vvEPA
United States
Environmental Protection
Agency
Water
Permits Divisit n
Washington, DC
Guidance Manual
for Implementing
Total Toxic Organics (TTO)
Pretreatment Standards
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GUIDANCE MANUAL FOR
IMPLEMENTING TOTAL TOXIC
ORGANICS PRETREATMENT STANDARDS
Prepared by
Permits Division (EN-336)
Office of Water Enforcement and Permits
Office of Water
September 1985
U.S. Environmental Protection Agency
401 M Street, S.W.
Washington, D.C. 20460
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TABLE OF CONTENTS
Chapter Page
1. INTRODUCTION
1.1. DEFINITION OF TTO 1-2
1.2. GENERAL ORGANIZATION 1-2
1.3. LIMITATIONS OF THIS MANUAL 1-3
2. REPORTING REQUIREMENTS
2.1. BASELINE MONITORING REPORT 2-1
2.2. PROGRESS REPORTS 2-3
2.3. 90-DAY COMPLIANCE REPORT 2-3
2.4. INDUSTRIAL USER SEMI-ANNUAL COMPLIANCE REPORT 2-3
3. INDUSTRIAL CATEGORIES WITH TTO REQUIREMENTS
3.1. ELECTROPLATING AND METAL FINISHING
3.1.1. TTO Limits 3-1
3.1.2. Alternative to TTO Monitoring 3-2
3.1.3. Sources of Toxic Organics 3-3
3.2. ELECTRICAL AND ELECTRONIC COMPONENTS
(PHASES I AND II)
3.2.1. TTO Limits 3-4
3.2.2. Alternative to TTO Monitoring 3-5
3.2.3. Sources of Toxic Organics 3-6
3.3. COPPER FORMING
3.3.1. TTO Limits 3-6
3.3.2. Alternative to TTO Monitoring 3-8
3.3.3. Sources of Toxic Organics 3-8
3.4. ALUMINUM FORMING
3.4.1. TTO Limits 3-8
3.4.2. Alternative to TTO Monitoring 3-13
3.4.3. Sources of Toxic Organics 3-13
3.5. COIL COATING
3.5.1. TTO Limit 3-14
3.5.2. Alternative to TTO Monitoring 3-16
3.5.3. Sources of Toxic Organics 3-16
4. GUIDANCE FOR THE PREPARATION OF A TOXIC ORGANIC
MANAGEMENT PLAN 4-1
5. USE OF THE COMBINED WASTESTREAM FORMULA
5.1 DEFINITIONS 5-1
5.2 CWF CONDITIONS 5-1
5.3 CALCULATION OF ALTERNATIVE TTO LIMITS
USING THE CWF 5-2
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TABLE OF CONTENTS (cont.)
Chapter
6. REMOVAL CREDITS
6.1 REMOVAL CREDITS FOR TTO 6-1
6.2 REMOVAL CREDITS FOR TTO SURROGATE OR
INDICATOR POLLUTANTS 6-2
7. TTO MONITORING GUIDANCE
7.1. SAMPLING CONSIDERATIONS
7.1.1. Sampling Location 7-1
7.1.2. Sample Collection Techniques 7-2
7.1.3. Sample Volumes 7-3
7.1.4. Sample Equipment .and Containers 7-12
7.1.5. Sample Preservation and Holding Times 7-13
7.1.6. Sample Type and Frequency for TTO
Monitoring 7-13
7.2. LABORATORY CONSIDERATIONS
7.2.1. Analytical Procedures 7-20
7.2.2. Laboratory Quality Control 7-21
7.3. OIL AND GREASE MONITORING CONSIDERATIONS
7.3.1. Oil and Grease Sampling Considerations 7-21
7.3.2. Analytical Considerations for
Oil and Grease 7-21
APPENDIX A: 40 CFR Section 403.12: Reporting Requirements
for POTWs and Industrial Users A-1
APPENDIX B: Electroplating and Metal Finishing Category:
List of Toxic Organic Compounds Regulated as
Components of Total Toxic Organics B-l
APPENDIX C: Electrical and Electronic Components Category:
List of Toxic Organic Compounds Regulated as
Components of Total Toxic Organics
(By Subcategory) C-1
APPENDIX D: Example Toxic Organic Management Plan D-1
APPENDIX E: 40 CFR Section 465.03: Monitoring and Reporting
Requirements E-l
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1. INTRODUCTION
The National Pretreatment Program establishes an overall
strategy for controlling the introduction of nondomestic wastes
to publicly owned treatment works (POTWs) in accordance with the
overall objectives of the Clean Water Act. Sections 307(b) and
(c) of the Act authorize the Environmental Protection Agency to
develop national pretreatment standards for new and existing
dischargers to POTWs. The Act made these pretreatment standards
enforceable against dischargers to publicly owned treatment works.
The General Pretreatment Regulations (40 CFR Part 403)
established administrative mechanisms requiring certain POTWs
to develop local pretreatment programs to enforce the general
discharge prohibitions and specific Categorical Pretreatment
Standards. These Categorical Pretreatment Standards are
designed to prevent the discharge of pollutants which pass
through, interfere with, or are otherwise incompatible with the
operation of the POTWs. The standards are technology-based for
removal of toxic pollutants and contain specific numerical
limitations based on an evaluation of specific technologies for
each individual industry category.
Categorical Pretreatment Standards have been or are being
established for different categories of industries. Twenty-one
of these industrial categories must presently meet numerical Limits
for certain pollutants that are typically present in the waste
discharges from those industries. All categories must comply with
the generic prohibited discharge standards specified in 40 CFR
403.5(b) and any local limits established by the POTW in which
the industry is located pursuant to the General Pretreatment
Regulat ions.
Six of the industrial categories have a pretreatment standard
established for total toxic organics (TTO). The categories
affected by a TTO limit are:
0 Electroplating
0 Metal Finishing
0 Electrical and Electronic Components (Phases I and II)
0 Copper Forming
0 Aluminum Forming
0 Coil Coating (Can-Making Subcategory only)
The reason for a TTO limit in each of these categories is
that industry studies have shown there is a significant potential
for TTO discharge by these industries.
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1.1. DEFINITION OF TTO
The TTO is defined as the sum of the masses or concentrations
of specific toxic organic compounds found in the industrial user's
process discharge at a concentration greater than 0.01 mg/1. Each
Categorical Standard lists the specific toxic organic compounds
that are to be included in the summation to define TTO for the
category.
1.2. GENERAL ORGANIZATION
This manual will be useful to both POTWs and their indirect
dischargers/industrial users (lUs) who are subject to a categorical
pretreatment standard for TTO. It will help POTWs by providing
them with a better understanding of how to implement the TTO
standard and how the alternative provided in each regulation may
be useful in lieu of IDs monitoring their TTO discharges to docu-
ment their compliance status. Through this manual, Ills will
understand their reporting responsibilities relative to TTO and
the available alternative under the applicable regulation.
Chapter 2, REPORTING REQUIREMENTS, provides information on
the various reports which a regulated IU must submit under the
General Pretreatment Regulations (40 CFR Part 403). This chapter
will be most useful for lUs subject to the Electrical and Electronic
Components (Phase I and II), the Copper Forming, the Aluminum Forming,
and the Coil Coating regulations. Industrial users subject to the
Electroplating and Metal Finishing regulations, have already received
similar guidance in the Guidance Manual for Electroplating and Metal
Finishing Pretreatment Standards (February 1984).
Chapter 3, INDUSTRIAL CATEGORIES WITH TTO REQUIREMENTS,
discusses each industry category that contains a TTO pretreatment
standard. It presents the individual toxic organic compounds
which are regulated as a component of TTO, the specific TTO
limitations and the applicable compliance date for both existing
and new source pretreatment standards. It also discusses the
TTO monitoring alternative and potential sources of toxic organics
in each category.
Chapter 4, GUIDANCE FOR THE PREPARATION OF A TOXIC ORGANIC
MANAGEMENT PLAN, walks an industrial user and a Control Authority
through the steps necessary to develop an acceptable management plan.
Chapter 5, USE OF THE COMBINED WASTESTREAM FORMULA, and Chapter 6,
REMOVAL CREDITS, discuss the applicability of these two provisions of
the General Pretreatment Regulations to TTO pretreatment standards.
Chapter 7, TTO MONITORING GUIDANCE, presents specific guidance
on sampling and analyzing TTO and on oil and grease monitoring for
the industry categories which provide that TTO monitoring alternative.
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1.3. LIMITATIONS OF THIS MANUAL
This manual presents information and guidance only on the
implementation of categorical pretreatment standards for TTO.
It does not deal with any problems or issues related to any
individual toxic organic compounds regardless of whether they
are regulated as a TTO component. These more specific, localized
problems are better addressed on a case-by-case basis by the
industrial users and their Control Authority.
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2. REPORTING REQUIREMENTS
The General Pretreatment Regulations (40 CFR Part 403)
require that indirect dischargers regulated under a National
Categorical Pretreatment Standard submit various reports at
specified times. Section 403.12 of the General Pretreatment
Regulations delineates what reports each regulated indirect
discharger must submit, the information to be contained in
each report, and when each report must be submitted to the
Control Authority. Appendix A contains a copy of Section
403.12. The Control Authority is the indirect discharger's
receiving POTW if its pretreatment program has been approved.
If the POTW's program has not been approved, the Control
Authority is the State if its pretreatment program has been
approved or the appropriate EPA Regional Office if the State
does not have an approved pretreatment program.
2.1 BASELINE MONITORING REPORT
Under the provisions of Section 403.12 of the General
Pretreatment Regulations, all industrial users (lUs) of a publicly
owned treatment works (POTW) subject to categorical pretreatment
standards are required to submit a Baseline Monitoring Report (BMR).
The BMR must be submitted by an existing source within 180 days
after the effective date of an applicable categorical pretreatment
standard or within 180 days after the final decision on a category
determination request submitted under Section 403.6(a). New sources
must submit a report which contains the information delineated in
40 CFR Section 403.12(b)(l) to (5). The term "New source" means any
building, structure, facility, or installation from which pollutants
are discharged or may be discharged and the construction of which was
started after the publication of any proposed applicable pretreatment
standard under section 307(c) of the Clean Water Act if such standard
is finally promulgated in accordance with section 307(c).
The BMR must contain the name and address of the facility
including the name of the operator and owners; a list of environmen-
tal control permits held by or for the facility; a brief description
[including a flow-diagram of regulated processes] of the nature,
average rate of production, and SIC codes of the operations; the
measured average daily and maximum daily flow from regulated process
streams and other streams as necessary for using the combined waste-
stream formula; and the results of sampling and analysis identifying
the nature and concentration or mass of the regulated pollutants in
each regulated process' discharge.
The indirect discharger shall provide the concentration or
mass as required by either the pretreatment standard or the
Control Authority. Where feasible, the indirect discharger
shall use flow proportional composite sampling techniques
specified in the applicable standard. If flow metering is not
available, then time proportional composite sampling techniques
may be used. When composite sampling is not feasible, a grab
sample is acceptable.
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The BMR shall indicate the time, date, and place of sampling,
the methods of analysis, and shall certify that the sampling and
analysis is representative of normal work cycles and expected
pollutant discharges. Additionally, the BMR shall include an
authorized representative's certification, endorsed by a qualified
professional, that pretreatment standards are or are not being met
on a consistent basis. If not being met, the BMR shall also contain
a compliance schedule for implementing additional operation and
maintenance (O & M) and/or pretreatment necessary for meeting the
applicable standards and requirements.
An authorized representative as a minimum shall be a vice
president-level individual if the indirect discharger is a corpora-
tion; a general partner or proprietor if the discharger is a
partnership or sole proprietorship, respectively; or an authorized
representative if the representative is responsible for the facility's
operat ion.
If a regulated indirect discharger is not meeting the applicable
pretreatment standards and his BMP. contains a compliance schedule,
the compliance schedule must contain the shortest schedule by which
the industrial user (IU) will provide the additional 0 & M and/or
pretreatment necessary to comply with the standards. The schedule
will contain increments of progress for the start and finish of
major events leading to construction and operation of the necessary
O & M and/or pretreatment. No increment of progress shall exceed
9 months; the completion date shall not be later than the compliance
date for the applicable pretreatment standards.
TTO monitoring must be submitted in the BMR for all categorical
industries subject to a TTO standard except those facilities
that plan to use alternate oil and grease limits provided in the
Aluminum Forming, Copper Forming, and Coil Coating regulations.
The General Pretreatment Regulations establish a sampling
frequency which lUs must use in preparing their BMRs. The sampling
frequency is related to the flow of the stream being sampled. If
the flow is less than or equal to 950,000 liters per day (approxi-
mately 250,000 gpd), the IU must take three samples within a
two-week period. If the flow is greater than 950,000 liters/day
(approximately 250,000 gpd), the "U must take six samples within
a two-week period.
2.2 PROGRESS REPORTS
No later than 14 days following each date in its compliance
schedule and the final compliance date, the IU must submit a
progress report to the Control Authority. The report must state
whether or not it complied with the increment of progress to be
met. If the increment step was not met, the report must further
state when that step will be finished, the reason for the delay,
and the steps which will be taken by the IU to get back on schedule.
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IDs can not exceed 9 months between any two progress reports.
These reports will not contain any sampling and analysis
results for TTO or any available alternative.
2.3 NINETY-DAY COMPLIANCE REPORT
Section 403.12(d) of the General Pretreatment Regulations
requires categorical industrial facilities subject to pretreatment
standards to submit a 90-day compliance report to the POTW. This
report provides initital verification that the iu is in compliance
with the applicable standards and requirements for their discharge.
Existing categorical industrial users must file a final compliance
report within 90 days following the final compliance date specified
in a categorical regulation or within 90 days of the compliance date
specified by the Control Authority, whichever is earlier. New
source industrial users must file a compliance report within 90 days
after the commencement of a discharge to the POTW system.
The contents of this report must include: results of sampling
of industrial wastestreams for regulated pollutants; average and
maximum daily flow for industrial process wastewaters being regulated;
a statement of compliance; and, where necessary, a statement as to
whether additional 0 & M changes and/or pretreatment equipment are
needed to bring the industrial user into compliance.
Control Authorities must require that lUs include in their
90-day compliance report the results of their sampling and analysis
for TTO unless an alternative oil and grease limitation is provided
and adopted. If an IU elects to use an alternative oil and grease
limitation, then the 90-day compliance report must contain results
of oil and grease sampling and analysis. An authorized represen-
tative as discussed above must sign this report. Additionally,
a qualified professional must certify the report.
For the 90-day compliance report, Control Authorities should
require that their regulated Ills use the sampling frequency specified
for BMRs in 40 CFR Section 403 .12(b) (5) (iv) .
2.4 INDUSTRIAL USER SEMI-ANNUAL COMPLIANCE REPORTS
The General Pretreatment Regulations require categorical
industrial users to report the results of self-monitoring of their
regulated waste discharges to the Control Authority at least semi-
annually. The regulations [Section 403 .12(e)(1)] state that the
reports are to contain information "indicating the nature and
concentration of pollutants in the effluent which are limited by
such Categorical Pretreatment Standards. In addition, this
report shall include a record of measured or estimated average
and maximum daily flows for the reporting period..." The reports
must be submitted at least semi-annually in June and December.
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However, the regulations state that the Control Authority may
at its discretion alter the specific months during which the
self-monitoring reports are due to account for such factors as
high or low flow rates, budget cycles, holidays, etc.
In all cases, the self-monitoring reports should be required
to be submitted within fifteen calendar days of the date on which
the last sample analysis is received. The report should include
all self-monitoring data for the semi-annual period just ended.
At a minimum, the following information should be reported
to the Control Authority:
0 Date the sample and flow measurement was taken
0 Results of analysis for all required parameters
0 Other information (unusual process or operating
conditions, equipment, problems, etc.) that may
affect sample results
0 Signed statement of accuracy by an authorized
representative.
In these reports, the IU is nat required to submit the results
of TTO monitoring and analysis to demonstrate continued compliance
with the applicable TTO pretreatment standard if he elects to use
the applicable alternative available to his facility. Where TTO
monitoring is required, the Control Authority will establish the
required monitoring frequency.
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3. INDUSTRIAL CATEGORIES WITH TTO REQUIREMENTS
This chapter presents information concerning the TTO limits,
alternatives to the requirement for TTO monitoring (where available)
and brief discussions of potential sources of the regulated toxic
organics within each category affected by a TTO standard. Each
category with a TTO standard is addressed. Discussion of the
Electroplating and Metal Finishing categories is combined as is
the discussion of the Electrical and Electronic Components Phase I
and Phase II categories because of the similarity of operations and
standards.
3.1 ELECTROPLATING AND METAL FINISHING
3.1.1 TTO Limits
The Electroplating/Metal Finishing regulations include a TTO
pretreatment standard. Appendix B contains a list of the indivi-
dual toxic organic compounds which must be included in the TTO
summation when they are present in a regulated wastestream in a
concentration greater than 0.01 mg/1. Industrial users subject
to these regulations must sample and analyze their wastestreams
for TTO and report the results of this TTO monitoring in their
BMRs and in their 90-day compliance report. However, these lUs
are only required to sample and analyze for those individual
compounds listed in Appendix B which would reasonably be expected
to be present in their wastestream. This is in accordance with
40 CFR Section 413.03(c) and 40 CFR Section 433.12(a) of the
Electroplating and Metal Finishing Regulations, respectively.
Before regulated lUs conduct any BMR and 90-day compliance
report monitoring for TTO, they should seek their Control Authority's
agreement on which of the individual toxic organics listed in Appen-
dix B can reasonably be expected to be present in their regulated
wastestreams. Control Authorities should require that their regulated
lUs support with appropriate documentation their determination of
reasonably expected presence. Appropriate documentation may include
a new material inventory, an engineering study, and/or a process
balance.
The following table gives the TTO pretreatment standards for
the Electroplating and Metal Finishing categories and the applicable
compliance date for each.
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Industry Category
Electroplat ing
_< 10,000 gpd
> 10,000 gpd
Metal Finishing
Interim
Final
Lim i t
Daily Maximum'
4.57
2.13
4.57
2.13
\mg/l) Compliance Date
July 15, 1986
July 15, 1986
June 30, 1984
February 15, 1986
3.1.2 Alternative to TTO Monitoring
Rather than monitor TTO, lUs may request that their Control
Authority allow them to make the following certification:
"Based on my inquiry of the person or persons
directly responsible for managing compliance
with the pretreatment standard for total toxic
organics (TTO), I certify that to the best of
my knowledge and belief, no dumping of con-
centrated toxic organics into the wastewater
has occurred since filing of the last semi-
annual compliance report. I further certify
that this facility is implementing the solvent
management plan submitted to the Control
Authority ."
The Ills must include this certification in each semi-annual
compliance report which they submit to their Control Authority. The
lUs1 use of the certification statement is solely at their Control
Authority's discretion.
When requesting to use this certification as an alternative
to TTO monitoring the IDs must submit a toxic organic management
plan (TOMP) that satisfies the Control Authority regarding:
(1) the identification of the toxic organics listed in
Appendix R which the IU uses;
(2) the method of disposal, such as incineration,
contract hauling, or reclamation; and
(3) procedures for assuring that toxic organics do not
routinely spill or leak into the wastestream.
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The lUs must submit and implement this TOMP as early as
possible in order to demonstrate that it will provide the degree
of control necessary for the ID to achieve compliance with the TTO
pretreatment standard. Chapter 4 presents guidance on the develop-
ment of a TOMP. Appendix D is an example of such a plan.
However, if the Control Authority samples and analyzes its
IDs' wastestream to confirm compliance with an applicable TTO
pretreatment standard and the results show non-compliance, the
Control Authority can require that the IU initiate TTO sampling
and analysis on a frequency which the Control Authority establishes.
The Control Authority must also require that the IU take the
remedial actions necessary to come into compliance with the
applicable TTO standard as expeditiously a° possible.
3.1.3 Sources of Toxic Organics
Toxic organics are used extensively in electroplating and
metal finishing processes. The list of regulated toxic organics
includes 110 compounds, as noted in Appendix B. The main
sources of the toxic organics generated by these industries
are primarily from the dumping of spent solvents or dragout of
organic compounds used in degreasing and paint stripping opera-
tions. Other sources may include parts washing and various
surface preparation and painting operations. Degreasing, however,
is the most prevalent source.
Both production/process areas and storage areas are potential
sources for the introduction of toxic organics into the POTW sewer
system. Production/process introductions can be in the form of
solvent rinse dragout, spray/mist wash runoff, paint booth runoff,
and spent solvent dumping. Storage area toxic organic introduc-
tions can occur from spills which enter floor drains. The dumping
of spent, contaminated or unwanted solvents into the sewer system
is also a significant source.
Industrial users have the responsibility to identify the toxic
organic constituents of any solvents and degreasers that use commer-
cial or trademark names and do not list the actual chemical name(s).
Control Authorities may verify that its IDs1 commercial degreasers
and solvents do not contain any toxic organics by requesting that
the IDs submit a list of components for any commercial or trademark
solvents and degreasers which they may use.
Table 3.1 presents some examples of halogenated and non-
halogenated toxic organic compounds which may be found in
commercial grade solvents and degreasers.
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TABLE 3.1
Example Toxic Constituents of
Organic Solvents
Halogenated Solvent Constituents
Di,tri,tetra-chloromethanes
Di,tri,tetra-chloroethanes
Di,tri,tetra-chloroethylenes
Chlorinated Benzenes
Methylene Chloride
Non-Halogenated Solvent Constituents
Benzene
Phenol
Ni trobenzene
Ethylbenzene
Toluene
Acrylonitri le
Napthalene
3.2 ELECTRICAL AND ELECTRONIC COMPONENTS (PHASES I AND II)
3.2.1. TTO Limits
The Electrical and Electronic Components category has four
subcategories: (a) Semiconductors, (b) Electronic Crystals,
(c) Cathode Ray Tubes, and (d) Luminescent Materials. Semicon-
ductors, Electronic Crystals, and Cathode Ray Tubes all have TTO
limits. The remaining subcategory, Luminescent Materials, has no
TTO restrictions. The following table gives the limitation and
compliance date for each regulated subcategory.
Limit
Subcategory (Daily Max.) (mg/1)1 Compliance Date
Semiconductors 1.37 July 1, 1984
Electronic Crystals 1.37 July 1, 1984
Cathode Ray Tubes 1.58 July 14, 1986
Limits in each subcategory apply to both new and existing sources
in that subcategory.
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ihe specific toxic organic compounds regulated as iTO are
delineated in Appendix C. These compounds must be included in
the TTO summation when they are present in a regulated wastestream
in concentrations greater than 0.01 mg/1 . Additionally, lUs in
these subcategories must sample and analyze for all the toxic
organics listed in Appendix C. They may not limit their testing
to those toxic organics reasonably expected to be present in
their regulated wastestreams. The Agency has already determined
that all these pollutants are reasonably expected to be present.
Regulated IDs must report the results of their TTO sampling and
analysis in their BMRs and in their 90-day compliance reports.
The applicable sampling frequency for these two reports is found
in Sections 2.1 and 2.3, respectively, of this manual.
3.2.2 Alternative to TTO Monitoring
Industrial users as an alternative to monitoring TTO to
determine compliance with the applicable standard may certify
with the Control Authority's approval that there has been no
dumping of concentrated toxic organics into the wastewater and
that it is implementing the solvent management plan submitted
to the Control Authority.
The regulated IDs must submit this certification as a comment
to their semi-annual compliance reports. The specific certifi-
cation language is found in 40 CFR Section 469.13(c) and the
requirement that the IDs electing to use this certification
submit and then implement a solvent managment plan is found in
40 CFR Section 469.13(d). The specific certification language
is as follows:
"Based on my inquiry of the person or persons directly
responsible for managing compliance with the pretreat-
ment standard for total toxic organics (TTO), I certify
that to the best of my knowledge and belief, no dumping
of concentrated toxic organics into the wastewater has
occurred since filing of the last semi-annual compliance
report. I further certify that this facility is
implementing the solvent management plan submitted to
the Control Authority."
3.2.3 Sources of Toxic Organics
Toxic organics are used similarly in the three regulated
subcategories. They appear almost exclusively as constituents of
solvents. These solvents are used in cleaning, degreasing, and some
etching operations. Both production/process areas and storage areas
are potential sources for the introduction of toxic organics into
the POTW sewer system. Production/process introductions can be in
the forms of solvent rinse dragout, spray/mist wash runoff, etching
solution dumping, and spent solvent dumping. Storage area toxic
organic introductions can occur from spill entry via floor drains
and dumping of spent or unwanted solvents in the sewer system.
Industries are responsible for identifying the toxic organic
constituents in any solvents that use commercial or trademark names
and do not list the actual chemical name(s).
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3.3 COPPER FORMING
3.3.1 TTO Limits
Copper forming consists of five basic processes used to form
copper or copper alloys: hot rolling, cold rolling, extrusion,
drawing, and forging. These are the core processes; ancillary
operations consist of annealing witn oil or water, pickling, alkaline
cleaning, solution heat treatment, tumbling, burnishing, surface
coating, hydrotesting, surface milling and sawing.
The toxic organic compounds identified as comprising TTO
under the categorical standards for copper forming are:
Be nzene
1 , 1 ,1-Trichloroethane
Chloroform
2 ,6-dinitrotoluene
F.thylbenzene
Methylene chloride
Napthalene
N-nitrosodiphenylamine
An thracene
Phenanthrene
Toluene
Trichloroethylene
The final compliance date for the pretreatment standards for
existing sources is August 15, 1986; new sources must comply on
the date they begin operation.
Table 3.2 presents the TTO pretreatment standards for both
existing and new sources for each of the regulated core processes
and ancillary operations. Reg la (id lUs subject to this regula-
tion ;Tiust sample and analyze for a.l the above compounds unless
they elect to use the oil and grease alternative; they can not
sample and analyze for those compounds which are reasonably
expected to be in their wastestreams. IMs must submit their TTO
or oil and grease sampling and analysis results in their BMRs
and in their 90-day compliance reports. The applicable sampling
freguency for these two reports is found in Sections 2.1 and 2.3
of the manual, respectively. Monitoring freguency for TTO or
oil cuid grease in their semi-annual compliance reports will be
established by the Control Authority.
Section 468.01(b) of the Copper Forming regulation limits the
applicability of the existing source and new source pretreatment
standards for drawing spent lubricant discharges (40 CFR Section
463.14(c) and 468.15(c)). These standards only apply to those
copper forming facilities which actually discharge this spent
lubricant wastestream to their POTW. These standards do not apply
when this spent lubricant is hauled off-site for disposal or is
otherwise not discharged from the facility.
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TABLE 3.2
COPPER FORMING CATEGORY
Subpart A
a. Hot Rolling
b.
c.
d.
e.
f.
g.
h.
1.
J-
k.
1.
•-
n.
o.
P-
1-
Spent Lubricant
Cold Rolling
Spent Lubricant
Drawing Spent
Lubricant
Solution heat
treatment
Extrusion heat
treat Mnt
Annealing with
Water
Annealing with
Oil
Alkaline
Cleaning Rinse
Alkaline
Cleaning Rinse
for forged parts
Alkaline
Cleaning Bath
Pickling Rinse
Pickling Rinse
for forged parts
Pickling bath
Pickling fuaw
scrubber
Tu«hl 1 ng or
Burnishing
Surface Coating
Mlscellaneoua
Wastestreaajs
Mg/Off-Kg or TTO AND OIL AND C«EASR STANDARDS
Iba/Mllllon PSES PSNS
off-lba of TTO Oil & Creaae TTO Oil i (
copper or Max. for Monthly Max. for Monthly Max. for Monthly Max. for
copper alloy any 1 day MX. aug. any 1 day aax. aug. any 1 day m»x. aug. any 1 day
hot rolled 0.066 0.035 2.060 1.236 0.035 1.030
cold rolled 0.246
drawn 0.055
heat treated 0.419
heat treated 0.0010
on an extrusion
press
annealed with 0.806
water
annealed with 0
oil
alkaline 2.739
cleaned
alkaline 8.217
cleaned
alkaline 0.030
cleaned
pickled 0.848
forged parta 2.540
pickled
pickled 0.075
pickled 0.406
tunhlrd or 0.378
burnished
surface coated 0.482
forced 0.014
0.128 7.580
0.028 1.700
0.219 12.920
0.00068 0.040
0.421 24.8000
0 0
1.432 84.280
4.298 252.840
0.015 0.83
0.444 26.120
1.332 78.360
0.039 2.320
0.212 12.520
0.198 11.660
0.252 14.860
0.007 0.436
3-7
4.548
1.020
7.752
0.024
14.880
0
50.568
151.704
0.56
15.672
47.016
1.392
7.512
6.996
8.916
0.261
0.128
0.028
0.219
0.00068
0.421
0
1.432
4.298
0.015
0.198
0.596
0.039
0.212
0.196
0.252
0.007
3.790
0.850
6.460
0.020
12.400
0
42.140
126.420
0.46
5.B50
17.550
1.160
6.260
5.B30
7.430
0.218
-------
3.3.2 Alternative to TTO Monitoring
As an alternative to TTO monitoring, regulated ILJs may monitor
for oil and grease (O&G) and meet the O&G monitoring standards.
The alternate °*< G monitoring standards are included in Table 3.2.
The maximum monthly average is the same value as the one-day
maximum although the monthly values are not shown in the table.
Any IU choosing the alternative O&G monitoring standards is not
subject to the Copper Forming TTO standard.
Regulated lUs electing to use this alternative must sample
and analyze for O&G and submit these results in their BMRs,
their 90-day compliance reports, and their subsequent semi-annual
compliance reports.
Additionally, Section 468.03(a) requires that regulated lUs
comply with the monthly discharge limit regardless of the number
of samples analyzed and averaged.
Sampling frequency for BMRs and for 90-day compliance reports
is discussed in Sections 2.1 and 2.3 of this manual. Sampling
frequency for the semi-annual compliance report will be established
by the Control Authority.
3.3.3 Sources of Toxic Organics
Wastewater from copper forming plants is generated by both
the core and ancillary operations. The core operations utilize
oil/water emulsions as lubricants to reduce wear on the forming
equipment and to prevent adhesion of the copper to the equipment.
The spent lubricants become part of the regulated wastestream.
Ancillary operations use water and/or oil to cool, clean and
rinse the formed metal. Wastestreams from these ancillary
operations are also regulated. The lubricants and cleaners used
in these operations usually contain one or more of the toxic
organics regulated by the Copper Forming regulation as a TTO
component.
3.4 ALUMINUM FORMING
3.4.1 TTO Limits
The Aluminum Forming category is divided into six subcategories:
A) Rolling with Neat Oils
B) Rolling with Emulsions
C) Extrusion
3-8
-------
D) Forging
E) Drawing with Neat Oils
F) Drawing with Emulsions.
The various processes used by the industry required this division
into subcategories based on differences in the methods of production.
Each subcategory listed above has pretreatment standards for the core
operation and ancillary operations that may be associated with the
core process. Each subcategory is discussed separately in this
document identifying the core process and noting all sources for
contaminated wastestreams.
The toxic organic compounds regulated under the TTO standards
for each subcategory are listed below. The term "Total Toxic Organics'
for this category is the sum of the masses or concentrations of each
of the following toxic organic compounds found at a concentration
greater than 0.01 mg/1 in a regulated wastestream
p-chloro-m-cresol
2-chlorophenol
2,4-d initrotoluene
1,2-diphenylhydrazine
ethylbenzene
fluoranthene
isophorone
napthalene
N-nitrosodiphenylamine
phenol
benzo(a)pyrene
benzo(ghi)perylene
fluorene
phenanthrene
dibenzo(a,h)anthracene
indeno(1,2,3,-c,d)pyrene
pyrene
tetrachloroethylene
toluene
tr ichloroethylene
endosulfan sulfate
bis(2-ethyl hexyl)phtalate
diethylphthalate
3,4-benzofluoranthene
benzo(k)fluoranthene
acenaphthylene
anthracene
chrysene
di-n-butyl phthalate
endrin
endrin aldehyde
PCB 1242, 1254, 1221
PCS 1232, 1248, 1260, 1016
acenaphthene
Table 3.3 presents the applicable TTO limits for each
subcategory. The final compliance date for the pretreatment
standards for existing sources was October 24, 1983; new sources
must comply on the date they begin operating.
The sampling frequency which the regulated lUs must use for
TTO or oil and grease sampling for its BMR and 90-day compliance
report is specified in Sections 2.1 and 2.3, respectively, of
this manual. For these two reports, all the toxic organics
listed above must be analyzed for. The lUs will only sample and
analyze TTO for inclusion in these reports if they elect, not to
use the available alternative described in the next section.
If they elect to use the oil and grease alternative, then they
must report their oil and grease sampling and analysis results
in these reports.
3-9
-------
TABLE 3.3
Subpart A:
Co_rei
Core without an Annealing
Furnnce Scrubber
Core with an Annealing
Furnice Scrubber
Degreaalng
Sawing Operation*
And 1 lary Frocttteti
Contlnuoua Sheet Caatlng
Suiiiiltin Heat Treatment
Cle.inlnx or Etching Bath
Clr.inlnK or Etching Ulnae
Uasteatreana
Spent Lubricant
Spent Lubricant
Scrubber Liquor
Spent Solvent
Spent Lubricant
Spent Lubricant
Contact Cooling Water
Bath Water
Rlntc Water
Cleaning or Etching Scrubber Scrubber Liquor
Subpart B:
Rolling with Eauilalona
Cor_e:
Rolling with Eawlalona
Sawing
Ancillary Froceaaea
Direct Chill Caatlng
Solution Heat Treatment
Cleaning or Etching Bath
Cleaning or Etching tlnae
Spent Eaulelont
Spent Lubricant
Contact Coolief Water
Contact Cooling Water
Bath Water
Ulnae Water
AI.I7HINUN mUHlNG CATEGORY
TTO AND OIL AND CKRASK STANDARDS
PSKS
Hg/Off-ICg or
Ih/Hllllon
off-lb of
alvialnu*
Ol 1 i Creaee-
TTO Alternative Paraawter
Max. for Ha«. for Max. for
any I day any I day Monthly av
rolled with neal olla 0.057
rolled with neat olla O.OJA
part of core proceaa
part of core proceaa
caat
quenched
cleaned or etched
cleaned or etched
cleaned or etched
•"Iinning or Etching Scrubber Scrvater Llq«e>r
rolled with eaulalona 0.090
part of core
caat
quenched
cleaned «r etched
cleaned or etched
cleaned or etched
1.64
I.II
2.60
0.98
0.67
1.56
PSNS
TTO Oil I Crcaa* - Alternative
Max. for Has. for any I HAY •>'>'' H«x.
any I day for Monthly Avrr.i/r
O.OS7
0.0)»
O.fO
0.817
0.5*
0.0014
1.41
0.124
0.96
1.34
0.040
40.74
3.58
27.82
38.7
0.024
24.45
2.15
16.69
23.20
0.0014
1.41
0.124
0.96
1.34
0.20
20.37
1.79
13.91
19.31
1.3O
0.92
1.41
0.124
0.9*
I.M
2«.M
40.74
1.58
27.82
1«.M
13.9*
24.44
2.1)
l*.*9
23.20
•.ff*
1.41
0.124
0.9*
I.M
>V»
20.17
1.79
11.91
19.11
3-10
-------
TABLE 3.3 (cont.)
PSP.S
Suhpart C:
Kxt rua Ion
Core:
Cxtrualon
F.xtrualon Prtaa Leakage
Oegrcaalng
Sawing
Die Cleaning
Ancillary Proceaiea
Direct Chill Caatlng
Fresa Meat Treatment
Solution Meat Treatment
Cleaning or Etching Bath
Cleaning or Ftchlng Rlnae
Glen-ling or F.trhlng Scrubber
Sul>p.irt 0:
Forging
Core:
Fnrr.lnf.
DrRrr^lnn
S.iwlnf,
Anclllntjr Proceaaee
Forr.lnr. Srruhber Liquid
Solution llrat Treatment
Clr.inlng or F.trhlng Bath
Clennlng or F.trhlng Rlnae
Waateatreaaia
Duany (lock Cooling
Water
Spent Solvent
Spent Lubricant
lath and Hint* Water
Scrubber Liquor
Contact Cooling Water
Contact Cooling Water
Contact Cooling Water
Bath Water
Rinse Water
Scrubber Liquor
—
Spent Solvent
Spent Lubricant
Scrubber Liquor
Contact Cooling Water
Bath Water
Rlnae Water
ri-vinlnp. or Ftchlng Scrubber Scrubber Liquor
Mg/Off-Kg or
Ib/Mllllon
off-lb of
aluminum
extruded
hard alloy alum.
extruded
part of core
part of core
part of core
caat
quenched
quenched
cleaned or etched
cleaned or etched
cleaned or etched
forged
part of core
part of core
forged
quenched
cleaned or etched
cleaned or etched
cleaned or etched
Oil I Creaae-
TTO Alternative Parameter
Max. for Max. for Max. for
any 1 day any 1 day Monthly '
0.24 6.78 4.07
1.02 29.56 17.74
._
__
—
0.92 26.58 15.95
1.41 40.74 24.45
1.41 40.74 24.45
1.24 3.58 2.16
0.96 27.82 16.69
1.34 38.66 23.20
0.035 1.00 0.60
„
__
0.065 1.89 1.13
1.41 40.74 24.45
0.123 3.58 2.15
O.t6 27.82 16.70
1.34 38.66 23.20
3-11
PSNS
TTO Oil & Cream- - Alternative
Ma«. for Max. for nny I 'lay nnH M.ix.
any I Hay for Monthly Average
0.24
0.21
0.92
1.41
1.41
0.124
0.96
1.34
0.03S
0.065
1.41
0.124
0.96
1.34
1.40
7..9B
13.29
20.37
20.37
I .79
13.91
19. )1
0.50
0.95
20.37
1.79
13.91
19.33
-------
TABLE 3.3 (cont.)
PSES
PSNS
Subpart Et
Drawing with Neat OJla
Core;
Drawing with Heal Olli
Degreaalng
Sawing
Ancillary rroeesaea
Contlnuoua Mod Calling
Continuous Rod Catting
Solution Heat Tte*t«ent
Cleaning or Etching Bath
rl*an(ng nr F.trMng Rtnae
Snhpnrt F:
Drawing with Ewilalona
or Sonpa
Core:
Prnulnf. with F.anilalona
or So.ipa
Sawing
Anr I 1 1/iry Prnceaaes
Continuous Rod Caatlng
Continuous Rod Canting
Solution Heat Treata>ent
Clrnnlnf. or Etching Bath
Clcnnlnf or F.tehlng Ulnae
Vait*stre«*a
Spant Lubricant
Spent Solvent
Spent Uibrlcant
Spent Lubricant
Contact Cooling Water
Contact Cooling Water
Bath Water
Rlnae Water
Scrubher Liquor
Spent Extilalona
Spent Solvent
Spent Lubricant
Spent Lubricant
Contact Cooling Water
Contact Cooling Water
Bath Wnter
Rlnae Water
Scrubber Liquor
Mg/Ofl-Kg or
Hi/Hi 11 Ion
off-lb of
•lu»lnu»
drawn with neat olla
part of core
part of core
rod caat
rod quenched
tod quenched
cleaned or etched
cleaned or etched
cleaned or etched
drawn
rod caat
rod quenched
rod quenched
cleaned or etched
cleaned or etched
cleaned or etched
TTO
Max. for
any 1 day
0.015
0.0014
O.I 31
1.41
0.124
0.96
1.31
0.32
0.0014
0.114
1.1*
0.124
0.96
1.11
Oil 4 Cream
Alternative
Hax. for
any 1 day
1. 00
0.40
3.878
40.74
1.58
27.82
18.66
9.33
0.040
3.88
40.74
1.58
27.82
38.66
p-
Paraneter
HAX. for
Monthly avf.
0.60
0.024
0.134
24.. 4}
2. IS
16.70
23.20
5.60
0.024
2.33
24.44
2.15
16.69
23.20
O.Oli
0.0014
0.072
t.M
0.124
0.96
1.14
0.12
0.0014
0.134
1.41
0.124
0.96
1.14
TTO Oil 4 Crcasr - A1 r rrn.ir I vr
Hn». for Max. 'or any I H»r nn«l Ma«.
any I clay for Monthly A yrr.•»!!'•
1.94
0.020
1.04
20.17
1.79
n.9|
19.11
4.17
0.020
1.94
20.17
1.79
11.91
19.11
3-12
-------
3.4.2 Alternative to TTO Monitoring
Section 467.03(b) of the Aluminum Forming regulation provides
regulated lUs with an alternative to TTO monitoring. The regu-
lated lUs may measure and limit oil and grease (O&G) to the limits
specified in Table 3.3.
For BMRs and 90-day compliance reports, IDs must use the sampling
schedules discussed in Section 2.1 and 2.3 of this manual. For the
required semi-annual progress reports the Control Authority will
establish the appropriate sampling schedules.
3.4.3 Sources of Toxic Organics
The sources of toxic organics in the Aluminum Forming category
are similar to the sources described for Copper Forming: lubricants
and emulsified oils and associated degreasing/cleaning agents contain
the regulated toxic organic compounds. This section briefly describes
the operations of each subcategory as an aid in determining where the
toxic organics originate in the wastewater discharged to the POTW.
Subpart A: Rolling with Neat Oils
This rolling operation uses cast aluminum ingots to form a
variety of end products. Neat oils such as mineral oils or kerosene-
based lubricants are applied to the rollers to prevent wear and adhe-
sion. Coolants are sprayed directly onto the metal and the rollers
to maintain a uniform operating temperature. The coolants and
lubricants are collected, filtered and recycled; spent material is
continuously bled or periodically batch dumped to the wastestream.
Annealing furnaces can utilize wet scrubbers to control the
atmospheric gases during the annealing process. The discharge of
scrubber liquor results in a regulated wastestream. Wastestreams
from degreasing and sawing operations containing spent solvents and
lubricants are also considered in the core operations.
Ancillary operations that produce wastestreams are continuous
sheet casting and solution heat treatment contact cooling water, and
cleaning or etching liquids, including the scrubber liquor.
Subpart B: Rolling with Emulsions
The rolling with emulsions process is very similar to rolling
with neat oils. In this subpart, the coolants and lubricants used
are oil/water emulsions that range from 10-15 percent oil. This
process also uses lubricants in sawing operations. Annealing
furnaces are not utilized although other heat treatments may be
employed.
Ancillary operations that produce contact cooling water
wastestreams include solution heat treatment and direct chill
casting. Cleaning or etching operations are also performed.
3-13
-------
Subpart C: Extrusion
This process uses pressure exerted on a cast aluminum billet
to form the desired product. The aluminum is generally heated,
extruded, and then subjected to heat treatment. Lubricants are
used on tho ale and the ingot container walls to prevent adhesion.
However, in cold extrusion the walls and billet surface are lubri-
cated with a thin film of viscous or solid lubricant. Occasionally,
liquid nitrogen will be used in place of an oil-based lubricant.
Contact cooling water applied to the product after extrusion carries
away some of the lubricant that has not been vaporized. Die cleaning
also produces a wastestream through the dressing and repair of dies.
Ancillary operations producing contaminated wastestreams include:
contact cooling waters from direct chill casting, press heat treatment,
solution heat treatment and wastewater from cleaning, etching, and
scrubber liquor.
Subpart D: Forging
Forging consists of applying compression to hot aluminum to
form the desired shape. Colloidal graphite in water or oil is used
as a lubricant for the dies. Although it is a dry process, smoke
and particulate matter from partial combustion of the lubricants
may require air pollution controls. If wet scrubbers are used to
control the emissions they are considered part of an ancillary
operation and their wastewater is regulated. Additionally, all
solution heat treatment and cleaning or etching wastewaters are
regulated.
Subpart E: Drawing with Neat Oils
Drawing is a process of pulling metal through a series of dies
to reduce its diameter. Lubricants are used on the dies to assure
uniform drawing temperatures and to reduce wear on the dies. As in
Subparts A and B, the difference is in the lubricants and coolants
used in the process. Oil based lubricants are generally used for
heavy draws (higher reduction in diameter), oil in water emulsions
and soap solutions are used for some of the lighter draws.
Annealing is required between draws. The metal is degreased
prior to annealing so that the lubricant will not burn in the
furnace. Solution heat treatment is also used, and is considered
an ancillary operation along with continuous rod casting and
cleaning or etching.
3.5 COIL COATING CATEGORY
3.5.1 TTO Limit
The only TTO pretreatment standard in the Coil Coating Category
is in Subpart D - Canmaking Subcategory. Within the subcategory,
only the manufacture of seamless can bodies which are washed is
regulated. Since no wastewater is generated from the three other
manufacturing processes included ir the subcategory, they are
3-14
-------
exempted from all effluent limitations. These exempted processes
include: (a) manufacture of seamed cans, (b) manufacture of seamless
cans from coated stock, and (c) manufacture of can ends and tops.
The limits promulgated for this category are production-based mass
limits. The fourteen (14) toxic organics regulated under this
category are:
1,1,1-trichloroethane
1,1-dichloroethane
1 ,1,2,2-tetrachloroethane
Bis (2-chloroethyl) ether
Ch1oroform
1,1-dichloroethylene
Methylene chloride (dichloromethane)
Pentachlorophenol
Bis (2-ethylhexyl) phthalate
Butyl benzylphthalate
Di-N-butyl phthalate
Phenanthrene
Tetrachloroethylene
Toluene
Compliance with the TTO limit is demonstrated by summing the mass
of the individual toxic organic compounds present in the regulated
wastestream in concentrations above 0.01 mg/1 . This summation is
then compared with the TTO standard to determine the IU's compliance
status. Both a maximum daily limit and a maximum monthly average
have been promulgated. Both limits must be met to achieve compliance
Table 3.4 presents the TTO limit for existing sources (PSES) and for
new sources (PSNS). The compliance date for the PSES TTO limit is
November 17, 1986. For the PSNS limit, it is when the new source
commences its discharges.
The sampling schedule for the IU's BMR and 90-day compliance
report is found in Sections 2.1 and 2.3, respectively in this
manual. All 14 toxic organics must be analyzed for unless the
oil and grease alternative discussed in the next section is
adopted by the IU.
TABLE 3.4
COIL COATING - SUBCATEGORY
TTO AND OIL AND GREASE
D (CANMAKING)
STANDARDS
Maximum Daily
Poll
PSES
PSES
PSNS
PSNS
utant
TTO
O&G
TTO
O&G
g/106
cans manf .
26.85
1678.00
20.35
1272.00
lb/106
cans manf .
0.059
3.699
0.045
2 .804
g/106
cans manf
12.59
1006.80
9.54
763.20
Maximum Monthly Average*
lb/106
cans manf.
0.028
2.220
0.0210
1 .683
Compliance is reguired regardless of the number of samples
analyzed and averaged.
3-15
-------
3.5.2 Alternative to TTO Monitoring
As an alternative to TTO, regulated IDs may elect to monitor
for and comply with the OS.G standards listed in Table 3.4 above.
lUs subject these OS.G standards, will not be subject to the TTO
standards .
Again the BMR and 90-day compliance report sampling frequencies
are discussed in Section 2.1 and 2.3, respectively, of this manual.
Sampling frequencies for the semi-annual compliance reports shall be
established by the Control Authority.
Specific to this regulation is the Oil and Grease analytical
method promulgated on November 17, 1983 (40 CFR Section 465.03(c);
48 FR 52399^. Corrections were promulgated on April 10, 1984
(49 FR 14104). The corrected method is presented in Appendix E.
Any ID electing to use the O&G alternative must use this methodology
in determining the amount of hydrocarbon oil and grease in each
sample analyzed.
3.5.3 Sources of Toxic Organics
The 14 regulated toxic organics commonly occur as constituents
in lubricants, solvents, and surface coatings. A recommended approach
in identifying toxic organic sources is to compare the labels of these
products to the list of regulated toxics above. Substitute compounds
can often be found for these polyaromatic hydrocarbons and organic
solvents, thus avoiding their use and introduction into the waste-
stream. Introduction of toxic organics into the wastestream entering
the POTW can occur from poor production/process management such as the
dumping of spent solvents, sloppy use of lubricants and surface
coatings, and release of highly contaminated rinse waters. Storage
area spills entering through floor drains represent another possible
source of toxic organic introdution into the POTW.
3-16
-------
4. GUIDANCE FOR THE PREPARATION OF A TOXIC ORGANIC MANAGEMENT PLAN
As previously discussed, one alternative to routine TTO
monitoring is the preparation of a toxic organic management plan
(TOMP). This option is available to regulated industrial users in
the Electroplating, Metal Finishing, and Electrical and Electronic
Components (both Phase I and Phase II) categories.
A TOMP must specify the toxic organic compounds used, the
method of disposal used (instead of discharge into wastestreams),
and procedures for assuring that toxic organics do not routinely
spill or leak into wastewater discharged to the POTW. Guidelines
for preparation of a TOMP are presented below as four basic steps:
Step 1 - Process engineering analysis
A process engineering analysis should be conducted to
determine the source and type of toxic organic compounds found in
a facility's wastewater discharge, including sources and compounds
that could reasonably be expected to enter the wastewater in the
event of spills, leaks, etc., based on the type of operations
conducted at a particular plant. Such an analysis should be
based on the results of one or more analyses of the plant's
wastewater for the toxic organic pollutants which are included in
the definition of TTO for that industrial category and which can
reasonably be expected to be present (see TTO monitoring guidance) .
The process engineering analysis should include:
a. An examination of published reports on the specific
i ndustry;
b. A water flow diagram to identify all possible wastewater
sources;
c. A list of raw materials used in the industrial processes,
including chemical additives, water treatment chemicals
and cleaning agents, and the wastewater stream that each
regulated toxic organic could potentially enter;
d. Comparison of the toxics found in the effluent with the
list of raw materials and selection of the most probable
wastewater source;
e. Evaluation of the toxics found in the effluent, but not
on the raw materials list and determination of those
formed as reaction products or by-products;
f . Examination of sources such as equipment corrosion or
raw materials' impurities that could result in release
to wastewaters of toxic organic pollutants.
4-1
-------
Step 2 - Pollutant control evaluation
An evaluation should be made of the control options that
could be implemented to eliminate the toxic compound(s) or the
source or potential source of toxic organic compound introduction
to the treatment system. This may include in-plant modifications,
solvent or chemical substitution, partial or complete recycle,
reuse, neutralization, and operational changes. The analysis
should be conducted on a case-by-case basis and will often result
in one or more feasible options to control each soure or potential
source of toxic pollutant discharge. Finally, evaluation of the
available control options, including the advantages and disadvan-
tages of each, may lead to a decision of whether a TOMP is a
feasible alternative to TTO monitoring.
Step 3 - Preparation of Toxic Organic Management Plan
A toxic organic management plan should include the following
items at a minimum:
a. A complete inventory of all toxic organic chemicals in
use or identified through sampling and analysis of the
wastewater from regulated process operations (organic
constituents of trade-name products should be obtained
from the appropriate suppliers as necessary);
b. Descriptions of the methods of disposal other than
dumping used for the inventoried compounds, such as
reclamation, contract hauling, or incineration;
c. The procedures for ensuring that the regulated toxic
organic pollutants do not. spill or routinely leak into
process wastewaters, floor drains, non-contact cooling
water, groundwater, surface waters (i.e., Spill Preven-
tion, Control, and Countermeasures (SPCC) Plan) or any
other location which allows discharge of the compounds;
and
d. Determinations or best estimates of the identities and
approximate guantities of toxic organic pollutants used
as well as discharged from the regulated manufacturing
processes. Compounds present in wastestreams that are
discharged to sanitary sewers may be a result of
regulated processes or disposal, spills, leaks, rinse
water carryover, air pollution control, and other sources,
4-2
-------
Step 4 - Submission of Toxic Organic Management Plan and Certifi-
cation Statement
The TOMP should be submitted to the Control Authority at the
time the baseline monitoring report is required if the ID'S initial
election is to choose this option. Alternatively, an ID may submit
a TOMP at any later time and request that TTO monitoring require-
ments be discontinued upon approval and implementation of the TOMP.
A prerequisite for use of this certification approach is a fully
approved, implemented, and ongoing toxic organic management plan.
In addition, a certification statement must be included at the time
of submission of the TOMP and with each subsequent IU report (i.e.,
semi-annual compliance report). It must be signed by an officer
of the company or manager responsible for overall plant operations.
A statement such as the following should be required.
"Based on my inquiry of the person or persons directly
responsible for managing compliance with the TTO limita-
tions, I certify that, to the best of my knowledge and
belief, no dumping of concentrated toxic organics into
the wastewaters has occurred since filing of the last
report. I further certify that this facility is imple-
menting the toxic organic pollutant management plan
submitted to the Control Authority on (date to be
speci f ied) .
(date) (Officer)
If the user is unable to make the above certification
statement, the user should notify the Control Authority sixty
days (60) prior to the due date for filing the compliance reports
At that time, the Control Authority should determine the appro-
priateness of requiring sampling and analysis for specific
toxicants and notify the user accordingly.
A sample Toxic Organic Management Plan and certification
statement are included as Appendix D.
4-3
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5. APPLICATION OF THE COMBINED WASTESTREAM FORMULA
One provision of the General Pretreatment Regulations that
will often be necessary for POTWs and industries to use for proper
monitoring and reporting on compliance with an applicable TTO limit
is the Combined wastestream Formula (CWF) [40 CFR 403.6(d)]. The
CWF is a mechanism for calculating alternative limitations when
regulated wastestreams are mixed with unregulated or dilution
streams. The CWF is applied to the mixed effluent to account for
the presence of the additional wastestream.
The following definitions and conditions are important for
properly using the CWF.
5.1 DEFINITIONS
0 Regulated Process Wastestream - an industrial process waste-
stream regulated by a national categorical pretreatment standard
0 Dilute Wastestream - Boiler blowdown, sanitary wastewater,
noncontact cooling water, and certain process wastestreams
that have been excluded from regulation in categorical
pretreatment standards because they contain none of the
regulated pollutant or only trace amounts of it.
0 Unregulated Process Wastestream - any wastestream that is
neither a regulated nor a dilute wastestream
Note; Definitions apply to individual pollutants. A waste-
stream from a process may be "regulated" for one
pollutant and "unregulated" for another. Example cases
are presented later in this section to illustrate these
d ist inctions.
0 Concentration-based Limit - a limit based on the relative
strength of a pollutant in a wastestream, usually expressed
in mg/1.
0 Production-based Limit - a limitaiton based on the actual
quantity of a pollutant in a wastestream per unit of production.
5.2 CWF CONDITIONS
To ensure proper application of the CWF, the following
conditions must be met by a municipality and its regulated
industries [40 CFR 403.6(d)]:
o
Alternative discharge limits that are calculated in place
of a categorical pretreatment standard must be enforceable
as categorical standards.
5-1
-------
0 Calculation of alternative limits must be performed by
the Control Authority.
0 Alternative limits must be established for all regulated
pollutants in each of the regulated processes.
0 The Control Authority and/or the industrial user may use
production-based limitations in place of the concentration-
based limitations, when they are provided by a given
categorical pretreatment standard such as electroplating
or porcelain enameling.
0 Both daily maximum and average (e.g., monthly) alternative
limits must be calculated for each regulated pollutant,
as required. [The TTO standard is generally only a daily
max imum.]
0 If process changes at an industry warrant, the Control
Auhtority may recalculate the alternative limits at its
discretion or at the request of the industrial user.
The new alternative limits must be calculated and become
effective within 30 days of the process change.
0 The Control Authority may impose stricter alternative
limits, but may not impose alternative limits which are
less stringent than the calculated limits.
0 A calculated alternative l.mit cannot be used if it is
below the analytical detect.ion limit for that pollutant.
If a calculated limit is bolow the detection limit, the
industrial user must either: 1) not combine the dilute
streams prior to the sampling point, or 2) segregate all
wastestreams entirely.
5.3 CALCULATION OF ALTERNATIVE TTO LIMITS USING THE CWF
The actual combined wastestream formula is presented in
Table 5.1. When used for determining alternative TTO limits,
the TTO limit for the applicable categorical standard (i) is
presented in both the equations by C^ and M^.
The individual organic compounds that make up the TTO value
vary depending on the applicable categorical standard. For
example, for Copper Forming industries, TTO refers to the sum of
12 individual organic compounds, whereas for Aluminum Forming
industries, TTO refers to the sum of 39 individual organic
compounds. (Only six organic compounds are common to both indus-
trial categories) . The CWF will only determine an alternative
TTO value, independent of the individual organic compounds
needed for each TTO limit. Therefore, if an industry has
combined wastewater discharges frcm processes regulated by
5-2
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TABLE 5.1
COMBINED WASTESTREAM FORMULAS
Alternative Concentration Limit Formula:
Vi \ /Fc.Fd \
ct ' ( 1:1 x ' <£<• 5-i)
Fi I \ F< I
C - alternative concentration limit for the pollutant
C - Categorical Pretreatment Standard concentration limit for the pollutant
in regulated stream i
F - average daily flow (at least 30 day average) of regulated stream i
F - average daily flow (at least 30 day average) of dilute w»ste«tream(«)
F - average daily flow (at least 30 day average) through the combined
treatment facility (including regulated, unregulated and dilute
was test reams)
N - total number of regulated streams
Alternate Mass Limit Formula
(Eq. 5-2)
M^_ - alternative mass limit for the pollutant
M - Categorical Pretreatnent Standard mass limit for the pollutant in
regulated stream i
F - average daily flow (at least 30 day average) of regulated itre»a i
F, - average dally flow (at least 30 day average) of dilute waatetcreaa(s)
d
F_ - average daily flow (at least 30 day average) through the combined
trestrenc facility (Including regulated, unregulated and dilute
wastes'reans)
N - total r.ucber of regulctec streams.
5-3
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different categorical standards with specific TTO limits, the
alternative TTO limit calculated using the CWF would refer to
the sum of the individual toxic organic compounds that make up
the TTO limit in each of the categorical standards. Thus, in
the example given above, the alternative TTO limitation calcu-
lated by using the CWF would be monitored by analyzing for all
45 toxic organic compounds regulated by one or both of the
categorical standards (Copper Forming and Aluminum Forming) and
summing the concentrations greater than 0.01 mg/1.
5.3.1 Example Calculation
the CWF
for Alternative TTO Limits Using
Following are three examples of how the CWF is used to
calculate alternative TTO limits. The examples assume mixing
prior to treatment of the following process wastestreams at an
industrial facility:
Industrial Category Type
Regulated
Wastestream Flow Daily Max.
TTO Limit
Metal Finishing
(Etching)^
Aluminum Forming
(Forging: Etching
Bath) 2
Sanitary Waste
Regulated
Dilution
(mgd)
0.1
Compliance
Date
4.57 mg/1 June 30, 1984
2.13 mg/1 Feb. 15, 1986
0.075 0.123 mg/1 Oct. 24, 1986
of f-kg3
0.05 N/A
N/A
1 This is not a subcategory but a metal finishing process.
2 Aliminum Forming, Subpart D - Forging, Subcategory - Cleaning
or Etching Bath.
3 off-kg means the mass of aluminum removed from a forging or
ancillary operation at the end of a process cycle for transfer
to a different machine or process.
Examples 1 and 2 are applicable in all cases because they reflect
the situation prior to the Aluminum Forming final compliance date.
Example 3 is applicable after the Aluminum Forming final compliance
date when the IU does not use the Aluminum Forming oil and grease
alternat ive .
Example 4 is applicable after the Aluminum Forming compliance
date when the IU does use the Aluminum Forming and the Metal
Finishing TTO alternative. In this example, the CWF must be used
to calculate both an alternative TTO and an alternative oil and
grease limit.
5-4
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Example 1: Calculation of alternative TTO discharge limit for an
integrated industrial facility from June 30, 1984 (compliance date
for Metal Finishing, interim TTO limit) until February 15, 1986
(compliance date for Metal Finishing, final TTO limit).
Metal Finishing
(Etching)
Aluminum Forming
(Forg ing)
(Etching Bath)
Sanitary Waste
0 = 0.1 mgd
TTO = 4.57 mg/1
0 =
0.075 mgd
TTO = N/A
0 = 0.225
Treatment
0 = 0.05 mgd
TTO = N/A
0 = Flow
TTO
Applicable
TTO Categorical
Standard
A concentration limitation is being calculated.
Equation 5-1, Table 5-1 is used.
Therefore,
The flow from the Metal Finishing process is considered a
regulated wastestream since it is subject to a TTO pretreatment
standard. The flow from the Aluminum Forming operation is also
subject to a TTO pretreatment standard. The Aluminum Forming
flow, however, is at present considered an unregulated waste-
stream, since the compliance date for Aluminum Forming Standards
(October 24, 1986) has not yet arrived. The sanitary waste is
considered a dilute wastestream. The alternate TTO limitation
is, then, calculated as follows:
TTOcwf = (4.57 mg/1 x 0.1 mgd) X (0.1 mgd + 0.075 mgd + 0.05 mgd - 0.05 mgd)
0.1 mgd 0.225 mgd
TTOcwf = 3.55 mg/1
Rather than monitor TTO to determine compliance with this
alternative limit, the owner/operator may elect with the Control
Authority's approval to exercise the available alternative under
the Metal Finishing regulation, the certification procedure
incorporating a toxic organic management plan. For an integrated
facility subject to a TTO standard with this alternative, and
5-5
-------
electing to use the alternative, the required solvent management
plan should focus on the entire facility, not just on the regulated
metal finishing operation(s). However, the Control Authority
must still use the CWF to develop t.he alternative limit for its
necessary monitoring activity. When the Control Authority conducts
sampling and analysis to verify continued compliance, it will
compare its sampling results with the applicable alternative TTO
limit developed using the CWF as in Example 1.
Example 2: Calculation of alternative TTO discharge limit for an
integrated industrial facility fron February 15, 1986 (compliance
date for Metal Finishing, final TTO limit) until October 24, 1986
(compliance date for Aluminum Forming).
Metal Finishing
(Etching)
Aluminum Forming
(Forg ing)
(Etching Baih)
Sanitary Waste
0=0.1 mgd
TTO = 2.13 mg/1
0 =
0 .075 mgd
TTO = N/A
0
TTO
0.05 mgd
N/A
0 = 0.225
Treatment
Q = Flow
TTO
Applicable
TTO Categorical
Standard
The difference between this example and the previous one is
that the metal finishing wastewater is now subject to a more
stringent limitation. Since the compliance date for aluminum
forming has still not arrived it is still considered unregulated.
TTOcwf - (2.13
TTOcwf =
mg/1
0.1
mg/1
x 0
mgd
1 mgd) X (0.1 mgd + 0.075
mgd + 0.05
0.225 mgd
mgd - 0.05 mgd)
In this example, the use of the TTO alternative available under
the Metal Finishing regulation follows the guidance discussed
i n Example 1.
5-e
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Example 3: Calculation of alternative TTO discharge limit for an integrated
industrial facility after October 24, 1986 (compliance date for Aluminum
Forming) when the Aluminum Forming oil and grease alternative is not used.
Because the TTO limit for Aluminum Forming is expressed as a production-
based limit, the first step necessary is the conversion of the production-based
TTO limit to the equivalent concentration-based TTO limit. Based on the following
production data for the industry:
Aluminum Forming (Forging: Etching Bath) = 0.12 mg/off-kg of aluminum forged
Maximum Daily Limit for TTO
Average Daily Production During Previous = 85,000 off-kg of aluminum forged
12 Ntonths per day
Average Daily Water Usage in Forging = 75,000 gpd
During Previous 12 Nbnths
The conversion of production-based TTO limit to a concentration-based TTO limit
is as follows:
TTO (concentration = (Production-Based Limit)(Avg. Daily Production)
equivalent) (Avg. Daily Flow From Regulated Process)(Conversion Factor)
TTO (concentration = (0.123 mg/off-kg)(85,000-kg/day) = 0.037 mg/1
equivalent) 75,000 gpd (3.785 liters/gallon)
Once the equivalent concentration-based TTO limit is determined the alternate
TTO limit can be calculated as follows (aluminum forming wastes are now a
regulated wastestream):
Metal Finishing Aluminum Forming Sanitary Waste
(Etching) (Forging)
(Etching Bath)
0 = 0.1 mgd 0 = 0.075 mgd 0 = 0.05 mgd
TTO = 2.13 mg/1 TTO = 0.037 mg/1 TTO = N/A
0 = 0.225
Treatment
5-7
-------
TTOcwf = (2.13 mg/1 x 0.1 mgd) + (0.037 mg/1 x 0.075 mgd)
(0.1 mgd + 3.075 mgd) X
(0.1 mgd + 0.075 mgd + 0.05 mgd - 0.05 mgd)
0.225 mgd
TTOcwf = °-96 rog/1
Note: The alternate TTO discharge limit is based on Metal
Finishing and Aluminum Forming Categorical Standards and is
proportioned by the flow of both the regulated wastestreams.
Due to dilution from sanitary waste, the alternate discharge
limit is reduced.
The TTO limit is the sum of the cor.centrations of the toxic organic
compounds listed in the Metal Finishing and Aluminum Forming regu-
lations, respectively, and found in the facility's discharge in
concentrations greater than 0.01 mg/l. In this example, all
Aluminum Forming TTO constituents and those Metal Finishing TTO
constituents reasonably expected to be present must be analyzed
for.
Example 4: Calculation of alternative TTO and oil and grease
discharge limits for an integrated facility after October 24, 1986
(compliance date for Aluminun Forming) when the Aluminum Forming
oil and grease alternative is used.
This example presents a somewhat more complicated situation when
considering the alternatives to TT3 monitoring. The Metal
Finishing regulation provides the alternative certification proce-
dure with a toxic organic management plan. The Aluminum Forming
regulation provides alternative Oil and Grease (O&G) limitations.
In this situation an industrial facility electing (with its Control
Authority's approval) to exercise the TTO monitoring alternatives
should proceed as follows. First, the owner/operator must make
the necessary certification and develop and implement a toxic
organic management plan (TOMP) as required by the Metal Finishing
regulation. The TOMP should apply to all operations and facilities
where toxic organics may enter the sewer.
Then, the CWF must be used to develop the alternative TTO limit.
Example 2 should be used in this calculation because the Aluminum
Forming wastestream is considered "unregulated" for TTO because
the IU is using the Aluminum Forming oil and grease alternative.
Second, the owner/operator using the CWF must develop an alter-
native O&G limitation for his facility. With the Control
Authority's approval, the owner/operator can use either the stated
production-based O&G limitation for developing the alternative
limit or convert the given production-based limit to the equivalent
concentration-based O&G limit and then calculate the alternative
limit using the CWF.
5-3
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Calculation of the alternative O & G production-based
limitation for an integrated facility after October 24, 1986
(compliance date for Aluminum Forming) is as follows. In this
situation the metal finishing wastestream is an unregulated
wastestream because it is not regulated for O&G.
Metal Finishing
(Etching)
Aluminum Forming
(Forging)
(Etching Bath)
Sanitary Waste
0 = 0.1 mgd
TTO = 2.13 mg/1
0 = 0.075 mgd
O&G = 3.58 mg/off-kc
0 = 0.05 mgd
TTO = N/A
0 = 0.225 mgd
Treatment
O & G = (3.58 mg/off-kg) x (0.1 mgd + 0.075 mgd + 0.05 mgd - 0.05 mgd)
0.225 mgd
O
G = 2.78 mg/off-kg
When the Control Authority allows conversion to a concentration-
based alternative O&G standard, the calculation of the alternative
O&G concentration-based limitation after October 24, 1986 is as
follows. Again, the metal finishing wastestream is an unregulated
wastestream.
Because the O&G limit is a production-based limit the first
step is to convert this limit to its equivalent concentration-based
limit.
The following is hypothetical production data for the industry:
Aluminum Forming (Forging & Etching Bath
Maximum Daily O&G Limit
Average Daily Production During
Previous Twelve Months
Average Daily Water Use in Forging
During Previous Welve Months
= 3.58 mg/off-kg of Al
forged
= 85,000 off-kg of Al
forged per day
= 75,000 gpd
5-9
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The conversion of the production-based O & 0 limit to an equivalent
concentration-based O & G limit is as follows:
O (, G
(concent rat ion
equivalent)
= (Production-Based Limit)(Avg. Daily Production)
(Avg. Daily Flow From Reg. Process)(Conversion Factor)
= (3.58 mg/off-kg)(85,000 off-kg/day)
(75,000 qpd) (3.785 liters/gallon)
1.07 mg/liter
Now, the alternative 0 & G limit can be calculated as follows:
Metal Fi n i sh i ng
(Etching)
O = 0.1 mgd
O&G = N/A
Aluminum Forming
(Forg ing)
(Rtching Bat.h)
0
O&G
0 .075 mgd
1 .07 mg/1
0 = 0.225
Treatment
Sanitary Waste
0 = 0.05 mgd
O&G = N/A
0&GCW£ t (1.07 mg/liter x 0.075 mgd)
0.075 mgd
x (0.1 mgd + 0.075 mgd + 0.05 mgc - 0.05 mgd)
0 .225 mgd
o&Gcwf = 0.83 mg/1
5-10
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6. REMOVAL CREDITS
Another provision of the General Pretreatment Regulations
that POTWs and industrial users will sometimes use is the Removal
Credit Provision. EPA promulgated on August 3, 1984 a revised
§403.7, Removal Credits [49 FR 31212]. This provision allows
POTWs to provide their categorical industrial users with a credit
(in the form of adjusted categorical pretreatment standards) for
removal of pollutants by the POTWs1 treatment systems. Industrial
users of such a POTW may be allowed by their POTWs to discharge
greater quantities of regulated pollutants than otherwise permitted
by applicable categorical standards. POTWs have complete discretion
in deciding whether to grant removal credits to the industrial users
after it has obtained the authority to grant such credits from its
Approval Authority.
6.1 REMOVAL CREDITS FOR TTO
The Electroplating, Metal Finishing, and Electrical Electronic
Components (Phase I and Phase II), Copper Forming, Aluminum Forming
and Coil Coating categorical pretreatment standards regulate TTO
discharges to POTWs. POTWs under §403.7 of the General Pretreatment
Regulation can grant removal credits to lUs regulated under any of
these standards. Before granting a removal credit to an ID, a POTW
must first obtain the authority to do so from its Approval Authority.
More complete information on the procedures which POTWs must use to
obtain Removal Credit authority can be found in the Guidance Manual
for Preparation and Review of Removal Credit Applications (September,
1985) .
POTWs should carefully consider any decision to seek removal
credit authority for TTO. In assessing the appropriateness of a
TTO removal credit the following should be considered:
0 The specific organic compounds included as a TTO
component in each regulation vary from regulation
to regulation.
o
Toxic organic removal by the POTW may be for a different
mixture of TTO constituents than those discharged by an
industrial user.
0 Easing of TTO limits in Electroplating, Metal Finishing,
and Electrical and Electronic Components contradicts the
policy promoting best management practices by the ID and
negates the inherent benefits of such practices.
0 For the Aluminum Forming, Coil Coating and Copper Forming
regulations the Agency has provided an alternative oil and
grease standard for easier implementation.
6-1
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0 Most TTO constituents are stripped, not treated, by
conventional POTW treatment (which may be hazardous
to POTW workers and the environment).
Based on the previous factors, the Agency does not
encourage applications for TTO removal credits.
6.2 REMOVAL CREDITS FOR TTO SURROGATE OR INDICATOR POLLUTANTS
Section 403.7(a)(2) of the General Pretreatment Regulations
states that removal credits may only be given for indicator or
surrogate pollutants regulated in a categorical pretreatment
standard when the categorical pretreatment standard specifically
so authorizes.
The Copper Forming, Aluminum Forming and the Coil Coating
pretreatment standards regulate oil and grease as a surrogate or
indicator pollutant for TTO monitoring. However, none of these
regulations specifically authorizes removal credits for oil and
grease. Therefore/ POTWs shall not grant any oil and grease
removal credit to ILJs regulated under these regulations.
6-2
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7. TTO MONITORING GUIDANCE
7.1 SAMPLING CONSIDERATIONS
The representativeness and validity of industrial user (IU)
discharge data is important to ensure compliance with categorical
pretreatment standards. Monitoring to assess compliance with TTO
discharge standards may involve monitoring simultaneously for
several different organic pollutant parameters. Therefore, the
validity of TTO discharge data, collected by either the Control
Authority performing industrial compliance monitoring or an IU
performing self-monitoring, is contingent upon utilization of the
proper sampling and analytical procedures. This section will
present guidelines and considerations for sampling and analysis of
IU discharges to help ensure that a representative and uncontaminated
TTO sample is collected and properly analyzed.
Much of the following guidance was obtained from documents
that address sample collection and preservation and flow measurement.
Since this section presents only limited specific guidelines and
considerations for TTO monitoring, it is recommended that these
references be utilized by the IU and Control Authority to ensure
proper sample collection techniques. They include, among others:
0 Guidelines Establishing Procedures for the Analysis of
Pollutants; Final Rule (40 CFR Part 136) October 26, 1984
0 Handbook for Samplng and Sample Preservation of Water
and Wastewater, U.S. Environmental Protection Agency,
Environmental Monitoring and Support Laboratory,
September 1982. Report No. EPA-600/4-82-029. NTIS
PB83-124503.
o
Methods for Chemical Analysis of Water and Wastes. U.S.
Environmental Protection Agency, Environmental Monitoring
and Support Laboratory, 1983. Report No. EPA-600/4-79-020.
NTIS PB 297686.
0 Compliance Evaluation Inspection Manual, EPA, Office of
Water Enforcement, July 1976.
0 NPDES Compliance Sampling Inspection Manual-MCD-51, USEPA
Enforcement Division, Office of Water Enforcement,
Compliance Branch.
7.1.1 Sampling Location
The location of sampling points within an industry's pretreatment
system or conveyance lines cannot always be specified by general rule
as conditions (i.e., processes, rate of production) vary with each
industry. Therefore, exact sampling locations must be identified
on a case-by-case basis. However, certain general principles can be
suggested for both IU self-monitoring and Control Authority monitoring
as follows:
7-1
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0 A permanent sampling location(s) should be identified
for use by both the Control Authority and industry.
This is typically accomplished during a Control Authority
inspection of the IU so that both parties agree on and are
familiar with the location(s).
0 The sampling location should be easily accessible and
relatively free of safety hazards (i.e., confined space)
0 For categorical industries, there should, if possible, be
no discharge present other than from the regulated process.
If other wastestreams (regulated, unregulated, or dilution)
are combined with the regu.'.atecl wastestream prior to the
sampling location, the combined wastestream formula (40 CFR
403.6(e)) will need to be utilized. Chapter 5 of this
manual provides specific guidance for using the combined
wastestream formula.
0 If the rate of industrial process discharge flow is needed
(i.e., where mass limitations are applied), the sampling
location will need to be located where the flow of the
wastestream is known or can be measured or estimated.
0 Repetitive samples (both for IU self-monitoring and Control
Authority compliance monitoring) should always be obtained
from the same sampling location.
7.1.2 Sample Collection Technique^
Generally, there are two types of samples (grab and composite
c:»mples) that can be collected eit.her manually or with automatic
sampling equipment. Grab samples are individual samples collected
over a period not exceeding 15 minutes; the grab sample is usually
collected manually. The collection of a grab sample is appropriate
when a sample is needed to:
0 Provide information about instantaneous concentrations
of a pollutant at specific times
0 Allow collection of a variable sample volume
0 Gather information more quickly than composite sampling
allows
0 Collect samples for parameters not amenable to automatic
sampling (e.g., oil and crease, volatile organics, coli-
form bacteria) .
Composite samples consist of: (1] grab samples collected at equal
intervals and combined proportional to wastestream flow, (2) samples
collected continuously and proportional to wastestream flow, or
(3) equal volumes taken at varying time intervals. Composite
samples are used when:
0 Determining average pollutant concentration during the
compositing period
7-2
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0 Calculating mass/unit time loadings
° Wastewater characteristics are significantly variable.
Particular regulated organic pollutants, each of which account
for part of the applicable TTO value for an IU, have particular
techniques that need to be followed during sample collection. For
example, a sample for acrolein must be a discrete grab, whereas a
sample for 1,3-dichlorobenzene may be a grab or composite sample.
Table 7.1 presents the sampling techniques for all the organic
parameters that may be included in an TTO value. For those para-
meters that can only be collected by a grab sample (Purgeable
Halocarbons, Purgeable Aromatics, Acrolein and Acrylonitrile), a
special sampling technique is used due to their volatile nature.
A 40-milliliter glass sample bottle (or vial) should be filled in
such a manner that no air bubbles pass through the sample as the
bottle is being filled. The bottles then should be sealed so that
ho air bubbles are entrapped in it. This hermetic seal must be
maintained until the time of sample analysis. It is often difficult
to fill the 40 milliliter bottle directly from the wastestream, in
which case a larger glass bottle may be used to collect (grab) the
sample from the wastestream and transfer the sample to the smaller
sample container.
It is also important to note that Purgeable Halocarbons,
Purgeable Aromatics, Acrolein and Acrylonitrile samples can only
be taken as discrete grab samples, and cannot be composited in the
field. Compositing of purgeable parameter samples must be performed
in the laboratory.
7.1.3 Sample Volumes
The volume of samples collected depends on the type and number
of analyses that are needed, as reflected in the parameters to be
measured. The volume of the sample obtained should be sufficient
to perform all the required analyses plus additional amounts to
provide for any split samples or repeat analyses.
Table 7.2 presents the sample volumes required for all the
organic priority pollutants that may be analyzed as part of the
TTO value. Note that required volumes are given for analysis of
each class of organic compound (which include specific organic
pollutants) even if only a specific pollutant analysis is needed.
The volumes listed also include the two procedures that analyze
for all the purgeable organic parameters and for all the remaining
organic pollutant parameters (Acids, Base/Neutrals, Pesticides).
It is important that the IU or Control Authority consult the
laboratory performing the analysis to determine if any additional
sample volume will be needed.
7-3
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TABLE 7.1
SAMPLE COLLECTION TECHNIQUES FOR ORGANIC PRIORITY POLLUTANT
Collection Technique
Parameter Grab Composite
Purgeable Halocarbons X
(Includes: Broraoform
Bromodichloromethane
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethylvinyl ether
Chloroform
Chloromethane
Dibromochloromethane
I,2-Dichlorobenzene
1,3-Dichlorobenzene
I,4-Dichlorobenzene
Dichlorodifluoromethane
I,1-Dichloroethane
I,2-Dichloroethane
I,l-Dichlhloroethene
trans-I,2-Dlchloroethene
I,2-Dichloropropane
cis-l,3-Dichloropropene
trans-I,2-Dichloroporpene
Methylene chloride
I, I, Z,2-Tetrachloroethane
Tetrachloroethene
1,1, l-Trichloroethane
1, 1,2-Trichloroethane
Trichloroethene
Trichlorofluoromethane
Vinyl chloride)
Purgeable Aromatics
(Includes: Benzene
Chlorobenzene
1,2-Dichlorobenzene
L,3-Dichlorobenzene
1,^-Dichlorobenzene
Ethylbenzene
Toluene)
\crolein and Acrylonitrile
7-4
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TABLE 7.1
SAMPLE COLLECTION TECHNIQUES FOR ORGANIC PRIORITY POLLUTANT (Continued)
Parameter
Phenols
(Includes:
Collection Technique
Grab Composite
4-Chloro-3-raethylphenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dimethylphenol
2-Methyl-4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
2,4,6-Trlchlorophenol)
Benzidlnes
(Includes:
Benz idene
3,3-Dichlorobenzidene)
Phthalate Esters
(Includes: Benzyl butyl phthalate
Bts(2-ethylexyl) phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Dtethyl phthalate
Dimethyl phthalate)
N itrosamlnes
(Includes:
N-nitrosodimethylamine
N-nitrosodiphenylamine
N-nltrosodi-n-propylamlne)
7-5
-------
TABLE 7.1
SAMPLE COLLECTION TECHNIQUES FOR ORGANIC PRIORITY POLLUTANT (Continued)
Parameter
Organochlor ine
(Includes:
Pesticides and PCB ' s
ALdrln
a-BHC
b-BHC
d-BHC
g-BHC
Chlordane
4,4-DDD
4,4-DDE
4,4-DDT
DieLdrin
Endosultan I
Endosultan II
EndosuLtan Sulfate
Endr in
Endrin Aldehyde
Heptachlor
Heptachlor Epoxide
Toxaphene
PCB-L016
PCB-1221
PCB-1232
PCB-12^2
PCB-1248
PCB-1254
Collection Technique
Grab Composite
X
Sic roaromat ics
(Includes:
and Isophorone
Isophorone
Nitrobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene)
7-6
-------
TABLE 7.1
SAMPLE COLLECTION TECHNIQUES FOR ORGANIC PRIORITY POLLUTANT (Continued)
Collection Technique
Parameter Grab Composite
Pol/nuclear Aromatic Hydrocarbons X X
(Includes: Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
BenzoC b)pyrene
Benzo(b)thuoranthene
Benzo(g)perylene
Benzo(k)fluoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
IndenoC1,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pvrene)
Haloethers
(Includes: Bis(2-chloroethy1) ether
Bis(--chloroethoxy) methane
Bis(2-chloroisopropyl) ether
-»-3romophenyl phenyl ether
•4-Chlorophenyl phenyl ether)
Chlorinated Hydrocarbons
(Includes: Hexachlorocyclopentadiene
Hexachlorobenzine
Hexachlorobutadiene
Hexachloroethane
1,2-Dichlorobenzene
1,2,4-Dichlorobenzene
I,3-Diehiorobenzene
1,4-Dichlorobenzene
2-chloronaphthalene)
2,3,7,8-Tetrachlorodibenzeno-p-dioxln X
Purgeables X
Base/N'eutral, Acids and Pesticides X
Source: 40 CFR Part 136
7-7
-------
TABLE 7.2
SAMPLE VOLUMES FOR ORGANIC PRIORITY POLLUTANT ANALYSIS*
Parameter Required Minimum Sample Volume (ml)
Purgeable Halocarbons ^0
(Includes: Bromoform
Bromodichlorome thane
Bromome thane
Carbon tetrachlorlde
Chlorobenzene
Chloroethane
2-Chloroethylvinyl ether
Chloroform
Chloromethane
Dlbromochlorome thane
1 , 2-Dlchlorobenzene
1 ,3-Dlchlorobenzene
1 , 4-Dlchlorobenzene
Dlch lor odlfluor one thane
1 , l-Dichloroethane
1 ,2-Dichloroethane
1 , 1-Dlchlhloroethene
trans-1 , 2-Dlchloroethene
1 , 2-Dlchloropropane
cls-1 ,3-Dlchloropropene
trana-1 , 2-Dlchloroporpene
Methylene chloride
1 , I ,2,2-Tetrachloroethane
Tetrachloroethene
1,1, 1-Trlchloroethane
1,1, 2-Trlchloroethane
Trichloroethene
Trichlorof luorome thane
Vinyl chloride)
Purgeable Aromatlca
(Includes: Benzene
Chlorobenzene
1 ,2-Dlchlorobenzene
I , 3-Dlchlorobenzene
1 ,4-Dlchlorobenzene
Ethylbenzene
Toluene)
Acroleln and Acrylonltrlle
7-8
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TABLE 7.2
SAMPLE VOLUMES FOR ORGANIC PRIORITY POLLUTANT ANALYSIS* (Continued)
Parameter
Phenols
(Includes:
4-Chloro-3-methylphenol
2-Chlorophenol
2,4-Dichlorophenol
2,4-Dlmethylphenol
2-Methyl-4,6-dinltrophenol
2-Nttrophenol
4-Nltrophenol
Pentachlorophenol
Phenol
2,4,6-Trichlorophenol)
Required Minimum Sample Volume (ml)
1,000
Benzidines
(Includes:
1,000
Benzidene
3,3-Dichlorobenzidene)
Phthalace Esters
(Includes: Benzyl butyl phthalate
Bis(2-ethylexyl) phthalate
Di-n-butyl phthalate
Di-n-octyl phthalate
Diethyl phthalate
Dimethyl phthalate)
1,000
Nitrosamines
(Includes:
1,000
N-nitrosodimethylaaine
N-nitrosodiphenylamine
N-nitrosodi-n-propylaaine)
7-9
-------
TABLE 7.2
SAMPLE VOLUMES FOR ORGANIC PRIORITY POLLUTANT ANALYSIS* (Continued)
Parameter
Organochlorlne
(Includes:
Pesticides and PCB's
Aldrln
a-BHC
b-BHC
d-BHC
g-BHC
Chlordane
4,4-DDD
4,4-DDE
4,4-DDT
Dleldrln
Endosultan I
Endosultan II
Endosultan Sulfate
Endrln
Endrln Aldehyde
Heptachlor
Heptachlor Epoxide
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
PCB-1260)
Required Minimum Sample Volume (ml)
1,000
Nltroaromattcs and Isophorone
(Includes: Isophorone
Nitrobenzene
2,4-Dlnttrotoluene
2,6-Dinitrotoluene)
1,000
7-10
-------
TABLE 7.2
SAMPLE VOLUMM FOR ORGANIC PRIORITY POLLUTANT ANALYSIS* (Continued)
Parameter Required Minimum Sample Volume (ml)
Polynuclear Aromatic Hydrocarbons 1,000
(Includes: Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)pyrene
Benzo(b)thuoranthene
Benzo(g)perylene
Benzo(k)fluoranthene
Chrysene
DibenzoCa,h)anthracene
Fluoranthene
Fluorene
Indeno(1,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene)
Haloethers 1,000
(Includes: Bls(2-chloroethyl) ether
Bis(2-chloroethoxy) methane
Bls(2-chlorolsopropyl) ether
4-Bromophenyl phenyl ether
4-Chlorophenyl phenyl ether)
Chlorinated Hydrocarbons 1,000
(Includes: Hexachlorocyclopentadlene
Hexachlorobenzine
Hexachlorobutadlene
Hexachloroethane
1,2-Dlchlorobenzene
1,2,4-Dlchlorobenzene
1,3-Dlchlorobenzene
1,4-Dichlorobenzene
2-chloronaphthalene)
2,3,7,8-Tetrachlorodibenzeno-p-dloxln 1,000
Purgeables 40
Base/Neutral, Acids and Pesticides 1,000-2,000
Source: 40 CFR Part 136
7-11
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7.1.4 Sample Equipment and Containers
The equipment that can be used for sampling industrial process
wastestreams ranges from a simple bucket to highly complex automatic
samplers. The type of equipment that will be used by an IU and the
Control Authority depends upon not only the pollutant parameter to
be sampled, but also the sample location, sample frequency, sample
volume, etc.
When sampling activities are relatively complex, such as flow
proportional composite sampling over extended time periods, auto-
matic samplers may be much more efficient. Many automatic samplers
can directly correlate process wastestream flow with both sample
volume and time. In hazardous sampling situations, which may occur
when sampling wastestreams containing organic priority pollutants,
use of automatic samplers can reduce the risk of injury to sampling
personnel. The disadvantages of automatic samplers are high capital
costs and maintenance requirements. However an IU or Control
Authority can frequently offset these disadvantages through reduced
labor requirements and a good equipment maintenance program.
There are a number of commerically manufactured automatic
samplers available for use by an IU or Control Authority. EPA has
outlined criteria for selecting automatic samplers in their NPDES
Compliance Sampling Inspection Manual. Examples of some of the
criteria include weight of sampler, minimum sample, lift velocity,
purge cycle, etc. When sampling for organic priority pollutants
to de'-^'-mine a TTO value, certain criteria for use of automatic
samplers must be followed to ensure the collection of an uncon-
taminated sample. At a minium, these criteria include:
0 The automatic sample collection equipment must be free
of tygon and other potential sources of contamination
0 The automatic sampler must be able to keep the samples
refrigerated at all times
0 The automatic sampler must be able to accommodate glass
collection containers.
The selection and preparation of sample containers is based
on the parameters to be measured. All organic priority pollutant
samples (whether grab or composite) must be collected and stored
using glass containers. Therefore, if manual grab samples will
be composited, both the grab collection container and composite
container must be made of glass. Before containers are transported
to the laboratory, caps with a teflon lining (or foil for non-
purgeable parameters if the sample is not corrosive) must be used
to seal the sample container.
7-12
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7.1.5 Sample Preservation and Holding Times
In most cases, industrial wastewater samples contain one or
more unstable pollutants that require immediate analysis or preser-
vation. Prompt analysis is the most positive assurance against
error from sample deterioration, but this is not feasible for
composite samples, in which portions may be stored for as long as
24 hours. For some pollutants, deterioration can be sufficiently
deferred by preservation of the samples during compositing and
transfer to the laboratory. Procedures used to preserve samples
include refrigeration, pH adjustment, and chemical treatment.
Prior preservation and holding time for organic pollutant samples
is essential to the integrity of any monitoring program. Table
7.3 provides the recommended preservatives and maximum holding
times that should be used for the specific classes of organic
pollutants.
The procedures outlined in Table 7.3 should be used at the
start of sample collection in the field. However, aliquots of
a composite sample that would require multiple preservatives, can
be preserved only by maintaining the sample aliquots at 4°C until
compositing and sample splitting are completed.
7.1.6 Sample Type and Frequency for TTO Monitoring
The type of sample and frequency of sampling necessary for
reporting TTO compliance data depends upon: (1) IU self-monitoring
requirements, and (2) Control Authority compliance monitoring
procedures.
The sample type prescribed for any of the above reports consists
of a composite sample collected at intervals that would properly
represent the process wastestream flows from typical daily operations
at an ID. Where feasible, composite samples should be flow-propor-
tioned. Depending on the types of organic pollutant parameters sampled
for TTO and the wide variety of processes existing at different IDs,
the IU may be allowed by the Control Authority to collect and report
the results of a grab sample.
Industrial self-monitoring requirements for each categorical
standard have not been promulgated to date. However, Section 403.12
of the General Pretreatment Regulations requires the submission of
self-monitoring reports to the Control Authority which must contain
industrial process wastestream discharge data for the pollutant
parameters regulated by the applicable categorical standard. These
reports were discussed in Chapter 2 of this document.
The frequency with which the above composite samples should be
taken to comply with all industrial self-monitoring requirements
depends on the discharge flow of each IU. The minimum number of
consecutive sampling days for the reporting period is three in a
two-week period for facilities discharging less than 250,000 GPD,
and six in a two-week period for facilities discharging more than
250,000 GPD. Sampling must occur during peak operational periods.
7-13
-------
TABLK 7.3
SAMPLE PRESERVATION AND HOLDING TIMKS KOK ORGANIC PRIORITY POLLUTANT ANALYSIS
Parameter
Purgeable Halorarbons
(Includes: Broraoforra
Bromod 1 chl or ome thane
Broraome thane
Carbon tetrachloride
Ch1orobenzene
Chloroethane
2-Chloroelhylvinyl ether
Chloroform
Chlorom«?thane
1)1 broraochlororaethane
I ,2-Dichiorobenzene
1.3-Di chlorobenzene
1,4-Dichlorobenzene
Dichlorodif1uoromcthano
1,1-Diehi oroethane
1 ,2-I)ichloroethane
I ,I-Di chlhloroethene
t rans-1,2-Dichloroelhene
1 , 2-I)i fhl oroprupaue
cis~l,3-Dichloropropene
t rans-1 , 2-!>i rhloroporpene
Mcthylene chloride
1,1,2, 2-Tet rachl oroel liane
Telrachloroethene
1,1, l-Trii-hloroeth.ini'
1 , 1 , 2-Tr ichloroelliane
Tr ichloroelhene
Tr it: hi or of I uorome thane
Vinyl chloride)
KPA Method No.
601
Preservat ive
Cool, 4°C
0.0082 Na
Maxinnim Holding Time
14 days
7-14
-------
TABLK 7.3 (Continued)
SAMJ'LK PRESERVATION AND HOLDING TIMKS KOK ORGANIC PRIORITY POLLUTANT ANALYSIS (Continued)
Parameter
Purgeablc Aroroatics
(Includes: Benzene
Chlorobenzene
1 ,2-Dichlorobenzene
1,3-Dichlorobenzene
1 ,4-Dlchlorobenzene
Kthylbenzene
Toluene)
KPA Method No.
602
PreservatIve
Cool, 4°C
S.O*
1: 1 HC1 to pH <2
Maximum Holding Time
14 Days
Acrolein and Acrylonltr1le
603
Cool, 4°C
0.008Z Na2S 0
Adjust pH to 4-5
14 Days
(3 days for acrol-eln
If pH not adjusted)
Phenols
(Includes:
604
4-Chloro-3-methy1 phenol
2-Chlorophenol
2,4-Dlchlorophenol
2,A-Dimethyl phenol
2-Methyl-4,6-dinltrophenol
2-Nltrophenol
A-N1trophenol
Pentathlorophenol
Phenol
2,A,6-Trlchlorophenol)
Cool, 4°C
0.0082 N
7 days until extraction,
40 days after extraction
BenzldInes
(Includes:
Benzldene
3,3-Dichlorobenzldene)
605
Cool, 4'C
0.008Z Na
7 days until extraction,
40 days after extraction
7-15
-------
1AHI.K /• ' (Com timed)
SAMPLE PRESERVATION AND HOLDING TIMES KUR ORGANIC PRIORITY POLLUTANT ANALYSIS (Continued)
er
Phlhalale Esters
(Includes: Rvnzyl butyl |>i.« li.i 1 .11 e
Bl s(2-elhy lexy 1 ) phlh.ilale
l)l~n-butyl phlhalale
Ui-n-octyl phthalale
Dietliyl pluhalate
Dimethyl phlhalale)
KPA Melhod No,
Presetvat Ive
Cool, <.°C
Maximum Holding Tl»
/ days mull extraction,
'iO days .jfter exlfacllon
Nit rosamlnes
(Inc1udes :
N-n iirosodImelhy1anlne
N-II( t rosod f pheny lamine
N-n It rosodl-n-propy laiilne)
60 /
Cool, 4*C
Store In dark,
0.008Z Na S20
1:I NaOH to pH 7-
10'
1 days until extraction,
40 days alter extraction
7-15
-------
TABLE 7.3 (Continued)
SAMPLE PRESERVATION AND HOLDING TIMES KOR ORGANIC PRIORITY POLLUTANT ANALYSIS (Continued)
\'.\ I mil I f i
Organochlorlne Pesticides and PCB ' s
(Includes: Aldrln
a-BHC
b-BHC
d-BIIC
g-BHC
Cli lordane
A, A -ODD
4,4-DDE
4, 4 -DDT
Dieldrln
Endosultan I
Endusul tan i I
EndoHiiltan Sulf.ilc
Endr lit
Emir in Aldehyde
Me pi at hi or
llcpt
-------
TABl.K ; • ' (Goal Inued)
SAfU'l.K 1'KKSKRVATION AND UOl.OlNi; TlHKS KOK ORGANIC PRIORITY f'OI.LUTANT ANALYSIS (Continued)
t'.i i .iinet er
N11 roaromat irs and Isophorone
(Includes: Isophorone
N iirobenzene
2 , 4-l)lni trotoluene
2,6-I) in it rololuene)
KI'A Mi'lluxl No.
hU9
Preserval 1 ve
Cool,
Maximum Holding Tiae
/ days until extraction,
40 days .iller extraction
Po I ymic lear Aromatic Hydrocarbons
(1 nc I udes : Acenaplithene
Acenaphthylene
Anlhracctie
Benzo( b)pyr«>ne
Henzo( b)lhnoranlhi*iu>
hc'nzo( g) pur yleue
Benzo(k) f luor ant hoiu-
Chrysene
Ui benzo( a ,li )unthraceno
Kl no rant lieiu-
VI norene
I ndiMio( I , 2 , )-cd ) pyre iii-
N.iphl li,i lent*
I'hen.int hrcix*
I'yrene)
hit)
Cool, 4°C
Store in dark,
O.U082 Na^S l>3
/ days until extraction,
40 days alter extraction
ll.i lot-1 hers
( Inc1udes :
61 1
Bis(2-t -liloroelliy I ) .-ther
Rln(2-clilor<>ft lioxy) met II.IMI-
lit s( 2-i III 010 i so p ropy 1 ) el ln-r
4 -Hromopheny I plu-nyl ellier
4-Chloropheny 1 phenyl ellu-r)
Cool. 4°C
0.008Z Na S.,
/ days mil I I exlracl Ion,
40 d.iys after extraction
7-18
-------
TABLK 7.1 (ConlInued)
SAMPLK PRESERVATION AND HOLDING TIMKS KOR ORGANIC PRIORITY POLLUTANT ANALYSIS (ComInued)
KPA Mi-1 hod No.
Preservat I ve
Ch lor 1 n,i ted Hydrocarbons
(Includes: Hexachlorocy-
nl.id it-lie
llexachlorobe. .
I , 3-Dlchlorobenzene
I ,4-lHchlorohenzene
2-chloronaphlhalene)
Cool,
Maximum Holding ii. •
days until extraction,
days after extraction
,8-Tet rachlorodIbenzeno-p-d ioxIn
613
Cool, 4°C
0.008Z Na S20
^ days until extraction,
40 days after extraction
Purgeables
624
Cool, 4°C
0.008X Na
14 days
(3 days for acroleln and
aery lonltrite)
Base/Nt'ul ral, Adds and Pesticides
Should only be used in the presence of residual chlorine
For d1phenyInltrosamlne only
Aldrin only
Cool, 4'C
0.008X Na2S20
Adjust ptt to b-9
Store In dark
1 days until extraction,
40 days after extraction
7-19
-------
Industri.il TTO compliance monitoring procedures will vary
between Control Authorities and between I Us regulated by a Control
Authority. Some will take daily composite samples several times
a year for each IU. Others will only take grab samples until
noncompliance is Pound, which would then trigger a more frequent
sample collection at the IU.
7.?. LABORATORY CONSIDERATIONS
Valid TTO discharge data not only hinges on proper sampling
techniques, but also on the proper laboratory analysis of the
samples collected. This section provides guidance for the IU and
Control Authority in performing the necessary TTO analyses.
7.2.1 Analytical Procedures
Determination of TTO in an industrial process wastestream
involves the analysis of the individual organic pollutant parameters
specified in the applicable Categorical Standard. Procedures for
the analysis of toxic organic pollutants have been mandated by EPA
in Guidelines Establishing Test Procedures for the Analysis of
Pollutants: Final Rule (40 CFR Part 136).
Generally, the EPA guidelines recognize two methods for organic
pollutant analyses: gas chromatography (GC) with selective detectors
or GC coupled with mass spectrophotometry (GC/MS). The GC methods
are provided for the following 12 classes of organic pollutants:
0 Purgeable Halocarbons (EPA Method 601)
0 Purgeable Aromatics (EPA Method 602)
0 Acrolein/Acrylonitrile (EPA Method 603)
Phenols (EPA Method 604)
0 Benzidenes (EPA Method 605)
0 Phthalate Esters (EPA Method 606)
0 Nitrosamines (EPA Method 607)
0 Organochlorine Pesticides and PCBs (EPA Method 608)
0 Nitroaromatics and Isophoront (EPA Method 609)
0 Polynuclear Aromatic Hydrocarbons (EPA Method 610)
0 Haloethers (EPA Method 611)
0 Chlorinated Hydrocarbons (EPA Method 612) .
The GC/MS methods can also be u5;ed to quantify organic pollutant
levels in a sample. Although higher costs are associated with GC/MS
analyses, simultaneous measurement of large numbers of organic
pollutants are possible. Also GC/MS analyses can overcome specific
interferences that would mask organic pollutant responses obtained
with a GC. Three specific GC/MS methods have been promulgated by EPA:
0 Purgeable (Method 624) - Determines volatile organic
pollutant concentrations, including those parameters
covered by GC Methods 601, 602, and 603
7-20
-------
0 Base/Neutral, Acids, and Pesticides (Method 625) - Determines
numerous organic pollutant concentrations, including those
par am?ters covered by GC Methods 604 through 612
0 2 ,3,7,3-Tetrachlorodibenzene-p-Dioxin (Method 613) -
Determines concentration of 2,3,7 , 8-Tetrachlorodibenzene
(TCDD).
The EPA procedures include quality control techniques, sample
container requirements, and sample preservation procedures for toxic
organic pollutants. All analytical laboratories utilized should,
have ready access to the October 26, 1984 Federal Register publication
This publication provides information necessary for a trained labora-
tory technician to perform all analyses required for TTO analysis.
7.2.2 Laboratory Quality Control
Although not as great as the error associated with poor sampling
techniques, the potential for error occurring during analysis of
industrial wastewater samples can have a great impact on the accept-
ability of TTO monitoring data. Without the aid of independent checks
and general quality control, a laboratory may report erroneous results
without being aware that a problem exists. Analytical quality control
guidance is available from EPA in a document entitled Handbook for
Analytical Quality Control in Water and Wastewater Laboratories
(PB213884). This handbook is published by the EPA Technology Transfer
Program and is available through NTIS . Specific information is
provided that can guide the laboratory toward sound and reliable
techniques and procedures.
7.3 OIL AND GREASE MONITORING CONSIDERATIONS
In lieu of monitoring for TTO, the following categorical
standards allow an IU to alternatively monitor for oil and grease:
o
Aluminum Forming (40 CFR 467) - All subcategories
0 Coil Coating (40 CFR 465) - Subcategory D (Canmaking) only
0 Copper Forming (40 CFR 468) - All subcategories.
This section provides guidance for the IU and Control Authority
when monitoring for the alternative oil and grease parameter.
7.3.1 Oil and Grease Sampling Considerations
Due to the potential losses of oil and grease on sampling
equipment (including containers), the collection of a composite
oil and grease sample would not be representative of an industrial
wastestream discharge. Therefore, separate oil and grease grab
samples must be taken at regular intervals throughout a required
monitoring time period and analyzed separately to obtain the average
concentration over the monitoring period.
7-21
-------
Sampling location considerations discussed previously in this
chapter would still he valid when moiitjrinq for oil and qrease.
Oil and grease samples must he taken in a glass bottle, preferably
narrow mouth. To ensure an adequate volume of sample for oil and
grease laboratory analysis, at least one-liter of sample must be
collected. Once an oil and grease sample is collected, it must be
preserved by lowering the sample pH to below 2 with concentrated
1 + 1 sulfuric acid (112304) or concentrated hydrochloric acid (HCL)
and store', at 4 C. All properly preserved oil and grease samples
must be a na 1 y /.>• 1 within 28 days of collection.
As discussed previously for TTC, the sampling frequency for
oil and grease will depend on the type of monitoring being performed;
either TU se1f-monitor ing or Control Authority compliance monitoring.
Regardless of the type, however, both the in and Control Authority
must ensure that the sampling frequency will be representative of
the daily operations and subsequent prjcess wastewater discharge of
the IU.
7.3.2 Analytical Considerations for' Oil and Grease
The F, PA approved method for oil and grease analysis (liquid-
liquid extraction with tr ichlorot r i 1: luoroethane ; gravametric) can
be found in the following sources:
0 Methods for Chemical Analysis of Water and Waste, Method
413.1 (19'-i;), U.S. EPA, Cincinnati, Ohio. EPA-600/4-79-020.
0 Standard Methods for the Examination of Water and Wastewater,
Method 503A 15th Edition (1930), APHA, AWWA, WPCF,
Washington, D.C .
The Coil Coating Regulation [40 CFR Part 465] delineates a
specific procedure for analyzing wastewater samples to determine
the concentration of oil and grease in the sample. Control
Authorities and IDs subject to this regulation must use this
procedure. The procedure is contained in Section 465.03(c) and
is included in this manual in Appendix F, .
Reference to the above documents should be made to ensure
proper analysis of an oil and grease sample.
7-22
-------
APPENDIX A
40 CFR Section 403.12
Reporting Requirements for
POTWs and Industrial Users
-------
9452 Federal Register/ Vol. 46, No. 18 / Wednesday, January 28, 1981 / Rules and Regulations
the Approval Authority shall commence
its review. Within 5 days after making a
determination that a submission meets
the requirements of §403.9(b), and
where removal allowance approval is
sought, §§403.7(d) and 403.9(d), or at
such later time under §403.7(c) that the
Approval Authority elects to review the
removal allowance submission, the
Approval Authority shall:
(1) Issue a public notice of request for
approval of the submission:
(i) This public notice shall be
circulated in a manner designed to
inform interested and potentially
interested persons of the Submission
Procedure for the circulation of public
notice shall include:
(A) Mailing notice of the request for
approval of the Submission to
designated 206 planning agencies,
Federal and State fish, shellfish, and
wildlife resource agencies; and to any
other person or group who has
requested individual notice, including
those on appropriate mailing lists; and
(B) Publication of a notice of request
for approval of the Submission in the
largest daily newspaper within the
jurisdiction(s) served by the POTW.
(ii) The public notice shall provide a
period of not less than 30 days following
the date of the public notice during
which time interested persons may
submit their written views on the
Submission.
(iii) All written comments submitted
during the 30 day comment period shall
be retained by the Approval Authority
and considered in the decision on
whether or not to approve the
Submissions. The period for comment
may be extended at the discretion of the
Approval Authority: and
(2) Provide an opportunity for the
applicant, any affected State, any
interested State or Federal agency
person or group of persons to request a
public hearing with respect to the
Submission.
(i) This request for public hearing
shall be filed within 30 day (or
extended) comment period described in
paragraph (b)(l)(ii) of this section and
shall indicate the interest of the person
filing such request and the reasons why
a hearing is warranted.
(ii) The Approval Authority shall hold
a hearing if the POTW so requests. In
addition, a hearing will be held if there
is a significant public interest in issues
relating whether or not the
Submission should be approved.
Instances of doubt should be resolved in
favor of holding the hearing.
(iii) Public notice of a hearing to
consider a Submission and sufficient to
inform interested parties of the nature of
the hearing and the right to participate
shall be published in the same
request for approval of the Submission
under paragraph (b)(l)(i)(B) of this
section. In addition, notice of the
hearing shall be sent to those persons
requesting individual notice.
(3) Whenever the approval Authority
elects to defer review of a submission
which authorizes the POTW to grant
conditional revised discharge limits
under §403.7(b)(2) and 403.7(c), the
Approval Authority shall publish public
notice of its election in accordance with
paragraph (b)(l) of this section.
(c) Approval authority decision. At
the end of the 30 day (or extended)
comment period and within the 90 day
(or extended) period provided for in
paragraph (a) of this section, the
Approval Authority shall approve or
deny the Submission based upon the
evaluation in paragraph (a)_ of this section, the
section and taking into consideration
comments submitted during the
comment period and the record of the
public hearing, if held. Where the
Approval Authority makes a
determination to deny the request, the
Approval Authority shall so notify the
POTW and each person who has
requested individual notice. This
notification shall include suggested
modifications and the Approval
Authority may allow the requestor
additional time to bring the Submission
into compliance with applicable
requirements.
(d) EPA objection to Director's
decision. No POTW pretreatment
program or authorization to grant
removal allowances shall be approved
by the Director if following the 30 day
(or extended) evaluation period
provided for in paragraph (b)(l)(ii) of
this section and any hearing held
pursuant to paragraph (b)(2) of this
section of the Regional Administrator sets
forth in writing objections to the
approval of such Submission and the
reasons for such objections. A copy of
the regional Administrator's objections
shall be provided to the applicant, and
each person who has requested
individual notice. The Regional
Administrator shall provide an
opportunity for written comments and
may convene a public hearing on his or
her objections. Unless retracted, the
Regional Administrator's objections
shall constitute a final ruling to deny
approval of a POTW pretreatment
program or authorization to grant
removal allowances 90 days after the
date the objections are issued
(e) Notice of decision. The Approval
Authority shall notify those persons who
submitted comments and participated in
the public hearing, if held, of the
approval or disapproval of the
Submission. In addition, the Approval
Authority shall cause to be published a
notice of approval or disapproval in the
same newspapers as the original notice
of request for approval of the
Submission was published. The
Approval Authority shall identify in any
notice of POTW Pretreatment Program
approval any authorization to modify
categorical Pretreatment Standards
which the POTW may make, in
accordance with §403.7, for removal of
pollutants subject to Pretreatment
Standards.
(f) Public access to submission. The
Approval Authority shall ensure that the
Submission and any comments upon
such Submission are available to the
public for inspection and copying.
§403.12 Reporting requirements for
POTW's and industrial users.
(a) Definition, The term "Control
Authority" as it used in this section
refers to: (1) The POTW if the POTW's
Submission for its pretreatment program
(§403.3(t)(l)) has been approved in
accordance with the requirements of
§403.11; or (2) the Approval Authority if
the Submission has not been approved.
(b) Reporting Requirement for
industrial users upon effective date of
categorical pretreatment standard--
baseline report. Within 180 day after
the effective date of a categorical
Pretreatment Standard, or 180 days after
the final administrative decision made
upon a category determination
submission under §403.6(a)(4).
whichever is later, existing Industrial
User s subject to such categorical
Pretreatment Standards and currently
discharging to or scheduled to discharge
to POTW shall be required to submit
to the Control Authority a report which
contains the information listed in
paragraph (b)(l)--(7) of this section.
Where reports containing this
information already have been
submitted to the Director or Regional
Administrator in compliance with the
requirements of 40 CFR 128.140(b), the
industrial user will not be required to
submit this information again. New
sources shall be required to submit to
the Control Authority a report which
contains the information listed in
paragraphs (b)(l)--(5) of this section:
(1) Identifying information. The user
shall submit the name and address of
the facility including the name of the
operator or owners.
(2) Permits. The user shall submit a
list of any environmental control permits
held by or for the facility.
(3) Description of operations. The
User shall submit a brief description of
the nature, average rate of production
A - 1
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Fedenl Register / Vol. 48. No. 18 / Wednesday. January 28. 1981 / Rules and Regulations 2;-,
and Standard Industnil GaisiGcauon of
the operation!s) earned out by such
Industrial User This description should
Include a schematic process diagram
which indicates points of Discharge to
the POTW from the regulated processes.
(4) Flow meaturement. The User shall
submit information showing the
measured average daily and maximum
dally flow, in gallons per day. to the
POTW from each of the following;
(I) regulated process streams: and
(U) other streams as necessary to
allow use of the combined wastestream
formula of \ 403.B(e). (See paragraph
(b)(S)(v) of this section.)
The Control Authority may allow for
verifiable estimates of theM flows
where justified by cost or feasibility
consideration*.
(3) Meatureaient of Pollutants, (i) The
ua«r shall identify the Pretreatment
Standards applicable to each regulated
process:
(U) In addition, the User shall submit
the rmulu of sampling and analysis
Identifying the nature and concentration
(or mas*, when required by the
Standard or Control Authority) of
regulatadjollutants in the Discharge)
from MCB regulated process. Both daily
maximum and average concentration (or
mass, whan required) shall b« reported.
The sample shall be representative of
dally operations:
(lii) Where feasible, samples must be
obtained through the now-proportional
composite sampling techniques specified
in the applicable categorical
Pretreatment Standard. Where
composite sampling is not feasible, a
grab sample is acceptable:
(Iv) Where the Cow of the stream
being sampled 1s less than or equal to
B50.000 liters/day (approximately
250.000 gpd). the User must take three
samples within a two-week period.
Where the flow of the stream being
sampled is greater than 950.000 liters/
day (approximately 250.000 gpd). the
User must take six samples within a
two-week period;
i (v) Samples should be taken
Immediately downstream from
pretreatment facilities if such exist or
Immediately downstream from the
regulated process if no pretreatment
exists. If other wastewaters are mixed
with the regulated waatewater pnor to
pretreatment the User should measure
the Qows and concentrations necessary
to allow use of the camoined
wasteetream formula of I 403.81 el in
order to evaluate comouance wna -_aa
Pretreatment Standaros. Where an
alternate concentration or mass limit
has been calculated in accordance witn
i 403-fl(e) this adjusted limit along with
supporting data shall be submitted to
the Control Authority:-
(vi) Sampling and analysis shall be
performed in accordance with the
techniques prescribed in 40 CFR Part 136
and amendments thereto. Where 40 CFR
Part 136 does not contain sampling or
analytical techniques for the pollutant In
question, or where the Administrator
determines that the Part 130 sampling
and analytical techniques are-
inappropriate for the pollatant in
question, sampling and analysis shall be
performed by using validated analytical
methods or any other applicable
sampling and analytical procedure*.
including procedures suggested by the
POTW or other parties, approved by the
Administrator
(vii) The Control Authority may allow
the submission of a baseline report
which u allies only historical data so
long as the data provides information
sufficient to determine the need for
industrial pretreatment measures;
(vtii) The baseline report shall '
indicate the time, date and place, of
sampling, and methods of analysis, and
theU certify that such sampling *nt^
analysts U representative of normal
work cydes and expected pollutant
Discharges to the POTW:
(0) Certification. A statement
reviewed by an authorized
representative of the Industrial User (as
defined in subparagraph fk) of this
section) and certified to by a qualified
professional indicating whether
Pretreatment Standards are being met
on a consistent basis, and, if not.
whether additional operation and
m«tTit«T<«nr'« (Q and M) and/or
additional pretreatment :s required for
the Industrial User to meet the
Pretreatment Standards and
Requirements: and
(7) CompUaact Schedule. If additional
pretreatment and/or O and M will be
required to meet the Pretreatment
Standards: the shortest schedule by
which the Industrial User .will provide
such additional pretraatment and/or O
and M. The completion Gate in this
schedule shall not be later than the
compliance date established for the
applicable Pretreatment Standard.
(i) Where the Industrial User's
categorical Pretreatment Standard has
been modified by a removal allowance
(i 4017). the combined wastestream
formula (I 403.o(e)). and/or a
Fundamentally Different Factor)
variance t| 403.13) at taa ume iae User
suomits tne reoon reoureo oy
paragrapo (0) oi cms secuon. tne
information required by paragraphs
fbj(6) and (7) of this section shall pertain
to the modified limits.
A-2
(ii) If the categorical Pretreatment
Standard is modified by a removal
allowance (5 403.7). the combined
w.ste.tream formula (| 403.6jeJ). and/or
a Fundamentally Duferent Factors
variance (| 403.13) after the User
submits the report required by
paragraph (b) of tus secuon. any
necessary amendments to the
information requested by paragraphs
(b](6) and (7) of this secuon snali be
submitted by the User to the Control
Auihonry within 00 days after the
modified Limit is tpproved.
(c) Compliance Schedule for Meeting
Categorical Pntrvaunent Siandaras
The following condiuons shall apply to
the schedule required by paragraph
(b](7) of this secuon:
(1) The schedule shall contain
increments of progress in the form of
dates for the commencement. and
completion of major events leading to
the construction and operation of
additional pretreatment required for the
Industrial User to meet the applicable
categorical Pretreatment Standaras (e.g..
hiring an engineer, completing
preliminary plans, completing Anal
plans, executing contract for major
components, commencing construction.
completing construction, etc.).
(2) No increment referred to in
paragraph (c)(l) of :his section shall
exceed 9 months.
(3) Not later than 14 days following
each date in the schedule and the unaJ
date for compliance, tne Industrial User
shall submit a progress report to the
Control Authority including, at a
minimum, whether or not it complied
with the increment of progress to be met
on such date and. If not the date on
which it expects to comply with this
increment of progress, tie reason for
delay, and the steps being taken by the
Industrial User to. return the
construction to the schedule established.
In no event shall more than 9 monuu
elapse between such progress reports to
the Control Authority.
(d) Report on compliance with
categorical pretreatment standard
deadline. Within 90 days following the
date for final compliance with
applicable categorical Pretreatment
Standards or in the case of a New
Source following commencement of the
introduction of wastewater into the
POTW. any Industrial User subject to
Pretreatment Standards and
Requirements shall submit to the
Control Authority i reran sixains th;
oarure ana concenincsa a: id
jouutants in vae Ciscrane rom — e
reguiatea process wa.ca are u3i;;ec. zy
Pretreatment Standards and
Requirements and ihe average and
maximum daily Qow for these process
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§454 Federal Register / Vol. 46. No. 18 / V. -rnesday. January 28. 1981 / Rules and Regulations
units in the Industrial UMT which en
limited by such Pretreatment Standards
and Requirements. The rtpart shall state
whether the applicable Pretreatment
Standards or Requirement* ere beinf
met on e consistent buia end. if not.
whet additional O aad M end/or
pretreatmeot is necessary to brmf the
Industrial UMT mto compiienoe wath mar
applicable Prttnatmeat Standards or
Requirements. This statement •nail be
signed by an aathortied fepiesaiitaave
of the Industrial User, as defined in
paragraph (k) of this section, and
certified to by a qualified professional
(e) Periodic report* on eontutufd
camptiaoc*. (l) Any Industrial User
suofect to e categorical *^****i^ti*>*
Standard, after the rompllanre data of
toch Pretreatmeat Standard or. m the
case of e New Some. after
w ..... ,&*••• -n> at the diaeherfe mto the
POTW. thill submit to the Control
Authority dunnf the months of June end
Dsc brr. unleae required more
frequently in the Pretreatment Standard
or by the Control Aathority or the
Approval Authority, a report «
the nature and :jne L.ttonof
poflntants in the affluent which are
ttmlieQ by each categorical Prevee
Standard*. In addition, this report shell
iDCteVaW t rvcofn of ttUeVwd or
GaVQaBeltatQ flVtffVflM flttd WlaMTYfWHeW QAuY
flows for the reporting penod for the
Discharge reported hi part graph (b)(4)
of this section except that the Control
Authority mey require more detailed
reporting of flow*. At the discretion of
the Control Authority end in
w^d r»ioa of such factors ee beau
high or tow flow rates, holidays, budget
cydea. etc. the Control Authority mey
agree to alter the months daring which
the ebova reports are to be submitted
(2) Where the Control Authority has
lopoeed mass limitations on Industrial
Users ea provided far by I 40U(d). the
report required by paragraph (s)(l) of
this eection shall indicate the maaa of
pollutants regulated by Pretreaonent
Standards in the Discharge from the
Induafftal User
(f) Aboee of slug /coding. The
Industrial User shall notify the POTW
immediately of any slug 1«~f*"g. aa
defined by I «oaj(b((4). by the
industrial User.
(gj Moutonng and aaoJjrmu to
ofcewtwoote eoaaaiud aoatplianct. The
reports required 0 paragraphs (b)(3).
(dj. aad (e) of this section shall contain
me roeolo) of sampling
of
Discharge. tm*mmM tta Sow
toe nature and ooncea^raoon* or
production and men where requeatea
by the Control Authority, of pollutants
contained therein which an limited by
the applicable Pretreaonent Standard*.
"Us frequenc-/ of momtormg shall be
prescribed in the applicable
Prttraaonant Standard. All analyses
shaU be performed m aceonunce with
p«. : r ' ts sstaMahed by the
Administrator pursuant to secnon 304(gJ
of the Act and contained in 40 CFR Part
U8 tad amendment! thereto or with any
other teat procedures approvad by the
AdminiaO'eior. Scampi ^ng *fiMH be
performed in accordance with the
tachniqnes approved bj the
/'fcHiitMOator. Where 40 CTR Part 13«
does not include sampling or analytical
tachmquae for the pollutants m question,
or where the Administrator detarminaa
that the Part 13e •^fpp'ipg and analytical
tachniqnee are mappropnata /or the
pollniant in question, sampling and
anaiyaae shall be periuimed using
validated analytical met bode or any
other seBpiiAg and analytical
pn.-- ' ir, infliMjtngproeedurea
suggeeied by the POTW or other parttae.
approvad by the Administrator.
(h) Cc9tr''mf» actooWe for POTWt.
The fallowing ««*"Wi^'«"« ^^d reporting
r /^..i, ----- nt* »h^n fflply to ****
compliance srhediile tor developmeDt of
an approvmble POTW Pretraa|meni
Program required by 1 40XL
(1) The scheduk shall contain
Increments of piupeea in the fan of
dates far the T: v -ntud
completion of ma^or rrants leading to
a POTW Pretreatment Program (aj.
acquirtmj required ecthontUa.
liqmmliiphtm tnrtdhtm • --L«nt«n»«
acquiring e^uipa—i):
(2) No increment referred to hi
paragraph (nfll) of this section shaO
exceed nine *•«•'»*«•?
(3) Not later than 14 dart following
each date hi the schedule *"^ ths ft««i
date for op^p«««^ ma POTW ihaH
submit a progress report to the Approval
whether or not it compiled with the
l&uw t of progreee to be met on SUCA
date aad If not the date on which it
i to comply with mm ifiwMu^it of
, the reason for delay, aad the
steae taken by me POTW to return to
tbs schedule ««nNI"»J In no event
shall more than nine months alepee
between such ptogreae reports to the
Approval Authority.
[I) InzOoJ POTW nport on eoatpUao
J oJJowanc*. A
POTW which has received authorization
to modify categorical Pretreaoaent
Standards for aatltuaats removac by the
POTW in acsareaace with the
.eumemeaa 01 1 4CX7 ouet snonut to
t&e Approval Authority within ae days
aftar the eflectiva date of a Pretreetmaat
Standard for which authorization to
modify has been approved a raport
which contains the in/ormaUon nqurtd
by H 40X7ld)(2). 4C3-1d)(3) »nd
4tnJ>(d)(8). A minimum of oat sanple
par month dunng ma rtporuaj panoa u
required
(jj Ptnodtc nporu by POT\V to
demonstrate conunuta comouanc* with
natoraJ oUowonc*. Tze rtpons ru'crrvd
to m paragraph (i) of 'Ju* itcaon w\u oe
subnuned to tna Approval Autaonty at
Vmontb intervals oagmmng wich th«
nhmtM.oa of ths uuuai rtpon reftrrsd
to in paragraph (i) of Lu» section ualass
required more frequently by ihe
Approval Authority.
(k) Signatory n^uirtmtntt for
induttnaJ uurrtporu. Tha rtpons
required by paragraphs fb). (d). and (t).
of this section mast be ugnad by an
aa'Kcr»-d representsDve of the
in/4u*tj4*i Usec. An auuonzed
r*p»..~*"«Qve may be:
(1) A principal axacudve officer of it
least the level of vice president. J ih«
Industrial User submitting the reports
required by paragraphs fb). (d) and (a) of
this section is a corporation,
(2) A general partner or proprietor if
the Industrial User menu t tint, the report
required by paragraphs (b). (d) and (e) of
this section is a panoenjup or sole
proprietorship respectively. "
(3) A duly authorized representative
of the individual designated in
subpengrapfa (1) or (2) of this paragraph
if such repreMntettve is responsible for
the overall operation of the facility tram
which the Indirect Discharge originate*.
(I) Sjgnatorf nquinmtno for POTW
JBUWUU. Reports submitted to tne
Approval Aathority by the POTW in
accordance with paragraphs fh). ff] and
0) of this section must be signed by a
principal executive officer, ranking
elected official or other duly authorized
employee if such employee is
responsible for overall opera don of the
POTW.
(m) Pruruiuru gauming fraud and
foist statements. The reporti required
by paragraphs fb). (d). (e). (M. (i) and (J)
of this section shall be subject to the
provisions of IS U.S.C lecnon 1001
relating to fraud and false statements
and the provisions of section 300(c)(2] of
the Act ^wuini false statements.
representations or certifications m
reports raqmreo under the Act.
(D) ftfcord-Jutpatf rvovj/vmcncs.
(1) Any Industrial User and POTW
subject to the reporting requirements
established in this section shall
•"•""•i" records of ail infarruaon
tsuitm* tern env momtanz: acmaes
reouirea by tfitf lecncn. Suu rtcoras
shall include for all sampler
(i) The date, exact place, mstnod and
time of sampling and ibe names of ihs
person or persons taking the samples:
A-3
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Federal Register ,' Vol. -;6. No. 18 / '.Vedr.escay. ar.uary :3. 1531 / Rules and Regulations
(ii) The data* analyse* wen
performed:
(iii) Who performed the analyses:
(iv) The analytic*! techniques/
methods use: and
(v) The results of such analyses.
(2) Any Industrial User or POTW
subject to the reporting requirements
esublitbed in this section shall be
required to retain for a minimum of 3
years any records of monitoring
activities and results (whtther or not
such monitoring activities are required
by this section) and shall make such
records available for inspection and
copying by the Director and the
Regional Administrator (and POTW In
the case of an Industrial User). This
period of retention shall be extended
during the course of any unresolved
litigation regarding the Industrial User
or POTW or when requested by the
Director or the Regional Administrator.
(3) Any POTW to which reports are
submitted by an Industrial User
pursuant to paragraphs (b), (d), and (e)
of this section shall retain such reports
for a «»«<»dtimti» of 3 years and shall make
such reports available for inspection
and copying by the Director and the
Regional Administrator. This period of
retention shall be extended during the
course of any unresolved litigation
regarding the discharge of pollutants by
the Industrial User or the operation of
the POTW Pretreatment Program or
when requested by the Director or the
Regional Administrator.
1403.11 Var1anc««tromc.tiQBrk '
piAbrAn.nl a* V~ dt for fun*-. » W 1y
tta
(a) Definition. The term "Requester"
meant an Industrial Uaer or a POTW or
other interested person seeking a
variance from the limits specified in a
categorical Pretreatment Standard.
(b) PurpoSf and scoot. In establishing
categorical Pretreatment Standards for
existing sources, the EPA will take into
account all the information it can
collect devalop and solicit regarding the
factor* relevant to pretreatment
standards under section 307(b). In some
cases, information which may affect
these Pretreatment Standards will not
be available or. for other reasons, will
not be considered during their
development As a result it may be
necessary on a case-by-case basis to
adjust the limits in categorical
Pretreatment Standards, making them
either more or less soingent as they
apply to a certain Industrial User within
an Industrial category or subcategory.
This will only be done if data specific to
that Industrial User indicates it presents
factors fundamentally different from
those considered by EPA in developing
the limit at issue. Any interested person
believing that factors relating to an
Industrial User are fundamentally
different from the factors considered
during development 01 a categorical
Pretreatment Standard applicable to
that User and further, that the existence
of those factors justifies a different
discharge limit from that specified in the
applicable categorical Pretreatment
Standard, may request a fundamentally
different factors variance under this
section or such a variance request may
be Initiated by the EPA.
(c) Criteria.— (1) C*/?«ro7 criteria. A
request for a variance based upon
fundamentally different factors shall be
approvad only if:
(i) There is an applicable categorical
Pretreatment Standard which
specifically controls the pollutant for
which alternative limits have been
requested: and
(ii) Factors relating to the discharge
controlled by the categorical
Pretreetment Standard are
fundamentally different from the factors
considered by EPA in establishing the
Standards: and
(Ui) The request for a variance ii
made in accordance with the procedural
requirements in paragraphs fjj and (h)
of this section.
(2) Cfituia applicabit to Jta
stnngtnt limit*. A variance request for
the establishment of limit* las* stringent
than required by the Standard shall be
approved only it
(i) The alternative limit requested ia
no less stringent than Justified by the
fmiH»mn)t§J difference:
(ii) The alternative limit will not result
m a violation of prohibitive discharge
standards prescribed by or established
under | 4034;
(iii) The alternative Unit will not
result in a non-water quality
environmental impact (Including energy
requirements) ^
advene than the impact considered
during development of laa Pntreatment
Standard*; mru$
(iv) CompHeppf with the Standards
(either by using the technologies upon
which the Standards are based or by
using other control alternatives) would
result in either
(A) A removal cost (adjusted for
inflation) wholly out of |/f
-------
APPENDIX B
ELECTROPLATING & METAL FINISHING CATEGORY:
List of Toxic Organic Compounds Regulated as a
Component of Total Toxic Organics
-------
APPENDIX B
TOXIC ORGANIC COMPOUNDS REGULATED
UNDER ELECTROPLATING & METAL FINISHING TTO PRETREATMENT STANDARD
Acenaphthene
Acrolein
Acrylonitrile
Benzene
Benzid ine
Carbon tetrachloride
(tetrachioromethane}
Chlorobenzen-?
1,2,4-trichlorobenzene
Hexachlorobenzene
1,2-dichloroethane
1,1,1-trichloroethane
Hexachloroethane
1, 1-dichl or oe thane
1,1,2-trichloroethane
1,1,2,2-tetrachloroethane
Chloroethane
Bis (2-chloroethyl) ether
2-chloroethyl vinyl ether (mixed
2-chloronaphthalene
2,4,6-trichlorophenol
Parachlorometa cresol
chloroform (trichloromethane)
2-chlorophenol
1, 2-d ichlorobenzene
1,3-d ichlorobenzene
1,4-dichlorobenzene
N-nitrosod i-n-propylamine
Pentachlorophenol
Phenol
Bis (2-ethylhexyl) phthalate
Butyl benzyl phthalate
Di-n-butyl phthalate
Di-n-octyl phtalate
-------
Diethyl phthalate
Dimethyl phthalate
1,2-benzanthracene
(benzo(a)anthracene)
Benzo(a)pyrene (3,4-benzopyrene)
3,4-Benrofluoranthene
(benzo(b)fluoranthene)
11,12-benzofluoranthene
(benzo(k)fluoranthene)
Chrysene
Acenaphthylene
Anthracene
1,12-benzoperylene
(benzo(gh i)pery lene)
Fluorene
Phenanthrene
1,2,5,6-dibenzanthracene
(dibenzo(a,h)anthracene)
Indeno (1,2,3-cd)pyrene
(2,3-o-phenylene pyrene)
Pyrene
Tetrachloroethylene
Toluene
Trichloroethylene
Vinyl Chloride (chloroethylene)
3,3-dichlorobenzidine
1,1-dichloroethylene
1,2-trans-dichloroethylene
2,4-di chlorophenol
1,2-dichloropropane
(1,3-dichloropropene)
2,4-dimethylphenol
4-chlorophenyl phenyl ether
4-bromophenyl phenyl ether
Bis (2-chloroisonropy1) ether
Bis (2-chlolroethoxy) methane
Methylene chloride (dichloronethane)
Methvl chloride (chloromethane)
Methyl bromide (bromomethane)
Bromoform (tribromomethane)
Di chlorobromomethane
Chlorodibromomethane
Hexachlorobutadiene
Hexachlorocyclopentadiene
Isophorone
Naphthalene
Nitrobenzene
2-nitrophenol
4-nitrophenol
2,4-dinitrophenol
N-n i t rosod ime thy 1 am i ne
N-nitrosodiphenylamine
Aldrin
Dieldrin
Chlordar.3 (technical mixture and
metabolites)
4,4-DDT
4,4-DDE (p,p-DDX)
4,4-DDD (p,p-TDE)
Alpha-endosulfan
Beta-endosulfan
B-2
-------
2,6-dinitrotoluene
1,2-diphenylhydrazine
Ethylbenzene
Fluoranthene
Heptachlor epoxide (BHC -
hexachlorocyclohexane)
Alpha-BHC
Beta-BHC
Gama-BHC
Delta-BHC
(PCB-Dolychlorinated biphenyls)
PCB-1242 (Arochlor 1242)
PCB-1254 (Arochlor 1254)
PCB-1221 (Arochlor 1221)
PCB-1232 (Arochlor 1232)
PCB-1248 (Arochlor 1248)
PCB-1260 (Arochlor 1260)
PCB-1016 (Arochlor 1016)
Toxaphene
2,3,7,8-tetrachlorodibenzo-p-dioxin
(TCDD)
Endosulfan sulfate
Endrin
Endrin aldehyde
Heptachlor
4,6-d i ni tro-o-cresol
2,4-dinitrotoluene
B-3
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APPENDIX
ELECTRICAL AND ELECTRONIC COMPONENTS CATEGORY
List of Toxic Organic Compounds Regulated as a
Component of Total Toxic Organics (By Subcategory
-------
APPENDIX C
TOXIC ORGANIC COMPOUNDS REGULATED UNDER
ELECTRICAL AND ELECTRONIC COMPONENTS TTO PRETREATMENT STANDARDS
Subcategories A and B (Seminconductors and Electronic Crystals)
1,2,4 trichlorobenzene chloroform
1,2 dichlorobenzene
1,3 dichlorobenzene
1,4 dichlorobenzene ethylbenzene
1,1,1 trichloroethane methylene chloride napthalene
2 nitrophenol phenol bis (2-ethylhexyl)
phthalate tetrachloroethylene toluene
trichloroethylene
2 chlorophenol
2,4 dichlorophenol
4 notrophenol pentachlorophenol di-n-butyl
1,2 diphenylhydrazine isophorone butyl
benzyl phthalate
1,1 dichloroethylene
2,4,6 trichlorophenol carbon tetrachloride
1,2 dichloroethane
1,1,2 trichloroethane dichlorobromoethane
Subcategory C (Cathode Ray Tubes)
chloroform
trichloroethane
methylene chloride
bis(2-ethylhexyl) phthalate
toluene
trichloroethylene
C-l
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APPENDIX D
Analytical Procedure for Determining
Oil and Grease Concentrations Under
Coil Coating Regulation
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APPENDIX D
TOXIC ORGANIC MANAGEMENT PLAN
ABC REFRIGERATION CORPORATION
HIGH POINT PLANT
I. Description of Facilities and Solvent Use
A. Process Description
The ABC Refrigeration Corporation, High Point Plant,
manufactures automotive radiators, condensers, and compressors
from metal coils and metal castings manufactured by other
suppliers. The forming and assembly processes include metal
forming, degreasing, chromating, and brazing in preparation for
painting and final assembly. The metal castings are machined,
washed, assembled, and degreased prior to final assembly.
Wastewater types and volumes and the current wastewater
treatment system are depicted in Figure 1. The primary sources
of process wastewater are the degreasing, chromating, fluxing,
and parts washing operations. Other sources of wastewater are
cooling tower blowdown and boiler blowdown. Wastewater from the
degreasing operations is treated by dispersed air floatation for
oil and grease removal and then discharged to a combined waste-
stream containing the wastewater from all other sources. The
combined wastestream is then treated by coagulation/flocculation
with chemical and polymer addition for solids and metals reduction,
The treated effluent is discharged to the city sewer system.
B. Identification of Toxic Organic Chemicals Entering the
Plant Wastewaters
1. Chemical Analysis of Treated Wastewaters
Samples were taken of the plant's treated wastewaters for
analysis for the 110 toxic organics regulated under the metal
finishing categorical pretreatment standards. Samples collected
were 24-hour flow proportioned composite samples for acid extrac-
tible and base/neutral compounds. Grab samples for volatile
organics were taken every four hours and were composited before
analysis. Samples were taken over a period when all production
lines were operating at peak production rates. Samples were
analyzed by gas chromatography with compound identification and
quantification by mass spectrophotometer (GC/MS). EPA procedures
624 and 625 were followed for GC/MS analysis. Toxic organic
compounds detected at concentrations greater than 0.01 mg/1 are
1isted in Table 1.
D-l
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Table 1
Compound Concentration (mg/1)
1,1,1-Trichloroethane 1.320
Napthalene 0.210
Chloroethane 0.131
Benzene 0.532
Phenol 0.681
2. Identification of Solvents Used in Manufacturing Operations
a. Greasefree is a degreasing solvent used in the forming
process. Greasefree's principle ingredient is 1,1,1-
trichloroethane. We have contacted the manufacturer of
Greasefree, Doubt Chemical Corporation, who informs us that
their analysis of Greasefree indicates that no other priority
toxic pollutants are contained in Greasefree. Doubt's letter
confirming its analysis is enclosed as Attachment 1.
b. Rinsewash is a degreasing solvent used in the metal
castings process. Rinsewash is a mu1ticomponent solvent we
purchase from Pound Chemical Corporation. At our request
Pound has analyzed Rinsewash and found it contains napthalene,
benzene, and phenol. Pound represents that no other toxic
organic pollutants were identified in its analysis of
Rinsewash. Pound's letter documenting its analysis is
enclosed as Attachment 2.
c. Rustaway is a corrosion inhibitor used during the metal
castings washing process to prevent rust formation. We buy
Rustaway from the Rxit Chemicals Corporation. The primary
ingredient of Rustaway is carbon disulfide. Exit refused
our request for a chemical analysis of Rustaway. We, there-
fore, submitted an aliquot of Rustaway to Whatsinit
Laboratories, Inc. for analysis. Whatsinit's report is
enclosed as Attachment 3 and documents that Rustaway con-
tains chloroethane. No other toxic organics were detected.
3. Identification of Other Potential Sources of Toxic Organic
Pollutant Introduction to the Wastewater Treatment System
a. Durable Paints are used to finish the forming process
items. Although not detected in the wastewater analysis,
Durable Paints are known to contain toluene. The floor
drains in the forming process painting area discharge to
the wastewater treatment system. Therefore, any spilled
paint would enter the process wastewater treatment system.
D-3
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b. Degreasing Areas - Floor trains in both decreasing areas
similarly are connected to the main wastewater system. Therefore,
spills of degreasing agents could enter the treatment system.
c. Solvent Storage Areas - Solvents, paints, and corrosion
inhibitors are stored in bulk quantities in four different
areas of the plant — the two degreasing areas, the washing
area, and the painting area. Spills could occur by accidental
dumping, spillage during routine transfer, etc. Such spills
would enter the wastewater treatment system through t-He floor
drains.
II. Description of Control Options Explored
A. Solvent Substitution
For the degreasing, corrosion inhibitor, and painting sources
of toxic organics, ABC explored the feasibility of substituting
another product that does not contain toxic organic materials.
Obviously, this would be the most effective manner of eliminating
toxic organic discharges both from process operations and from
potential spillage into floor drairs. ABC obtained samples of
degreasing agents, corrosion inhibitors, and paints that do not
contain toxic organics from vendors and conducted pilot tests of
their effectiveness. ABC concluded after these tests that the
alternative degreasing agents and paints could not be used without
adversely affecting the process and final products. The alterna-
tive degreasing agents were not nearly as effective as the ones
currently used and, therefore, would impair the effectiveness of
subsequent operations. Alternative paints could not be applied
evenly to our products. One alternative corrosion inhibitor,
Chromisorb, appears to be an accept.able alternative to the
Rustaway and contains the toxic metals zinc and chromium. Thus,
the option of eliminating chloroethane discharges by substituting
Chromasorb for Rustaway as a corrosion inhibitor was considered.
B. Process Modifications
The major alternative to the substitution of degreasing
agents is to institute changes in the degreasing process that do
not result in wastewater discharge. This would be accomplished
by wiping parts rather than rinsing them. After a thorough
wipedown, parts would be air dried in an area under a vacuum hood.
The vacuum hood is integrated with the facility's air pollution
control devices. Any material used for wiping would, of course,
be treated as a hazardous material. It would be transferred to
drums and disposed of to a licensed disposer or reclaimer.
Thus, process changes could be made that would eliminate discharge
of process wastewaters containing 1,1,1-trichloroethane, napthalene,
benzene, and phenol. Solid waste generation would, of course,
i ncrease.
D-4
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C. Segregated Drain System
Spills of toxic organics could be eliminated from the process
wastewater stream if a segrega-ted floor drain system were
constructed. ABC investigated this option and found that, because
of the location of some existing drain pipes, such modification
would require a major disruption of the plant and would cost far
more than routine TTO monitoring. Moreover, such an option would
create a significant additional wastewater treatment problem for
those cases in which drained water is not contaminated by spilled
material.
D. Sealing Floor Drains
Introduction of toxic organics to wastewaters through floor
drains could be eliminated if floor drains were sealed. In the
process areas this option is not feasible because of State safety
requirements. In storage areas, however, such an option may be
pract ical.
E. Installing Sumps in the Floor Drains
Under this option sumps would be installed such that prior
to entering the drain, floor waters would pass through a sump or
holding tank. The sump would be as large as the largest spill of
solvent reasonably expected plus a 10 percent freeboard allowance.
Thus, if a solvent spilled, the discharge to the drain would be
turned off. The solvent could, then, collect in the sump and be
recovered.
III. Toxic Organic Management Plan
As a result of the above analyses, ABC believes that all
of its toxic organic pollutant discharges can be controlled by a
toxic organic management plan in lieu of routine toxic organic
moni tor ing.
A. Solvent Substitution
Discharge of chloroethane will be eliminated by use of a
substitute rust inhibitor. ABC will discontinue use of Rustaway
as a rust inhibitor. Instead, ABC will use Chromasorb to
prevent rust formation in its metal casting line. Chromasorb is
a zinc-chromate rust inhibitor that can be used to prevent rust
formation in place of Rustaway. Chromasorb contains the toxic
metals chromium and zinc. The existing wastewater treatment
system, however, is designed to remove metallic pollutants. By
adjustment of the chemical and polymer feed, ABC anticipates
that it can maintain current levels of metals discharge while
eliminating chloroethane discharges.
D-5
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B. Process Changes
ABC will eliminate discharge of process wastewaters
containing 1 ,1 ,1-trichloroethane, napthalene, benzene, and phenol
by instituting changes in the degreasing process. Solvent cleaning
will be accomplished by immersion and manual wipedown. Parts
will be allowed to air dry in an area covered by a vacuum hood
prior to any water washing. Materials used for wipedown will be
collected in drums, sealed, stored in a secure area and transferred
to Usitagin Reclamation Company. Usitagin is a licensed hazardous
waste disposer.
C. Solvent Storage Procedures
Storage procedures for all solvents containing toxic organic
compounds will be changed. Storage will be in a central location
for all such materials, including paints. The storage area will
be diked to contain a volume equal to the largest container
stored, 55 gallons, plus 50 percent. There will be no floor
drains in this area.
All incoming containers of solvents or paints will be labeled
upon receipt with the following information:
***************************************************************
* Material Contains Regulated Organic Solvents *
* *
* 1. Use only in designated areas *
* *
* 2. Do not permit this material t.o enter plant wastewater *
* stream *
* *
* 3. Dispose of only in designated and identified containers *
* *
***************************************************************
All in-plant usage containers will also be marked with the above
i nformat ion.
D. Installation of Sumps in Process Areas
In all process areas where materials containing toxic
organic compounds are used, sumps will be installed prior to any
floor drains. The sumps will be designed to allow rapid shut-off
of flow to the drain and to hold a volume equal to the largest
container of solvent used in that area plus ten percent.
E. Spent Solvent Disposal Practices
Spent solvents are collected in 55 gallon drums, sealed, and
stored in an existing, secured storage area. The storage area
contains no floor drains. ABC sells spent solvent to the Usitagin
Reclamation Company.
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F. Training
All personnel involved in degreasing, chromating, painting,
and clean-up activities will receive instruction in the proper
handling and disposal of solvents and clean-up materials in. order
to keep regulated toxic organics out of industrial wastewater.
New employees will he trained in these procedures immediately.
All personnel working in these activities are familiar with this
toxic organic management plan and will follow the procedure
established in that standard to eliminate regulated organics from
entering the water wash system.
Training consists of classroom instruction which reviews
the following:
1. The organic solvents and cleaners known to be in use
at the plant and the areas in which they are used.
2. The location of lift stations and drains with emphasis
upon the location of pretreatment sewer systems for each
area in the plant.
3. The Toxic Organic Management Plan and the proper proce-
dures for handling and disposing of the respective
solvents.
G. Inspections
1. Degreasers, spray booths, and cleaning operations will
be inspected routinely by the area supervisor to verify
cleaning procedures and adherence to this Toxic Organic
Management Plan to insure that TTO does not spill or
leak into plant sewers.
2. Centrally located cleaning and solvent handling, reuse,
and collection areas, as well as raw material and waste
solvent storage areas, will be inspected weekly by a
designated environmental representative to verify proper
solvent storage, handling, and collection. A log of
inspections and sign-off will be maintained by the
designated environmental representative.
H. Implementation
All provisions of this plan will be fully implemented by
April 1, 1984.
D-7
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IV. Certification
"Based on my inquiry of the person or persons directly
responsible for managing compliance with the TTO limitations, I
certify that, to the best of my knowledge and belief, no dumping
of concentrated toxic organics into the wastewaters has occurred
since filing of the last report. T further certify that this
facility is implementing this toxic organic pollutant management
plan submitted to the Control Authority on January 2, 1984."
John Smith
Plant Manager
High Point Plant
Telephone: (617) 617-6176
D-8
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APPENDIX E
Analytical Procedure for Determining
Oil and Grease Concentrations Under
Coil Coating Regulation
-------
§465.03 Monitoring and reporting
requirements
(c) The following determination
method shall be used for the
determination of the concentration of oil
and grease in wastewater samples from
all subcategories of coil coating (Based
on Standards Methods, 15th Edition.
methods 503A and 503E). In this method,
a partition gravimetric procedure is used
to determine hydrocarbon (petroleum
based) oil and grease (O&G-E).
(1) Apparatus, (i) Separately funnel. 1
liter, with TEE stopcock.
(ii) Glass stoppered flask, 125 ml.
(iii) Distilling flask, 125 ml.
(iv) Water bath.
(v) Filter paper, 11 cm diameter.2
(vi) Glass Funnel.
(vii) Magnetic stirrer and Teflon
coated stir bar.
(2) Reagents, (i) Hydrochloric acid.
HC1. 1+1.
(ii) Trichlorotrifluoroethane.3 (1.1.2-
trichloro-1.2.2-trifluoroethane), boiling
point 47°C. The solvent should leave no
measurable residue on evaporation:
distill if necessary. Do not use any
plastic tubing to transfer solvent
between containers.
(iii) Sodium sulfate. Na2SO4
anhydrous crystal.
(iv) Silica gel, 60 to 200 mesh. Dry at
110°C for 24 hours and store in a tightly
sealed container.
(3) Procedure. To determine
hydrocarbon oil and grease, collect
about 1 liter of sample and mark sample
level in a bottle for later determination of
sample volume. Acidify to pH 2 or
lower; generally, 5 ml HC1 is sufficient
Transfer to separatory funnel.
Carefully rinse sample bottle with 30 ml
trichlorofluoroethane and add solvent
washings to separatory funnel.
Preferably shake vigorously for 2
minutes. However, if it is suspected that
a stable emulsion will form, shake
gently for 5 to 10 minutes. Let layers
separate. Drain solvent layer through a
funnel containing solvent-moistened
filter paper into a tared clean flask. If a
clear solvent layer cannot be obtained.
add Ig Na2SO4 to the filter paper cone
and slowly drain emulsified solvent onto
the crystals. Add more Na2SO4 if
necessary. Extract twice more with 30
ml solvent each but first rinse sample
container with each solvent portion.
Combine extracts in tared flask and
wash filter with an additional 10 to 20
ml. solvent. Add 3.0 g silica gel. Stopper
flask and stir on a magnetic stirrer for 5
minutes. Filter solution through filter
paper and wash silica gel and filter
paper with 10 ml solvent and combine
with filtrate in tared distilling flask.
Distill solvent from distilling flask in a
water bath at 70°C. Place flask on a
water bath at 70°C for 15 minutes and
draw air through it with an applied
vacuum for the final 1 minute. Cool in a
desiccator for 30 minutes and weigh.
(4) Calculations.-Calculation of
O&G-E: If the organic solvent is free of
residue the gain in weight of the tared
distilling flask is due to hydrocarbon oil
and grease. Total gain in weight, E, is
the amount of hydrocarbon oil and
grease in the sample (mg):
mg (hydrocarbon oil and grease)/! =
(3) Use of O&G-E: The value, O&G-E
shall be used as the measure of
compliance with oil and grease
limitations and standards set forth in
this regulation except where total O&G
is specifically required.
'Teflon or equivalent.
Whatman No. 40 or equivalent.
Freon or equivalent.
4Davidson Grade 950 or equivalent.
U.S. Government Printing Office: 1986 - 491-191/46114
E-l
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