Alabama Administrative Code › Title 335 - ALABAMA DEPARTMENT OF ENVIRONMENTAL MANAGEMENT › AIR DIVISION - AIR POLLUTION CONTROL PROGRAM › APPENDICES › Appendix F - FORMS

Current through Register Vol. 42, No. 9, June 28, 2024
U. S. ENVIRONMENTAL PROTECTION AGENCY CAPTURE
				  EFFICIENCY PROCEDURES
The complete text of the U. S. Environmental Protection
				  Agency's procedures to determine the capture efficiency of a volatile organic
				  compound (VOC) control system of a VOC emissions source is reproduced in this
				  Appendix.
The procedures contained in this Appendix are as
				  follows:
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)
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 and contained for discharge through ducts that
				  allow for the accurate measurement of 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.
Click to
				  view image
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 shall not continue to
				  increase, and must not exceed the safe level according to 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:
Click to
				  view image
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:
Click to
				  view image
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
(See following page)
Figure 204-1 - The Crumpler Chart
See master code for chart
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 a 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 120 ± 5 °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 °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 120
				  ± 5 °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 100 ± 5 °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
				  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
				  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 & 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.
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:
The initial (beginning) VOC containing liquid mixture.
Any solvent added during the test run.
Any coating added during the test run.
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 ±0.1 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 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 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 C and that the water bath temperature is
				  100 ± 5 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.
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.
[THETA]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.
Click to
				  view image
10.2.2
Liquid Sample Analysis System Response
				  Factor for Systems Using Integrators, Grams/Area Count.
Click to
				  view image
10.2.3
VOC Content of the Liquid Sample.
Click to
				  view image
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.
(See following pages)
Figure 204A-1 - Liquid Analysis Sample System
See master code for chart
Figure 204A-2 - VOC sampling vessel
See master code for chart
Figure 204A-3 - Critical Orifice Calibration Apparatus
See master code for chart.
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 gas/gas protocols for
				  determining VOC capture efficiency (CE) for surface coating and printing
				  operations. The procedure may not be acceptable in certain site-specific
				  situations.
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 (LC) 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.
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 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 CapturedEmissions
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 120 ± 5 °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.
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,
				  ft2.
AN = total area of all NDO's in the
				  enclosure, ft2
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.
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.
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 captured
				  emissions.
9.2 Calculations
9.2.1 Total VOC Captured Emissions.
Click to
				  view image
9.2.2 VOC Concentration of the Captured Emissions at
				  Point j.
Click to
				  view image
9.2.3 Background VOC Concentration at Point
				  I.
Click to
				  view image
9.2.4 Average Background Concentration.
Click to
				  view image
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
(See following pages)
Figure 204B-1 - Gas VOC Concentration Measurement
				  System
see master code for chart.
Figure 204B-2 - Background Measurement System
See master code for form.
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.
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 (qC) 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
				  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 a 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, 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 °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.
[THETA]C
= total duration
				  of CE sampling run, min.
9.2 Calculations
9.2.1 Total VOC Captured Emissions.
Click to
				  view image
9.2.2
VOC Concentration of the Captured
				  Emissions at Point j.
Click to
				  view image
9.2.3 Dilution Factor.
Click to
				  view image
9.2.4
Background VOC Concentration at Point
				  I.
Click to
				  view image
9.2.5
Average Background Concentration.
Click to
				  view image
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
(See following pages)
Figure 204C-1 - Capture Emissions Measurement System
see master code for form.
Figure 204C-2 - Background Measurement System
see master code for copy of form.
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 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.
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 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 emissions
				  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 tot he 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 120 ± 5 IC.
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.
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,
				  ft2.
AN
= total area of all
				  NDO's in the enclosure, ft2.
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/(m3-ppm).
n
= number of measurement points.
Qfj
= average effluent volumetric flow rate
				  corrected to standard conditions at uncaptured emissions point j,
				  m3/min.
[]
f
= total duration of uncaptured emissions
				  sampling run, min.
9.2 Calculations
9.2.1 Total VOC Fugitive Emissions.
Click to
				  view image
9.2.2
VOC Concentration of the Uncaptured
				  Emissions at Point j.
Click to
				  view image
9.2.3 Background VOC Concentration at Point
				  I.
Click to
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9.2.4 Average Background Concentration.
Click to
				  view image
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
(See following pages)
Figure 204D-1 - Fugitive emissions measurement system.
see master code for copy of chart.
Figure 204D-2 - Background measurement system
see master code for copy of chart.
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.
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 more 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 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 °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/(m3-ppm).
n
= number of measurement points.
QFj
= average effluent
				  volumetric flow rate corrected to standard conditions at uncaptured emissions
				  point j, m3/min.
[]
f
= total duration of CE sampling run,
				  min.
9.2 Calculations
9.2.1 Total VOC Uncaptured Emissions from the
				  Building.
Click to
				  view image
9.2.2
VOC Concentration of the Uncaptured
				  Emissions at Point j.
Click to
				  view image
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
(See following pages)
Figure 204E-1 - Fugitive Emissions Measurement System.
see master code for copy of form.
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°C.
4.2.6 Analytical Balance.
To measure
				  ±0.01 mg.
4.2.7 Microliter Syringe.
10-µl
				  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 °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 °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 °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 °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 calibration gas mixtures may be used with
				  prior approval of the Administrator.
5.3.1 Fuel.
The FIA manufacturer's recommended
				  fuel should be used. A mixture of 40 percent H2/60
				  percent He, or 40 percent H2/60 percent
				  N2 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
				  re-distilled 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: the initial (beginning) VOC
				  containing liquid mixture; any solvent added during the test run;
any coating added during the test run; and
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 ±0.1 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 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 °C per minute.
8.2.2.8
After the hot oil bath has reached a
				  temperature of 50°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 °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,
				  °K.
TSTD
= Standard absolute
				  temperature, 293°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
(See following pages)
Figure 204F-1 - VOC distillation system apparatus.
see master code for copy of form.
Figure 204F-2 Tedlar gas bag generation system
				  apparatus.
See Master Code for copy of form.
Author:
Statutory Authority: