during the year then the
total amount applied towards acid aerosol thresholds would be 2500 pounds. This reflects a one
time per year counting of all of the acid molecules as being in the acid aerosol form rather than
counting them over and over again each time the acid aerosol form is generated and subsequently
used. Since in these acid reuse systems the acid aerosols are "manufactured" and then
D-5
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ii'f'ii1"
Hi: j
"Qthervyjse used" the 10,000 pound "otherwise use" threshold would be the threshold that would
first trigger reporting from such systems.
This guidance applies only to acid reuse systems and the reporting of sulfuric acid
aerosols under EPCRA section 313. This guidance does not apply to any other types of processes
of to any other listed chemical.
2.2. Sulfuric Acid Aerosols Removed By Scrubbers
When a scrubber is used to remove sulfuric acid aerosols prior to or in a stack, the acid
aerosols are usually converted to the non-aerosol form. The non-aerosol forms of sulfuric acid
are not feportable under EPCRA section 313 because the qualifier to the sulfuric acid listing
includes only acid aerosol forms. Sulfuric acid as a discrete chemical has not actually been
destroyed by the scrubber, but the form of sulfuric acid reportable under EPCRA section 313 has
been destroyed. Therefore, since sulfuric acid aerosols removed by scrubbers are converted to a
non-reportable form, the quantity removed by the scrubber can be reported as having been treated
for destruction.
!.
2.3. Sulfuric Acid Aerosols Generated In Storage Tanks
Sulfuric acid aerosols are generated in the empty space (head space) above sulfuric acid
solutions contained in storage tanks. The amounts of acid aerosols generated in such storage
tanks are to be applied towards the "manufacture" threshold for sulfuric acid aerosols. In such
storage tanks the sulfuric acid molecules are constantly moving between the atmosphere and the
solution. EPA does not intend for facilities to count such movement of the acid molecules in and
out of the stored acid solution as continuous "manufacture" of sulfuric acid aerosols. For such
storage tanks the amount of acid aerosol to be applied towards the "manufacture" threshold is the
avlrage amount that existed in the atmosphere above the acid solution during the year.
Each facility should determine the average conditions for their specific storage tank (i.e.,
the capacity of the tank, the average amount in the tank, the average head space in the tank, the
concentration of the acid solution stored, the temperature, and other information that may have
an impact on aerosol calculations) and make the appropriate calculation of the amount of acid
aerosol to apply towards the "manufacture" threshold. Any amounts of sulfuric acid aerosols that
may be released from the storage tank through venting or fugitive releases must also be included
in the threshold determination. If the storage tank is refilled and drawn down several times
during the year then the calculations should be based on all of the acid that was stored in the
tajJK. For ejcample, if a 10,000 pound capacity tank is refilled and drawn down 6 times during the
year (such that 60,000 pounds of acid were stored in the tank during the year) then the tank
calculations, based on the average condition for one 10,000 pound tank of acid, should be
multiplied by 6.
Section 3.0. Sulfuric Acid And Its Formation In Air
Sulfunc acid (H2SO4) is miscible in water in all proportions and has a strong attraction for
water. The annydrous chemical boils at 279.6EC (1). Commercial sulfuric acid normally contains
93 to 98% sulfuric acid with the remainder being water. A boiling point-composition diagram
D-6
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(Figure 1, Appendix 1) for aqueous sulfuric acid, indicates that below 75% H2SO4, the vapor
evaporating from a solution of the acid is essentially water. This fact is illustrated in Table la of
Appendix 1, which contains the partial pressure of sulfuric acid and total vapor pressure of the
solution over aqueous sulfuric acid solutions at various concentrations (1). Since the partial
pressure of concentrated sulfuric acid is very low, little sulfuric acid is expected to volatilize
from sulfuric acid solutions such as may be present in storage tanks. However, as discussed
above, the amount of acid aerosols generated is dependent on the quantity of acid in the tank(s)
during the year, the concentration, temperature, and other factors. The information in Appendix 1
and the guidance in section 2.3 can be used to assist in determining if significant amounts of
sulfuric acid aerosols are present in storage tanks.
Sulfuric acid containing dissolved sulfur trioxide (SO3) is known as oleum, fuming
sulfuric acid or disulfuric acid. The vapor pressure of sulfuric acid over oleum containing 10% to
30% of free SO3 by weight is shown in Table 2a of Appendix 1 (2). Since the vapor pressure of
sulfur trioxide over oleum is high, sulfuric acid aerosols also form when oleum is exposed to air
containing moisture.
Sulfuric acid is generally formed by the oxidation of sulfur dioxide (SO2) and the reaction
of the resulting sulfur trioxide (SO3) with water.
SO2
so,-
->S03
H2S04
While thermodynamically, SO2 has a strong tendency to react with oxygen to form SO3; under
normal tropospheric (lower atmosphere) conditions the reaction rate is very slow in the gas phase
(3, 17, 18, 19). Other than within a reaction chamber, SO2 is unlikely to generate SO3 and then
sulfuric acid. However, once SO3 is formed, it is converted to H2SO4 so rapidly (within
milliseconds) at normal humidities, that any reaction in which SO is formed in moist air is
equivalent to forming H2SO4 (3,18). In stacks from combustion processes, moisture in the stack
would be expected to convert any SO3 present into sulfuric acid aerosols. This being the case, the
quantity of SO generated in such stacks (multiplied by 98.08/80.07, the molecular weight of
sulfuric acid divided by the molecular weight of sulfur trioxide) should be included with those of
H2SO4. If SO3 is produced within a stack or unit of the plant without moisture present, sulfuric
acid aerosols would not be produced. Although the SO3 releases may be converted to H2SO4 in
the environment, facilities are not responsible for conversions that may take place in the
environment after a chemical that is not listed under EPCRA section 313, such as SO3, has been
released. Therefore, if SO3 is the chemical that is released from the facility, the facility is not
required to include it, or any H2SO4 produced in the environment from the released SO3, in any
EPCRA section 313 calculations of thresholds or releases.
Section 3.1. Industrial Sources Of Sulfuric Acid Aerosols
It is clear that industries required to report sulfuric acid aerosol releases will be among
those that had previously reported sulfuric acid releases to air under EPCRA section 313.
Facilities that previously reported over 25,000 pounds of sulfuric acid releases to air have
exceeded the manufacturing threshold quantity of sulfuric acid aerosols necessary for reporting
under the new listing. Additional facilities may be required to report because releases of sulfuric
D-7
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*:
,,i n :, .. i .V'ii i ' ^,1^, , n , ' ^
acid to air would npt frave included, for example, amounts of sulfuric acid aerosols that were
produced in the stack and subsequently removed by scrubbers or produced internally during
sulfuric acid manufacturing, processing, or use and that were removed by scrubbers prior to the
stack. Since these amounts of sulfuric acid aerosols do count towards the EPCRA section 313
threshold determinations, facilities with less than 25,000 pounds of air releases are not excluded
from reporting. In addition, some facilities may be using sulfuric acid aerosols in excess of
10,000 pounds and would also be required to report. According to the 1993 Toxics Release
Inventory (TRI), there were 191 facilities reporting releases of 25,000 pounds or more of sulfuric
acid to air. The number of these facilities in each of 2-digit standard industrial categories (SIC) is
shown in Table 1, as well as the prominent types of industries within the category that have
reported sulfuric acid emissions to air. The industries shown in italics include 34 facilities that
are in the 80th percentile (over 178,000 pounds per year) for sulfuric acid releases to air. These
34.facilities' air emissions are almost entirely from point sources, suggesting that either sulfuric
acp }s .formecjin (fee stack frorn sulfur trioxide or sulfuric acid is aerosolized in a process that
leads'to its relfasein the stack, Thirty two of these sites reported producing the sulfuric acid; the
copper smelters and phosphate fertilizer plants produced sulfuric acid for sale or distribution.
' i ' ' "' ' ' ' ' " "'' ' ' '' '
Taljle 1. Industrial Categories of Facilities Emitting over 25,000 Ibs/yr o^ Sulfuric Acid
Aerosols in 19^3
'!-?; ,. I:1"1! ..! ' . . ' i '.' '.i>..: :' I
Category (SIC Code)
Paper and Allied Products (26)
Chemicals and Allied Products (28)
Primary metal industries (33)
Food and Kindred Products (20)
Lumber, Wood Products (24)
Stone, clay, glass, concrete (32)
Petroleum refining (29)
Metal Products, except machinery (34)
Tobacco Manufacturers (21)
No. Sites*
185
53
23
11
8
6
4
4
1
Major Industries**
Pulp, paper and paperboard mills.
Phosphate fertilizers; Industrial inorganic chemicals.
Copper smelting; Blastfurnaces and steel mills
Wet corn milling; fats and oils; liquors; malt beverages.
Sawmills; Reconstituted wood products
Glass
Petroleum refining
Metal coatings
Tobacco stemming and redrying
*A, site may list more that one SIC code.
** The industries shown in italics include facilities that are in the 80th percentile for sulfuric acid releases to air.
The industrial breakdown does not necessarily indicate that emissions result from
processes unique to the industry. For example, phosphate fertilizer manufacturers, which use
sulfuric acid to make phosphoric acid and normal superphosphate, may produce their own
sulfuric acid from elemental sulfur and may also use it captively. Sulfuric acid emissions from
phosphate fertilizer manufacturing may therefore be primarily from sulfuric acid manufacturing.
Similarly, sulfuric acid is a known component in flue gas from fossil fuel combustion and waste
incineration. The SO3/H2S04 (SO3, as stated previously is immediately transformed into sulfuric
acid in the presence of water) produced from combustion sources is between 1 and 3% of the SOX
emitted by these sources (the rest being SO2). It is not clear why sulfuric acid is emitted from
|
'': '!' !i;i! !" , D-8 ' "
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combustion sources. A possible explanation is that there are substances in the flue gas or on the
stack walls that catalyze the oxidation of sulfur dioxide to sulfur trioxide, similar to the
heterogeneous reactions that can occur in the atmosphere (17-19). Sulfuric acid is also formed in
some flue desulfurization processes (7).
Section 3.1.1 Pulp and Paper Mills
The kraft pulping process involves the digesting of wood chips at elevated temperature in
"white liquor", an aqueous solution of sodium sulfide and sodium hydroxide, to dissolve the
lignin that binds the cellulose fibers of the wood together. The spent liquor used to digest wood
chips, called "black liquor", is combusted in recovery furnaces to recover heat and cooking
chemicals. Sulfuric acid is present in flue gas from kraft recovery furnaces and has been cited as
being one of the five most prevalent air toxics released from recovery furnaces of the direct
contact evaporator (DCE) and non-direct contact evaporator (NDCE) types (21). In a DCE, the
flue gas comes in contact with the black liquor, whereas in a NDCE, it does not. Field tests on
five Kraft recovery furnaces showed SO3/H2SO4 levels ranging from 0 to 3 ppm in the flue gas,
with an average level of 0.81 ppm, or about 10% of that found in fossil fuel plants burning fuel
containing 1-3% sulfur (4). In these tests, no correlation was found between SO2 and SO3/H2SO4
levels. Therefore, one cannot estimate emission factors for SO3/H2SO4 based on those for SO2.
While EPA has compiled emission factors for pollutants from kraft, acid sulfite, and neutral
sulfite semichemical (NSSC) pulping (9), no emissions factors have been presented for
SO3/H2SO4. However, industry tests of Kraft recovery furnaces have been performed between
1989 and 1993 and the results are presented in Table 2 (20).
Table 2. Emission Factors from Kraft Recovery Furnaces *
Mill Code (date built/rebuilt)**:
Control device/ Type evaporator
A: WB, Cascade
B:ESP
RFI (1973): WB ESP, Cascade
RFRIG1 (1991):WB ESP, Cyclone
RFRIG2 (1991): WB ESP, Cyclone
SUMMARY
C:DB
D: DB ESP
E:ESP
RFO (1986): DB ESP
SUMMARY
Type
DCE
DCE
DCE
DCE
DCE
DCE
NDCE
NDCE
NDCE
NDCE
NDCE
BLS
MPPD
3.12
16.56
0.85
2.63
9.84
18.60
12.00
1.90
H2SO4 Emissions in Ib/ton BLS
Range
ND to 4.7E-02
ND to 1.5E-02
4.60 ND to 2.5E-02
NDtol.9E-02
ND to 1.9E-02
0.21 to 0.91 ppm
0.1 7 to 2.98 ppm
0.49 to 1.71 ppm
NDto 1.6E-01
Average
1.6E-02
8.4E-03
1.4E-02
ND(2.0E-02)
8.2E-03
8.4E-03 (Median)
3.3E-02
7.1E-02
5.1E-02
ND(1.3E-02)
4.2E-02 (Median)
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tAbbreviations: BLS = black liquor solids; ND = not detected; DCE = direct contact evaporator; NDCE = non-
direct contact evaporator; ESP = electrostatic precipitator; WB = wet bottom; DB = dry bottom; MPPD = million
pounds per day. Type evaporator given for DCE types only.
** Iv|in|wi||i codes not preceded by "RF " are from a 1980 study (4). Dates wjien these mills were built or rebuilt
alfe not available.
The median sulfuric acid emissions from the directrcontact (DCE) and non-direct contact
III) , "Mi,,:* I IPI I Hill l ' ',: IB": h,, i HIM I " '..''.ft..! I-!1'1! : , " .,:!:'.!' ' ill!' t , '.' :: Ml ft ,ir /i!.,:-i'. I ,,,-1.ii,i i,,.,i..-,. . 11.
(NDCE) evaporator recovery furnaces, 8.4E-03 pounds per ton black liquor solids (BLS) and
C2E-Q2 pounds per ton BLS, respectively, can be used to estimate sulfuric acid emissions. For
example, if a kraft mill using 1100 air dry tons of unbleached pulp per day (ADTUBPD)
generates 3300 pounds BLS per ADTUBPD and operates two DCE furnaces 365 days per year,
the pounds bTH2S04, H, emitted during the year will be:
H - 1100 ADTUBPD x 365 days/year x (3300 Ibs. BLS/ADTUBPD x tonBLS/2000 Ibs BLS)
x[ 8.4E-03 Ibl: H SO /ton BLS = 5,565 Ibs. of H2SO4
The pounds of sulfuric acid aerosols produced in recovery furnaces on si|e should be combined
with that produced from fuel oil and coal combustion. Should the total equal or exceed 25,000
pounds per year, reporting would be required under EPCRA Section 313. It should be noted that
sulfuric acid used at the site for such purposes as QO2 generation, pH control, and ion exchange
generation no longer must be reported since aerosol forms of H2SO4 are not involved.
Section 3.1.2 Acid Aerosols from Sulfuric Acid Manufacture
j|
Sulfuric acid may be manufactured commercially by either the lead chamber process or
(lie contact process. However, sulfuric acid is usually produced by the contact process (1,2, 10,
22). In the contact process, sulfur is oxidized to SO2 which is subsequently fed into a converter
where it is catalytically oxidized to SO3. Finally, the sulfur trioxide is absorbed in a strong
sulfuric acid solution or oleum. Sulfuric acid plants are further classified by feedstock: elemental
sulflir burning, spent sulfuric acid and hydrogen sulfide burning, and metal sulfide ores and
smelter gas burning. Contact sulfuric acid, plants vary in design depending on the raw material
used to produce SO2. Oleum is also produced in contact plants, where SO3-containing gases are
passed through a special oleum tower. Regeneration of spent sulfuric acid is another form of
sulfuric acid manufacture, often performed in order to comply with antipollution regulations (1).
|i
Sjilfuric; Acid Manufacture
The amount of sulfuric acid aerosols produced in sulfuric acid manufacture is a function
of the type of sulfur feedstock, the concentration of the absorbing acid, and the conditions in the
absorber (1,2, 22). Elemental sulfur produces little acid mist when burned because there is little
water present. However the hydrocarbons in other feedstock (such as spent acid) produce water
ia'por during combustion. The affect of acid strength on mist production is illustrated by results
§Epwing 0.5 to 5.0 kilograms (kg) of uncontrolled acid aerosol emissions per Megagfam (Mg) of
acid produced (1.0 to 10.0 pounds (Ib) of acid emissions per ton of acid produced) from oleum
plants burning spent acid compared with 0.2 to 2.0 kg/Mg (0.4 to 4.0 Ib/ton) of emissions from
98% sulfuric acid plants burning elemental sulfur. In addition, the aerosol particle size from
oleum plants is finer than that from the 98% sulfuric acid plants. The operating temperature of
the absorption tower affects SO3 absorption and, accordingly, acid mist formed in the exit gas.
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In an elemental sulfur burning plant, after the sulfur is burned to SO2 and catalytically converted
to SO3, the gas enters one or multiple absorption towers (packed columns), usually operated
in countercurrent, in which the sulfur trioxide is absorbed in sulfuric acid of 98-99%
concentration to form more suifUric acid (1, 2, 22). The optimal operating temperature of the
absorption tower depends on the strength of the acid produced, throughput rate, inlet sulfur
trioxide concentrations and other factors peculiar to a particular plant. The optimal concentration
of the absorbing acid is the azeotrope (see Appendix 1), 98.3%, where the combined vapor
pressures of H2SO4, SO3, and water are at a minimum. At lower concentrations, the water vapor
partial pressure is higher and there is a greater risk of sulfuric acid mist formation. At higher
concentrations the tail gas will contain increased amounts of H2SO4 and SO3 because of their
higher partial pressures. Both sulfuric acid mist formed within the system and gaseous sulfuric
acid vaporized from the concentrated acid in the absorption towers and carried along with the
predominant sulfur trioxide gas, constitute sulfuric acid aerosols that are being manufactured and
therefore contributing to the manufacturing threshold of sulfuric acid aerosols for reporting under
section 313 of EPCRA. Sulfuric acid mists entrained in tail gas are separated by special filters
and determined by measurement of the acid content.
Regeneration of Spent Sulfuric Acid
The regeneration of spent sulfuric acid normally comprises two major steps,
concentration to the highest feasible level and decomposition of the spent acid (1). Water is
essentially the only substance evaporated (other than volatile organic impurities) in concentrating
the acid to <75% H2SO4. Vapors evolved during the concentration of spent sulfuric acid to a
more highly concentrated state (93-98% H2SO4) contain significant quantities of gaseous sulfuric
acid (1). The formation of this gaseous sulfuric acid contributes to the manufacturing threshold
of sulfuric acid aerosols for reporting under section 313 of EPCRA. Spent sulfuric acid may be
concentrated in either vacuum or drum concentrators. While vacuum concentrators yield
negligible emissions, those from drum concentrators contain acid mist. Exit gas is passed through
scrubbers before being vented to the atmosphere. Emissions from acid drum concentrators
operating at 55, 73, and 100% of capacity are reported to be 7034, 2401, and 2334 metric ton/day
(12).
Acid Aerosol Emissions
Nearly all the sulfuric acid aerosols emitted from sulfuric acid manufacturing plants come
from the absorber exit gases. The exit gas contains small amounts of SO2, even smaller amounts
of SO3, and sulfuric acid vapor and mist. Even with efficient gas drying, mist formation is
impossible to eliminate completely. Once formed, these aerosols are of such a fine particle size
and so stable that only a small amount can be removed in the absorber. Sulfuric acid is normally
combined with SO3 in determining an emission factor because SO3 reacts so rapidly with water
vapor. The emission factor for SO3 is calculated as 100% H SO and added to the H2SO4 value.
Sulfuric acid mists are always formed when sulfur trioxide combines with water vapor at .
temperatures below the dew point of sulfur trioxide. The dew point is a function of gas
composition and pressure and is generally around 140-170EC. Equations are available that
predict the dewpoint for different concentrations of H2O and H2SO4 (4). Examples are given in
Section 3.1.5 in Tables 6 and 8 for coal and fuel oil combustion.
D-ll
-------
Use:X>f Sulfuric Acid Emission Monitoring Data
Some suifuric acid manufacturing facilities may nave sulfuric acid emission monitoring
§'! ' V ''*** i! " 1 " ."''I' :."'"! . ° I <.... , ,r . . I, II" « °
data available that can be used to estimate emissions for sulfuric acid mist under the Clean Air
4ct Ne;vy Source Performance Standards (NSPS). Sulfuric acid plants constructed or modified
after August 17, 1971, are subject to a sulfuric acid mist emissions limit of 6.15 pounds of
sUlfurfc acid per ton of 100% sulfuric acid produced (see Part 60 Subpart H of Title 40 of the
Code of Federal Regulations). If such information is available, it is preferable to use such data
for estimating uncontrolled emissions of sulfuric acid, rather than published emission factors
since, monitoring data should be the best available data. If the measured data available is for
controlled emissions, then the amount of sulfuric acid generated prior to emission controls
should be calculated based on the average actual control efficiency for the acid mist.
Uncontrolled H2SO4 emissions = actual emissions to air/(l-efficiency)
,,,; ;; (Efficiency expressed as a fraction)
';: :: , ' " " ' : i. ' ' ,:''!:
Emission factors for sulfuric acid plants have been compiled by EPA (10). Uncontrolled
Emission factors for various sulfuric acid plants are shown in Table 3. Table 4 contains emission
'1C i i ' . . a; '"»;-;: ; , T. : / r , . , . , ,.
factors for plants using three of the most commonly used fiber mist eliminator control devices,
vertical tube, vertical panel, and horizontal duel pad types.
1 i ' :,':: ' , : |i
Table 3. Uncontrolled Emission Factors for Sulfuric Acid Plants
Raw material
Recovered sulfur
Bright virgin sulfur
Dark virgin sulfur
Spent acid
*
Oleum produced
% Total output
0-43
0
0-100
0-77
Emissions of H2SO4 aerosol per unit product
kg/Mg
0.174-0.4
0.85
0.16-3.14
1.1-1.2
Ib/ton
0.348-0.8
1.7
0.32-6.28
2.2-2.4
*Sulfuric acid containing dissolved sulfur trioxide. Also known as fuming sulfuric acid or disulfuric acid.
t;
= >. .
Table 4. Controlled Emission Factors for Sulfuric Acid Plants
' ' '
Raw material
Elemental sulfur
Dark virgin sulfur
Spent acid
Oleum produced
% Total output
0-13
0-56
Emissions of H2SO4 aerosol per unit product
kg/Mg
0.064
0.26-1.8
0.014-0.20
Ib/ton
0.128
0.52-3.6
0.28-0.40
*Sulfuric acid containing dissolved sulfur trioxide. Also known as fuming sulfuric acid or disulfuric acid.
D-12
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Section 3.1.3. Smelters
Sulfuric acid is a byproduct of metals production, notably copper, and is accordingly
sometimes referred to as smelter acid. Smelters produce sulfuric acid by the contact process with
the raw material being classified as 'metal sulfide ores and smelter gas burning' (see Section
3.1.2). The smelter gas (SO2 from the smelter furnace) is passed through cyclone dust collectors,
electrostatic dust and mist precipitators, and scrubbing and gas cooling towers to remove dust,
acid, mist and other impurities. The gas is then converted to SO3 and then H2SO4 in processes
similar to those used in sulfuric acid plants using elemental sulfur as a raw material (Section
3.1.2). Therefore, the potential for sulfuric acid aerosols formation is similar to the described
above in the third paragraph of Section 3.1.2.
Section 3.1.4. Petroleum Refining
Crude oil contains a small amount of sulfur as an impurity. As a result, sulfur oxides are
emitted from petroleum refineries. EPA has compiled emission factors of sulfur oxides, SOX, for
petroleum refining, but factors for sulfuric acid are not provided (11). However, according to
information provided by the American Petroleum Institute (API), the staff in API's Health and
Environmental Sciences Department uses the following EPA reference for sulfuric acid emission
factors: EPA. 1995. Compilation of Air Pollutant Emission Factors. Vol. 1: Stationary Point and
Area Sources. Section 8.10, AP-42, 5th ed. (January 1995). Research Triangle Park, NC: U.S.
EPA, OAQPS.
Section 3.1.5. Sulfuric Acid Aerosol Formation In Stacks From Combustion Processes
Sulfuric acid aerosols are often formed in flue gas in a stack during combustion of fuel
oil, coal, or other sulfur-containing fuels. Both water and sulfur trioxide are combustion products
and they have great affinity for each other; as discussed they react quickly to form sulfuric acid.
When flue gas is cooled to temperatures at or below the dew point, a sulfuric acid mist will form
from any sulfuric acid gas present (16). The dew point is the temperature at which the air
becomes saturated and produces dew; sulfuric acid mists are always formed when sulfur trioxide
combines with water vapor at temperatures below the dew point of sulfur trioxide. Because of the
enormous attraction between sulfur trioxide and water "only a very small amount of sulfur
trioxide in combustion gas is required to draw water from the gas and form a fairly concentrated
acid" (16). In fact, flue gas containing 1% sulfuric acid has the corrosive properties of 85%
sulfuric acid solution. All sulfuric acid produced within the stack, including the gas not just the
mist, falls under the EPCP\A section 313 definition of a sulfuric acid aerosol. The information on
dew points can be used to determine if any of the sulfuric acid present as gas will form a mist
that could potentially condense inside the stack.
Tables 5 and 7 below contain expected sulfur trioxide levels in flue gas resulting from the
combustion of fuel oil and coal, respectively, as a function of the sulfur content of the fuel and
the percent of excess air available (16). If water is present in the stack, Tables 5 and 7 can be
used to estimate the amount of sulfuric acid gas that can be formed. Tables 6 and 8 contain
empirically-derived dew points of SO3 for different concentrations of SO3 in stack gas of oil- and
coal-fired units, respectively. These tables can be used to determine whether the stack
temperature is below the dew point of SO3 and sulfuric acid mists are being formed in the stack
D-13
-------
1111 111
HI Illilllili I Ill
influe gas. Examples of how to use these tables to determine the dew point of SO3 are given
below. r
Assume a typical oil-fired unit is burning fuel oil containing 2% sulfur and that 17%
excess a|r is present. From Table 5, we see that 15 ppm of SO3 will be present in the flue gas and
available to form sulforic acid gas. From Table 6, we find that the dew point of SO3 should be
139°C. Therefore, if the temperature in the stack is at or below 139°C, sulfuric acid mists will
Very likely form in the stack.
As an example dealing with coal combustion, assume a typical unit is burning coal
containing 3% sulfur in the presence of 25% excess air. From Table 7, we see that between 20
arjd 4,0 ppm of'SO3 will be present in the flue gas and available to form sulfuric acid gas. From
fable 8, we Indthat the dew point should be between 136 ° C and 143 ° C . Therefore, if the
temperature in the stack is at or below 136°C to 143°C, sulfuric acid mists will very likely form
irt the stack.
I I II ' Ml I I III I ' . i; 1", ', . . " , . ',:. r.
,1! ^ :L , ; ;' ;;';
Table 5. SO, Production in Oil Fired Units
Excess air (%)
Sulfur in fuel (%)
5
11
17
25
SO3 Concentration in Flue Gas (ppm)
0.5
2
6
10
12
1.0
3
7
13
15
2.0
3
8
15
18
3.0
4
10
19
22
4.0
5
12
22
26
5.0
6
14
25
30
Table 6. Dew Point of SO, in Stacks of Oil Fired Units*
SO in gas (ppm)
Dew point (°C)
5
130
10
135
15
139
20
141
25
143
30
145
35
147
40
148
45
149
50
150
55
151
60
152
65
153
70
154
*Using typical value of 10% water in oil
Table 7. SO3 Production in Coal Fired Units
Excess air (%)
Sulfur in fuel (%)
25
SO3 Concentration in Flue Gas (ppm)
0.5
3-7
1.0
7-14
2.0
14-28
3.0
20-40
4.0
27-54
5.0
33-66
Table 8. Dew Point of SO, in Stacks of Coal Fired Units*
ISO in gas (ppm)
Dew point (°C)
5
125
10
130
15
134
20
136
25
138
30
140
35
142
40
143
45
144-
50
145
55
146
60
147
65
148
70
149
D-14
-------
*Using typical value of 6% water in coal
Steel stacks are generally designed and operated so that a temperature between 135 °C (275 °F)
and 149°C (300°F) is maintained throughout the stack (16). These stack temperatures are such
that they may be below the dew point for SO3 in the flue gas, leading to the formation of sulfuric
acid mists in the stacks.
Section 3.1.6. Coal Combustion
Sulfuric acid aerosols are produced as a byproduct from boilers during coal combustion.
U.S. coals contain from 0.2% to 7% sulfur by weight (13). On average, about 95% of sulfur
present inbituminous coal will be emitted as gaseous sulfur oxides (SOX) when burned, whereas
somewhat less will be emitted when subbituminous coal is burned (15). In general, boiler size,
firing configuration, and boiler operations have little effect on the percent conversion of sulfur in
fuel to sulfur oxides. About 0.7% of fuel sulfur is emitted as SO3/H2SO4 (15). This information
can be expressed as an uncontrolled emission factor (EF) of 0.43 x S pounds H2SO4 per ton of
coal burned, where S is the weight percent sulfur in coal. The uncontrolled emission factor also
represents the amount of sulfuric acid produced in the stack, as well as that released to the
atmosphere in the absence of scrubbers or other emission control devices. The emission factor for
sulfur oxides (SOX) for bituminous coal combustion should not be used to estimate sulfuric acid
emissions since the factor includes sulfur dioxide. If C is the tons of coal burned, the pounds of
H2SO4 generated (H), would be:
H = 0.43 x S x C
For example, if 9,000 tons of coal were burned and the coal contained 3% sulfur, then:
H = 0.43 x 3 x 9,000 = 11,610 pounds of H2SO4
Note that the values for the variables C and S have been chosen as an illustration. Values must be
chosen that are appropriate for the particular operations at each facility.
Section 3.1.7. Fuel Oil Combustion
Sulfuric acid aerosols are produced during fuel oil combustion from the oxidation of
sulfur contained in the fuel. There are various types of fuel oil combustion operations; the type of
operation depends on the type of fuel oil burned. There are mainly five types of fuel oil used for
commercial, industrial, and residential use in the U.S. The No. 1 and No. 2 fuel oils are known as
distillate oils. They have high volatility, low viscosity, and <0.3% sulfur by weight. They are
primarily used in domestic and small commercial operations. The No. 5 (also called low sulfur
No. 6) and No. 6 fuel oils are known as residual oils. They have low volatility, high viscosity,
and high sulfur content. They are mainly used in industrial operations. The No. 4 fuel oil is a
mixture of distillate and residual oils and can be used for both types of operations. Typical sulfur
contents of fuel oil are (13):
D-15
-------
Fuel Oil Grade
No. 1
No. 2
No. 4
No. 5
No. 6
Sulfur Content (wt %)
0.09
!!
0.22
1.35
0.84
3.97' '
Uncontrolled SOX emissions are almost entirely dependent on the sulfur content of the
fuel and are not affected by boiler size and design or the grade of fuel being burned. On the
average, over 95% of the sulfur in fuel oil is converted to SO2 on combustion; about 1 to 5
p'ercent is further oxidized to sulfur trioxide where it readily reacts with water vapor in flue gas to
form sulfuric acid aerosols. The emission factor (°F) for uncontrolled fuel qil combustion from
industrial boilers is 0.002 x S pounds SO3 per gallon of fuel oil burned (14) or 0.00245 x S
pounds HjSO^ per gallon of fuel oil burned, where S is the weight percent sulfur in the fuel oil.
The uncontrolled emission factor also represents the amount of sulfuric acid produced in the
stack, as well as that released to the atmosphere in the absence of scrubbers or other emission
control devices. All example of the use of the emission factor (°F) to calculate the pounds of
sulfuric acid generated is shown below. If F is the number of gallons of fuel oil burned, the
pounds of H2SO4 generated (H), would be:
H = 0.00245 xS X.F
il
For example, if 4,500,000 gallons of fuel oil were burned and the fuel oil contained 3.97% sulfur,
then:
H = 0.00245 x 3.97 x 4,500,000 = 43,769 pounds of H2SO4
Note that the values for the variables F and S have been chosen as an illustration. Values must be
chosen that are appropriate for the particular operations at each facility.
Section. 4.0. IVleasurement Methods
For source sampling, EPA has specified extractive sampling trains
procedures for SOj and sulfuric acid aerosols (7, 8). Separation of particles
raay present problems in cases such as Kraft paper mills (4). If sodium sulfate
analytical results for sulfuric acid would be high.
and analytical
containing
is present,
D-16
-------
References
(1) Muller H. 1994. Sulfuric Acid and Sulfur Trioxide. Ullmann 's Encyclopedia of Industrial
Chemistry, Vol A25, pp. 635-702.
(2) Donovan JR, Salamone JM. 1983. Sulfuric Acid and Sulfur Trioxide. Kirk Othmer
Encyclopedia of Chemical Technology, 3rd ed. Vol 22, pp. 190-232.
(3) Calvert JG. 1984. SO2, NO and NO2 Oxidation Mechanisms: Atmospheric Considerations.
Buttersworth Publishers, pp. 1-62.
(4) National Council for Air and Stream Improvement (NCASI). 1980. A Study of SOX
measurement procedures and their use at Kraft recovery furnaces. Atmospheric Quality
Technical Bulletin No. 106, National Council for Air and Stream Improvement, New York, NY.
April 17, 1980.
(5) EPA. 1995. Sulfuric acid: Toxic chemical release reporting: Community right-to-know. Final
rule. 60 FR 34182. June 30, 1995.
(6) Wolff GT. 1991. Air pollution. Kirk Othmer Encyclopedia of Chemical Technology, 4th ed.
Vol Al, pp. 725.
(7) Crocker BB. 1991. Air pollution control methods. Kirk Othmer Encyclopedia of Chemical
Technology, 4th ed. Vol 1, pp. 749-825.
(8) EPA. 1975. Part 60 - Standards of performance for new stationary sources. Emission mon-
itoring requirements and revisions to performance testing methods. 40 FR 46250 October 1975.
(9) EPA. 1990. Compilation of Air Pollutant Emission Factors (AP-42). Wood Products
Industry. Chemical Wood Pulping. 10.2-1 to 10.2-20. September, 1990. Research Triangle Park,
NC: U.S. EPA, OAQPS.
(10) EPA. 1993. Compilation of Air Pollutant Emission Factors (AP-42). Inorganic Chemical
Industry. Sulfuric acid. 8.10-1 to 8.10-10. July, 1993. Research Triangle Park, NC: U.S. EPA,
OAQPS.
(11) EPA. 1993. Compilation of Air Pollutant Emission Factors (AP-42). Petroleum industry.
Petroleum refining. 5.1-1 to 5.1-16. January, 1995. Research Triangle Park, NC: U.S. EPA,
OAQPS.
(12) Gerstle RW, Katari VS. 1977. Industrial Process Profiles for Environmental Use: Chapter
23. Sulfur, Sulfur Oxides and Sulfuric Acid. Prepared for Industrial Environmental Research
Laboratory, Cincinnati, OH, Austin, TX: Radian Corporation. [NTIS PB-281 490]
(13) Perry RH, Green DW. 1984. Perry's Chemical Engineers' Handbook, 6th Edition, pp. 3-68,
9-38 to 9-50. New York, NY: McGraw-Hill Book Company.
D-17
-------
(14) EPA. 1995. Compilation of Air Pollutant Emission Factors (AP-42). Fuel Oil Combustion
(AP-42). pp. 1.3-1 to 1.3-34. January 1995. Research Triangle Park, NC: U.S. EPA, OAQPS.
(15) EPA. 1995. Compilation of Air Pollutant Emission Factors (AP:42). Bituminous and
Subbituminous Coal (AP-42). pp. 1.1-1 to 1.1-40. January 1995. Research Triangle Park, NC:
US. EPA, OAQPS.
(16) Pierce R, 1977- Estimating acid dew points in stack gases. Chemical Engineering, April 11,
1997, vol. 89, pp. 125-128.
(17) Eatough DJ, Caka FM, Farber RJ. 1994. The conversion of SO2 to sulfate in the atmosphere.
Israel Journal of Chemistry 34: 301-314.
(18) EPA. 1982. Air Quality Criteria for Particulate Matter and Sulfur Oxides, Volume II, EPA-
6|p/8-82-029J>. R|search Triangle Park, NC: U.S. EPA, Environmental Criteria and Assessment
Office, pp. 2-1 to 2-100.
(19J EPA.19J8. Acid Aerosols Issue Paper. EPA-600/8-88-005a. Washington, D.C.: Office of
Heath and Environmental Assessment, pp. 2-1 to 2-74.
I i
(20) National Council for Air and Stream Improvement (NCASI). 1995. Compilation of'Air
Toxic' and total hydrocarbon emission data for sources at chemica! wood pulp mills. Volume 2.
Technical Bulletin No. 701, National Council for Air and Stream Improvement, Research
Triangle Park, NC. October 1995.
(21) National Council for Air and Stream Improvement (NCASI). 1996. Proceedings of the 1995
NCASI Southern Regional Meeting. Volume 2. Special Report No. 96-01, National Council for
Air and Stream Improvement, Research Triangle Park, NC. October 1995. P. 326.
(22) Muller TL. 1992. Air Pollution Engineering Manual. Buonicore, AJ and Davis WT, eds,
Van Nostrand Reinhold, New York., pp.469-476.
'"'IKliii,:! i,';i .."mil
D-18
-------
APPENDIX 1
Figure la. Boiling curves for sulfuric acid at 1013 mbar a)
Vapor; b) Liquid (reference 1).
Information in the above figure shows that if the vapor above a solution of 85% sulfuric
acid, boiling at 223 °C, were to be completely condensed it would contain approximately 7
percent H2SO4. At concentrations below approximately 75% H2SO4, the vapor that evaporates
from the solution is essentially water.
Table la. Sulfuric Acid Partial Pressure and Total Vapor Pressure (bar) over Aqueous Sulfuric Acid*
°F
32
68
104
140
176
212
302
392
482
572
Weight Percent Sulfuric Acid
20.0
.843E-20
(.534E-02)
.769E-18
(.205E-01)
.389E-16
(.649E-01)
.121E-14
(.175)
.254E-13
(.417)
.381E-12
(.891)
.106E-09
(4.132)
.883E-08
(13.107)
.312E-06
(31.939)
.591E-05
(64.407)
40.0
.344E-17
(.326E-02)
.193E-15
(.130E-01)
.649E-14
(.427E-01)
.144E-12
(.119)
.225E-11
(.290)
.264E-10
(.634)
.460E-08
(3.090)
.278E-06
(10.245)
.793E-05
(26.056)
.130E-03
(54.869)
60.0
.438E-14
(.836E-03)
.149E-12
(.367E-02)
.317E-11
(.131E-01)
.462E-10
(.395E-01)
.492E-09
(.104)
.402E-08
(.244)
.316E-06
(1.392)
.975E-05
(5.312)
.156E-03
(15.351)
.156E-02
(36.361)
80.0
.161E-10
(.197E-04)
.305E-09
(.115E-03)
.379E-08
(.531E-03)
.334E-07
(.204E-02)
.222E-06
(.668E-02)
.117E-05
(.192E-01)
.343E-04
(.170)
.457E-03
(.913)
.358E-02
(3.439)
.266E-01
(9.916)
98.0
.187E-08
(.117E-07)
.224E-07
(.121E-06)
.191E-06
(.914E-06)
.122E-05
(.538E-05)
.622E-05
(.257E-04)
.261E-04
(.103E-03)
.493E-03
(.180E-02)
.470E-02
(.166E-01)
.278E-01
(.985E-01)
.117E-00
(.425)
0.0
.228E-08
(.323E-08)
.273E-07
(.435E-07)
.230E-06
(.425E-06)
.147E-05
(.319E-05)
.743E-05
(.193E-04)
.310E-04
(.966E-04)
.574E-03
(.287E-02)
.538E-02
(.427E-01)
.314E-01
(.389)
.130E-00
(2.476)
* Total pressure is in parentheses. Conversion Factors: 1 bar = 0.98677 atmospheres = 14.7 psia = 760 mm Hg = 0.1
MPa
D-19
-------
The above table contains the partial pressure of sulfuric acid and total vapor pressure of
the solution (in parentheses) over aqueous sulfuric acid solutions in the concentration range of 20
to 100 weight percent sulfuric acid (1). From Table la we see that the partial pressure of sulfuric
acid above a sulfuric acid solution is very low compared to the total vapor pressure for sulfuric
'.""{'I t ,' '' I:?*', ' 4! , , ', M 'I, "' I , ^ ' : ' > * '»',.. ^ ,1 ^ , : I
a£ld solutions below 80% sulfuric acid; the bulk of the vapor being composed of water.
Consequently when a solution of sulfuric acid boils, more water than sulfuric acid is volatilized,
so that the concentration of the remaining acid increases and the boiling point of the solution
rises. This process continues until the acid concentration reaches 98.3 weight % H2SO4, when an
a^eotrope (a mixture of two liquids that boils at constant composition; i.e., the composition of the
vapor is the same as that of the liquid) is formed and the concentration of sulfuric acid in the
vapor is the same as that of the solution. The vapor above sulfuric acid solutions containing more
than 98.3 weight % H2SO4 also includes considerable amounts of SO3, thus the difference
between the partial pressure and total pressure of 100% sulfuric acid is the partial pressure of
Slilfur trJQxide. Since the partial pressure of concentrated sulfuric acid is very low, little sulfuric
acid is expected to volatilize from sulfuric acid solutions such as may be present in storage tanks.
No experimental data are available on sulfuric acid aerosol emissions from storage tanks.
Above 340°C, H2SO4 decomposes into sulfur trioxide and water. Trie vapor-phase
reaction of sulfur, trioxide and water results in aerosols of sulfuric acid. The H2SO4/H2O/SO3
system is important in the production of sulfuric acid by the contact process as well as in the
prevention of corrpsionfrom condensing sulfuric acid in stack emissions from the combustion of
sulfur-containing fuels. Sulfuric acid containing dissolved sulfur trioxide is known as oleum,
fuming sulfuric acid or disulfuric acid. The vapor pressure of sulfuric acid over oleum containing
10% to 30% of free SO3 by weight is shown in Table 2a (2). Since the vapor pressure of sulfur
trioxide over oleum is high, sulfuric acid aerosols also form when oleum is exposed to air
containing moisture.
, , i; ' , ,
Table 2a. Sulfuric Acid Partial Pressure (bar) over Oleum *
°c
20
40
60
80
100
Free SO3 in oleum, %
10
.227 E-08
.1467E-07
.7333 E-07
.3066 E-06
.1067E-05
20
.120 E-08
.667 E
.400 E-07
.1600 E-06
.5333 E-06
30
.40 E-09
-08 .267 E-08
.1333 E-07
.600 E-07
.2133 E-06
,
Conversion Factors: 1 bar-= 0.98677 atmospheres = 14.7 psia = 760 mm Hg = 0.1 Mpa;
"F=
-------
Appendix E
LIST OF TOXIC CHEMICALS WITHIN THE WATER DISSOCIABLE
NITRATE COMPOUNDS CATEGORY AND GUIDANCE FOR REPORTING
-------
cl!
-------
United States
Environmental Protection
Agency
Office of Pollution Prevention and
Toxics
Washington, DC 20460
Revised May 1996
EPA 745-R-96-004
TOXICS RELEASE INVENTORY
List of Toxic Chemicals Within the Water Dissociable Nitrate
Compounds Category and Guidance for Reporting
EPCRA Section 313 of the Emergency Planning and Community Right-to-Know Act of
1986 (EPCRA) requires certain facilities manufacturing, processing, or otherwise using listed
toxic chemicals to report their environmental releases of such chemicals annually. Beginning
with the 1991 reporting year, such facilities also must report pollution prevention and recycling
data for such chemicals, pursuant to section 6607 of the Pollution Prevention Act, 42 U.S.C.
13106. When enacted, EPCRA Section 313 established an initial list of toxic chemicals that was
comprised of more than 300 chemicals and 20 chemical categories. EPCRA Section 313(d)
authorizes EPA to add chemicals to or delete chemicals from the list, and sets forth criteria for
these actions.
CONTENTS
Section 1. Introduction E-2
1.1 Who Must Report E-2
1.2 Thresholds E-2
1.3 Chemicals within the Water Dissociable Nitrate Compounds Category E-3
1.4 De Minimis Concentrations E-3
Section 2. Guidance for Reporting Chemicals within the Water Dissociable Nitrate
Compounds Category E-4
2.1 Chemicals within the Water Dissociable Nitrate Compounds Category E-4
2.2 Determining Threshold and Release Quantities for Nitrate Compounds E-4
2.3 Reporting Nitrate Compounds Generated from the Partial or Complete
Neutralization of Nitric Acid E-5
2.3.1 Estimating Nitric Acid Releases E-6
2.3.2 Estimating Treatment Efficiencies for Nitric Acid
Neutralization E-8
2.3.3 Estimating Releases of Nitrate Compounds Generated from the
Neutralization of Nitric Acid E-9
2.4 Generation of Nitrate Compounds from Biological Wastewater Treatment .. E-10
Section 3. CAS Number List of Some of the Individual Chemicals within the Water
Dissociable Nitrate Compounds Category E-l 1
E-l
-------
H
i:'!'"!:
' IE
II
Seciton 1. Introduction
OpNovem|er 30, 1994 EPA added 286 chemicals and chemical categories, which
infclude 39 chemicals as part of two delineated categories, to the list of toxic chemicals subject to
reporting under EptJRA Section 313 of the Emergency Planning and Community Right-to-Rnow
Act of 1986 (EPCRA), 42 U.S.C. 11001. These additions are described at 59 FR 61432, and are
effective January 1, 1995 for reports due July 1,1996. Six chemical categones (nicotine and
salts, strychnine arid salts, polycyclic aromatic compounds, water dissociable nitrate compounds,
di|Spcyanates,and poiychlorinated alkanes) are included in these additions. At the time of the
addition, EPA indicated that the Agency would develop, as appropriate, interpretations and
guidance that the Agency determines are necessary to facilitate accurate reporting for these
categories. This document constitutes such guidance for the water dissociable nitrate compounds
category.
,;>, . ' . 'ill sii ,..".. ' ,i> . i i 1: : :
Section 1.1 Who Must Report
''I . " , I; . ..'.'i . . . , . . , , v , - i.- i , ,. ,
A plant, factory, or other facility is subject to the provisions of EPCRA Section 313, if it
rngets all three of the following criteria:
K '! !"!;
;;-,; i f!; ;, ', , ; ;;, I, !
It conducts manufacturing operations (is included in Standard Industrial Classification
(SIC) codes 20 through 39); and
« It has 10 or more full-time employees (or the equivalent 20,000 hours per year); and
It manufactures, imports, processes, or otherwise uses any of the toxic chemicals
listed on the EPCRA Section 313 list in amounts greater than the "threshold"
quantities specified below.
Section 1.2 Thresholds
Tliresliplds are specified amounts of toxic chemicals used during the calendar year that
trigger reporting requirements.
F
111 "" ' ' ' " ' ' [
If a facility manufactures or imports any of the listed toxic chemicals, the thresholds
quantity will be:
in., iv ", , . ;;., . ;-. i
25,000 pounds per toxic chemical or category over the calendar year.
If a facility processes any of the listed toxic chemicals, the threshold quantity will be:
25,000 pounds per toxic chemical or category over the calendar year.
If a facility otherwise uses any of the listed toxic chemicals (without incorporating it
into any product or producing it at the facility), the threshold quantity is:
10,000 pounds per toxic chemical or category over the calendar year.
E-2
-------
EPCRA Section 313 requires threshold determinations for chemical categories to be
based on the total of all chemicals in the category manufactured, processed or otherwise used.
For example, a facility that manufactures three members of a chemical category would count the
total amount of all three chemicals manufactured towards the manufacturing threshold for that
category. When filing reports for chemical categories, the releases are determined in the same
manner as the thresholds. One report is filed for the category and all releases are reported on this
form.
Section 1.3 Chemicals Within the Water Dissociable Nitrate Compounds Category
EPA is providing a list of CAS numbers and chemical names to aid the regulated
community in determining whether they need to report for the water dissociable nitrate
compounds category. The list includes individual chemicals within the water dissociable nitrate
compounds category. If a facility is manufacturing, processing, or otherwise using a chemical
which is on this list, they must report this chemical. However, this list is not exhaustive. If a
facility is manufacturing, processing, or otherwise using a water dissociable nitrate compound,
they must report the chemical, even if it does not appear on the list.
Section 1.4 De Minimis Concentrations
The water dissociable nitrate compounds category is subject to the one percent de
minimis concentration. Thus, mixtures that contain members of this category in excess of the de
minimis should be factored into threshold and release determinations.
E-3
-------
"if!1
' in
Section 2. Guidance for Reporting Chemicals within the Water Dissociable Nitrate
Compounds Category
ji! , ", ""\i ,:J::j|ji,|i,. ;'» , _ ii;1; ; , , i" ;;; : . : '" . ; i :.j. Mfc. . «lj>i'' ' ,.l .''';.' I ' .,.- .',,';,. ,
Note: for the purposes of reporting under the nitrate compounds category, water
dissociable means that the nitrate ion dissociates from its counterfoil when in solution.
" .ill:, , ,, : ,' I. lair?!1 Kill1 '. I"1 , l,.;» '; !' '" ' ',:'': ,i, ' , ' ''i1,, ...,'!!:;, ; " 'fv.;i:!, ,. , !:«;r v 'I, ,.:, !' l|1.,Ji, ' . ,|'
Section 2.1 Chemicals within the Water Dissociable Nitrate Compounds Category
Chemicals within the nitrate compounds category are only reportable when in aqueous
solution. All water dissociable nitrate compounds are included in the nitrate compounds
category, including ammonium nitrate. Specifically listed EPCRA Section 313 chemicals are
not included in threshold determinations for chemical categories such as the water dissociable
nitrate compounds category. Specifically listed toxic chemicals are subject to their own
individual threshold determinations. As of December 1, 1994, ammonium nitrate (solution) is
n6t an individually listed chemical on the EPCRA Section 313 list. However, ammonium nitrate
is still subject to reporting under the nitrate compounds category. In addition, the aqueous
alppibnia from thg dissociation of anjmonium nitrate when in aqueous solution is subject to
reporting under the ammonia listing.
Section 2,2 Determining Threshold and Release Quantities for Nitrate Compounds
>,,! !' if. ',., ;, :ii' ..[ill , i '','! ! , ; , i .',,-; ',' (»:n i iiS1"!!',::;, i", :' .f.ir''r , > ,:, :: ;.-,
The total nitrate compound, including both the nitrate ion portion and the counterion, is
included in the nitrate compounds category. When determining threshold amounts, the total
weight of the nitrate compound is to be included in all calculations. However, only the nitrate
ion portion is to be included when determining the amount of the chemicals within the nitrate
compounds category that is released, transferred, or otherwise managed in wastes.
Example.!.: In a calendar year, a facility processes 100,000 pounds of ammonium nitrate
(NH4NO3), in aqueous solution, which is released to wastewater streams then transferred to a
POTW. The quantity applied towards threshold calculations for the nitrate compounds
category is the total quantity of the nitrate cornpound or 100,000 pounds. Since this quantity
exceeds the 25,000 pound processing threshold, the facility is required to report for the nitrate
compounds category. Under the nitrate compounds category, only the weight of the nitrate ion
portion of ammonium nitrate is included in release transfer calculations. The molecular
weight of the ammonium nitrate is 80.04 and the weight of the nitrate ion portion is 62.01 or
77.47 percent of the molecular weight of ammonium nitrate. Therefore, the amount of nitrate
ion reported as transferred to the POTW is 77.47 percent of 100,000 pounds or 77,470 pounds
(reported as 77,000 pounds). The aqueous ammonia from ammonium nitrate is reportable
under the EPCRA Section 313 listing for ammonia. For determining thresholds and
calculating releases under the ammonia listing, see the separate directive, Guidance for
Reporting Aqueous Ammonia (EPA document #745-R-95-0003, July 1995).
E-4
-------
Example 2: In a calendar year, a facility manufactures as by-products 20,000 pounds of
sodium nitrate (NaNO3) and 10,000 pounds of calcium nitrate (Ca(NO3)2), both in aqueous
solutions, and releases these solutions to wastewater streams. The total quantity of nitrate
compounds manufactured by the facility is the sum of the two chemicals, or 30,000 pounds,
which exceeds the manufacturing threshold quantity of 25,000 pounds. The facility therefore
is required to report for the nitrate compounds category. By weight, the nitrate ion portion is
72.96 percent of sodium nitrate and is 75.57 percent of calcium nitrate. Of the 20,000 pounds
of the sodium nitrate in solution, 72.96 percent or 14,592 pounds is nitrate ion, and similarly,
of the 10,000 pounds of the calcium nitrate in solution, 75.57 percent or 7,557 pounds is
nitrate ion. The total nitrate ion in aqueous solution released by the facility is the sum of the
nitrate ion in the two solutions or 22,149 pounds (reported as 22,000 pounds).
Section 2.3 Reporting Nitrate Compounds Generated from the Partial or Complete
Neutralization of Nitric Acid
Nitric acid is an individually listed chemical on the original EPCRA Section 313, list and
is reported as a separate chemical if the manufacture, process, or otherwise use thresholds are
exceeded. The partial or complete neutralization of nitric acid results in the formation of nitrate
compounds which are reported as chemicals within the nitrate compounds category if their
manufacture, process, or otherwise use thresholds are exceeded.
Mineral acids such as nitric acid may be present in aqueous waste streams that are sent to
on-site neutralization or are discharged to a publicly owned treatment works (POTW) or other
off-site treatment facility. As stated in the Toxic Chemical Release Inventory Reporting Form R
and Instructions document (revised 1993 version, EPA 745-K-94-001), on-site acid
neutralization and its efficiency must be reported in Part II, section 7 A of Form R (waste
treatment methods and efficiency section). For purposes of reporting on Form R, EPA considers
a waste mineral acid at a pH 6 or higher to be 100 percent neutralized (water discharges to
receiving streams or POTWs are reported as zero). The nitrate compounds produced from the
complete neutralization (pH 6.0 or above) of nitric acid are reportable under the nitrate
compounds category and should be included in all threshold and release calculations. Two Form
R reports would be required if the manufacture, process or otherwise use thresholds are exceeded
for nitric acid and for the nitrate compounds category.
If the nitric acid treatment efficiency is not equal to 100 percent (pH is less than 6), the
amount of the acid remaining in the waste stream which is released to the environment on-site or
off-site must be reported in Part II of Form R. The nitrate compounds produced from the partial
neutralization of nitric acid are reportable under the nitrate compounds category and should be
included in all threshold and release calculations. Two reports would again be required if the
manufacture, process or otherwise use thresholds are exceeded for nitric acid and for the nitrate
compounds category.
E-5
-------
Section 2.3.1 Estimating Nitric Acid Releases
Mill
n: »i v
The pH of the waste stream can be used to calculate the amount of nitric acid in the
stream and the efficiency of neutralization. The pH is a measure of the acidity or alkalinity of a
waste stream anS can be obtained readily using a pH meter or pM sensitive paper. The pH scale
itself varies fronjiO Jo 14. f t i , ( i (i i ,, "
The total nitric acid concentration (ionized and un-ionized) in pounds per gallon can be
calculated by using the pH value of the solution, the molecular weight and ionization constant of
the acid, an3 appropriate conversion factors. The total acid concentration for nitric acid for
different pH values is listed in Table 1. The calculation of mineral acid concentrations and the
derivation of Table 1are discussed in a separate directive, Estimating Releases for Mineral Acid
Discharges Using pH Measurements, and an addendum to this directive.
'I'lli!! T? , ,- ,,S' I ,i , ,l" I .' » ,i -: , / ,,r , , r '
i'
The procedure outlined in this guidance document for calculating the quantity of nitrate
compounds formed from the complete or partial neutralization of nitric acid can be used if nitric
acid is the only mineral acid in a solution. In addition, the calculation of nitric acid releases
using only pH measurements is a rough estimate. The subsequent calculation of nitrate
dom|oilnd releases is therefore also only a rough estimate. The estimates can be made for a
wasle stream with a steady pH below 6 or for one whose pH temporarily drops to below pH 6.
Facilities should use jheir best engineering judgement and knowledge of the solution to evaluate
ho\v reasonable me estimates are!
iv:w
rfii1
I'liF
Example 3: In a calendar year, a facility transfers 1.0 million gallons of a solution containing
nitric acid (HNO3), at pH 4, to a POTW. Using Table 1 (next page), a pH of 4 corresponds to
a concentration of 0.0000520 Ibs HNO3/gallon of solution. The weight of HNO3 transferred
can be estimated using the equation:
Transfer of HNO3 = (Concentration of HNO3) x (effluent flow rate)
Substituting the example values into the above equation yields:
Transfer of HNO, = 0.0000520 Ibs/gal HNO, x 1,000,000 gal solution/year = 52 Ibs/year
Example 4: A facility had an episodic release of nitric acid (HNO3) in which the "waste stream
was temporarily below pH 6. During the episode, the wastewater (pH 2.0) was discharged to a
river for 20 minutes at a rate of 100 gallons per minute. Using Table 1, a pH of 2.0 for HNO3
represents a concentration of 0.0052000 Ibs HNO3/gallon of solution. The amount of the
HNOj released can be estimated using the following equation:
Release of HNO3 = (concentration of HNO3) x (effluent flow rate)
Substituting the example values hi the above equation:
Release of HNO3 = 0.0052000 Ibs/gal x 100 gal/min x 20 min
= 10 Ibs
E-6
-------
Table E-l
Nitric Acid Concentration Versus pH
pH
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
Nitric Acid Concentration
(Ibs/gallon)
0.5200000
s. 0.3300000
0.2100000
0.1300000
0.0830000
0.0520000
0.0330000
0.0210000
0.0130000
0.0083000
0.0052000
0.0033000
0.0021000
0.0013000
0.0008300
pH
3.0
3.2
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
5.8
6.0
Nitric Acid Concentration
(Ibs/gallon)
0.0005200
Of 0003300
010002100
+0.0001300
0.0000830
0,0000520
0.0000330
0.0000210
0.0000130
0.0000083
0.0000052
0.0000033
0.0000021
0.0000013
0.0000008
0.0000005
Section 2.3.2 Estimating Treatment Efficiencies for Nitric Acid Neutralization
Nitric acid solutions that are neutralized to a pH of 6 or above have a treatment efficiency
of 100 percent. If nitric acid is neutralized to a pH less than 6, then the reportable treatment
efficiency is somewhere between 0 and 100 percent. It is possible to estimate the neutralization
treatment efficiency using nitric acid concentration values directly from Table 1 in the equation
given below. The concentrations correspond to the pH values before and after treatment.
(I-E)
Treatment efficiency = -x 100
where:
I = Acid concentration before treatment; and
E = Acid concentration after treatment.
E-7
-------
I).
Jjllj '
i?
il
Example 5: A nitric acid (HNO3) waste stream of pH 2.4 is neutralized to pH 4.6. Using
Table 1, the initial nitric acid concentration is 0.0021000 mol/liter and the final concentration
is 0.0000130 mol/liter. Substituting these values into the equation for treatment efficiency:
Treatment Efficiency =
(0.0021000-0.0000130)
0.0021000
= 99.4 percent
xlOO
11 i i?:,!!
For strong acids only (including nitric acid), the net difference in pH before and after
treatment can be. used to estimate the treatment efficiency since pH is directly proportional to the
acid concentration. For example, a pH change of one unit results in a treatment efficiency of 90
percent, whether the pH change is from pH 1 to pH 2 or from pH 4 to pH 5. Table 2 summarizes
treatment efficiencies for various pH changes (the pH change is the difference between the initial
pH and the pH after neutralization). In the table, some pH changes result in the same treatment
efficiency values due to rounding to one decimal place.
E-8
;:!;;:;
-------
Table E-2
Nitric Acid Treatment Efficiencies for Various pH Changes
pH Unit Change
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
Treatment Efficiency
(%)
90.0
92.1
93.7
95.0
96.0
96.8
97.5
- 98.0
98.4
98.7
pH Unit Change
2.0
2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
3.0
Treatment Efficiency
(%)
99.0
99.2
99.4
99.5
99.6
99.7
99.8
99.8
99.8
99.9
99.9
Example 6: If a nitric acid (HNO3) waste stream of pH 2 is treated to pH 4, the pH change is 2
units. Using Table 2 above, the treatment efficiency is given as 99.0 percent.
Section 2.3.3 Estimating Releases of Nitrate Compounds Generated from the
Neutralization of Nitric Acid
The nitrate compounds produced from the complete neutralization (pH 6.0 or above) or
partial neutralization (pH less than 6) or nitric acid are reportable under the nitrate compounds
category if the appropriate threshold is met and should be included in all threshold and release
calculations. In order to determine the quantity of a nitrate compound generated and released,
the quantity of nitric acid released must be known (or calculated from the equations used in
Examples 3 and 4 above) as well as the nitric acid treatment efficiency (calculated from the
equations used in Examples 5 and 6 above).
The neutralization of nitric acid will most likely result in the generation of monovalent
nitrate compounds (such as sodium nitrate and potassium nitrate). The quantity of these
compounds formed in kilomoles will be equal to the quantity of the nitric acid neutralized in
kilomoles. If divalent nitrate compounds are formed (such as calcium nitrate), the quantity of
these compounds formed in kilomoles will be equal to one-half the quantity of the nitric acid
neutralized in kilomoles. Similarly, if trivalent nitrate compounds are formed (such as iron (III)
nitrate), the quantity formed of these compounds in kilomoles will be equal to one-third the
quantity of the nitric acid neutralized in kilomoles. Note: to calculate the releases of nitrate
compounds generated from the neutralization of nitric acid, the molecular weight of the nitrate
compound formed must be used. Molecular weights of some of the individual chemicals within
the water dissociable nitrate compounds category are given in Table 3.
E-9
-------
i
f
Example 7r In a calendar year, a facility transfers 50,000 pounds of nitric acid (H1SFO3) to an
on-site treatment facility. The nitric acid treatment efficiency is 95 percent, and the nitrate
compound formed as a result of the treatment is sodium nitrate (NaNO3). The quantity of
nitric acid transferred that is neutralized (generating sodium nitrate) is 95 percent of 50,000
pounds or 47,500 pounds. The molecular weight of nitric acid is 63.01 kg/kmol, and the
molecular weight of sodium nitrate is 84.99 kg/kmol. The quantity of nitric acid neutralized is
converted first to kilograms then to kilomoles using the following equations:
Kilograms HNO3 neutralized = (Ibs HNO3 neutralized) x (0.4536 kg/lb)
Kilomoles HNO3 neutralized = (kg HNO3) * (MW of HNO3 in kg/kmol)
Substituting the example values into the above equation yields:
Kilograms HNO3 neutralized = 47,500 Ibs x 0.4536 kg/lb = 21.546 kg
Kilomoles HNO3 neutralized = 21,546 kg -H 63.01 kg/kmol = 341.9 kmol
The quantity of sodium nitrate generated in kilomoles is equal to the quantity of nitric acid
neutralized (341.9 kmol). The quantity of sodium nitrate generated in kilomoles is converted
first to kilograms then to pounds using the following equations:
Kilograms NaNO3 generated = (kmol NaNO3) x (MW of NaNO3 in kg/kmol)
Pounds NaNO3 generated = (kg NaNO3) x (2.205 Ibs/kg)
Substituting the values into the above equation yields:
Kilograms NaNO3 generated = 341.9 kmol x 84.99 kg/kmol = 29,058 kg
Pounds NaNO3 generated = 29,058 kg x 2.205 Ibs/kg = 64,073 pounds (reported as
64,000 pounds)
The 64,000 pounds of sodium nitrate generated is the quantity used to determine whether
thresholds have been met or exceeded. The quantity of nitrate ion released is calculated as in
Example 1 above.
Section 2.4 Generation of Nitrate Compounds from Biological Wastewater Treatment
'..:, I , , ! 111!!1 IB , ',,.' , ' 'I..*. . . . ', ,. , .... .! .| . ,
If a facility treats wastewater on-site biologically, using the activated sludge process, for
eljample, the facility may be generating nitrate compounds as by-products of this biological
process. The nitrate ion generated from this process will be associated with various counterions
(eTg., sodium ion, potassium ion). In the absence of information on the identity of the
caftriteripn, a facility should assume for the purposes of EPCRA Section 313 threshold
determinations that the counterion is sodium ion.
"KB.,. I:
E-10
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Section 3. CAS Number List of Some of the Individual Chemicals within the Water
Dissociable Nitrate Compounds Category
EPA is providing the following table of CAS numbers and chemical names to aid the
regulated community in determining whether they need to report for the water dissociable nitrate
compounds category. If a facility is manufacturing, processing, or otherwise using a chemical
which is listed below, they must report this chemical. However, this list is not exhaustive. If a
facility is manufacturing, processing, or otherwise using a water dissociable nitrate compound,
they must report this chemical, even if it does not appear on the following list.
Table E-3
Listing by CAS Number and Molecular Weight of Some of the Individual
Chemicals within the Water Dissociable Nitrate Compounds Category
Chemical Name
Aluminum nitrate, nonahydrate
Ammonium nitrate
Cerium (III) ammonium nitrate, tetrahydrate
Cerium (IV) ammonium nitrate
Barium nitrate
Beryllium nitrate, trihydrate
Cadmium nitrate
Cadmium nitrate, tetrahydrate
Calcium nitrate
Calcium nitrate, tetrahydrate
Cerium (III) nitrate, hexahydrate
Cesium nitrate
Chromium (HI) nitrate, nonahydrate
Cobalt (II) nitrate, hexahydrate
Copper (II) nitrate, trihydrate
Copper (II) nitrate, hexahydrate
Dysprosium (HI) nitrate, pentahydrate
Erbium (III) nitrate, pentahydrate
Gadolinium (III) nitrate, hexahydrate
Gallium nitrate, hydrate
Iron (III) nitrate, hexahydrate
Iron (III) nitrate, nonahydrate
Molecular Weight*
213.00
80.04
486.22
548.23
261.34
133.02
236.42
236.42
164.09
164.09
326.13
194.91
238.01
182.94
187.56
187.56
348.51
353.27
343.26
255.73
241.86
241.86
CAS Number
7784-27-2
6484-52-2
13083-04-0
10139-51-2
10022-31-8
7787-55-5
10325-94-7
10022-68-1
10124-37-5
13477-34-4
10294-41-4
7789-18-6
7789-02-8
10026-22-9
10031-43-3
13478-38-1
10031-49-9
10031-51-3
19598-90-4
69365-72-6
13476-08-9
7782-61-8
E-ll
-------
l«iiH^ Pi iiBiV'!1!!! !l"l« lI'H'i
rilNttii Ril NMMf ":SW"Ph1':>l:"' i '" T f'tlfi 1
" ' ' ' ' ' ' ' '
Table E-3 (Continued)
Chemical Name
Lanthanum (HI) nitrate, hexahydrate
Lead (II) nitrate
Lithium nitrate
Lithium nitrate, trihydrate
Magnesium nitrate, dihydrate
Magnesium nitrate, hexahydrate
Manganese (n) nitrate, tetrahydrate
Neodymium (HI) nitrate, hexahydrate
Nickel (II) nitrate, hexahydrate
Potassium nitrate
Rhodium (IE) nitrate, dihydrate
Rubidium nitrate
Samarium (IE) nitrate, hexahydrate
Scandium (ffl) nitrate
Scandium (HI) nitrate, tetrahydrate
Silver nitrate
Sodium nitrate
Strontium nitrate
Strontium nitrate, tetrahydrate
Terbium (HI) nitrate, hexahydrate
Thorium (TV) nitrate
Thorium (IV) nitrate, tetrahydrate
Yttrium (III) nitrate, hexahydrate
Yttrium (HI) nitrate, tetrahydrate
Zinc nitrate, trihydrate
Zinc nitrate, hexahydrate
Zirconium (IV) nitrate, pentahydrate
Molecular Weight*
324.92
331.21
68.95
68.95
148.31
148.31
178.95
330.25
182.70
101.10
288.92
147.47
336.37
230.97
230.97 ,
169.87
84.99
211.63
211.63
344.94
480.06
480.06
274.92
274.92
189.39
189.39
339.24
CAS Number
10277-43-7
10099-74-8
7790-69-4
13453-76-4
15750-45-5
13446-18-9
20694-39-7
16454-60-7
13478-00-7
7757-79-1
13465-43-5
13126-12-0
13759-83-6
13465-60-6
16999-44-3
7761-88-8
7631-99-4
10042-76-9
13470-05-8
13451-19-9
13823-29-5
13470-07-0
13494-98-9
13773-69-8
131446-84-9
10196-18-6
13986-27-1
*For hydrated compounds, e.g., aluminum nitrate, nonahydrate, the molecular weight excludes the weight of the hydrate portion.
For example, the same molecular weight is provided for aluminum nitrate, nonahydrate and aluminum nitrate.
E-12
-------
Appendix F
UNIT CONVERSION FACTORS
(From U.S. Coast Guard Commandant Instruction M.I6465.12A)
-------
I'l'iil'
3,',! Ill'
lii "
"111!' r
!f r
:,.'![ ,'1'
-------
CONVERSION FACTORS
To Convert
To
Multiply By
Length
inches
inches
feet
feet
feet
feet
yards
yards
miles (U.S. statute)
miles (U.S. statute)
miles (U.S. statute)
miles (U.S. statute)
meters
meters
meters
nautical miles
millimeters
feet
inches
meters
yards
miles (U.S. statute)
feet
miles (U.S. statute)
feet
yards
meters
nautical miles
feet
yards
miles (U.S. statute)
miles (U.S. statute)
25.4
0.0833
12
0.3048
0.3333
0.0001894
3
0.0005682
5280
1760
1609
0.868
3.271
1.094
0.0006214
1.152
Area
square inches
square inches
square feet
square feet
square meters
square miles
square yards
square centimeters
square feet
square inches
square meters
square feet
square yards
square feet
6.452
0.006944
144
0.09290
10.76
3,097,600
9
Volume
cubic inches
cubic inches
cubic feet
cubic feet
cubic feet
cubic meters
liters
quarts (U.S. liquid)
U.S. gallons
U.S. gallons
U.S. gallons
barrels (petroleum)
Imperial gallons
milliliters
cubic centimeters
cubic feet
cubic inches
cubic meters
U.S. gallons
cubic feet
quarts (U.S. liquid)
liters
barrels (petroleum)
cubic feet
Imperial gallons
U.S. gallons
U.S. gallons
cubic centimeters
16.39
0.0005787
1728
0.02832
7.481
35.31
1.057
0.9463
0.02381
0.1337
0.8327
42
1.201
1
F-l
-------
To Convert
CONVERSION FACTORS (Continued)
1 ^ , ' ^ ' '"_['_ n 'j'
To Multiply By
Time
seCbiids
seconds
segpnels
minutes
minutes
minutes'
hours
hours
hours
minutes
hours
days
seconds
hours
days
seconds
minutes
days
0.01667
0.0002778
0.00001157
60 ;!
0.01667
0.0006944
3600
60
0.04167
Mass or Weight
iiiii i . ": ........ .................... '
pounds
pounds
pounds
pounds
tons (short)
..... !*' f i. - & ...... , ...... ........
tons (metnc)
tons (long)
kilograms
tonnes (metric tons)
Energy
calories
calories
Btu (British thermal units)
Btu ........
1 joules"
joules ....................
Velocity
feet per second
feet per second
feet per second
meters per second
meters per second
miles per hour
miles per hour
' ' '' *
ititi!"
if'iii
'knots
,
pounds per cubic foot
grams per cubic centimeter
grams er cubic centimeter
kilograms per cubic meter
kilograms
short tons
long tons
metric tons
pounds
pounds
pounds
pounds
kilograms
Btu
joules
calories
joules
calories
Btu
meters per second
miles per hour
knots
feet per second
miles per hour
meters per second
feet per second
meters per second
miles per hour
feet per second
grams per cubic centimeter
pounds per cubic foot
kilograms per cubic meter
grams per cubic centimeter
0.4536
0.0005
0.000464
0.0604536
2000
2205
2240
2.205
1000
0.00396,8
4.187
252.0
1055 ","'
0.2388 |
0.0009479
0.3048
0.6818
0.5921
3.281
2.237
0.4470
1.467
0.5148
1.151
1.689
0.01602
62.42
1000
0.001
F-2
-------
To Convert
CONVERSION FACTORS (Continued)
To Multiply By
Pressure
ponds per square inch (absolute) (psia)
psia
psia
psia
pounds per square inch (gauge) (psig)
millimeters of mercury (torr)
millimeters of mercury (torr)
inches of water
kilograms per square centimeter
inches of water
kilograms per square centimeter
atmospheres
kilograms per square centimeter
atmospheres
bars
kilonewtons per square meter (kN/m2)
bars
kilonewtons per square meter (kN/m2)
bars
kilonewtons per square meter (kN/m2)
atmospheres
inches of water
millimeters of mercury (torr)
psia
psia
kN/m2
psia
millimeters of mercury (torr)
kN/m2
atmospheres
kN/m2
psia
psia
kN/m2
psia
atmospheres
atmospheres
kilograms per square centimeter
6.895
0.0680
27.67
51.72
add 14.70
0.01934
0.1333
0.03614
735.6
0.2491
0.9678
101.3
14.22
14.70
100
0.1450
0.9869
0.009869
1.020
Viscosity
centipoises
pounds per foot per second
centipoises
centipoises
poises
grams per centimeter per second
Newton seconds per square meter
pounds per foot per second
centipoises
poises
Newton seconds per square meter
grams per centimeter per second
poises
centipoises
0.0006720
1488
0.01
0.001
1
1
1000
Thermal Conductivity
Btu per hour per foot per °F
Btu per hour per foot per °F
watts per meter-kelvin
kilocalories per hour per meter per °C
kilocalories per hour per meter per °C
Heat Capacity
Btu per pound per °F
Btu per pound per °F
joules per kilogram-kelvin
calories per gram per °C
watts per meter-kelvin 1.731
kilocalories per hour per meter per ° C 1.488
Btu per hour per foot per °F 0.5778
watts per meter-kelvin 1.163
Btu per hour per foot per °F 0.6720
calories per gram per ° C 1
joules per kilogram-kelvin 4187
Btu per pound per °F 0.0002388
Btu per pound per °F 1
F-3
-------
Hi!
fii
To Convert
CONVERSION FACTORS (Continued)
To Multiply By
Concentration (in water solution)
piWs per million (ppm)
milligrams per liter
milligrams per cubic meter
grains per cubic centimeter
grams per cubic centimeter
pounds per cubic foot
milligrams per liter
ppm
grams per cubic centimeter
milligrams per cubic meter
pounds per cubic foot
grams per cubic centimeter
IxlO9
62.42
0.01602
Temperature
degrees Kelvin (yK)
degrees Rankine (°R)
degrees centigrade (°C)
degrees Fahrenheit (°F)
degrees centigrade (°C)
degrees Fahrenheit (°F)
degrees Rankine (°R)
degrees Kelvin (°K)
degrees Fahrenheit (°F)
degrees centigrade (°C)
degrees Kelvin (°K)
degrees Kelvin (°K)
1.8
0.5556'
first multiply by 1.8, then add 32
first subtract 32, then multiply by
0.5556
add 273.2
add 459.7
Flow
cubic feet per second
U.S. gallons per minute
U.S. gallons per minute
cubic feet per second
448.9
0.002228
Universal Gas Constant (R)
8,314 joules per gram mole-kelvin
l.$87 calories per gram mole-kelvin
1.987 Btu per pound mole per °F
!Cjj73 psia-cubic feet per pound mole per °F
82j057 atnvpubjecentimeters per gram mole-kelvin
62,361 millimeters mercury liter per gram mole-kelvin
F-4
-------
INDEX
The pages listed in bold text in the index correspond to the primary uses or definitions of the
associated term. Additionally, this index includes a list of primary purposes for examples and
common errors that are presented throughout the document.
Acid aerosol (see Sulfuric acid and Hydrochloric acid) 3-5, 3-7
Common error, acid aerosol reporting 4-40
Activity
Chemical use, subcategories 3-7 to 3-12
Exemption (see Exemptions)
Thresholds (see Threshold)
Air emissions
Fugitive or non-point 4-4, 4-20, 4-25, 4-33, 4-34, 4-38, 4-42, 4-45, 4-48
Stack or point source 4-5, 4-22, 4-24, 4-25, 4-34, 4-35, 4-38, 4-39, 4-42,
4-43,4-45,4-51
Article exemption (see Exemptions)
Automated toxic chemical release inventory software (ATRS) 2-11
Chemical-specific
Acid aerosols 3-5, 3-7, 4-40
Ammonia 2-8, 2-9, 3-6, 3-18, 4-19, 4-36 to 4-39, 4-45, 4-46, Appendix C
Chlorine 3-11, 4-19, 4-31, 4-36, 4-37, 4-39, 4-40, 4-50, 4-51
Hydrochloric acid 2-8, 2-10, 3-5, 3-15, 4-31,4-33, 4-34, 4-40, 4-42, 4-45
Methanol 2-8, 3-11, 3-18, 4-33, 4-34, 4-45, 4-47
Nitrate compounds 2-8, 2-9, 3-6, 3-9, 4-41 to 4-43, 4-53, Appendix E
Sulfuric acid 2-8, 3-6, 3-7, 3-9, 3-17, 4-33, 4-34, 4-40, 4-42,
4-45, Appendix D
Chemical mechanical planarization 2-8, 4-29, 4-51 to 4-53
Chemical processing aid 3-11
Cleaning 2-8, 2-10, 3-9, 3-11, 3-17, 4-7, 4-24, 4-32, 4-43
Combustion 3-15, 3-18, 3-19, 4-3, 4-10, 4-12 to 4-14, 4-23
For energy recovery off-site 4-13 to 4-14
For energy recovery on-site 4-12
For treatment off-site 4-15
For treatment on-site 4-10
Common errors
Acid aerosol reporting 4-40
Assuming a threshold is exceeded 3-22
Coincidental manufacture 2-10
Double counting 4-16
Exempt activities 3-12
Mass balance 4-21
Nitric acid and nitrate compound reporting 4-41
Shipping container residue 4-8, 4-10
Solvent reporting 4-32
Threshold determination for recirculation 3-8
Treatment efficiencies 4-19
Index-i
-------
fijii.
$'
I!:.!
Zero release and other waste management quantities 3-22
Container residue 4-8 to 4-10, 4-45, 4-49, 4-56
Example, container residue 4-10
De minimis (see Exemptions)
Example, de minimis 3-13
Example, de minimis concentration ranges 3-14
Disposal ...'."..' ".'!' , 2-9, 3-9, 4-12
Land, on-site 4-6 to 4-8
' ,|r i \- , |La*id, off-site ...^4-7, 4-12 to 4-15, 4-33, 4-38
Do^umentatiqg (see Recordkeeping)
Doping .... I. ..'."....... . . . . ;: 2-8, 4-29, 4-48 to 4-51
Double counting 4-6, 4-16
Cpmnion error, double counting 4-16
Eniission factors... ..,.....,,., .| ', ,,.,.".,, ,... ,,,,,',,., ..,,14-17, 4-J8, 4-21 to 4-23, B-6
Bxample, emission factors 4-23, B-6
Employee equivalent calculation 2-7 to 2-8
Example, calculating employees 2-2
Energy recovery (see Combustion for energy recovery)
Engineering calculation ... 4-17, 4-18, 4-21, 4-23, 4-24, 4-39, 4-48, 4-51, B-l
Example, engineering calculations 4-24
EPCRAhotline 1-2, 1-3, 1-5, 2-7, 2-11
Establishment. ...... ... .,,..., ,,....., .',,., ,.. 2-1, 2-5
Example, multiple establishments .... 2-2
Example, primary SIC code 2-7
Etching 2-8, 2-10, 3-9, 3-11, 3-17, 4-29, 4-31, 4-39 to 4-43
Examples
Article exemption 3-17
; pli 1l:i::.li'!ii!l ' ,. '' ± ', ' , ', , ,/ . i , . , ' .-.in, i
-------
Relabeling , - 2-10
Thin films 4-39
Threshold determination 3-8
Threshold worksheet 3-23
Exempt activities 3-1, 3-7, 3-12, 3-18
Common error, exempt activities 3-12
Exemptions 3-12
Activity-related 3-12, 3-17
Article 3-12,3-15
De minimis 3-12 to 3-15, D-3, E-3
Drawn from environment .3-19
Evaluation of 3-12
Facility-related 3-17
Grounds maintenance 3-17
Janitorial 3-17
Laboratory 2-5, 3-17
Motor vehicle 3-18
Personal use, example 3-18
Structural components 3-18
Facility
Auxiliary facility 2-5
Covered facility 2-5, 2-14
Multi-establishment facilities (see Establishments)
Pilotplant 2-5, 3-17
Facility-related exemption (see Exemption)
Form A 1-3 to 1-5, 2-1, 2-2, 2-12 to 2-14, 3-20
Example Form A threshold .., 2-12
Form R 1-3 to 1-5, 2-2, 2-10 to 2-13, 3-20, 4-4 to 4-16, 4-25,
4,26, 4-28, 4-39, 4-47, 4-52, 4-53, 4-58, 4-59
Impurity 2-9, 3-9, 3-13
Laboratory exemption (see Exemption)
Manufacture/Manufacturing 2-9, 3-5, 3-9
Byproduct 3-9
Coincidental manufacture 3-18, 4-41, 4-42
Manufacturing subcategories 3-9
Mass balance 4-17 to 4-21, 4-34, 4-39, 4-48
Example, mass balance 4-20, 4-21
Methods (see Reportable amount estimate methods)
Mineral acids 4-43
Mixture 2-10, 3-1 to 3-3, 3-9 to 3-11, 3-14, 3-23
Monitoring data 4-18 to 4-20, 4-51, 4-57, B-l
Example, monitoring data 4-19
Motor vehicle exemption (see Exemption)
MSDS 3-4, 3-11
Otherwise use 2-7, 2-19, 3-11
Common error, mass balance for otherwise used chemicals 4-21
Owner/operator 1~3
Index-iii
-------
Penalties ... T|. .........., ,. 1-4
Photolithography 2-8, 4-29, 4-31 to 4-33, 4-35, 4-52
Pilot plant (see Facility)
Pojnt source (see Air emissions)
POTW .....". 4-7, 4-10, 4-11, 4-15, 4-16, 4-18, 4-19, 4-27, 4-33 to 4-35,
4-38, 4-39, 4-41 to 4-43, 4-45, 4-46, 4-51, 4-53
Process/processing 2-9, 3-10
Process equipment 3-17, 3-18
Example, process equipment chemical use 3-19
Process watej£. . ,.,] .,..... f.,'",,,........, ^ ',,.. 3-19
Example, chemicals in process water 3-19
Processing subcategories 3-10
Qualifiers 3-4
Recordkeeping 2-14
Recycling ... 3-8, 3-21, 4-31, 4-32
::: .;:: ,^Of^site i ,.,,.,......,,,. .,, ,... 4-14
On-site .' 4-14
Hi|",|. ' ' i'l'lin ii A! ,' . " ' ' "i ' " i 'lif! . , *| ..... r J.-T
Rglabeling, example 2-10
Release "....'.".. 71 ,'.!.' Chapter 4
Accidental 4-15
Estimates (steps to calculate) 4-1, 4-16
!i;i; :| '-SoiiSces ! 4-3, 4-33, 4-37, 4.41, 4-44, 4-50, 4-52
,;';: ; ; , ..'iJfyifes .V..... 4-4,4-33, 4^38, 4-42, 4-50, 4-53
Remedial actions 3-20, 4-15
Remediation 3-20, 4-16
Repackaging 2-10, 3-10
Reportable amount 2-12
Reportable amount estimate methods 1-4, 2-12
Emission factors 4-21
Engineering calculations 4-23
Mass balance '. 4-19
Monitoring data/records 4-18
Reporting criteria 2-1
Reuse 3-8,3-19
Sources (see Release) M M ' , . ! " , , '
Standaird Indiisjrial (5lassifica1ion (SIC) 2-4 to 2-7
!'f!BJ*r$mary SIC code 2-6, 2-7
Technically qualified individual 3-17
Thin films ,..., ,,,. 2-8, 4-29,4-36 to 4-39
Threshold worksheet ... . 3-22 to 3-24
Thresholds ; , : 3-8
Common error, threshold determination 3-8
Example, threshold determination ,--.. ,-. 3-8
Threshold determination .... Chapter 3, 3-21
Threshold worksheet 3-22
Total annual reportable amount (see Reportable amount)
Trade secret ,,.,"~....,,. .......... .. ,... , 1-4, 2-13
Index-iv
-------
Transfers ; . , 4 4-7, 4-13 to 4-16, 4-20, 4-33, 4-42, 4-45
Treatment efficiency 4-10, 4-11, 4-19
Treatment for destruction
On-site 4-10 to 4-15
Off-site , 4-15 to 4-16
Types (see Release)
Waste management Chapter 4
Waste treatment (see Treatment for destruction)
Common error, treatment efficiencies 4-19
Example, on-site waste treatment 4-11
Wastewater discharge 4-6
Wastewater treatment 4-7, 4-11, 4-19 to 4-20, 4-41, 4-43, 4-50
Index-v
-------
nit ' II
4,'ii'1 |l. INI
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