United States
Environmental Protection
Agency
Office of Pesticides
and Toxic Substances
&EPA Title III Section 313
Release Reporting
Guidance
EPA 560/4-88-004g
January 1988
Estimating Chemical Releases From
Electroplating Operations
-------
-------
Estimating Chemical Releases From
Electroplating Operations
Facilities engaged in electroplating opera-
tions may be required to report annually any
releases to the environment of certain chemi-
cals regulated under Section 313, Title III, of
the Superfund Amendments and Reautho-
rization Act (SARA) of 1986. If your facility is
classified under SIC codes 20 through 39
(electroplating facilities generally fall under
SIC code 3471) and has 10 or more full-time
employees, for calendar year 1987 you must
report all environmental releases of any Sec-
tion 313-listed chemical or chemical category
manufactured or processed by your facility in
an amount exceeding 75,000 pounds per year
or otherwise used in an amount exceeding
10,000 pounds per year. For calendar years
1988 and 1989 (and beyond), the threshold
reporting quantity for manufactured or pro-
cessed chemicals drops to 50,000 and 25,000
pounds per year, respectively.
This document has been developed to
assist those who perform electroplating
operations in the completion of Part III
(Chemical Specific Information) of the Toxic
Chemical Release Inventory Reporting Form.
Included herein is general information on
toxic chemicals used and process wastes
generated, along with several examples to
demonstrate the types of data needed and
various methodologies available for esti-
mating releases. If your facility performs
other operations in addition to electroplating,
you must also include any releases of toxic
chemicals from these operations.
Step One
Determine if your facility processes or
uses any of the chemicals subject to
reporting under Section 313.
•^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^
A suggested approach for determination
of the chemicals your facility uses that could
be subject to reporting requirements is to
make a detailed review of the chemicals and
materials you have purchased. If you do not
know the specific ingredients of a chemical
formulation, consult your suppliers for this
information. If they will not provide this
information, you must follow the steps out-
lined to handle this eventuality in the in-
structions provided with the Toxic Chemical
Release Inventory Reporting Form.
The list presented here includes chemi-
cals typically used in electroplating opera-
tions that are subject to reporting under
Section 313. This list does not necessarily
include all of the chemicals your facility uses
that are subject to reporting, and it may
include many chemicals that you do not use.
You should also determine whether any of the
listed chemicals are created during
processing at your facility.
Degreasing solvents: Perchloroethylene,
trichloroethylene, methylene chloride,
1,1,1-trichloroethane, and others
Alkaline cleaning agents: Sodium
hydroxide
Acid cleaning and pickling agents:
Sulfuric acid, hydrochloric acid, phos-
phoric acid, nitric acid, chromic acid
-------
Chelating agents: Thiourea, nitrilo-
triacetic acid (NTA), ethyleneimine
(aziridine)
Components of plating and other
process baths: Cadmium compounds,
chromium compounds, sodium
hydroxide, cobalt compounds, copper
compounds, lead compounds, nickel
compounds, silver compounds, zinc
compounds, cyanide compounds, sulfuric
acid, sodium sulfate, phosphoric acid,
ammonia, arsenic compounds, selenium
compounds, various aldehydes
Step Two
Determine if your facility surpassed the
threshold quantities established for
reporting of listed chemicals last year. .
^ ^
You must submit a separate Toxic Chemi-
cal Release Inventory Reporting Form for
each listed chemical that is "manufactured,"
"processed," or "otherwise used" at your
facility in excess of the threshold quantities
presented earlier. Manufacture includes
materials produced as byproducts or impu-
rities. Toxic compounds that are incorpo-
rated into your products (for example, metals
that are plated onto metal articles) would be
considered "processed" because they become
part of the marketed finished product. De-
greasing solvents, cleaning agents, and other
chemicals that do not become part of the
finished product would be considered
"otherwise used."
The amount of a chemical processed or
otherwise used at your facility represents the
amount purchased during the year, adjusted
for beginning and ending inventories. To
ascertain the amount of chemical in a mixed
formulation, multiply the amount of the
mixture (in pounds) by the concentration of
the chemical (weight percent) to obtain the
amount of chemical processed.
Example: Determining whether 1,1,1-
trichloroethane was used in sufficient
quantity to require reporting under
Section 313.
An electroplater purchased 95 percent
1,1,1 -trichlaroethanefor use in a vapor
degreaser. In 1987, 3,000 pounds of this
material was in storage at the beginning of
the year, 18,000 pounds was purchased,
and 6,000 pounds was in storage at the
end of the year. The quantity of 1,1,1-
trichloroethane used by the facility equals:
(3,000 Ib x 0.95) (beginning
inventory) +
(18,000 Ib x 0.95) (purchased) -
(6,000 Ib x 0.95) (ending inventory)
= 14,250 Ib
A listed chemical may be a component of
several formulations you purchase, so you
may need to ask your supplier for informa-
tion on the concentration (percentage) of the
chemical in each. For chemical categories,
your reporting obligations are determined by
the total amounts of all chemicals in the
category. For example, in a copper plating
bath, three cyanide-containing compounds
are used: CuCN, NaCN, and KCN. The
quantity of cyanide compounds used equals
the sum of the quantities of CuCN, NaCN,
and KCN used. For a substance such as
CuCN, the amount used must be considered
in determining whether the threshold is met
for both copper- and cyanide-containing
compounds.
You must complete a report for each
chemical for which a threshold is exceeded.
The thresholds apply separately; therefore, if
you both process and use a chemical and
either threshold is exceeded, you must report
for both activities. If neither threshold is
exceeded, no report is needed.
-------
Step Three
Identify points of release for the
chemical(s) subject to reporting.
AIR EMISSIONS •
An effective means of evaluating points of
release for listed toxic chemicals is to draw a
process flow diagram identifying the opera-
tions performed at your facility. The figure
on the right is an example flow diagram for
electroplating (chromium plating of zinc die
castings). Because each facility is unique,
you are strongly urged to develop a flow
diagram for your particular operations that
details the input of materials and chemicals
and the waste sources resulting from the
operation of each unit.
The largest source of toxic releases at
electroplating facilities will occur in the
wastewater. Wastewater is generated from a
variety of sources, including the rinsing of
parts between process baths during metal
cleaning, plating, and post-plating opera-
tions; the dumping of exhausted or spent
process baths; and the rinsing required
during auxiliary operations such as rack
stripping. Wastewater usually is centrally
collected and treated before discharge; thus,
all of these sources are aggregated into one
release point. Solid waste is generated
primarily from the treatment of wastewater.
Other sources include filter solids from
plating baths, anode wastes, spent degreaser
solvent and sludge, and precipitates from
electroless nickel bath regeneration. Two
notable air releases are solvents from metal-
degreasing operations and mists evolved from
electrolytic cleaning solutions and cyanide
and chromium plating solutions.
AIR EMISSIONS
SPENT SOLVENTS
AND SLUDGE
CLEAN
FILTER ^.
SOLIDS "*^
-»•
-*
V—
-_fe
1
ACID DIP
|
RINSE
I
CYANIDE
COPPER
STRIKE
1
I
ACID DIP
|
ACID
COPPER
PLATE
*
RINSE
*
NICKEL
PLATE
1
R1NSF
RINSE
^
r-»
NEUTRALIZE
AND
PRECIPITATE
AIR EMISSIONS •
FILTER SOLIDS •
TREATED
WATER
Example Flow Diagram of Chromium
Plating of Decorative Zinc Die Castings
-------
Step Four
Estimate releases of toxic chemicals.
After all of the toxic chemicals and waste
sources have been identified, you can esti-
mate the releases of the individual chemicals.
Section 313 requires that releases to air,
water, and land and transfers to offsite facili-
ties be reported for each toxic chemical meet-
ing the threshold reporting values. The usual
approach entails first estimating releases
from waste sources at your facility (that is,
wastewater, air release points, and solid
waste) and then, based on the disposal
method used, determining whether releases
from a particular waste source are to air,
water, land, or an offsite disposal facility.
In general, there are four types of release
estimation techniques:
• Direct measurement
• Mass balance
• Engineering calculations
• Emission factors
Descriptions of these techniques are provided
in the EPA general Section 313 guidance
document, Estimating Releases and Waste-
Treatment Efficiencies for the Toxic Chemical
Release Inventory Form.
Provisions of the Clean Air Act, Clean
Water Act, Resource Conservation and Re-
covery Act, and other regulations require
monitoring of certain waste streams. If
available, data gathered for these purposes
can be used to estimate releases. When only
a small amount of direct measurement data
is available, you must decide if another esti-
mation technique would give a more accurate
estimate. Mass balance techniques and
engineering assumptions and calculations
can be used in a variety of situations to
estimate toxic releases. These methods of
estimation rely heavily on process operating
parameters; thus, the techniques developed
are very site-specific. Emission factors are
available for some industries in publications
referenced in the general Section 313 guid-
ance document. Also, emission factors for
your particular facility can be developed in-
house by performing detailed measurements
of wastes at different production levels.
Toxic Releases Via Wastewater
' The U.S. Environmental Protection
Agency has set effluent limitations on electro-
plating wastewater discharges to publicly
owned treatment works (POTWs) and into ,
navigable waters. Your facility is therefore
probably required by a local pretreatment
permit or an NPDES permit to monitor dis-
charge wastewater for toxic metals, cyanide,
and various toxic organic compounds. The
data generated from this monitoring can be
used to estimate releases of these com-
pounds. The following example demonstrates
a wastewater release estimation based on
direct measurement.
Example: Using direct measurement
to estimate releases of cyanide via
wastewater.
An electroplating facility discharges its
pretreated wastewater to a POTW. The
municipality operating the POTW requires
the electroplater to monitor this discharge
once per month for various parameters,
including total cyanide. The mass loading
(pounds per day) of cyanide in the dis-
charge is calculated for each sampling day
by multiplying the daily flow by the
measured cyanide concentration and unit
conversionfactors:
Amount of cyanide released to
wastewater =
cyanide concentration (mg/ltter) x
wastewater flow (gal/day) x
3.78 liters/1 gal x
1 lb/453,000 mg
-------
Cyanide andjlow data from the days
when cyanide was monitored during 1987
and the calculated mass loadings of
cyanide are presented below:
Wastewater
flow,
Day gal/ day
Jan. 8
Feb. 12
Mar. 10
Apr. 15
May 9
June 13
July 1 1
Aug. 10
Sep. 8
Oct. 12
Nov. 10
Dec. 8
21,500
20,500
20,800
22,000
23,500
21,300
25,900
21,500
24,600
25,000
20,100
20,700
CN
cone.,
mg/ liter
1.5
0.8
0.6
0.5
0.7
1.9
2.1
1.0
0.9
0.8
0.6
0.2
CNmass
loading,
Ib/day
0.27
0.14
0.10
0.09
0.14
0.34
0.44
0.18
0.18
0.17
0.10
0.03
The average daily cyanide discharge
based on these monitoring data is 0.18
pound per day. Assuming the plant
operates 250 days per year, the total
quantity of cyanide released via waste-
water to the POTW equals:
0.18 Ib/day x 250 days/year
= 45 Ib
Monitoring data may not be available for
some of the toxic chemicals present in your
wastewater. In this case, you must use
another estimation method. The following
example demonstrates the use of a mass
balance combined with an engineering
calculation.
Example: Using a mass balance
combined with an engineering
calculation to estimate releases of
nitrilotriacetic acid (NTA) via
wastewater.
A facility used 12,970 pounds of NTA
in its electroless plating operation during
1987. Because it does not become part of
the product, all of the NTA used becomes
part of the facility's waste and is either
destroyed during waste treatment or
released from the facility. To estimate
releases of NTA, one needs the answers to
two questions:
• How much NTA is destroyed during
treatment?
• In whatformfs) is NTA released from
the facility (wastewater, solid waste,
air emissions)?
At this facility, NTA enters the waste-
water stream as a chelate-metal complex
during the rinsing of metal parts from the
plating bath. This wastewater stream
goes through apH adjustment/clarification
system where lime is added to precipitate
metals. Typically, chelating agents wiR
not be destroyed in this process, nor will
they precipitate along with the metals. On
the contrary, the purpose of chelating
agents is to keep the metal ions in solution
in the plating bath. An engineering
assumption can therefore be made that all
of the NTA entering waste treatment leaves
in the wastewater discharge. Given that
the wastewater is discharged to a POTW,
the plant in this example could report
wastewater releases of 13,000 pounds of
NTA.
If your facility uses a listed mineral acid
or base, but this acid or base is effectively
neutralized in use or during wastewater
treatment (to pH 6 to 9, as required by most
effluent standards), no release quantities
should be reported. If the acid or base is
transformed into a reportable substance,
however, you must estimate the quantity of
this substance manufactured to determine if
the "manufactured" threshold value has been
reached. For example, sulfuric acid neutral-
ized by sodium hydroxide yields sodium
sulfate, which is a listed chemical.
-------
Toxic Releases Via Solid Waste
Some solid wastes at electroplating facili-
ties are listed as hazardous under RCRA
regulations. Others may be deemed hazard-
ous based on the extraction procedure tox-
icity characteristic (EP toxicity). Generation,
transportation, and disposal of certain solid
wastes from electroplating may therefore be
regulated under RCRA. The RCRA manifest-
ing procedure for hazardous waste shipped
offsite requires documentation of quantities
shipped. Detailed chemical and physical
analyses may be performed on the wastes by
treatment, storage, and disposal facilities.
The electroplater also may perform analyses
on the waste. Release estimates for some
compounds can therefore be made by direct
measurement.
Example: Using direct measurement
to estimate releases of toxic metals
via solid waste.
Wastewater treatment sludge from an
electroplating operation is shipped to an
offsite secure chemical landfill for disposal.
Shipping manifests for the past year con-
tain detailed information on the quantity of
sludge sent to the landfill Shipments of
sludge were made on a monthly basis.
The landfill performed detailed chemical
analysis for nickel on representative
portions of each shipment before final
disposal As shown in the following table,
the information from the manifests and
landfill can be combined to estimate
releases of toxic metals and cyanide in the
wastewater treatment sludge.
Month
Jan.
Feb.
Mar.
Apr.
May
June
July
Aug.
Sep.
Oct.
Nov.
Dec.
Sludge
shipped,
Ib
6,000
5,400
4,700
5,500
6,100
6,800
7,200
6,400
5,900
4,500
5,200
5,300
Nickel
cone.,
ppm
50,600
51,900
48,500
37,000
30,000
75,000
84,000
55,500
50,000
105,500
69,000
20,000
Nickel in
sludge,
Ib
304
280
228
204
183
510
605
355
295
475
359
106
It should be noted that this example
only addresses nickel releases in waste-
water sludge. Nickel may also be present
in other wastes in the facility. Also, the
landfill probably would have analytical
data for other metals in this sludge that
could be used to calculate releases of
those compounds.
When direct measurement data are not
available, another method of estimating
releases is needed. The following example
demonstrates the use of an engineering
calculation to estimate toxic metal releases
via solid waste.
Example: Using an engineering
calculation to estimate toxic releases
of copper in wastewater treatment
sludge.
In an electroplating facility, rinse water
from a copper-plating unit is treated sep-
arately from other process wastewater.
The rinse water is first treated with
chlorine to oxidize cyanide. Sodium
hydroxide is then added to react with the
Cu in the wastewater. The precipitate
formedfrom this reaction is removed as
sludge from the facility's central clari-
fication unit.
-------
The reaction of NaOH and Cu++ in the rinse
water proceeds as follows:
Cu++
2NaOH
CufOHL + 2NO++
For each mole of Cu present in the rinse
water, two moles ofNaOH must be added
to precipitate the Cu. Purchasing and
inventory records indicate that 1,984
pounds ofNaOH was used for precipi-
tating Cu last year. The quantity ofCu
precipitated (and thus the quantity ofCu
releasedfrom this source of solid waste)
can be estimated by performing the
following calculations:
Molecular weight ofCu= 63.5 Ib/lb-mole
Molecular weight ofNaOH = 40 Ib/lb-mole
Amount ofCu released in sludge =
!,9841bNaOHx
lib-mole NaOH/40 Ib NaOHx
1 Ib-mole Cu/2 Ib-mole NaOH x
63.51bCu/l Ib-mole Cu
= 1,575 Ib
The plant in this example could therefore
report the release of 1,600 pounds of Cu in
the wastewater treatment sludge.
It should be noted that the NaOH in this
example only reacted with the Cu present in
the wastewater. If other metal ions are
present, they may also react with the NaOH,
which would make this estimation method
ineffective. In some instances, however, this
approach can result in a rough approxima-
tion of the quantity of releases.
Toxic Releases to Air
Typical emissions to air from electro-
plating facilities are fugitive in nature and are
not monitored. Alternative techniques must
therefore be used to estimate air releases.
Releases of toxic compounds contained in
mists evolved from plating and cleaning baths
can be estimated by mass balance (provided
sufficient information is available on the
quantity of chemical entering and leaving the
process) or engineering calculations. Sol-
vents emitted to air during metal cleaning
operations can usually be estimated by mass
balance or emission factors as shown in the
following example.
Example: Using a mass balance to
estimate air emissions of 1,1,1-
trichloroethanefrom a degreasing
operation.
In the example presented earlier in this
pamphlet, an electroplating facility op-
erating a vapor degreaser used 14,250
pounds of 1,1,1 -trichloroethane during the
past year. The vapor degreaser contains a
built-in local exhaust ventilation system to
reduce worker exposure to the solvent.
This system collects spray solventfum.es
and exhausts them to the atmosphere
through the roof of the facility. Spent
solvent and sludge that accumulate on the
bottom of the degreaser are collected in 55-
gallon drums for shipment to an offsite
solvent reclaimer. Last year, 13 drums of
spent solvent were sent to the reclaimer.
Because 1,1,1-trichloroethane is only
"used" in the process (i.e., it does not
become part of the product) and it is not
destroyed during the process or treatment,
the entire 14,250 pounds of the solvent is
releasedfrom the facility either as an air
emission or as solid waste. Thus, if the
quantity of spent solvent shipped to the
reclaimer is known, the quantity emitted to
air can be calculated by mass balance, as
shown in the following equations:
Volume of 1,1,1 -TCE to reclaimer =
13 drums x 55 gal/drum
= 715 gal
Mass of 1,1,1 -TCE to reclaimer =
715 gal x 11.05 Ib/gal
= 7,900 Ib
-------
Amount of 1,1,1 -TCE released to air =
14,250 tb (purchased) -
7,900 Ib (to reclaimer)
~ 6,350 Ib
The plant in this example could therefore
report the release of 6,400 pounds of
1,1,1-TCE to air and 7,900 pounds
shipped ojfsite as solid waste.
Emission factors for estimating releases of
solvents from different types of degreasing
units are presented in the EPA publication,
Compilation of Air Pollutant Emission Factors
(AP-42). To apply these factors properly, you
should carefully read the text that
accompanies them.
Other Toxic Releases
Electroplating operations produce other
wastes from which toxic chemicals may be
released. These include:
• Residues from pollution control
devices
• Wash water from equipment
cleaning
• Product rejects
• Used equipment
• Empty chemical containers
Releases from these sources may already
have been accounted for, depending on the
release estimation methods used. These
items (and any other of a similar nature)
should be included in your development of a
process flow diagram.
The contribution of sources of wastes
such as cleaning out vessels or discarding
containers should be small compared with
process losses. If you do not have data on
such sources (or any monitoring data on
overall water releases), assume up to 1 per-
cent of vessel content may be lost during
each cleaning occurrence. For example, if
you discard (to landfill) "empty" drums that
have not been cleaned, calculate the release
as 1 percent of normal drum content. If the
drums are washed before disposal, this may
contribute 1 percent of the content to your
wastewater loading.
Step Five
Complete the Toxic Chemical Release
Inventory Reporting Form.
After estimating the quantity of each
chemical released via wastewater, solid
waste, and air emissions, you must deter-
mine the amount of each chemical released to
water, land, or air or transferred to an offsite
disposal facility. This determination will be
based on the disposal method you use for
each of your waste streams. Enter the re-
lease estimates for each chemical or chemical
category in Part III of the Toxic Chemical
Release Inventory Reporting Form. Also enter
the code for each treatment method used, the
weight percent by which the treatment
reduces the chemical in the treated waste
stream, and the concentration of the chemi-
cal in the influent to treatment (see instruc-
tions). Report treatment methods that do not
affect the chemical by entering "0" for re-
moval efficiency.
8
-------
For More Information
Emergency Planning
arid Community
Right-to-Know
Hotline
(800) 535-0202
or
(202) 479-2449
(In Washington, D.C.
and Alaska)
Small Business
Ombudsman
Hotline
(800) 368-5888
or
(703) 557-1938
(in Washington, D.C.
and Virginia)
The EPA brochure, Title III Section 313
Release Reporting Requirements (EPA 560/4-
87-001) presents an overview of the new law.
It identifies the types of facilities that come
under the provisions of Section 313, the
threshold chemical volumes that trigger re-
porting requirements, and what must be
reported. It also contains a complete listing
of the chemicals and chemical categories
subject to Section 313 reporting. The EPA
publication, Estimating Releases and Waste-
Treatment Efficiencies for the Toxic Chemical
Release Inventory Form (EPA 560/4-88-002),
presents more detailed information on gen-
eral release estimation techniques than is
included in this document.
Additional Sources of Information
on Releases From Electroplating
Operations
U.S. Environmental Protection Agency. Com-
pilation of Air Pollutant Emission Factors,
Fourth Edition. AP-42. Research Triangle
Park, North Carolina. September 1985.
U.S. Environmental Protection Agency.
Development Document for Existing Source
Pretreatment Standards for the Electroplating
Point Source Category. EPA 440/1-79/003.
NTIS PB80-196488. Washington, D. C.
August 1979.
U.S. Environmental Protection Agency.
Assessment of Industrial Hazardous Waste
Practices - Electroplating and Metal Finishing
Industries - Job Shops. NTIS PB-264349.
Washington, D. C. September 1976.
B-U.S. Government Printing Office : 1988 - 516-002/80172
-------
United States
Environmental Protection
Agency
Office of Pesticides and
Toxic Substances, WH-562A
Washington, D.C. 20460
Official Business
Penalty for Private Use
$300
------- |