[Federal Register Volume 62, Number 115 (Monday, June 16, 1997)]
[Rules and Regulations]
[Pages 32500-32536]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 97-15374]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 51
[FRL-5836-1]
RIN 2060-AF02
Preparation, Adoption, and Submittal of State Implementation
Plans; Appendix M, Test Methods 204, 204A-204F
AGENCY: Environmental Protection Agency (EPA).
ACTION: Final rule.
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SUMMARY: This rule adds seven methods to Appendix M of 40 CFR Part 51
for capture efficiency (CE) testing to assist States in adopting
enforceable CE measurement protocols into their State implementation
plans (SIP's) for ozone. These final methods, in conjunction with the
protocols, would also improve EPA's ability to enforce State
regulations to reduce volatile organic compounds (VOC) emissions in
ozone nonattainment areas.
EFFECTIVE DATE: These methods are effective June 16, 1997.
ADDRESSES: Docket. A Docket A-91-70, containing materials relevant to
this rulemaking, is available for public inspection and copying between
8:00 a.m.-5:30 p.m., Monday through Friday, at the EPA's Air Docket
Section Mail Code: 6102, Room M-1500, Waterside Mall (ground floor),
401 M Street, S.W., Washington D.C. 20460. A reasonable fee may be
charged for copying.
FOR FURTHER INFORMATION CONTACT: Candace Sorrell, Source
Characterization Group A (MD-19), Emissions, Monitoring, and Analysis
Division, U.S. Environmental Protection Agency, Research Triangle Park,
North Carolina 27711, telephone (919) 541-1064.
SUPPLEMENTARY INFORMATION:
I. The Rulemaking
This rulemaking adds seven methods for measuring CE to Appendix M
of 40 CFR Part 51 to provide methods that States can use in their
SIP's.
II. Public Participation
The proposed rulemaking was published in the Federal Register (FR)
on August 2, 1995 (60 FR 39297).
The opportunity to hold a public hearing on August 30, 1995 at 10
a.m. was presented in the proposal notice, but no one desired to make
an oral presentation. The public comment period was from August 2, 1995
to October 2, 1995.
III. Electronic Access
The background information document for the promulgated test
methods is available on the Technology Transfer Network (TTN) on the
EPA's electronic bulletin boards. The document is entitled ``Summary of
Comments and Responses for Methods 204, 204A-F.'' If necessary, a
limited number of copies are available from Candace Sorrell, MD-19,
U.S. EPA, Research Triangle Park, North Carolina 27711, telephone
number (919) 541-1064.
IV. Significant Comments and Changes to the Proposed Rulemaking
Six comment letters were received from the proposal rulemaking. A
detailed discussion of these comments is contained in the background
document entitled ``Summary of Comments and Responses for Methods 204,
204A-F,'' which is referred to in the SUPPLEMENTARY INFORMATION section
of this preamble. The major comments raised in these letters and the
Agency's responses follow.
One commenter points out that even though Methods 204B and 204C
measure the same parameter, captured VOC stream, the applicability
sections of the methods were not consistent with respect to what type
of material balance is permissible.
The EPA reviewed the applicability section for both methods and
determined that there was an error in Method 204B. Method 204B is
intended to be used only in a gas/gas protocol, not in a liquid/gas
protocol. The method has been revised to correct this error.
One commenter suggests for Method 204D, section 8.2.4, and Method
204E, section 8.4, that EPA make it explicit that if on site gas
chromatography (GC) is used as an alternative to flame ionization
analyzers (FIA) than GC must also be used to measure the VOC
concentration of the other gas or liquid steams.
The Agency agrees that further explanation is needed to explain
that if a facility is conducting a gas/gas test and chooses to use the
alternative GC procedure, it must use the GC procedure for both the
captured and fugitive stream. If a facility wishes to conduct a liquid/
gas test using GC, the facility must use Method 204F for the liquid
steam. A GC is not an acceptable alternative to the FIA in Method 204A.
Another commenter suggests that Figure 204-1 of Method 204 be
expanded to address capture efficiencies less than 80 percent since
lower values are allowed in the current Reasonably Available Control
Technology (RACT) rules.
The EPA agrees that further guidance is needed and has added an
equation to section 7.2 to help in estimating the ventilation rate at
different capture efficiencies.
Three commenters mention that Method 204A, section 11, the
estimated uncertainty of 12 percent for the VOC fraction seemed too
high.
The EPA went back and reviewed the method evaluation report and
discovered that the 12 percent is an error. The estimated uncertainty
for this method is 4.0 percent. The method has been revised to correct
this error.
Two commenters note that several references in Method 204, sections
5.5 and 6.1, were incorrect.
The EPA agrees that several references in those sections are
incorrect. The method has been revised to correct these errors.
[[Page 32501]]
A commenter suggests that section 8.4 of Method 204 be revised to
be consistent with the Aerospace NESHAP concerning the verification of
air flow direction.
The EPA agrees with the comment and the method has been revised to
reflect these changes.
One commenter feels that dilutions systems calibrated using Method
205 should be allowed without approval of the Administrator in Methods
204A-E, section 5.1 and Method 204F, section 5.3.
The EPA agrees that calibration gas can be prepared using dilution
systems calibrated using Method 205 without approval of the
Administrator and the methods have been revised.
A commenter requested that Methods 204A-204F be revised to not
automatically invalidate the CE results if the drift check is in excess
of the proposed 3 percent calibration drift requirement. In such
situations the method should allow the FIA to be recalibrated and
whichever calibration results in the ``worst case'' results be
reported.
The EPA agrees with the comment and the methods have been revised.
One commenter suggests that Methods 204A-E, section 5.1.1 and
Method 204F, section 5.3.1, be revised to allow for the use of hydrogen
in air if appropriate adjustments are made to eliminate the oxygen
synergism effect.
The Agency agrees that alternative mixtures should be allowed if
the user can demonstrate to the Administrator that there is no oxygen
synergism effect. The method has been revised to allow alternative
mixtures.
One commenter notes that in Methods 204, 204A-F the term ``fugitive
emissions'' is used in a manner inconsistent with the definition
contained in 40 CFR 51.165(a)(1)(ix). The commenter suggests the word
``fugitive'' should be changed to ``uncaptured.''
The Agency agrees and the methods have been revised to change
``fugitive'' to ``uncaptured.''
A commenter feels that in Method 204A and 204F the required
accuracy of the input weight determinations should be changed to allow
the balance/digital scales to weigh within 2 lbs instead of the
proposed 0.2 lb.
The Agency believes that it is very important to get an accurate
measurement of the amount of coating used during a test and that scales
that read to within 2 lbs are not accurate enough in most test
situations. However, after reviewing this issue, the Agency also feels
that the 0.2 lb limit may be too restrictive in some situations.
Therefore, the method has been revised to read ``within 0.2 lb or 1.0
percent of the total weight of VOC liquid used.''
The EPA has recently discovered that the pressure drop specified in
section 8.3 of Method 204, which is suppose to correspond to the
minimum required face velocity of 3,600 m/hr (200 fpm), is too low.
According to the twenty first edition of the ``Industrial Ventilation''
handbook dated 1992 the required pressure drop is 0.013 mm Hg (0.007
in. H2O). Therefore, Method 204 has been revised to reflect
this finding.
IV. Administrative Requirements
A. Docket
The docket is an organized and complete file for all information
submitted or otherwise considered by EPA in the development of this
promulgated rulemaking. The principal purposes of the docket are: (1)
To allow interested parties to identify and locate documents so that
they can effectively participate in the rulemaking process, and
(2) To serve as the record in case of judicial review (except for
interagency review materials) [Clean Air Act Section 307(d)(7)(A)].
B. Office of Management and Budget Review
Under Executive Order 12866 (58 FR 51735 October 4, 1993), the EPA
is required to judge whether a regulation is ``significant'' and
therefore subject to Office of Management and Budget (OMB) review and
the requirements of this Executive Order to prepare a regulatory impact
analysis (RIA). The Order defines ``significant regulatory action'' as
one that is likely to result in a rule that may: (1) Have an annual
effect on the economy of $100 million or more or adversely affect in a
material way the economy, a sector of the economy, productivity,
competition, jobs, the environment, public health or safety, or State,
local, or tribal governments or communities; (2) create a serious
inconsistency or otherwise interfere with an action taken or planned by
another agency; (3) materially alter the budgetary impact of
entitlements, grants, user fees, or loan programs, or the rights and
obligation of recipients thereof; or (4) raise novel legal or policy
issues arising out of legal mandates, the President's priorities, or
the principles set forth in the Executive Order. Pursuant to the terms
of the Executive Order, this action has been determined to be ``not
significant.''
C. Regulatory Flexibility Act Compliance
The EPA has determined that it is not necessary to prepare a
regulatory flexibility analysis in connection with this final rule. The
EPA has also determined that this rule will not have a significant
adverse impact on a substantial number of small businesses. This
rulemaking does not impose emission measurement requirements beyond
those specified in the current regulations, nor does it change any
emission standard. As such, it will not present a significant economic
impact on a substantial number of small businesses.
D. Paperwork Reduction Act
The rule does not change any information collection requirements
subject of Office of Management and Budget review under the Paperwork
Reduction Act of 1980, 44 U.S.C. 3501 et seq.
E. Unfunded Mandates
Under Section 202 of the Unfunded Mandates Reform Act of 1995
(``Unfunded Mandates Act''), signed into law on March 22, 1995, EPA
must prepare a budgetary impact statement to accompany any proposed or
final rule that includes a Federal mandate that may result in estimated
costs to State, local, or tribal governments in the aggregate; or to
the private sector, of $100 million or more. Under Section 205, EPA
must select the most cost-effective and least burdensome alternative
that achieves the objectives of the rule and is consistent with
statutory requirements. Section 203 requires EPA to establish a plan
for significantly or uniquely impacted by the rule.
EPA has determined that this final action does not include a
Federal mandate that may result in estimated costs of $100 million or
more to either State, local, or tribal governments in the aggregate, or
to the private sector, nor does this action significantly or uniquely
impact small governments, because this action contains no requirements
that apply to such governments or impose obligations upon them.
Therefore, the requirements of the Unfunded Mandates Act do not apply
to this action.
F. Submission to Congress and the General Accounting Office
Under 5 U.S.C. 801(a)(1)(A) of the Administrative Procedures Act
(APA), as added by the Small Business Regulatory Enforcement Fairness
Act of 1996, the EPA submitted a report containing this rule and other
required
[[Page 32502]]
information to the U.S. Senate, the U.S. House of Representatives and
the Comptroller General of the General Accounting Office prior to
publication of the rule in today's Federal Register. This rule is not a
``major rule'' as defined by 5 U.S.C. 804(2).
List of Subjects in 40 CFR Part 51
Environmental protection, Administrative practice and procedure,
Air pollution control, Capture efficiency, Carbon monoxide,
Intergovernmental relations, Lead, Nitrogen dioxide, Ozone, Particulate
matter, Printing operations, Reporting and recordkeeping requirements,
Surface coating operations, Sulfur oxides, Volatile organic compounds.
Dated: May 30, 1997.
Carol M. Browner,
Administrator.
For the reasons set out in the preamble, Appendix M of 40 CFR Part
51 is amended as follows:
1. The authority citation for part 51 continues to read as follows:
Authority: 42 U.S.C. 7410.
2. Appendix M, Table of Contents is amended by adding seven entries
to read as follows:
Appendix M to Part 51--Recommended Test Methods for State
Implementation Plans
* * * * *
Method 204--Criteria for and Verification of a Permanent or
Temporary Total Enclosure.
Method 204A--Volatile Organic Compounds Content in Liquid Input
Stream.
Method 204B--Volatile Organic Compounds Emissions in Captured
Stream.
Method 204C--Volatile Organic Compounds Emissions in Captured
Stream (Dilution Technique).
Method 204D--Volatile Organic Compounds Emissions in Uncaptured
Stream from Temporary Total Enclosure.
Method 204E--Volatile Organic Compounds Emissions in Uncaptured
Stream from Building Enclosure.
Method 204F--Volatile Organic Compounds Content in Liquid Input
Stream (Distillation Approach).
* * * * *
3. By adding Method 204 to read as follows:
Method 204--Criteria for and Verification of a Permanent or Temporary
Total Enclosure
1. Scope and Application
This procedure is used to determine whether a permanent or
temporary enclosure meets the criteria for a total enclosure. An
existing building may be used as a temporary or permanent enclosure as
long as it meets the appropriate criteria described in this method.
2. Summary of Method
An enclosure is evaluated against a set of criteria. If the
criteria are met and if all the exhaust gases from the enclosure are
ducted to a control device, then the volatile organic compounds (VOC)
capture efficiency (CE) is assumed to be 100 percent, and CE need not
be measured. However, if part of the exhaust gas stream is not ducted
to a control device, CE must be determined.
3. Definitions
3.1 Natural Draft Opening (NDO). Any permanent opening in the
enclosure that remains open during operation of the facility and is not
connected to a duct in which a fan is installed.
3.2 Permanent Total Enclosure (PE). A permanently installed
enclosure that completely surrounds a source of emissions such that all
VOC emissions are captured and contained for discharge to a control
device.
3.3 Temporary Total Enclosure (TTE). A temporarily installed
enclosure that completely surrounds a source of emissions such that all
VOC emissions that are not directed through the control device (i.e.
uncaptured) are captured by the enclosure and contained for discharge
through ducts that allow for the accurate measurement of the uncaptured
VOC emissions.
3.4 Building Enclosure (BE). An existing building that is used as
a TTE.
4. Safety
An evaluation of the proposed building materials and the design for
the enclosure is recommended to minimize any potential hazards.
5. Criteria for Temporary Total Enclosure
5.1 Any NDO shall be at least four equivalent opening diameters
from each VOC emitting point unless otherwise specified by the
Administrator.
5.2 Any exhaust point from the enclosure shall be at least four
equivalent duct or hood diameters from each NDO.
5.3 The total area of all NDO's shall not exceed 5 percent of the
surface area of the enclosure's four walls, floor, and ceiling.
5.4 The average facial velocity (FV) of air through all NDO's
shall be at least 3,600 m/hr (200 fpm). The direction of air flow
through all NDO's shall be into the enclosure.
5.5 All access doors and windows whose areas are not included in
section 5.3 and are not included in the calculation in section 5.4
shall be closed during routine operation of the process.
6. Criteria for a Permanent Total Enclosure
6.1 Same as sections 5.1 and 5.3 through 5.5.
6.2 All VOC emissions must be captured and contained for discharge
through a control device.
7. Quality Control
7.1 The success of this method lies in designing the TTE to
simulate the conditions that exist without the TTE (i.e., the effect of
the TTE on the normal flow patterns around the affected facility or the
amount of uncaptured VOC emissions should be minimal). The TTE must
enclose the application stations, coating reservoirs, and all areas
from the application station to the oven. The oven does not have to be
enclosed if it is under negative pressure. The NDO's of the temporary
enclosure and an exhaust fan must be properly sized and placed.
7.2 Estimate the ventilation rate of the TTE that best simulates
the conditions that exist without the TTE (i.e., the effect of the TTE
on the normal flow patterns around the affected facility or the amount
of uncaptured VOC emissions should be minimal). Figure 204-1 or the
following equation may be used as an aid.
[GRAPHIC] [TIFF OMITTED] TR16JN97.000
Measure the concentration (CG) and flow rate (QG)
of the captured gas stream, specify a safe concentration
(CF) for the uncaptured gas stream, estimate the CE, and
then use the plot in Figure 204-1 or Equation 204-1 to determine the
volumetric flow rate of the uncaptured gas stream (QF). An exhaust fan
that has a variable flow control is desirable.
7.3 Monitor the VOC concentration of the captured gas steam in the
duct before the capture device without the TTE. To minimize the effect
of temporal variation on the captured emissions, the baseline
measurement should be made over as long a time period as practical.
However, the process conditions must be the same for the measurement in
section 7.5 as they are for this baseline measurement. This may require
short measuring times for this quality control check before and after
the construction of the TTE.
7.4 After the TTE is constructed, monitor the VOC concentration
inside the TTE. This concentration should not continue to increase, and
must not exceed the safe level according to
[[Page 32503]]
Occupational Safety and Health Administration requirements for
permissible exposure limits. An increase in VOC concentration indicates
poor TTE design.
7.5 Monitor the VOC concentration of the captured gas stream in
the duct before the capture device with the TTE. To limit the effect of
the TTE on the process, the VOC concentration with and without the TTE
must be within 10 percent. If the measurements do not agree, adjust the
ventilation rate from the TTE until they agree within 10 percent.
8. Procedure
8.1 Determine the equivalent diameters of the NDO's and determine
the distances from each VOC emitting point to all NDO's. Determine the
equivalent diameter of each exhaust duct or hood and its distance to
all NDO's. Calculate the distances in terms of equivalent diameters.
The number of equivalent diameters shall be at least four.
8.2 Measure the total surface area (AT) of the
enclosure and the total area (AN) of all NDO's in the
enclosure. Calculate the NDO to enclosure area ratio (NEAR) as follows:
[GRAPHIC] [TIFF OMITTED] TR16JN97.001
The NEAR must be 10.05.
8.3 Measure the volumetric flow rate, corrected to standard
conditions, of each gas stream exiting the enclosure through an exhaust
duct or hood using EPA Method 2. In some cases (e.g., when the building
is the enclosure), it may be necessary to measure the volumetric flow
rate, corrected to standard conditions, of each gas stream entering the
enclosure through a forced makeup air duct using Method 2. Calculate FV
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR16JN97.002
where:
QO = the sum of the volumetric flow from all gas streams
exiting the enclosure through an exhaust duct or hood.
QI = the sum of the volumetric flow from all gas streams
into the enclosure through a forced makeup air duct; zero, if there is
no forced makeup air into the enclosure.
AN = total area of all NDO's in enclosure.
The FV shall be at least 3,600 m/hr (200 fpm). Alternatively,
measure the pressure differential across the enclosure. A pressure drop
of 0.013 mm Hg (0.007 in. H2O) corresponds to an FV of 3,600
m/hr (200 fpm).
8.4 Verify that the direction of air flow through all NDO's is
inward. If FV is less than 9,000 m/hr (500 fpm), the continuous inward
flow of air shall be verified using streamers, smoke tubes, or tracer
gases. Monitor the direction of air flow for at least 1 hour, with
checks made no more than 10 minutes apart. If FV is greater than 9,000
m/hr (500 fpm), the direction of air flow through the NDOs shall be
presumed to be inward at all times without verification.
9. Diagrams
BILLING CODE 6560-50-P
[[Page 32504]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.026
BILLING CODE 6560-50-C
[[Page 32505]]
Method 204A--Volatile Organic Compounds Content in Liquid Input Stream
1. Scope and Application
1.1 Applicability. This procedure is applicable for determining
the input of volatile organic compounds (VOC). It is intended to be
used in the development of liquid/gas protocols for determining VOC
capture efficiency (CE) for surface coating and printing operations.
1.2 Principle. The amount of VOC introduced to the process (L) is
the sum of the products of the weight (W) of each VOC containing liquid
(ink, paint, solvent, etc.) used and its VOC content (V).
1.3 Sampling Requirements. A CE test shall consist of at least
three sampling runs. Each run shall cover at least one complete
production cycle, but shall be at least 3 hours long. The sampling time
for each run need not exceed 8 hours, even if the production cycle has
not been completed. Alternative sampling times may be used with the
approval of the Administrator.
2. Summary of Method
The amount of VOC containing liquid introduced to the process is
determined as the weight difference of the feed material before and
after each sampling run. The VOC content of the liquid input material
is determined by volatilizing a small aliquot of the material and
analyzing the volatile material using a flame ionization analyzer
(FIA). A sample of each VOC containing liquid is analyzed with an FIA
to determine V.
3. Safety
Because this procedure is often applied in highly explosive areas,
caution and care should be exercised in choosing, installing, and using
the appropriate equipment.
4. Equipment and Supplies
Mention of trade names or company products does not constitute
endorsement. All gas concentrations (percent, ppm) are by volume,
unless otherwise noted.
4.1 Liquid Weight.
4.1.1 Balances/Digital Scales. To weigh drums of VOC containing
liquids to within 0.2 lb or 1.0 percent of the total weight of VOC
liquid used.
4.1.2 Volume Measurement Apparatus (Alternative). Volume meters,
flow meters, density measurement equipment, etc., as needed to achieve
the same accuracy as direct weight measurements.
4.2 VOC Content (FIA Technique). The liquid sample analysis system
is shown in Figures 204A-1 and 204A-2. The following equipment is
required:
4.2.1 Sample Collection Can. An appropriately-sized metal can to
be used to collect VOC containing materials. The can must be
constructed in such a way that it can be grounded to the coating
container.
4.2.2 Needle Valves. To control gas flow.
4.2.3 Regulators. For carrier gas and calibration gas cylinders.
4.2.4 Tubing. Teflon or stainless steel tubing with diameters and
lengths determined by connection requirements of equipment. The tubing
between the sample oven outlet and the FIA shall be heated to maintain
a temperature of 1205 deg.C.
4.2.5 Atmospheric Vent. A tee and 0- to 0.5-liter/min rotameter
placed in the sampling line between the carrier gas cylinder and the
VOC sample vessel to release the excess carrier gas. A toggle valve
placed between the tee and the rotameter facilitates leak tests of the
analysis system.
4.2.6 Thermometer. Capable of measuring the temperature of the hot
water bath to within 1 deg.C.
4.2.7 Sample Oven. Heated enclosure, containing calibration gas
coil heaters, critical orifice, aspirator, and other liquid sample
analysis components, capable of maintaining a temperature of
1205 deg.C.
4.2.8 Gas Coil Heaters. Sufficient lengths of stainless steel or
Teflon tubing to allow zero and calibration gases to be heated to the
sample oven temperature before entering the critical orifice or
aspirator.
4.2.9 Water Bath. Capable of heating and maintaining a sample
vessel temperature of 1005 deg.C.
4.2.10 Analytical Balance. To measure 0.001 g.
4.2.11 Disposable Syringes. 2-cc or 5-cc.
4.2.12 Sample Vessel. Glass, 40-ml septum vial. A separate vessel
is needed for each sample.
4.2.13 Rubber Stopper. Two-hole stopper to accommodate 3.2-mm (\1/
8\-in.) Teflon tubing, appropriately sized to fit the opening of the
sample vessel. The rubber stopper should be wrapped in Teflon tape to
provide a tighter seal and to prevent any reaction of the sample with
the rubber stopper. Alternatively, any leak-free closure fabricated of
nonreactive materials and accommodating the necessary tubing fittings
may be used.
4.2.14 Critical Orifices. Calibrated critical orifices capable of
providing constant flow rates from 50 to 250 ml/min at known pressure
drops. Sapphire orifice assemblies (available from O'Keefe Controls
Company) and glass capillary tubing have been found to be adequate for
this application.
4.2.15 Vacuum Gauge. Zero to 760-mm (0- to 30-in.) Hg U-Tube
manometer or vacuum gauge.
4.2.16 Pressure Gauge. Bourdon gauge capable of measuring the
maximum air pressure at the aspirator inlet (e.g., 100 psig).
4.2.17 Aspirator. A device capable of generating sufficient vacuum
at the sample vessel to create critical flow through the calibrated
orifice when sufficient air pressure is present at the aspirator inlet.
The aspirator must also provide sufficient sample pressure to operate
the FIA. The sample is also mixed with the dilution gas within the
aspirator.
4.2.18 Soap Bubble Meter. Of an appropriate size to calibrate the
critical orifices in the system.
4.2.19 Organic Concentration Analyzer. An FIA with a span value of
1.5 times the expected concentration as propane; however, other span
values may be used if it can be demonstrated that they would provide
more accurate measurements. The FIA instrument should be the same
instrument used in the gaseous analyses adjusted with the same fuel,
combustion air, and sample back-pressure (flow rate) settings. The
system shall be capable of meeting or exceeding the following
specifications:
4.2.19.1 Zero Drift. Less than 3.0 percent of the span
value.
4.2.19.2 Calibration Drift. Less than 3.0 percent of
the span value.
4.2.19.3 Calibration Error. Less than 5.0 percent of
the calibration gas value.
4.2.20 Integrator/Data Acquisition System. An analog or digital
device or computerized data acquisition system used to integrate the
FIA response or compute the average response and record measurement
data. The minimum data sampling frequency for computing average or
integrated values is one measurement value every 5 seconds. The device
shall be capable of recording average values at least once per minute.
4.2.21 Chart Recorder (Optional). A chart recorder or similar
device is recommended to provide a continuous analog display of the
measurement results during the liquid sample analysis.
5. Reagents and Standards
5.1 Calibration and Other Gases. Gases used for calibration, fuel,
and combustion air (if required) are contained in compressed gas
cylinders. All calibration gases shall be traceable to National
Institute of Standards and Technology standards and shall be
[[Page 32506]]
certified by the manufacturer to 1 percent of the tag
value. Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than 2 percent from the
certified value. For calibration gas values not generally available,
dilution systems calibrated using Method 205 may be used. Alternative
methods for preparing calibration gas mixtures may be used with the
approval of the Administrator.
5.1.1 Fuel. The FIA manufacturer's recommended fuel should be
used. A 40 percent H2/60 percent He or 40 percent H2/60
percent N2 gas mixture is recommended to avoid an oxygen
synergism effect that reportedly occurs when oxygen concentration
varies significantly from a mean value. Other mixtures may be used
provided the tester can demonstrate to the Administrator that there is
no oxygen synergism effect.
5.1.2 Carrier Gas. High purity air with less than 1 ppm of organic
material (as propane) or less than 0.1 percent of the span value,
whichever is greater.
5.1.3 FIA Linearity Calibration Gases. Low-, mid-, and high-range
gas mixture standards with nominal propane concentrations of 20-30, 45-
55, and 70-80 percent of the span value in air, respectively. Other
calibration values and other span values may be used if it can be shown
to the Administrator's satisfaction that equally accurate measurements
would be achieved.
5.1.4 System Calibration Gas. Gas mixture standard containing
propane in air, approximating the undiluted VOC concentration expected
for the liquid samples.
6. Sample Collection, Preservation and Storage
6.1 Samples must be collected in a manner that prevents or
minimizes loss of volatile components and that does not contaminate the
coating reservoir.
6.2 Collect a 100-ml or larger sample of the VOC containing liquid
mixture at each application location at the beginning and end of each
test run. A separate sample should be taken of each VOC containing
liquid added to the application mixture during the test run. If a fresh
drum is needed during the sampling run, then obtain a sample from the
fresh drum.
6.3 When collecting the sample, ground the sample container to the
coating drum. Fill the sample container as close to the rim as possible
to minimize the amount of headspace.
6.4 After the sample is collected, seal the container so the
sample cannot leak out or evaporate.
6.5 Label the container to clearly identify the contents.
7. Quality Control
7.1 Required instrument quality control parameters are found in
the following sections:
7.1.1 The FIA system must be calibrated as specified in section
8.1.
7.1.2 The system drift check must be performed as specified in
section 8.2.
7.2 Audits.
7.2.1 Audit Procedure. Concurrently, analyze the audit sample and
a set of compliance samples in the same manner to evaluate the
technique of the analyst and the standards preparation. The same
analyst, analytical reagents, and analytical system shall be used both
for compliance samples and the EPA audit sample. If this condition is
met, auditing of subsequent compliance analyses for the same
enforcement agency within 30 days is not required. An audit sample set
may not be used to validate different sets of compliance samples under
the jurisdiction of different enforcement agencies, unless prior
arrangements are made with both enforcement agencies.
7.2.2 Audit Samples and Audit Sample Availability. Audit samples
will be supplied only to enforcement agencies for compliance tests. The
availability of audit samples may be obtained by writing: Source Test
Audit Coordinator (STAC) (MD-77B), Quality Assurance Division,
Atmospheric Research and Exposure Assessment Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711 or by
calling the STAC at (919) 541-7834. The request for the audit sample
must be made at least 30 days prior to the scheduled compliance sample
analysis.
7.2.3 Audit Results. Calculate the audit sample concentration
according to the calculation procedure described in the audit
instructions included with the audit sample. Fill in the audit sample
concentration and the analyst's name on the audit response form
included with the audit instructions. Send one copy to the EPA Regional
Office or the appropriate enforcement agency, and a second copy to the
STAC. The EPA Regional Office or the appropriate enforcement agency
will report the results of the audit to the laboratory being audited.
Include this response with the results of the compliance samples in
relevant reports to the EPA Regional Office or the appropriate
enforcement agency.
8. Calibration and Standardization
8.1 FIA Calibration and Linearity Check. Make necessary
adjustments to the air and fuel supplies for the FIA and ignite the
burner. Allow the FIA to warm up for the period recommended by the
manufacturer. Inject a calibration gas into the measurement system and
adjust the back-pressure regulator to the value required to achieve the
flow rates specified by the manufacturer. Inject the zero- and the
high-range calibration gases and adjust the analyzer calibration to
provide the proper responses. Inject the low- and mid-range gases and
record the responses of the measurement system. The calibration and
linearity of the system are acceptable if the responses for all four
gases are within 5 percent of the respective gas values. If the
performance of the system is not acceptable, repair or adjust the
system and repeat the linearity check. Conduct a calibration and
linearity check after assembling the analysis system and after a major
change is made to the system.
8.2 Systems Drift Checks. After each sample, repeat the system
calibration checks in section 9.2.7 before any adjustments to the FIA
or measurement system are made. If the zero or calibration drift
exceeds 3 percent of the span value, discard the result and
repeat the analysis.
Alternatively, recalibrate the FIA as in section 8.1 and report the
results using both sets of calibration data (i.e., data determined
prior to the test period and data determined following the test
period). The data that results in the lowest CE value shall be reported
as the results for the test run.
8.3 Critical Orifice Calibration.
8.3.1 Each critical orifice must be calibrated at the specific
operating conditions under which it will be used. Therefore, assemble
all components of the liquid sample analysis system as shown in Figure
204A-3. A stopwatch is also required.
8.3.2 Turn on the sample oven, sample line, and water bath
heaters, and allow the system to reach the proper operating
temperature. Adjust the aspirator to a vacuum of 380 mm (15 in.) Hg
vacuum. Measure the time required for one soap bubble to move a known
distance and record barometric pressure.
8.3.3 Repeat the calibration procedure at a vacuum of 406 mm (16
in.) Hg and at 25-mm (1-in.) Hg intervals until three consecutive
determinations provide the same flow rate. Calculate the critical flow
rate for the orifice in ml/min at standard conditions. Record the
vacuum necessary to achieve critical flow.
[[Page 32507]]
9. Procedure
9.1 Determination of Liquid Input Weight.
9.1.1 Weight Difference. Determine the amount of material
introduced to the process as the weight difference of the feed material
before and after each sampling run. In determining the total VOC
containing liquid usage, account for:
(a) The initial (beginning) VOC containing liquid mixture.
(b) Any solvent added during the test run.
(c) Any coating added during the test run.
(d) Any residual VOC containing liquid mixture remaining at the end
of the sample run.
9.1.1.1 Identify all points where VOC containing liquids are
introduced to the process. To obtain an accurate measurement of VOC
containing liquids, start with an empty fountain (if applicable). After
completing the run, drain the liquid in the fountain back into the
liquid drum (if possible) and weigh the drum again. Weigh the VOC
containing liquids to 0.5 percent of the total weight
(full) or 1.0 percent of the total weight of VOC containing
liquid used during the sample run, whichever is less. If the residual
liquid cannot be returned to the drum, drain the fountain into a
preweighed empty drum to determine the final weight of the liquid.
9.1.1.2 If it is not possible to measure a single representative
mixture, then weigh the various components separately (e.g., if solvent
is added during the sampling run, weigh the solvent before it is added
to the mixture). If a fresh drum of VOC containing liquid is needed
during the run, then weigh both the empty drum and fresh drum.
9.1.2 Volume Measurement (Alternative). If direct weight
measurements are not feasible, the tester may use volume meters or flow
rate meters and density measurements to determine the weight of liquids
used if it can be demonstrated that the technique produces results
equivalent to the direct weight measurements. If a single
representative mixture cannot be measured, measure the components
separately.
9.2 Determination of VOC Content in Input Liquids
9.2.1 Assemble the liquid VOC content analysis system as shown in
Figure 204A-1.
9.2.2 Permanently identify all of the critical orifices that may
be used. Calibrate each critical orifice under the expected operating
conditions (i.e., sample vacuum and temperature) against a volume meter
as described in section 8.3.
9.2.3 Label and tare the sample vessels (including the stoppers
and caps) and the syringes.
9.2.4 Install an empty sample vessel and perform a leak test of
the system. Close the carrier gas valve and atmospheric vent and
evacuate the sample vessel to 250 mm (10 in.) Hg absolute or less using
the aspirator. Close the toggle valve at the inlet to the aspirator and
observe the vacuum for at least 1 minute. If there is any change in the
sample pressure, release the vacuum, adjust or repair the apparatus as
necessary, and repeat the leak test.
9.2.5 Perform the analyzer calibration and linearity checks
according to the procedure in section 5.1. Record the responses to each
of the calibration gases and the back-pressure setting of the FIA.
9.2.6 Establish the appropriate dilution ratio by adjusting the
aspirator air supply or substituting critical orifices. Operate the
aspirator at a vacuum of at least 25 mm (1 in.) Hg greater than the
vacuum necessary to achieve critical flow. Select the dilution ratio so
that the maximum response of the FIA to the sample does not exceed the
high-range calibration gas.
9.2.7 Perform system calibration checks at two levels by
introducing compressed gases at the inlet to the sample vessel while
the aspirator and dilution devices are operating. Perform these checks
using the carrier gas (zero concentration) and the system calibration
gas. If the response to the carrier gas exceeds 0.5 percent
of span, clean or repair the apparatus and repeat the check. Adjust the
dilution ratio as necessary to achieve the correct response to the
upscale check, but do not adjust the analyzer calibration. Record the
identification of the orifice, aspirator air supply pressure, FIA back-
pressure, and the responses of the FIA to the carrier and system
calibration gases.
9.2.8 After completing the above checks, inject the system
calibration gas for approximately 10 minutes. Time the exact duration
of the gas injection using a stopwatch. Determine the area under the
FIA response curve and calculate the system response factor based on
the sample gas flow rate, gas concentration, and the duration of the
injection as compared to the integrated response using Equations 204A-2
and 204A-3.
9.2.9 Verify that the sample oven and sample line temperatures are
120 5 deg.C and that the water bath temperature is
100 5 deg.C.
9.2.10 Fill a tared syringe with approximately 1 g of the VOC
containing liquid and weigh it. Transfer the liquid to a tared sample
vessel. Plug the sample vessel to minimize sample loss. Weigh the
sample vessel containing the liquid to determine the amount of sample
actually received. Also, as a quality control check, weigh the empty
syringe to determine the amount of material delivered. The two coating
sample weights should agree within 0.02 g. If not, repeat the procedure
until an acceptable sample is obtained.
9.2.11 Connect the vessel to the analysis system. Adjust the
aspirator supply pressure to the correct value. Open the valve on the
carrier gas supply to the sample vessel and adjust it to provide a
slight excess flow to the atmospheric vent. As soon as the initial
response of the FIA begins to decrease, immerse the sample vessel in
the water bath. (Applying heat to the sample vessel too soon may cause
the FIA response to exceed the calibrated range of the instrument and,
thus, invalidate the analysis.)
9.2.12 Continuously measure and record the response of the FIA
until all of the volatile material has been evaporated from the sample
and the instrument response has returned to the baseline (i.e.,
response less than 0.5 percent of the span value). Observe the
aspirator supply pressure, FIA back-pressure, atmospheric vent, and
other system operating parameters during the run; repeat the analysis
procedure if any of these parameters deviate from the values
established during the system calibration checks in section 9.2.7.
After each sample, perform the drift check described in section 8.2. If
the drift check results are acceptable, calculate the VOC content of
the sample using the equations in section 11.2. Alternatively,
recalibrate the FIA as in section 8.1 and report the results using both
sets of calibration data (i.e., data determined prior to the test
period and data determined following the test period). The data that
results in the lowest CE value shall be reported as the results for the
test run. Integrate the area under the FIA response curve, or determine
the average concentration response and the duration of sample analysis.
10. Data Analysis and Calculations
10.1 Nomenclature.
AL=area under the response curve of the liquid sample, area
count.
AS=area under the response curve of the calibration gas,
area count.
CS=actual concentration of system calibration gas, ppm
propane.
K=1.830 x 10-9 g/(ml-ppm).
L=total VOC content of liquid input, kg.
[[Page 32508]]
ML=mass of liquid sample delivered to the sample vessel, g.
q = flow rate through critical orifice, ml/min.
RF=liquid analysis system response factor, g/area count.
S=total gas injection time for system
calibration gas during integrator calibration, min.
VFj=final VOC fraction of VOC containing liquid j.
VIj=initial VOC fraction of VOC containing liquid j.
VAj=VOC fraction of VOC containing liquid j added during the
run.
V=VOC fraction of liquid sample.
WFj=weight of VOC containing liquid j remaining at end of
the run, kg.
WIj=weight of VOC containing liquid j at beginning of the
run, kg.
WAj=weight of VOC containing liquid j added during the run,
kg.
10.2 Calculations
10.2.1 Total VOC Content of the Input VOC Containing Liquid.
[GRAPHIC] [TIFF OMITTED] TR16JN97.003
10.2.2 Liquid Sample Analysis System Response Factor for Systems
Using Integrators, Grams/Area Count.
[GRAPHIC] [TIFF OMITTED] TR16JN97.004
10.2.3 VOC Content of the Liquid Sample.
[GRAPHIC] [TIFF OMITTED] TR16JN97.005
11. Method Performance
The measurement uncertainties are estimated for each VOC containing
liquid as follows: W = 2.0 percent and V = 4.0
percent. Based on these numbers, the probable uncertainty for L is
estimated at about 4.5 percent for each VOC containing
liquid.
12. Diagrams
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[[Page 32509]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.036
[[Page 32510]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.037
[[Page 32511]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.038
BILLING CODE 6560-50-C
[[Page 32512]]
Method 204B--Volatile Organic Compounds Emissions in Captured Stream
1. Scope and Application
1.1 Applicability. This procedure is applicable for determining
the volatile organic compounds (VOC) content of captured gas streams.
It is intended to be used in the development of a gas/gas protocol for
determining VOC capture efficiency (CE) for surface coating and
printing operations. The procedure may not be acceptable in certain
site-specific situations [e.g., when: (1) direct-fired heaters or other
circumstances affect the quantity of VOC at the control device inlet;
and (2) particulate organic aerosols are formed in the process and are
present in the captured emissions].
1.2 Principle. The amount of VOC captured (G) is calculated as the
sum of the products of the VOC content (CGj), the flow rate
(QGj), and the sample time (C) from
each captured emissions point.
1.3 Sampling Requirements. A CE test shall consist of at least
three sampling runs. Each run shall cover at least one complete
production cycle, but shall be at least 3 hours long. The sampling time
for each run need not exceed 8 hours, even if the production cycle has
not been completed. Alternative sampling times may be used with the
approval of the Administrator.
2. Summary of Method
A gas sample is extracted from the source though a heated sample
line and, if necessary, a glass fiber filter to a flame ionization
analyzer (FIA).
3. Safety
Because this procedure is often applied in highly explosive areas,
caution and care should be exercised in choosing, installing, and using
the appropriate equipment.
4. Equipment and Supplies
Mention of trade names or company products does not constitute
endorsement. All gas concentrations (percent, ppm) are by volume,
unless otherwise noted.
4.1 Gas VOC Concentration. A schematic of the measurement system
is shown in Figure 204B-1. The main components are as follows:
4.1.1 Sample Probe. Stainless steel or equivalent. The probe shall
be heated to prevent VOC condensation.
4.1.2 Calibration Valve Assembly. Three-way valve assembly at the
outlet of the sample probe to direct the zero and calibration gases to
the analyzer. Other methods, such as quick-connect lines, to route
calibration gases to the outlet of the sample probe are acceptable.
4.1.3 Sample Line. Stainless steel or Teflon tubing to transport
the sample gas to the analyzer. The sample line must be heated to
prevent condensation.
4.1.4 Sample Pump. A leak-free pump, to pull the sample gas
through the system at a flow rate sufficient to minimize the response
time of the measurement system. The components of the pump that contact
the gas stream shall be constructed of stainless steel or Teflon. The
sample pump must be heated to prevent condensation.
4.1.5 Sample Flow Rate Control. A sample flow rate control valve
and rotameter, or equivalent, to maintain a constant sampling rate
within 10 percent. The flow rate control valve and rotameter must be
heated to prevent condensation. A control valve may also be located on
the sample pump bypass loop to assist in controlling the sample
pressure and flow rate.
4.1.6 Organic Concentration Analyzer. An FIA with a span value of
1.5 times the expected concentration as propane; however, other span
values may be used if it can be demonstrated to the Administrator's
satisfaction that they would provide equally accurate measurements. The
system shall be capable of meeting or exceeding the following
specifications:
4.1.6.1 Zero Drift. Less than 3.0 percent of the span
value.
4.1.6.2 Calibration Drift. Less than 3.0 percent of
the span value.
4.1.6.3 Calibration Error. Less than 5.0 percent of
the calibration gas value.
4.1.6.4 Response Time. Less than 30 seconds.
4.1.7 Integrator/Data Acquisition System. An analog or digital
device, or computerized data acquisition system used to integrate the
FIA response or compute the average response and record measurement
data. The minimum data sampling frequency for computing average or
integrated values is one measurement value every 5 seconds. The device
shall be capable of recording average values at least once per minute.
4.2 Captured Emissions Volumetric Flow Rate.
4.2.1 Method 2 or 2A Apparatus. For determining volumetric flow
rate.
4.2.2 Method 3 Apparatus and Reagents. For determining molecular
weight of the gas stream. An estimate of the molecular weight of the
gas stream may be used if approved by the Administrator.
4.2.3 Method 4 Apparatus and Reagents. For determining moisture
content, if necessary.
5. Reagents and Standards
5.1 Calibration and Other Gases. Gases used for calibration, fuel,
and combustion air (if required) are contained in compressed gas
cylinders. All calibration gases shall be traceable to National
Institute of Standards and Technology standards and shall be certified
by the manufacturer to 1 percent of the tag value.
Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than 2 percent from the
certified value. For calibration gas values not generally available,
dilution systems calibrated using Method 205 may be used. Alternative
methods for preparing calibration gas mixtures may be used with the
approval of the Administrator.
5.1.1 Fuel. The FIA manufacturer's recommended fuel should be
used. A 40 percent H2/60 percent He or 40 percent
H2/60 percent N2 gas mixture is recommended to
avoid an oxygen synergism effect that reportedly occurs when oxygen
concentration varies significantly from a mean value. Other mixtures
may be used provided the tester can demonstrate to the Administrator
that there is no oxygen synergism effect.
5.1.2 Carrier Gas. High purity air with less than 1 ppm of organic
material (as propane or carbon equivalent) or less than 0.1 percent of
the span value, whichever is greater.
5.1.3 FIA Linearity Calibration Gases. Low-, mid-, and high-range
gas mixture standards with nominal propane concentrations of 20-30, 45-
55, and 70-80 percent of the span value in air, respectively. Other
calibration values and other span values may be used if it can be shown
to the Administrator's satisfaction that equally accurate measurements
would be achieved.
5.2 Particulate Filter. An in-stack or an out-of-stack glass fiber
filter is recommended if exhaust gas particulate loading is
significant. An out-of-stack filter must be heated to prevent any
condensation unless it can be demonstrated that no condensation occurs.
6. Quality Control
6.1 Required instrument quality control parameters are found in
the following sections:
6.1.1 The FIA system must be calibrated as specified in section
7.1.
6.1.2 The system drift check must be performed as specified in
section 7.2.
6.1.3 The system check must be conducted as specified in section
7.3.
[[Page 32513]]
6.2 Audits.
6.2.1 Analysis Audit Procedure. Immediately before each test,
analyze an audit cylinder as described in section 7.2. The analysis
audit must agree with the audit cylinder concentration within 10
percent.
6.2.2 Audit Samples and Audit Sample Availability. Audit samples
will be supplied only to enforcement agencies for compliance tests. The
availability of audit samples may be obtained by writing: Source Test
Audit Coordinator (STAC) (MD-77B), Quality Assurance Division,
Atmospheric Research and Exposure Assessment Labortory, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711 or by
calling the STAC at (919) 541-7834. The request for the audit sample
must be made at least 30 days prior to the scheduled compliance sample
analysis.
6.2.3 Audit Results. Calculate the audit sample concentration
according to the calculation procedure described in the audit
instructions included with the audit sample. Fill in the audit sample
concentration and the analyst's name on the audit response form
included with the audit instructions. Send one copy to the EPA Regional
Office or the appropriate enforcement agency, and a second copy to the
STAC. The EPA Regional Office or the appropriate enforcement agency
will report the results of the audit to the laboratory being audited.
Include this response with the results of the compliance samples in
relevant reports to the EPA Regional Office or the appropriate
enforcement agency.
7. Calibration and Standardization
7.1 FIA Calibration and Linearity Check. Make necessary
adjustments to the air and fuel supplies for the FIA and ignite the
burner. Allow the FIA to warm up for the period recommended by the
manufacturer. Inject a calibration gas into the measurement system and
adjust the back-pressure regulator to the value required to achieve the
flow rates specified by the manufacturer. Inject the zero-and the high-
range calibration gases and adjust the analyzer calibration to provide
the proper responses. Inject the low- and mid-range gases and record
the responses of the measurement system. The calibration and linearity
of the system are acceptable if the responses for all four gases are
within 5 percent of the respective gas values. If the performance of
the system is not acceptable, repair or adjust the system and repeat
the linearity check. Conduct a calibration and linearity check after
assembling the analysis system and after a major change is made to the
system.
7.2 Systems Drift Checks. Select the calibration gas that most
closely approximates the concentration of the captured emissions for
conducting the drift checks. Introduce the zero and calibration gases
at the calibration valve assembly and verify that the appropriate gas
flow rate and pressure are present at the FIA. Record the measurement
system responses to the zero and calibration gases. The performance of
the system is acceptable if the difference between the drift check
measurement and the value obtained in section 7.1 is less than 3
percent of the span value. Alternatively, recalibrate the FIA as in
section 7.1 and report the results using both sets of calibration data
(i.e., data determined prior to the test period and data determined
following the test period). The data that results in the lowest CE
value shall be reported as the results for the test run. Conduct the
system drift checks at the end of each run.
7.3 System Check. Inject the high-range calibration gas at the
inlet of the sampling probe and record the response. The performance of
the system is acceptable if the measurement system response is within 5
percent of the value obtained in section 7.1 for the high-range
calibration gas. Conduct a system check before and after each test run.
8. Procedure
8.1. Determination of Volumetric Flow Rate of Captured Emissions.
8.1.1 Locate all points where emissions are captured from the
affected facility. Using Method 1, determine the sampling points. Be
sure to check each site for cyclonic or swirling flow.
8.1.2 Measure the velocity at each sampling site at least once
every hour during each sampling run using Method 2 or 2A.
8.2 Determination of VOC Content of Captured Emissions.
8.2.1 Analysis Duration. Measure the VOC responses at each
captured emissions point during the entire test run or, if applicable,
while the process is operating. If there are multiple captured emission
locations, design a sampling system to allow a single FIA to be used to
determine the VOC responses at all sampling locations.
8.2.2 Gas VOC Concentration.
8.2.2.1 Assemble the sample train as shown in Figure 204B-1.
Calibrate the FIA according to the procedure in section 7.1.
8.2.2.2 Conduct a system check according to the procedure in
section 7.3.
8.2.2.3 Install the sample probe so that the probe is centrally
located in the stack, pipe, or duct, and is sealed tightly at the stack
port connection.
8.2.2.4 Inject zero gas at the calibration valve assembly. Allow
the measurement system response to reach zero. Measure the system
response time as the time required for the system to reach the effluent
concentration after the calibration valve has been returned to the
effluent sampling position.
8.2.2.5 Conduct a system check before, and a system drift check
after, each sampling run according to the procedures in sections 7.2
and 7.3. If the drift check following a run indicates unacceptable
performance (see section 7.3), the run is not valid. Alternatively,
recalibrate the FIA as in section 7.1 and report the results using both
sets of calibration data (i.e., data determined prior to the test
period and data determined following the test period). The data that
results in the lowest CE value shall be reported as the results for the
test run. The tester may elect to perform system drift checks during
the run not to exceed one drift check per hour.
8.2.2.6 Verify that the sample lines, filter, and pump
temperatures are 1205 deg.C.
8.2.2.7 Begin sampling at the start of the test period and
continue to sample during the entire run. Record the starting and
ending times and any required process information as appropriate. If
multiple captured emission locations are sampled using a single FIA,
sample at each location for the same amount of time (e.g., 2 minutes)
and continue to switch from one location to another for the entire test
run. Be sure that total sampling time at each location is the same at
the end of the test run. Collect at least four separate measurements
from each sample point during each hour of testing. Disregard the
measurements at each sampling location until two times the response
time of the measurement system has elapsed. Continue sampling for at
least 1 minute and record the concentration measurements.
8.2.3 Background Concentration.
Note: Not applicable when the building is used as the temporary
total enclosure (TTE).
8.2.3.1 Locate all natural draft openings (NDO's) of the TTE. A
sampling point shall be at the center of each NDO, unless otherwise
specified by the Administrator. If there are more than six NDO's,
choose six sampling points evenly spaced among the NDO's.
8.2.3.2 Assemble the sample train as shown in Figure 204B-2.
Calibrate the FIA and conduct a system check according to the
procedures in sections 7.1 and 7.3.
[[Page 32514]]
Note: This sample train shall be separate from the sample train
used to measure the captured emissions.
8.2.3.3 Position the probe at the sampling location.
8.2.3.4 Determine the response time, conduct the system check, and
sample according to the procedures described in sections 8.2.2.4
through 8.2.2.7.
8.2.4 Alternative Procedure. The direct interface sampling and
analysis procedure described in section 7.2 of Method 18 may be used to
determine the gas VOC concentration. The system must be designed to
collect and analyze at least one sample every 10 minutes. If the
alternative procedure is used to determine the VOC concentration of the
captured emissions, it must also be used to determine the VOC
concentration of the uncaptured emissions.
9. Data Analysis and Calculations
9.1 Nomenclature.
Ai=area of NDO i, ft\2\.
AN=total area of all NDO's in the enclosure, ft\2\.
CBi=corrected average VOC concentration of background
emissions at point i, ppm propane.
CB=average background concentration, ppm propane.
CGj=corrected average VOC concentration of captured
emissions at point j, ppm propane.
CDH=average measured concentration for the drift check
calibration gas, ppm propane.
CDO=average system drift check concentration for zero
concentration gas, ppm propane.
CH=actual concentration of the drift check calibration gas,
ppm propane.
Ci=uncorrected average background VOC concentration measured
at point i, ppm propane.
Cj=uncorrected average VOC concentration measured at point
j, ppm propane.
G=total VOC content of captured emissions, kg.
K1=1.830 x 10-6 kg/(m\3\-ppm).
n=number of measurement points.
QGj=average effluent volumetric flow rate corrected to
standard conditions at captured emissions point j, m\3\/min.
C=total duration of captured emissions.
9.2 Calculations.
9.2.1 Total VOC Captured Emissions.
[GRAPHIC] [TIFF OMITTED] TR16JN97.006
9.2.2 VOC Concentration of the Captured Emissions at Point j.
[GRAPHIC] [TIFF OMITTED] TR16JN97.007
9.2.3 Background VOC Concentration at Point i.
[GRAPHIC] [TIFF OMITTED] TR16JN97.008
9.2.4 Average Background Concentration.
[GRAPHIC] [TIFF OMITTED] TR16JN97.009
Note: If the concentration at each point is within 20 percent of
the average concentration of all points, then use the arithmetic
average.
10. Method Performance
The measurement uncertainties are estimated for each captured or
uncaptured emissions point as follows: QGj=5.5
percent and CGj=5.0 percent. Based on these
numbers, the probable uncertainty for G is estimated at about
7.4 percent.
11. Diagrams
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[[Page 32515]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.027
[[Page 32516]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.028
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[[Page 32517]]
Method 204C--Volatile Organic Compounds Emissions in Captured Stream
(Dilution Technique)
1. Scope and Application
1.1 Applicability. This procedure is applicable for determining
the volatile organic compounds (VOC) content of captured gas streams.
It is intended to be used in the development of a gas/gas protocol in
which uncaptured emissions are also measured for determining VOC
capture efficiency (CE) for surface coating and printing operations. A
dilution system is used to reduce the VOC concentration of the captured
emissions to about the same concentration as the uncaptured emissions.
The procedure may not be acceptable in certain site-specific situations
[e.g., when: (1) direct-fired heaters or other circumstances affect the
quantity of VOC at the control device inlet; and (2) particulate
organic aerosols are formed in the process and are present in the
captured emissions].
1.2 Principle. The amount of VOC captured (G) is calculated as the
sum of the products of the VOC content (CGj), the flow rate
(QGj), and the sampling time (C) from
each captured emissions point.
1.3 Sampling Requirements. A CE test shall consist of at least
three sampling runs. Each run shall cover at least one complete
production cycle, but shall be at least 3 hours long. The sampling time
for each run need not exceed 8 hours, even if the production cycle has
not been completed. Alternative sampling times may be used with the
approval of the Administrator.
2. Summary of Method
A gas sample is extracted from the source using an in-stack
dilution probe through a heated sample line and, if necessary, a glass
fiber filter to a flame ionization analyzer (FIA). The sample train
contains a sample gas manifold which allows multiple points to be
sampled using a single FIA.
3. Safety
Because this procedure is often applied in highly explosive areas,
caution and care should be exercised in choosing, installing, and using
the appropriate equipment.
4. Equipment and Supplies
Mention of trade names or company products does not constitute
endorsement. All gas concentrations (percent, ppm) are by volume,
unless otherwise noted.
4.1 Gas VOC Concentration. A schematic of the measurement system
is shown in Figure 204C-1. The main components are as follows:
4.1.1 Dilution System. A Kipp in-stack dilution probe and
controller or similar device may be used. The dilution rate may be
changed by substituting different critical orifices or adjustments of
the aspirator supply pressure. The dilution system shall be heated to
prevent VOC condensation. Note: An out-of-stack dilution device may be
used.
4.1.2 Calibration Valve Assembly. Three-way valve assembly at the
outlet of the sample probe to direct the zero and calibration gases to
the analyzer. Other methods, such as quick-connect lines, to route
calibration gases to the outlet of the sample probe are acceptable.
4.1.3 Sample Line. Stainless steel or Teflon tubing to transport
the sample gas to the analyzer. The sample line must be heated to
prevent condensation.
4.1.4 Sample Pump. A leak-free pump, to pull the sample gas
through the system at a flow rate sufficient to minimize the response
time of the measurement system. The components of the pump that contact
the gas stream shall be constructed of stainless steel or Teflon. The
sample pump must be heated to prevent condensation.
4.1.5 Sample Flow Rate Control. A sample flow rate control valve
and rotameter, or equivalent, to maintain a constant sampling rate
within 10 percent. The flow control valve and rotameter must be heated
to prevent condensation. A control valve may also be located on the
sample pump bypass loop to assist in controlling the sample pressure
and flow rate.
4.1.6 Sample Gas Manifold. Capable of diverting a portion of the
sample gas stream to the FIA, and the remainder to the bypass discharge
vent. The manifold components shall be constructed of stainless steel
or Teflon. If captured or uncaptured emissions are to be measured at
multiple locations, the measurement system shall be designed to use
separate sampling probes, lines, and pumps for each measurement
location and a common sample gas manifold and FIA. The sample gas
manifold and connecting lines to the FIA must be heated to prevent
condensation.
Note: Depending on the number of sampling points and their
location, it may not be possible to use only one FIA. However to
reduce the effect of calibration error, the number of FIA's used
during a test should be keep as small as possible.
4.1.7 Organic Concentration Analyzer. An FIA with a span value of
1.5 times the expected concentration as propane; however, other span
values may be used if it can be demonstrated to the Administrator's
satisfaction that they would provide equally accurate measurements. The
system shall be capable of meeting or exceeding the following
specifications:
4.1.7.1 Zero Drift. Less than 3.0 percent of the span
value.
4.1.7.2 Calibration Drift. Less than 3.0 percent of
the span value.
4.1.7.3 Calibration Error. Less than 5.0 percent of
the calibration gas value.
4.1.7.4 Response Time. Less than 30 seconds.
4.1.8 Integrator/Data Acquisition System. An analog or digital
device or computerized data acquisition system used to integrate the
FIA response or compute the average response and record measurement
data. The minimum data sampling frequency for computing average or
integrated values is one measurement value every 5 seconds. The device
shall be capable of recording average values at least once per minute.
4.2 Captured Emissions Volumetric Flow Rate.
4.2.1 Method 2 or 2A Apparatus. For determining volumetric flow
rate.
4.2.2 Method 3 Apparatus and Reagents. For determining molecular
weight of the gas stream. An estimate of the molecular weight of the
gas stream may be used if approved by the Administrator.
4.2.3 Method 4 Apparatus and Reagents. For determining moisture
content, if necessary.
5. Reagents and Standards
5.1 Calibration and Other Gases. Gases used for calibration, fuel,
and combustion air (if required) are contained in compressed gas
cylinders. All calibration gases shall be traceable to National
Institute of Standards and Technology standards and shall be certified
by the manufacturer to 1 percent of the tag value.
Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than 2 percent from the
certified value. For calibration gas values not generally available,
dilution systems calibrated using Method 205 may be used. Alternative
methods for preparing calibration gas mixtures may be used with the
approval of the Administrator.
5.1.1 Fuel. The FIA manufacturer's recommended fuel should be
used. A 40 percent H2/60 percent He or 40 percent
H2/60 percent N2 gas mixture is recommended to
avoid an oxygen synergism effect that reportedly occurs when oxygen
concentration varies
[[Page 32518]]
significantly from a mean value. Other mixtures may be used provided
the tester can demonstrate to the Administrator that there is no oxygen
synergism effect
5.1.2 Carrier Gas and Dilution Air Supply. High purity air with
less than 1 ppm of organic material (as propane or carbon equivalent),
or less than 0.1 percent of the span value, whichever is greater.
5.1.3 FIA Linearity Calibration Gases. Low-, mid-, and high-range
gas mixture standards with nominal propane concentrations of 20-30, 45-
55, and 70-80 percent of the span value in air, respectively. Other
calibration values and other span values may be used if it can be shown
to the Administrator's satisfaction that equally accurate measurements
would be achieved.
5.1.4 Dilution Check Gas. Gas mixture standard containing propane
in air, approximately half the span value after dilution.
5.2 Particulate Filter. An in-stack or an out-of-stack glass fiber
filter is recommended if exhaust gas particulate loading is
significant. An out-of-stack filter must be heated to prevent any
condensation unless it can be demonstrated that no condensation occurs.
6. Quality Control
6.1 Required instrument quality control parameters are found in
the following sections:
6.1.1 The FIA system must be calibrated as specified in section
7.1.
6.1.2 The system drift check must be performed as specified in
section 7.2.
6.1.3 The dilution factor must be determined as specified in
section 7.3.
6.1.4 The system check must be conducted as specified in section
7.4.
6.2 Audits.
6.2.1 Analysis Audit Procedure. Immediately before each test,
analyze an audit cylinder as described in section 7.2. The analysis
audit must agree with the audit cylinder concentration within 10
percent.
6.2.2 Audit Samples and Audit Sample Availability. Audit samples
will be supplied only to enforcement agencies for compliance tests. The
availability of audit samples may be obtained by writing: Source Test
Audit Coordinator (STAC) (MD-77B), Quality Assurance Division,
Atmospheric Research and Exposure Assessment Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711 or by
calling the STAC at (919) 541-7834. The request for the audit sample
must be made at least 30 days prior to the scheduled compliance sample
analysis.
6.2.3 Audit Results. Calculate the audit sample concentration
according to the calculation procedure described in the audit
instructions included with the audit sample. Fill in the audit sample
concentration and the analyst's name on the audit response form
included with the audit instructions. Send one copy to the EPA Regional
Office or the appropriate enforcement agency, and a second copy to the
STAC. The EPA Regional Office or the appropriate enforcement agency
will report the results of the audit to the laboratory being audited.
Include this response with the results of the compliance samples in
relevant reports to the EPA Regional Office or the appropriate
enforcement agency.
7. Calibration and Standardization
7.1 FIA Calibration and Linearity Check. Make necessary
adjustments to the air and fuel supplies for the FIA and ignite the
burner. Allow the FIA to warm up for the period recommended by the
manufacturer. Inject a calibration gas into the measurement system
after the dilution system and adjust the back-pressure regulator to the
value required to achieve the flow rates specified by the manufacturer.
Inject the zero-and the high-range calibration gases and adjust the
analyzer calibration to provide the proper responses. Inject the low-
and mid-range gases and record the responses of the measurement system.
The calibration and linearity of the system are acceptable if the
responses for all four gases are within 5 percent of the respective gas
values. If the performance of the system is not acceptable, repair or
adjust the system and repeat the linearity check. Conduct a calibration
and linearity check after assembling the analysis system and after a
major change is made to the system.
7.2 Systems Drift Checks. Select the calibration gas that most
closely approximates the concentration of the diluted captured
emissions for conducting the drift checks. Introduce the zero and
calibration gases at the calibration valve assembly, and verify that
the appropriate gas flow rate and pressure are present at the FIA.
Record the measurement system responses to the zero and calibration
gases. The performance of the system is acceptable if the difference
between the drift check measurement and the value obtained in section
7.1 is less than 3 percent of the span value. Alternatively,
recalibrate the FIA as in section 7.1 and report the results using both
sets of calibration data (i.e., data determined prior to the test
period and data determined following the test period). The data that
results in the lowest CE value shall be reported as the results for the
test run. Conduct the system drift check at the end of each run.
7.3 Determination of Dilution Factor. Inject the dilution check
gas into the measurement system before the dilution system and record
the response. Calculate the dilution factor using Equation 204C-3.
7.4 System Check. Inject the high-range calibration gas at the
inlet to the sampling probe while the dilution air is turned off.
Record the response. The performance of the system is acceptable if the
measurement system response is within 5 percent of the value obtained
in section 7.1 for the high-range calibration gas. Conduct a system
check before and after each test run.
8. Procedure
8.1 Determination of Volumetric Flow Rate of Captured Emissions
8.1.1 Locate all points where emissions are captured from the
affected facility. Using Method 1, determine the sampling points. Be
sure to check each site for cyclonic or swirling flow.
8.2.2 Measure the velocity at each sampling site at least once
every hour during each sampling run using Method 2 or 2A.
8.2 Determination of VOC Content of Captured Emissions
8.2.1 Analysis Duration. Measure the VOC responses at each
captured emissions point during the entire test run or, if applicable,
while the process is operating. If there are multiple captured
emissions locations, design a sampling system to allow a single FIA to
be used to determine the VOC responses at all sampling locations.
8.2.2 Gas VOC Concentration.
8.2.2.1 Assemble the sample train as shown in Figure 204C-1.
Calibrate the FIA according to the procedure in section 7.1.
8.2.2.2 Set the dilution ratio and determine the dilution factor
according to the procedure in section 7.3.
8.2.2.3 Conduct a system check according to the procedure in
section 7.4.
8.2.2.4 Install the sample probe so that the probe is centrally
located in the stack, pipe, or duct, and is sealed tightly at the stack
port connection.
8.2.2.5 Inject zero gas at the calibration valve assembly. Measure
the system response time as the time required for the system to reach
the effluent concentration after the calibration valve has been
returned to the effluent sampling position.
8.2.2.6 Conduct a system check before, and a system drift check
after,
[[Page 32519]]
each sampling run according to the procedures in sections 7.2 and 7.4.
If the drift check following a run indicates unacceptable performance
(see section 7.4), the run is not valid. Alternatively, recalibrate the
FIA as in section 7.1 and report the results using both sets of
calibration data (i.e., data determined prior to the test period and
data determined following the test period). The data that results in
the lowest CE value shall be reported as the results for the test run.
The tester may elect to perform system drift checks during the run not
to exceed one drift check per hour.
8.2.2.7 Verify that the sample lines, filter, and pump
temperatures are 120 5 deg.C.
8.2.2.8 Begin sampling at the start of the test period and
continue to sample during the entire run. Record the starting and
ending times and any required process information as appropriate. If
multiple captured emission locations are sampled using a single FIA,
sample at each location for the same amount of time (e.g., 2 min.) and
continue to switch from one location to another for the entire test
run. Be sure that total sampling time at each location is the same at
the end of the test run. Collect at least four separate measurements
from each sample point during each hour of testing. Disregard the
measurements at each sampling location until two times the response
time of the measurement system has elapsed. Continue sampling for at
least 1 minute and record the concentration measurements.
8.2.3 Background Concentration.
Note: Not applicable when the building is used as the temporary
total enclosure (TTE).
8.2.3.1 Locate all natural draft openings (NDO's) of the TTE. A
sampling point shall be at the center of each NDO, unless otherwise
approved by the Administrator. If there are more than six NDO's, choose
six sampling points evenly spaced among the NDO's.
8.2.3.2 Assemble the sample train as shown in Figure 204C-2.
Calibrate the FIA and conduct a system check according to the
procedures in sections 7.1 and 7.4.
8.2.3.3 Position the probe at the sampling location.
8.2.3.4 Determine the response time, conduct the system check, and
sample according to the procedures described in sections 8.2.2.4
through 8.2.2.8.
8.2.4 Alternative Procedure. The direct interface sampling and
analysis procedure described in section 7.2 of Method 18 may be used to
determine the gas VOC concentration. The system must be designed to
collect and analyze at least one sample every 10 minutes. If the
alternative procedure is used to determine the VOC concentration of the
captured emissions, it must also be used to determine the VOC
concentration of the uncaptured emissions.
9. Data Analysis and Calculations
9.1 Nomenclature.
Ai=area of NDO i, ft2.
AN=total area of all NDO's in the enclosure, ft2.
CA = actual concentration of the dilution check gas, ppm
propane.
CBi=corrected average VOC concentration of background
emissions at point i, ppm propane.
CB=average background concentration, ppm propane.
CDH=average measured concentration for the drift check
calibration gas, ppm propane.
CD0=average system drift check concentration for zero
concentration gas, ppm propane.
CH=actual concentration of the drift check calibration gas,
ppm propane.
Ci=uncorrected average background VOC concentration measured
at point i, ppm propane.
Cj=uncorrected average VOC concentration measured at point
j, ppm propane.
CM=measured concentration of the dilution check gas, ppm
propane.
DF=dilution factor.
G=total VOC content of captured emissions, kg.
K1=1.830 x 10-6 kg/(m3-ppm).
n=number of measurement points.
QGj=average effluent volumetric flow rate corrected to
standard conditions at captured emissions point j, m3/min.
C=total duration of CE sampling run, min.
9.2 Calculations.
9.2.1 Total VOC Captured Emissions.
[GRAPHIC] [TIFF OMITTED] TR16JN97.010
9.2.2 VOC Concentration of the Captured Emissions at Point j.
[GRAPHIC] [TIFF OMITTED] TR16JN97.011
9.2.3 Dilution Factor.
[GRAPHIC] [TIFF OMITTED] TR16JN97.012
9.2.4 Background VOC Concentration at Point i.
[GRAPHIC] [TIFF OMITTED] TR16JN97.013
9.2.5 Average Background Concentration.
[GRAPHIC] [TIFF OMITTED] TR16JN97.014
Note: If the concentration at each point is within 20 percent of
the average concentration of all points, then use the arithmetic
average.
10. Method Performance
The measurement uncertainties are estimated for each captured or
uncaptured emissions point as follows: QGj=5.5
percent and CGj= 5 percent. Based on these
numbers, the probable uncertainty for G is estimated at about
7.4 percent.
11. Diagrams
BILLING CODE 6560-SO-P
[[Page 32520]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.029
[[Page 32521]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.030
BILLIING CODE 6560-50-C
[[Page 32522]]
Method 204D--Volatile Organic Compounds Emissions in Uncaptured
Stream From Temporary Total Enclosure
1. Scope and Application
1.1 Applicability. This procedure is applicable for determining
the uncaptured volatile organic compounds (VOC) emissions from a
temporary total enclosure (TTE). It is intended to be used as a segment
in the development of liquid/gas or gas/gas protocols for determining
VOC capture efficiency (CE) for surface coating and printing
operations.
1.2 Principle. The amount of uncaptured VOC emissions (F) from the
TTE is calculated as the sum of the products of the VOC content
(CFj), the flow rate (QFj) from each uncaptured
emissions point, and the sampling time (F).
1.3 Sampling Requirements. A CE test shall consist of at least
three sampling runs. Each run shall cover at least one complete
production cycle, but shall be at least 3 hours long. The sampling time
for each run need not exceed 8 hours, even if the production cycle has
not been completed. Alternative sampling times may be used with the
approval of the Administrator.
2. Summary of Method
A gas sample is extracted from the uncaptured exhaust duct of a TTE
through a heated sample line and, if necessary, a glass fiber filter to
a flame ionization analyzer (FIA).
3. Safety
Because this procedure is often applied in highly explosive areas,
caution and care should be exercised in choosing, installing, and using
the appropriate equipment.
4. Equipment and Supplies
Mention of trade names or company products does not constitute
endorsement. All gas concentrations (percent, ppm) are by volume,
unless otherwise noted.
4.1 Gas VOC Concentration. A schematic of the measurement system
is shown in Figure 204D-1. The main components are as follows:
4.1.1 Sample Probe. Stainless steel or equivalent. The probe shall
be heated to prevent VOC condensation.
4.1.2 Calibration Valve Assembly. Three-way valve assembly at the
outlet of the sample probe to direct the zero and calibration gases to
the analyzer. Other methods, such as quick-connect lines, to route
calibration gases to the outlet of the sample probe are acceptable.
4.1.3 Sample Line. Stainless steel or Teflon tubing to transport
the sample gas to the analyzer. The sample line must be heated to
prevent condensation.
4.1.4 Sample Pump. A leak-free pump, to pull the sample gas
through the system at a flow rate sufficient to minimize the response
time of the measurement system. The components of the pump that contact
the gas stream shall be constructed of stainless steel or Teflon. The
sample pump must be heated to prevent condensation.
4.1.5 Sample Flow Rate Control. A sample flow rate control valve
and rotameter, or equivalent, to maintain a constant sampling rate
within 10 percent. The flow control valve and rotameter must be heated
to prevent condensation. A control valve may also be located on the
sample pump bypass loop to assist in controlling the sample pressure
and flow rate.
4.1.6 Sample Gas Manifold. Capable of diverting a portion of the
sample gas stream to the FIA, and the remainder to the bypass discharge
vent. The manifold components shall be constructed of stainless steel
or Teflon. If emissions are to be measured at multiple locations, the
measurement system shall be designed to use separate sampling probes,
lines, and pumps for each measurement location and a common sample gas
manifold and FIA. The sample gas manifold and connecting lines to the
FIA must be heated to prevent condensation.
4.1.7 Organic Concentration Analyzer. An FIA with a span value of
1.5 times the expected concentration as propane; however, other span
values may be used if it can be demonstrated to the Administrator's
satisfaction that they would provide more accurate measurements. The
system shall be capable of meeting or exceeding the following
specifications:
4.1.7.1 Zero Drift. Less than 3.0 percent of the span
value.
4.1.7.2 Calibration Drift. Less than 3.0 percent of
the span value.
4.1.7.3 Calibration Error. Less than 5.0 percent of
the calibration gas value.
4.1.7.4 Response Time. Less than 30 seconds.
4.1.8 Integrator/Data Acquisition System. An analog or digital
device or computerized data acquisition system used to integrate the
FIA response or compute the average response and record measurement
data. The minimum data sampling frequency for computing average or
integrated values is one measurement value every 5 seconds. The device
shall be capable of recording average values at least once per minute.
4.2 Uncaptured Emissions Volumetric Flow Rate.
4.2.1 Method 2 or 2A Apparatus. For determining volumetric flow
rate.
4.2.2 Method 3 Apparatus and Reagents. For determining molecular
weight of the gas stream. An estimate of the molecular weight of the
gas stream may be used if approved by the Administrator.
4.2.3 Method 4 Apparatus and Reagents. For determining moisture
content, if necessary.
4.3 Temporary Total Enclosure. The criteria for designing an
acceptable TTE are specified in Method 204.
5. Reagents and Standards
5.1 Calibration and Other Gases. Gases used for calibration, fuel,
and combustion air (if required) are contained in compressed gas
cylinders. All calibration gases shall be traceable to National
Institute of Standards and Technology standards and shall be certified
by the manufacturer to 1 percent of the tag value.
Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than 2 percent from the
certified value. For calibration gas values not generally available,
dilution systems calibrated using Method 205 may be used. Alternative
methods for preparing calibration gas mixtures may be used with the
approval of the Administrator.
5.1.1 Fuel. The FIA manufacturer's recommended fuel should be
used. A 40 percent H2/60 percent He or 40 percent
H2/60 percent N2 gas mixture is recommended to
avoid an oxygen synergism effect that reportedly occurs when oxygen
concentration varies significantly from a mean value. Other mixtures
may be used provided the tester can demonstrate to the Administrator
that there is no oxygen synergism effect.
5.1.2 Carrier Gas. High purity air with less than 1 ppm of organic
material (as propane or carbon equivalent) or less than 0.1 percent of
the span value, whichever is greater.
5.1.3 FIA Linearity Calibration Gases. Low-, mid-, and high-range
gas mixture standards with nominal propane concentrations of 20-30, 45-
55, and 70-80 percent of the span value in air, respectively. Other
calibration values and other span values may be used if it can be shown
to the Administrator's satisfaction that equally accurate measurements
would be achieved.
5.2 Particulate Filter. An in-stack or an out-of-stack glass fiber
filter is recommended if exhaust gas particulate
[[Page 32523]]
loading is significant. An out-of-stack filter must be heated to
prevent any condensation unless it can be demonstrated that no
condensation occurs.
6. Quality Control
6.1 Required instrument quality control parameters are found in
the following sections:
6.1.1 The FIA system must be calibrated as specified in section
7.1.
6.1.2 The system drift check must be performed as specified in
section 7.2.
6.1.3 The system check must be conducted as specified in section
7.3.
6.2 Audits.
6.2.1 Analysis Audit Procedure. Immediately before each test,
analyze an audit cylinder as described in section 7.2. The analysis
audit must agree with the audit cylinder concentration within 10
percent.
6.2.2 Audit Samples and Audit Sample Availability. Audit samples
will be supplied only to enforcement agencies for compliance tests. The
availability of audit samples may be obtained by writing: Source Test
Audit Coordinator (STAC) (MD-77B) Quality Assurance Division,
Atmospheric Research and Exposure Assessment Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711 or by
calling the STAC at (919) 541-7834. The request for the audit sample
must be made at least 30 days prior to the scheduled compliance sample
analysis.
6.2.3 Audit Results. Calculate the audit sample concentration
according to the calculation procedure described in the audit
instructions included with the audit sample. Fill in the audit sample
concentration and the analyst's name on the audit response form
included with the audit instructions. Send one copy to the EPA Regional
Office or the appropriate enforcement agency, and a second copy to the
STAC. The EPA Regional Office or the appropriate enforcement agency
will report the results of the audit to the laboratory being audited.
Include this response with the results of the compliance samples in
relevant reports to the EPA Regional Office or the appropriate
enforcement agency.
7. Calibration and Standardization
7.1 FIA Calibration and Linearity Check. Make necessary
adjustments to the air and fuel supplies for the FIA and ignite the
burner. Allow the FIA to warm up for the period recommended by the
manufacturer. Inject a calibration gas into the measurement system and
adjust the back-pressure regulator to the value required to achieve the
flow rates specified by the manufacturer. Inject the zero-and the high-
range calibration gases and adjust the analyzer calibration to provide
the proper responses. Inject the low-and mid-range gases and record the
responses of the measurement system. The calibration and linearity of
the system are acceptable if the responses for all four gases are
within 5 percent of the respective gas values. If the performance of
the system is not acceptable, repair or adjust the system and repeat
the linearity check. Conduct a calibration and linearity check after
assembling the analysis system and after a major change is made to the
system.
7.2 Systems Drift Checks. Select the calibration gas concentration
that most closely approximates that of the uncaptured gas emissions
concentration to conduct the drift checks. Introduce the zero and
calibration gases at the calibration valve assembly and verify that the
appropriate gas flow rate and pressure are present at the FIA. Record
the measurement system responses to the zero and calibration gases. The
performance of the system is acceptable if the difference between the
drift check measurement and the value obtained in section 7.1 is less
than 3 percent of the span value. Alternatively, recalibrate the FIA as
in section 7.1 and report the results using both sets of calibration
data (i.e., data determined prior to the test period and data
determined following the test period). The data that results in the
lowest CE value shall be reported as the results for the test run.
Conduct a system drift check at the end of each run.
7.3 System Check. Inject the high-range calibration gas at the
inlet of the sampling probe and record the response. The performance of
the system is acceptable if the measurement system response is within 5
percent of the value obtained in section 7.1 for the high-range
calibration gas. Conduct a system check before each test run.
8. Procedure
8.1 Determination of Volumetric Flow Rate of Uncaptured Emissions
8.1.1 Locate all points where uncaptured emissions are exhausted
from the TTE. Using Method 1, determine the sampling points. Be sure to
check each site for cyclonic or swirling flow.
8.1.2 Measure the velocity at each sampling site at least once
every hour during each sampling run using Method 2 or 2A.
8.2 Determination of VOC Content of Uncaptured Emissions.
8.2.1 Analysis Duration. Measure the VOC responses at each
uncaptured emission point during the entire test run or, if applicable,
while the process is operating. If there are multiple emission
locations, design a sampling system to allow a single FIA to be used to
determine the VOC responses at all sampling locations.
8.2.2 Gas VOC Concentration.
8.2.2.1 Assemble the sample train as shown in Figure 204D-1.
Calibrate the FIA and conduct a system check according to the
procedures in sections 7.1 and 7.3, respectively.
8.2.2.2 Install the sample probe so that the probe is centrally
located in the stack, pipe, or duct, and is sealed tightly at the stack
port connection.
8.2.2.3 Inject zero gas at the calibration valve assembly. Allow
the measurement system response to reach zero. Measure the system
response time as the time required for the system to reach the effluent
concentration after the calibration valve has been returned to the
effluent sampling position.
8.2.2.4 Conduct a system check before, and a system drift check
after, each sampling run according to the procedures in sections 7.2
and 7.3. If the drift check following a run indicates unacceptable
performance (see section 7.3), the run is not valid. Alternatively,
recalibrate the FIA as in section 7.1 and report the results using both
sets of calibration data (i.e., data determined prior to the test
period and data determined following the test period). The data that
results in the lowest CE value shall be reported as the results for the
test run. The tester may elect to perform system drift checks during
the run not to exceed one drift check per hour.
8.2.2.5 Verify that the sample lines, filter, and pump
temperatures are 1205 deg.C.
8.2.2.6 Begin sampling at the start of the test period and
continue to sample during the entire run. Record the starting and
ending times and any required process information, as appropriate. If
multiple emission locations are sampled using a single FIA, sample at
each location for the same amount of time (e.g., 2 min.) and continue
to switch from one location to another for the entire test run. Be sure
that total sampling time at each location is the same at the end of the
test run. Collect at least four separate measurements from each sample
point during each hour of testing. Disregard the response measurements
at each sampling location until 2 times the response time of the
measurement system has elapsed. Continue sampling for at least 1 minute
and record the concentration measurements.
8.2.3 Background Concentration.
[[Page 32524]]
8.2.3.1 Locate all natural draft openings (NDO's) of the TTE. A
sampling point shall be at the center of each NDO, unless otherwise
approved by the Administrator. If there are more than six NDO's, choose
six sampling points evenly spaced among the NDO's.
8.2.3.2 Assemble the sample train as shown in Figure 204D-2.
Calibrate the FIA and conduct a system check according to the
procedures in sections 7.1 and 7.3.
8.2.3.3 Position the probe at the sampling location.
8.2.3.4 Determine the response time, conduct the system check, and
sample according to the procedures described in sections 8.2.2.3
through 8.2.2.6.
8.2.4 Alternative Procedure. The direct interface sampling and
analysis procedure described in section 7.2 of Method 18 may be used to
determine the gas VOC concentration. The system must be designed to
collect and analyze at least one sample every 10 minutes. If the
alternative procedure is used to determine the VOC concentration of the
uncaptured emissions in a gas/gas protocol, it must also be used to
determine the VOC concentration of the captured emissions. If a tester
wishes to conduct a liquid/gas protocol using a gas chromatograph, the
tester must use Method 204F for the liquid steam. A gas chromatograph
is not an acceptable alternative to the FIA in Method 204A.
9. Data Analysis and Calculations
9.1 Nomenclature.
Ai=area of NDO i, ft\2\.
AN=total area of all NDO's in the enclosure, ft\2\.
CBi=corrected average VOC concentration of background
emissions at point i, ppm propane.
CB=average background concentration, ppm propane.
CDH=average measured concentration for the drift check
calibration gas, ppm propane.
CD0=average system drift check concentration for zero
concentration gas, ppm propane.
CFj=corrected average VOC concentration of uncaptured
emissions at point j, ppm propane.
CH=actual concentration of the drift check calibration gas,
ppm propane.
Ci=uncorrected average background VOC concentration at point
i, ppm propane.
Cj=uncorrected average VOC concentration measured at point
j, ppm propane.
F=total VOC content of uncaptured emissions, kg.
K1=1.830 x 10-6 kg/(m\3\-ppm).
n=number of measurement points.
QFj=average effluent volumetric flow rate corrected to
standard conditions at uncaptured emissions point j, m\3\/min.
F=total duration of uncaptured emissions sampling
run, min.
9.2 Calculations.
9.2.1 Total Uncaptured VOC Emissions.
[GRAPHIC] [TIFF OMITTED] TR16JN97.015
9.2.2 VOC Concentration of the Uncaptured Emissions at Point j.
[GRAPHIC] [TIFF OMITTED] TR16JN97.016
9.2.3 Background VOC Concentration at Point i.
[GRAPHIC] [TIFF OMITTED] TR16JN97.017
9.2.4 Average Background Concentration.
[GRAPHIC] [TIFF OMITTED] TR16JN97.018
Note: If the concentration at each point is within 20 percent of
the average concentration of all points, use the arithmetic average.
10. Method Performance
The measurement uncertainties are estimated for each uncaptured
emission point as follows: QFj=5.5 percent and
CFj=5.0 percent. Based on these numbers, the
probable uncertainty for F is estimated at about 7.4
percent.
11. Diagrams
BILLING CODE 6560-50-P
[[Page 32525]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.031
[[Page 32526]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.032
BILLING CODE 6560-50-C
[[Page 32527]]
Method 204E--Volatile Organic Compounds Emissions in Uncaptured Stream
From Building Enclosure
1. Scope and Application
1.1 Applicability. This procedure is applicable for determining
the uncaptured volatile organic compounds (VOC) emissions from a
building enclosure (BE). It is intended to be used in the development
of liquid/gas or gas/gas protocols for determining VOC capture
efficiency (CE) for surface coating and printing operations.
1.2 Principle. The total amount of uncaptured VOC emissions
(FB) from the BE is calculated as the sum of the products of
the VOC content (CFj) of each uncaptured emissions point,
the flow rate (QFj) at each uncaptured emissions point, and
time (F).
1.3 Sampling Requirements. A CE test shall consist of at least
three sampling runs. Each run shall cover at least one complete
production cycle, but shall be at least 3 hours long. The sampling time
for each run need not exceed 8 hours, even if the production cycle has
not been completed. Alternative sampling times may be used with the
approval of the Administrator.
2. Summary of Method
A gas sample is extracted from the uncaptured exhaust duct of a BE
through a heated sample line and, if necessary, a glass fiber filter to
a flame ionization analyzer (FIA).
3. Safety
Because this procedure is often applied in highly explosive areas,
caution and care should be exercised in choosing, installing, and using
the appropriate equipment.
4. Equipment and Supplies
Mention of trade names or company products does not constitute
endorsement. All gas concentrations (percent, ppm) are by volume,
unless otherwise noted.
4.1 Gas VOC Concentration. A schematic of the measurement system
is shown in Figure 204E-1. The main components are as follows:
4.1.1 Sample Probe. Stainless steel or equivalent. The probe shall
be heated to prevent VOC condensation.
4.1.2 Calibration Valve Assembly. Three-way valve assembly at the
outlet of the sample probe to direct the zero and calibration gases to
the analyzer. Other methods, such as quick-connect lines, to route
calibration gases to the outlet of the sample probe are acceptable.
4.1.3 Sample Line. Stainless steel or Teflon tubing to transport
the sample gas to the analyzer. The sample line must be heated to
prevent condensation.
4.1.4 Sample Pump. A leak-free pump, to pull the sample gas
through the system at a flow rate sufficient to minimize the response
time of the measurement system. The components of the pump that contact
the gas stream shall be constructed of stainless steel or Teflon. The
sample pump must be heated to prevent condensation.
4.1.5 Sample Flow Rate Control. A sample flow rate control valve
and rotameter, or equivalent, to maintain a constant sampling rate
within 10 percent. The flow rate control valve and rotameter must be
heated to prevent condensation. A control valve may also be located on
the sample pump bypass loop to assist in controlling the sample
pressure and flow rate.
4.1.6 Sample Gas Manifold. Capable of diverting a portion of the
sample gas stream to the FIA, and the remainder to the bypass discharge
vent. The manifold components shall be constructed of stainless steel
or Teflon. If emissions are to be measured at multiple locations, the
measurement system shall be designed to use separate sampling probes,
lines, and pumps for each measurement location, and a common sample gas
manifold and FIA. The sample gas manifold must be heated to prevent
condensation.
4.1.7 Organic Concentration Analyzer. An FIA with a span value of
1.5 times the expected concentration as propane; however, other span
values may be used if it can be demonstrated to the Administrator's
satisfaction that they would provide equally accurate measurements. The
system shall be capable of meeting or exceeding the following
specifications:
4.1.7.1 Zero Drift. Less than 3.0 percent of the span
value.
4.1.7.2 Calibration Drift. Less than 3.0 percent of
the span value.
4.1.7.3 Calibration Error. Less than 5.0 percent of
the calibration gas value.
4.1.7.4 Response Time. Less than 30 seconds.
4.1.8 Integrator/Data Acquisition System. An analog or digital
device or computerized data acquisition system used to integrate the
FIA response or compute the average response and record measurement
data. The minimum data sampling frequency for computing average or
integrated values is one measurement value every 5 seconds. The device
shall be capable of recording average values at least once per minute.
4.2 Uncaptured Emissions Volumetric Flow Rate.
4.2.1 Flow Direction Indicators. Any means of indicating inward or
outward flow, such as light plastic film or paper streamers, smoke
tubes, filaments, and sensory perception.
4.2.2 Method 2 or 2A Apparatus. For determining volumetric flow
rate. Anemometers or similar devices calibrated according to the
manufacturer's instructions may be used when low velocities are
present. Vane anemometers (Young-maximum response propeller),
specialized pitots with electronic manometers (e.g., Shortridge
Instruments Inc., Airdata Multimeter 860) are commercially available
with measurement thresholds of 15 and 8 mpm (50 and 25 fpm),
respectively.
4.2.3 Method 3 Apparatus and Reagents. For determining molecular
weight of the gas stream. An estimate of the molecular weight of the
gas stream may be used if approved by the Administrator.
4.2.4 Method 4 Apparatus and Reagents. For determining moisture
content, if necessary.
4.3 Building Enclosure. The criteria for an acceptable BE are
specified in Method 204.
5. Reagents and Standards
5.1 Calibration and Other Gases. Gases used for calibration, fuel,
and combustion air (if required) are contained in compressed gas
cylinders. All calibration gases shall be traceable to National
Institute of Standards and Technology standards and shall be certified
by the manufacturer to 1 percent of the tag value.
Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than 2 percent from the
certified value. For calibration gas values not generally available,
dilution systems calibrated using Method 205 may be used. Alternative
methods for preparing calibration gas mixtures may be used with the
approval of the Administrator.
5.1.1 Fuel. The FIA manufacturer's recommended fuel should be
used. A 40 percent H2/60 percent He or 40 percent
H2/60 percent N2 gas mixture is recommended to
avoid an oxygen synergism effect that reportedly occurs when oxygen
concentration varies significantly from a mean value. Other mixtures
may be used provided the tester can demonstrate to the Administrator
that there is no oxygen synergism effect.
5.1.2 Carrier Gas. High purity air with less than 1 ppm of organic
material (propane or carbon equivalent) or less than 0.1 percent of the
span value, whichever is greater.
[[Page 32528]]
5.1.3 FIA Linearity Calibration Gases. Low-, mid-, and high-range
gas mixture standards with nominal propane concentrations of 20-30, 45-
55, and 70-80 percent of the span value in air, respectively. Other
calibration values and other span values may be used if it can be shown
to the Administrator's satisfaction that equally accurate measurements
would be achieved.
5.2 Particulate Filter. An in-stack or an out-of-stack glass fiber
filter is recommended if exhaust gas particulate loading is
significant. An out-of-stack filter must be heated to prevent any
condensation unless it can be demonstrated that no condensation occurs.
6. Quality Control
6.1 Required instrument quality control parameters are found in
the following sections:
6.1.1 The FIA system must be calibrated as specified in section
7.1.
6.1.2 The system drift check must be performed as specified in
section 7.2.
6.1.3 The system check must be conducted as specified in section
7.3.
6.2 Audits.
6.2.1 Analysis Audit Procedure. Immediately before each test,
analyze an audit cylinder as described in section 7.2. The analysis
audit must agree with the audit cylinder concentration within 10
percent.
6.2.2 Audit Samples and Audit Sample Availability. Audit samples
will be supplied only to enforcement agencies for compliance tests. The
availability of audit samples may be obtained by writing: Source Test
Audit Coordinator (STAC) (MD-77B), Quality Assurance Division,
Atmospheric Research and Exposure Assessment Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711 or by
calling the STAC at (919) 541-7834. The request for the audit sample
must be made at least 30 days prior to the scheduled compliance sample
analysis.
6.2.3 Audit Results. Calculate the audit sample concentration
according to the calculation procedure described in the audit
instructions included with the audit sample. Fill in the audit sample
concentration and the analyst's name on the audit response form
included with the audit instructions. Send one copy to the EPA Regional
Office or the appropriate enforcement agency, and a second copy to the
STAC. The EPA Regional Office or the appropriate enforcement agency
will report the results of the audit to the laboratory being audited.
Include this response with the results of the compliance samples in
relevant reports to the EPA Regional Office or the appropriate
enforcement agency.
7. Calibration and Standardization
7.1 FIA Calibration and Linearity Check. Make necessary
adjustments to the air and fuel supplies for the FIA and ignite the
burner. Allow the FIA to warm up for the period recommended by the
manufacturer. Inject a calibration gas into the measurement system and
adjust the back-pressure regulator to the value required to achieve the
flow rates specified by the manufacturer. Inject the zero-and the high-
range calibration gases, and adjust the analyzer calibration to provide
the proper responses. Inject the low-and mid-range gases and record the
responses of the measurement system. The calibration and linearity of
the system are acceptable if the responses for all four gases are
within 5 percent of the respective gas values. If the performance of
the system is not acceptable, repair or adjust the system and repeat
the linearity check. Conduct a calibration and linearity check after
assembling the analysis system and after a major change is made to the
system.
7.2 Systems Drift Checks. Select the calibration gas that most
closely approximates the concentration of the captured emissions for
conducting the drift checks. Introduce the zero and calibration gases
at the calibration valve assembly and verify that the appropriate gas
flow rate and pressure are present at the FIA. Record the measurement
system responses to the zero and calibration gases. The performance of
the system is acceptable if the difference between the drift check
measurement and the value obtained in section 7.1 is less than 3
percent of the span value. Alternatively, recalibrate the FIA as in
section 7.1 and report the results using both sets of calibration data
(i.e., data determined prior to the test period and data determined
following the test period). The data that results in the lowest CE
value shall be reported as the results for the test run. Conduct a
system drift check at the end of each run.
7.3 System Check. Inject the high-range calibration gas at the
inlet of the sampling probe and record the response. The performance of
the system is acceptable if the measurement system response is within 5
percent of the value obtained in section 7.1 for the high-range
calibration gas. Conduct a system check before each test run.
8. Procedure
8.1 Preliminary Determinations. The following points are
considered exhaust points and should be measured for volumetric flow
rates and VOC concentrations:
8.1.1 Forced Draft Openings. Any opening in the facility with an
exhaust fan. Determine the volumetric flow rate according to Method 2.
8.1.2 Roof Openings. Any openings in the roof of a facility which
does not contain fans are considered to be exhaust points. Determine
volumetric flow rate from these openings. Use the appropriate velocity
measurement devices (e.g., propeller anemometers).
8.2 Determination of Flow Rates.
8.2.1 Measure the volumetric flow rate at all locations identified
as exhaust points in section 8.1. Divide each exhaust opening into nine
equal areas for rectangular openings and into eight equal areas for
circular openings.
8.2.2 Measure the velocity at each site at least once every hour
during each sampling run using Method 2 or 2A, if applicable, or using
the low velocity instruments in section 4.2.2.
8.3 Determination of VOC Content of Uncaptured Emissions.
8.3.1 Analysis Duration. Measure the VOC responses at each
uncaptured emissions point during the entire test run or, if
applicable, while the process is operating. If there are multiple
emissions locations, design a sampling system to allow a single FIA to
be used to determine the VOC responses at all sampling locations.
8.3.2 Gas VOC Concentration.
8.3.2.1 Assemble the sample train as shown in Figure 204E-1.
Calibrate the FIA and conduct a system check according to the
procedures in sections 7.1 and 7.3, respectively.
8.3.2.2 Install the sample probe so that the probe is centrally
located in the stack, pipe, or duct, and is sealed tightly at the stack
port connection.
8.3.2.3 Inject zero gas at the calibration valve assembly. Allow
the measurement system response to reach zero. Measure the system
response time as the time required for the system to reach the effluent
concentration after the calibration valve has been returned to the
effluent sampling position.
8.3.2.4 Conduct a system check before, and a system drift check
after, each sampling run according to the procedures in sections 7.2
and 7.3. If the drift check following a run indicates unacceptable
performance (see section 7.3), the run is not valid. Alternatively,
recalibrate the FIA as in section 7.1 and report the results using both
sets of calibration data (i.e., data determined prior to the test
period and data determined following the test period). The data that
results in the lowest CE value shall be reported as the results for
[[Page 32529]]
the test run. The tester may elect to perform drift checks during the
run, not to exceed one drift check per hour.
8.3.2.5 Verify that the sample lines, filter, and pump
temperatures are 120 5 deg.C.
8.3.2.6 Begin sampling at the start of the test period and
continue to sample during the entire run. Record the starting and
ending times, and any required process information, as appropriate. If
multiple emission locations are sampled using a single FIA, sample at
each location for the same amount of time (e.g., 2 minutes) and
continue to switch from one location to another for the entire test
run. Be sure that total sampling time at each location is the same at
the end of the test run. Collect at least four separate measurements
from each sample point during each hour of testing. Disregard the
response measurements at each sampling location until 2 times the
response time of the measurement system has elapsed. Continue sampling
for at least 1 minute, and record the concentration measurements.
8.4 Alternative Procedure. The direct interface sampling and
analysis procedure described in section 7.2 of Method 18 may be used to
determine the gas VOC concentration. The system must be designed to
collect and analyze at least one sample every 10 minutes. If the
alternative procedure is used to determine the VOC concentration of the
uncaptured emissions in a gas/gas protocol, it must also be used to
determine the VOC concentration of the captured emissions. If a tester
wishes to conduct a liquid/gas protocol using a gas chromatograph, the
tester must use Method 204F for the liquid steam. A gas chromatograph
is not an acceptable alternative to the FIA in Method 204A.
9. Data Analysis and Calculations
9.1 Nomenclature.
CDH=average measured concentration for the drift check
calibration gas, ppm propane.
CD0=average system drift check concentration for zero
concentration gas, ppm propane.
CFj=corrected average VOC concentration of uncaptured
emissions at point j, ppm propane.
CH=actual concentration of the drift check calibration gas,
ppm propane.
Cj=uncorrected average VOC concentration measured at point
j, ppm propane.
FB=total VOC content of uncaptured emissions from the
building, kg.
K1=1.830 x 10-6 kg/(m \3\-ppm).
n=number of measurement points.
QFj=average effluent volumetric flow rate corrected to
standard conditions at uncaptured emissions point j, m \3\/min.
F=total duration of CE sampling run, min.
9.2 Calculations
9.2.1 Total VOC Uncaptured Emissions from the Building.
[GRAPHIC] [TIFF OMITTED] TR16JN97.019
9.2.2 VOC Concentration of the Uncaptured Emissions at Point j.
[GRAPHIC] [TIFF OMITTED] TR16JN97.020
10. Method Performance
The measurement uncertainties are estimated for each uncaptured
emissions point as follows: QFj=10.0 percent and
CFj= 5.0 percent. Based on these numbers, the
probable uncertainty for FB is estimated at about
11.2 percent.
11. Diagrams
BILLING CODE 6560-50-P
[[Page 32530]]
[GRAPHIC] [TIFF OMITTED] TR16JN97.033
BILLING CODE 6560-50-C
[[Page 32531]]
Method 204F--Volatile Organic Compounds Content in Liquid Input Stream
(Distillation Approach)
1. Introduction
1.1 Applicability. This procedure is applicable for determining
the input of volatile organic compounds (VOC). It is intended to be
used as a segment in the development of liquid/gas protocols for
determining VOC capture efficiency (CE) for surface coating and
printing operations.
1.2 Principle. The amount of VOC introduced to the process (L) is
the sum of the products of the weight (W) of each VOC containing liquid
(ink, paint, solvent, etc.) used, and its VOC content (V), corrected
for a response factor (RF).
1.3 Sampling Requirements. A CE test shall consist of at least
three sampling runs. Each run shall cover at least one complete
production cycle, but shall be at least 3 hours long. The sampling time
for each run need not exceed 8 hours, even if the production cycle has
not been completed. Alternative sampling times may be used with the
approval of the Administrator.
2. Summary of Method
A sample of each coating used is distilled to separate the VOC
fraction. The distillate is used to prepare a known standard for
analysis by an flame ionization analyzer (FIA), calibrated against
propane, to determine its RF.
3. Safety
Because this procedure is often applied in highly explosive areas,
caution and care should be exercised in choosing, installing, and using
the appropriate equipment.
4. Equipment and Supplies
Mention of trade names or company products does not constitute
endorsement. All gas concentrations (percent, ppm) are by volume,
unless otherwise noted.
4.1 Liquid Weight.
4.1.1 Balances/Digital Scales. To weigh drums of VOC containing
liquids to within 0.2 lb or 1.0 percent of the total weight of VOC
liquid used.
4.1.2 Volume Measurement Apparatus (Alternative). Volume meters,
flow meters, density measurement equipment, etc., as needed to achieve
the same accuracy as direct weight measurements.
4.2 Response Factor Determination (FIA Technique). The VOC
distillation system and Tedlar gas bag generation system apparatuses
are shown in Figures 204F-1 and 204F-2, respectively. The following
equipment is required:
4.2.1 Sample Collection Can. An appropriately-sized metal can to
be used to collect VOC containing materials. The can must be
constructed in such a way that it can be grounded to the coating
container.
4.2.2 Needle Valves. To control gas flow.
4.2.3 Regulators. For calibration, dilution, and sweep gas
cylinders.
4.2.4 Tubing and Fittings. Teflon and stainless steel tubing and
fittings with diameters, lengths, and sizes determined by the
connection requirements of the equipment.
4.2.5 Thermometer. Capable of measuring the temperature of the hot
water and oil baths to within 1 deg.C.
4.2.6 Analytical Balance. To measure 0.01 mg.
4.2.7 Microliter Syringe. 10-l size.
4.2.8 Vacuum Gauge or Manometer. 0- to 760-mm (0- to 30-in.) Hg U-
Tube manometer or vacuum gauge.
4.2.9 Hot Oil Bath, With Stirring Hot Plate. Capable of heating
and maintaining a distillation vessel at 110 3 deg.C.
4.2.10 Ice Water Bath. To cool the distillation flask.
4.2.11 Vacuum/Water Aspirator. A device capable of drawing a
vacuum to within 20 mm Hg from absolute.
4.2.12 Rotary Evaporator System. Complete with folded inner coil,
vertical style condenser, rotary speed control, and Teflon sweep gas
delivery tube with valved inlet. Buchi Rotavapor or equivalent.
4.2.13 Ethylene Glycol Cooling/Circulating Bath. Capable of
maintaining the condenser coil fluid at -10 deg.C.
4.2.14 Dry Gas Meter (DGM). Capable of measuring the dilution gas
volume within 2 percent, calibrated with a spirometer or bubble meter,
and equipped with a temperature gauge capable of measuring temperature
within 3 deg.C.
4.2.15 Activated Charcoal/Mole Sieve Trap. To remove any trace
level of organics picked up from the DGM.
4.2.16 Gas Coil Heater. Sufficient length of 0.125-inch stainless
steel tubing to allow heating of the dilution gas to near the water
bath temperature before entering the volatilization vessel.
4.2.17 Water Bath, With Stirring Hot Plate. Capable of heating and
maintaining a volatilization vessel and coil heater at a temperature of
100 5 deg.C.
4.2.18 Volatilization Vessel. 50-ml midget impinger fitted with a
septum top and loosely filled with glass wool to increase the
volatilization surface.
4.2.19 Tedlar Gas Bag. Capable of holding 30 liters of gas,
flushed clean with zero air, leak tested, and evacuated.
4.2.20 Organic Concentration Analyzer. An FIA with a span value of
1.5 times the expected concentration as propane; however, other span
values may be used if it can be demonstrated that they would provide
equally accurate measurements. The FIA instrument should be the same
instrument used in the gaseous analyses adjusted with the same fuel,
combustion air, and sample back-pressure (flow rate) settings. The
system shall be capable of meeting or exceeding the following
specifications:
4.2.20.1 Zero Drift. Less than 3.0 percent of the span
value.
4.2.20.2 Calibration Drift. Less than 3.0 percent of
the span value.
4.2.20.3 Calibration Error. Less than 3.0 percent of
the calibration gas value.
4.2.21 Integrator/Data Acquisition System. An analog or digital
device or computerized data acquisition system used to integrate the
FIA response or compute the average response and record measurement
data. The minimum data sampling frequency for computing average or
integrated value is one measurement value every 5 seconds. The device
shall be capable of recording average values at least once per minute.
4.2.22 Chart Recorder (Optional). A chart recorder or similar
device is recommended to provide a continuous analog display of the
measurement results during the liquid sample analysis.
5. Reagents and Standards
5.1 Zero Air. High purity air with less than 1 ppm of organic
material (as propane) or less than 0.1 percent of the span value,
whichever is greater. Used to supply dilution air for making the Tedlar
bag gas samples.
5.2 THC Free N2. High purity N2 with less
than 1 ppm THC. Used as sweep gas in the rotary evaporator system.
5.3 Calibration and Other Gases. Gases used for calibration, fuel,
and combustion air (if required) are contained in compressed gas
cylinders. All calibration gases shall be traceable to National
Institute of Standards and Technology standards and shall be certified
by the manufacturer to 1 percent of the tag value.
Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than 2 percent from the
certified value. For calibration gas values not generally available,
dilution systems calibrated using Method 205 may be used. Alternative
methods for preparing
[[Page 32532]]
calibration gas mixtures may be used with the approval of the
Administrator.
5.3.1 Fuel. The FIA manufacturer's recommended fuel should be
used. A 40 percent H2/60 percent He, or 40 percent
H2/60 percent N2 mixture is recommended to avoid
fuels with oxygen to avoid an oxygen synergism effect that reportedly
occurs when oxygen concentration varies significantly from a mean
value. Other mixtures may be used provided the tester can demonstrate
to the Administrator that there is no oxygen synergism effect.
5.3.2 Combustion Air. High purity air with less than 1 ppm of
organic material (as propane) or less than 0.1 percent of the span
value, whichever is greater.
5.3.3 FIA Linearity Calibration Gases. Low-, mid-, and high-range
gas mixture standards with nominal propane concentration of 20-30, 45-
55, and 70-80 percent of the span value in air, respectively. Other
calibration values and other span values may be used if it can be shown
that equally accurate measurements would be achieved.
5.3.4 System Calibration Gas. Gas mixture standard containing
propane in air, approximating the VOC concentration expected for the
Tedlar gas bag samples.
6. Quality Control
6.1 Required instrument quality control parameters are found in
the following sections:
6.1.1 The FIA system must be calibrated as specified in section
7.1.
6.1.2 The system drift check must be performed as specified in
section 7.2.
6.2 Precision Control. A minimum of one sample in each batch must
be distilled and analyzed in duplicate as a precision control. If the
results of the two analyses differ by more than 10 percent
of the mean, then the system must be reevaluated and the entire batch
must be redistilled and analyzed.
6.3 Audits.
6.3.1 Audit Procedure. Concurrently, analyze the audit sample and
a set of compliance samples in the same manner to evaluate the
technique of the analyst and the standards preparation. The same
analyst, analytical reagents, and analytical system shall be used both
for compliance samples and the EPA audit sample. If this condition is
met, auditing of subsequent compliance analyses for the same
enforcement agency within 30 days is not required. An audit sample set
may not be used to validate different sets of compliance samples under
the jurisdiction of different enforcement agencies, unless prior
arrangements are made with both enforcement agencies.
6.3.2 Audit Samples. Audit Sample Availability. Audit samples will
be supplied only to enforcement agencies for compliance tests. The
availability of audit samples may be obtained by writing: Source Test
Audit Coordinator (STAC) (MD-77B), Quality Assurance Division,
Atmospheric Research and Exposure Assessment Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711 or by
calling the STAC at (919) 541-7834. The request for the audit sample
must be made at least 30 days prior to the scheduled compliance sample
analysis.
6.3.3 Audit Results. Calculate the audit sample concentration
according to the calculation procedure described in the audit
instructions included with the audit sample. Fill in the audit sample
concentration and the analyst's name on the audit response form
included with the audit instructions. Send one copy to the EPA Regional
Office or the appropriate enforcement agency, and a second copy to the
STAC. The EPA Regional Office or the appropriate enforcement agency
will report the results of the audit to the laboratory being audited.
Include this response with the results of the compliance samples in
relevant reports to the EPA Regional Office or the appropriate
enforcement agency.
7. Calibration and Standardization
7.1 FIA Calibration and Linearity Check. Make necessary
adjustments to the air and fuel supplies for the FIA and ignite the
burner. Allow the FIA to warm up for the period recommended by the
manufacturer. Inject a calibration gas into the measurement system and
adjust the back-pressure regulator to the value required to achieve the
flow rates specified by the manufacturer. Inject the zero-and the high-
range calibration gases and adjust the analyzer calibration to provide
the proper responses. Inject the low-and mid-range gases and record the
responses of the measurement system. The calibration and linearity of
the system are acceptable if the responses for all four gases are
within 5 percent of the respective gas values. If the performance of
the system is not acceptable, repair or adjust the system and repeat
the linearity check. Conduct a calibration and linearity check after
assembling the analysis system and after a major change is made to the
system. A calibration curve consisting of zero gas and two calibration
levels must be performed at the beginning and end of each batch of
samples.
7.2 Systems Drift Checks. After each sample, repeat the system
calibration checks in section 7.1 before any adjustments to the FIA or
measurement system are made. If the zero or calibration drift exceeds
3 percent of the span value, discard the result and repeat
the analysis. Alternatively, recalibrate the FIA as in section 7.1 and
report the results using both sets of calibration data (i.e., data
determined prior to the test period and data determined following the
test period). The data that results in the lowest CE value shall be
reported as the results for the test run.
8. Procedures
8.1 Determination of Liquid Input Weight
8.1.1 Weight Difference. Determine the amount of material
introduced to the process as the weight difference of the feed material
before and after each sampling run. In determining the total VOC
containing liquid usage, account for: (a) The initial (beginning) VOC
containing liquid mixture; (b) any solvent added during the test run;
(c) any coating added during the test run; and (d) any residual VOC
containing liquid mixture remaining at the end of the sample run.
8.1.1.1 Identify all points where VOC containing liquids are
introduced to the process. To obtain an accurate measurement of VOC
containing liquids, start with an empty fountain (if applicable). After
completing the run, drain the liquid in the fountain back into the
liquid drum (if possible), and weigh the drum again. Weigh the VOC
containing liquids to 0.5 percent of the total weight
(full) or 1.0 percent of the total weight of VOC containing
liquid used during the sample run, whichever is less. If the residual
liquid cannot be returned to the drum, drain the fountain into a
preweighed empty drum to determine the final weight of the liquid.
8.1.1.2 If it is not possible to measure a single representative
mixture, then weigh the various components separately (e.g., if solvent
is added during the sampling run, weigh the solvent before it is added
to the mixture). If a fresh drum of VOC containing liquid is needed
during the run, then weigh both the empty drum and fresh drum.
8.1.2 Volume Measurement (Alternative). If direct weight
measurements are not feasible, the tester may use volume meters and
flow rate meters (and density measurements) to determine the weight of
liquids used if it can be demonstrated that the technique produces
results equivalent to the direct weight measurements. If a single
representative mixture cannot be
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measured, measure the components separately.
8.2 Determination of VOC Content in Input Liquids
8.2.1 Collection of Liquid Samples.
8.2.1.1 Collect a 1-pint or larger sample of the VOC containing
liquid mixture at each application location at the beginning and end of
each test run. A separate sample should be taken of each VOC containing
liquid added to the application mixture during the test run. If a fresh
drum is needed during the sampling run, then obtain a sample from the
fresh drum.
8.2.1.2 When collecting the sample, ground the sample container to
the coating drum. Fill the sample container as close to the rim as
possible to minimize the amount of headspace.
8.2.1.3 After the sample is collected, seal the container so the
sample cannot leak out or evaporate.
8.2.1.4 Label the container to identify clearly the contents.
8.2.2 Distillation of VOC.
8.2.2.1 Assemble the rotary evaporator as shown in Figure 204F-1.
8.2.2.2 Leak check the rotary evaporation system by aspirating a
vacuum of approximately 20 mm Hg from absolute. Close up the system and
monitor the vacuum for approximately 1 minute. If the vacuum falls more
than 25 mm Hg in 1 minute, repair leaks and repeat. Turn off the
aspirator and vent vacuum.
8.2.2.3 Deposit approximately 20 ml of sample (inks, paints, etc.)
into the rotary evaporation distillation flask.
8.2.2.4 Install the distillation flask on the rotary evaporator.
8.2.2.5 Immerse the distillate collection flask into the ice water
bath.
8.2.2.6 Start rotating the distillation flask at a speed of
approximately 30 rpm.
8.2.2.7 Begin heating the vessel at a rate of 2 to 3 deg.C per
minute.
8.2.2.8 After the hot oil bath has reached a temperature of
50 deg.C or pressure is evident on the mercury manometer, turn on the
aspirator and gradually apply a vacuum to the evaporator to within 20
mm Hg of absolute. Care should be taken to prevent material burping
from the distillation flask.
8.2.2.9 Continue heating until a temperature of 110 deg.C is
achieved and maintain this temperature for at least 2 minutes, or until
the sample has dried in the distillation flask.
8.2.2.10 Slowly introduce the N2 sweep gas through the
purge tube and into the distillation flask, taking care to maintain a
vacuum of approximately 400-mm Hg from absolute.
8.2.2.11 Continue sweeping the remaining solvent VOC from the
distillation flask and condenser assembly for 2 minutes, or until all
traces of condensed solvent are gone from the vessel. Some distillate
may remain in the still head. This will not affect solvent recovery
ratios.
8.2.2.12 Release the vacuum, disassemble the apparatus and
transfer the distillate to a labeled, sealed vial.
8.2.3 Preparation of VOC standard bag sample.
8.2.3.1 Assemble the bag sample generation system as shown in
Figure 204F-2 and bring the water bath up to near boiling temperature.
8.2.3.2 Inflate the Tedlar bag and perform a leak check on the
bag.
8.2.3.3 Evacuate the bag and close the bag inlet valve.
8.2.3.4 Record the current barometric pressure.
8.2.3.5 Record the starting reading on the dry gas meter, open the
bag inlet valve, and start the dilution zero air flowing into the
Tedlar bag at approximately 2 liters per minute.
8.2.3.6 The bag sample VOC concentration should be similar to the
gaseous VOC concentration measured in the gas streams. The amount of
liquid VOC required can be approximated using equations in section 9.2.
Using Equation 204F-4, calculate CVOC by assuming RF is 1.0
and selecting the desired gas concentration in terms of propane,
CC3. Assuming BV is 20 liters, ML, the
approximate amount of liquid to be used to prepare the bag gas sample,
can be calculated using Equation 204F-2.
8.2.3.7 Quickly withdraw an aliquot of the approximate amount
calculated in section 8.2.3.6 from the distillate vial with the
microliter syringe and record its weight from the analytical balance to
the nearest 0.01 mg.
8.2.3.8 Inject the contents of the syringe through the septum of
the volatilization vessel into the glass wool inside the vessel.
8.2.3.9 Reweigh and record the tare weight of the now empty
syringe.
8.2.3.10 Record the pressure and temperature of the dilution gas
as it is passed through the dry gas meter.
8.2.3.11 After approximately 20 liters of dilution gas have passed
into the Tedlar bag, close the valve to the dilution air source and
record the exact final reading on the dry gas meter.
8.2.3.12 The gas bag is then analyzed by FIA within 1 hour of bag
preparation in accordance with the procedure in section 8.2.4.
8.2.4 Determination of VOC response factor.
8.2.4.1 Start up the FIA instrument using the same settings as
used for the gaseous VOC measurements.
8.2.4.2 Perform the FIA analyzer calibration and linearity checks
according to the procedure in section 7.1. Record the responses to each
of the calibration gases and the back-pressure setting of the FIA.
8.2.4.3 Connect the Tedlar bag sample to the FIA sample inlet and
record the bag concentration in terms of propane. Continue the analyses
until a steady reading is obtained for at least 30 seconds. Record the
final reading and calculate the RF.
8.2.5 Determination of coating VOC content as VOC
(VIJ).
8.2.5.1 Determine the VOC content of the coatings used in the
process using EPA Method 24 or 24A as applicable.
9. Data Analysis and Calculations
9.1. Nomenclature.
BV=Volume of bag sample volume, liters.
CC3=Concentration of bag sample as propane, mg/liter.
CVOC=Concentration of bag sample as VOC, mg/liter.
K=0.00183 mg propane/(liter-ppm propane)
L=Total VOC content of liquid input, kg propane.
ML=Mass of VOC liquid injected into the bag, mg.
MV=Volume of gas measured by DGM, liters.
PM=Absolute DGM gas pressure, mm Hg.
PSTD=Standard absolute pressure, 760 mm Hg.
RC3=FIA reading for bag gas sample, ppm propane.
RF=Response factor for VOC in liquid, weight VOC/weight propane.
RFJ=Response factor for VOC in liquid J, weight VOC/weight
propane.
TM=DGM temperature, deg.K.
TSTD=Standard absolute temperature, 293 deg.K.
VIJ=Initial VOC weight fraction of VOC liquid J.
VFJ=Final VOC weight fraction of VOC liquid J.
VAJ=VOC weight fraction of VOC liquid J added during the
run.
WIJ=Weight of VOC containing liquid J at beginning of run,
kg.
WFJ=Weight of VOC containing liquid J at end of run, kg.
WAJ=Weight of VOC containing liquid J added during the run,
kg.
9.2 Calculations.
9.2.1 Bag sample volume.
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9.2.2 Bag sample VOC concentration.
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9.2.3 Bag sample VOC concentration as propane.
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9.2.4 Response Factor.
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9.2.5 Total VOC Content of the Input VOC Containing Liquid.
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10. Diagrams
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[FR Doc. 97-15374 Filed 6-13-97; 8:45 am]
BILLING CODE 6560-50-C