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AIR MEASUREMENT SERVICES, INC.
Horizon Test No.: C33-026-FR Date Tested: December 20, 2017 Report Date: January 24, 2018 Revision Number: 0
EMISSION COMPLIANCE TEST ON LANDFILL GAS FLARE NO. 2
Chiquita Canyon Landfill
Facility ID No. 119219 Permit to Operate No. G23473 (A/N 491442)
Prepared for:
Chiquita Canyon Landfill 29201 Henry Mayo Drive
Valencia, California 91355
Prepared by.
Horizon Air Measurement Services, Inc. 310 Cortez Circle
Camarillo, California 93012
Regulatory Agency:
South Coast Air Quality Management District 21865 East Copley Drive
Diamond Bar, California 91765
nue), Sc • tt H. Bunc
Sr' •19 . ci '!na er /
l'i AV' Rich rd J. Vacherot
T hnical Director
310 CORTEZ CIRCLE, CAMARILLO, CALIFORNIA 93012 • (805) 482-8753
FAX (805) 482-8754 WWW.HORIZONAIRMEASUREMENT.COM
MI MI API!. MUM MI 4111b, -- -Il&MIff MEIJI/ IIMI Aril( MUM MI ‘1=l IM=I NMI 71 MOM IL•Mi■ l■
AIR MEASUREMENT SERVICES, INC.
January 24, 2018
Via Email & UPS Mr. Steve Cassulo Chiquita Canyon Landfill 29201 Henry Mayo Drive Valencia, California 91355
Dear Mr. Cassulo:
Please find enclosed one (1) copy of the Final Report entitled "Emission Compliance Test on Landfill Gas Flare No. 2." Please note that one (1) copy and a disc have been sent directly to Mr. Charlie Tupac with SCAQMD.
If you have any questions, please call me at (805) 482-8753.
Sincerely,
HORIZON AIR MEASUREMENT SERVICES, INC.
214. Ee,(itd1--(4) Joseph M. Bennett Technical Operations Manager
ec Mr. Solavann Sim SCS Mr. Dan Vidal, SCS Mr. Mike Dean, Chiquita Canyon
APPENDIX A - Methods Description APPENDIX B - Computer Printout of Results APPENDIX C - Field Data APPENDIX D - Laboratory Data APPENDIX E - Operating Data APPENDIX F - Strip Chart Records APPENDIX G - Calibration Data APPENDIX H - Correspondences APPENDIX I - Permit to Operate APPENDIX J - Certifications APPENDIX K - No Conflict of Interest Form
1. INTRODUCTION
Under the current facility Permit to Operate (PTO), Facility ID No. 119219 Condition 12,
Chiquita Canyon Landfill of California (CCL) is required to conduct an annual source test on the
subject landfill gas flare (Flare No. 2) located at the Chiquita Canyon Landfill in Valencia,
California. Horizon Air Measurement Services, Inc. (Horizon) has been retained to conduct the
annual compliance test.
The test program was completed on December 20, 2017 by Horizon in accordance with the
SCAQMD-approved Test Plan (Horizon No. C33-026-TP). The test was not observed by SCAQMD,
even though SCAQMD had been notified in advance. The test matrix is shown in Table 1-1.
The results of the testing program, with respect to PTO limits, are summarized in Section 2,
Summary of Results. A brief description of the flare and flare operating conditions during testing is
provided in Section 3. Section 4 provides a detailed description of the sampling/analytical techniques
utilized. Section 5 provides a more detailed results summary/discussion. A detailed quality
assurance/quality control summary is provided in Section 6.
Horizon Air Measurement Services, Inc. C33-026-FR (2018)
Note: All values preceded by "<" are below the detection limit - reported values are detection limit values.
NA - Not applicable: Destruction efficiency cannot be calculated since both inlet and outlet values are below the detection limit. Horizon Air Measurement Services, Inc. C33-026-FR (2018)
Page 14
6. QUALITY ASSURANCE/QUALITY CONTROL SUMMARY
A strict QA/QC Program was adhered to through all phases of the test program as detailed
below.
6.1 Field Sampling
6.1.1 SCAQMD Method 2.1
The SCAQMD Method 2.1 field sampling QC requirements are as follows:
properly calibrated equipment within the required time interval . successful pre and post-test leak checks . cyclonic flow check completed
proper number of sample points utilized sample locations confirmed to Method 1 requirements
. range of AP gauge used is of sufficient sensitivity for subject measurements
All Method QC requirements were successfully fulfilled.
6.1.2 SCAQMD Method 4.1
The SCAQMD Method 4.1 field sampling QC requirements are as follows:
. properly calibrated equipment within the required time interval
. successful pre and post-test leak checks
. minimum sample volume obtained
. proper chain of custody maintained
. field data sheets properly completed
. sample trains components maintained within Method temperature requirements
All Method QC requirements were successfully fulfilled.
6.1.3 SCAQMD Method 5.1
The SCAQMD Method 5.1 field sampling QC requirements are as follows:
• properly calibrated equipment within the required time interval • successful pre and post-test leak checks • minimum sample volume obtained • isokinetic rates between 90% and 110%, where applicable • proper chain of custody maintained • field data sheets properly completed
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• sample trains components maintained within Method temperature requirements • field blank sample obtained
All Method QC requirements were successfully fulfilled.
6.1.4 SCAQMD Method 25.3
The SCAQMD Method 25.3 field sampling QC requirements are as follows:
• SUMMA canisters verified to be of sufficient cleanliness • sample apparatus verified to be of sufficient cleanliness • successful pre and post-test leak checks • sample collection integrated over sample period • sample impingers stored on ice • final container pressure within Method guidelines
All Method QC requirements were successfully fulfilled.
6.1.5 SCAQMD Method 100.1
The SCAQMD Method 100.1 Continuous Emissions Monitoring System (CEMS) QC
requirements are as follows:
. measured concentrations were within the applicable measurement range of the analyzer scale used (10/20% - 95% scale)
. Sampling conditioning requirements were maintained and recorded including probe temperature, heated line temperature and knock-out temperature
. ammonia scrubber used, where appropriate
. successful system leak check
. calibration gases recorded and within certification time requirements
. a linearity check (+1%) completed at the start and end of CEMS use (per day at minimum)
. successful stratification check completed and/or stack traversed with proper number of sample ports
. successful system bias check (+5%) completed prior to sampling response times recorded
. NO2 conversion efficiency (> 90%) completed zero and calibrations drift checks (+ 3%) completed at proper intervals
. strip charts properly annotated with calibration gas values/id, calibrations, response times, sample points, start/end times, etc.
. data acquisition system (DAS) values averaged and recorded with proper annotation for calibrations, start/end times, sample ports and at a minimum of one minute intervals
Horizon Air Measurement Services, Inc. C33-026-FR (2018)
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All Method QC requirements were successfully fulfilled.
6.1.6 EPA Method TO-15
The EPA Method TO-15 field sampling QC requirements are as follows:
sample containers verified to be of sufficient cleanliness sample apparatus verified to be of sufficient cleanliness successful system pre and post-leak check sample collection integrated over sample period (+10%) sample stored properly pending analyses (tedlar bags protected from sunlight) data sheets completed
•
final container pressure within Method guidelines (if applicable) recovery study completed (if required)
All Method QC requirements were successfully fulfilled
6.1.7 SCAQMD Method 307.91
The SCAQMD Method 307.91 field sampling QC requirements are as follows:
• proper sampling container utilized (Tedlar bag with Teflon fittings or siliconized SUMMA canister)
• sample container verified to be leak-free • sample apparatus verified to be leak-free • sample containers new (Tedlar bag) or verified to be of sufficient cleanliness
(siliconized SUMMA canister)
All Method QC requirements were successfully fulfilled.
6.2 Laboratory Analyses
6.2.1 SCAQMD Method 5.1
The SCAQMD Method 5.1 analytical QC requirements are as follows:
• proper chain of custody maintained • use of approved procedures • analytical balance with current third-party certifications • analytical balance calibrations verified with Class S weights prior to analyses • proper laboratory environmental conditions maintained • samples properly stored and conditioned (dried-down, baked and desiccated) prior
to gravimetric analysis • samples achieve a consistent weight, as defined in the Method
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reagents used are of required quality field and laboratory blanks analyzed and found to be acceptable all calculations checked
All Method analytical QC requirements were successfully fulfilled.
6.22 SCAQMD Method 25.3
The SCAQMD Method 25.3 analytical QC requirements are as follows:
total concentration less than 50 ppm or condensate fraction less than 25 ppm proper chain of custody maintained
• samples analyzed within holding time
duplicate analyses within limits (<20%) calibration verification standard withing limits (85-115%) method blank within acceptable limits
• matrix spike within acceptable limits (75-125%)
All Method analytical QC requirements were successfully fulfilled
6.2.3 EPA Method TO-15
The EPA Method TO-15 analytical QC requirements are as follows:
proper chain of custody maintained samples analyzed within holding time duplicate analyses within limits
• pre and post calibration verification standard within limits (70% - 130%)
method blank within acceptable limit§ •
laboratory control spikes within recovery limits (70% - 130%)
All Method analytical QC requirements were successfully fulfilled.
6.2.4 ASTM Method D3588
The ASTM Method D3588 analytical QC requirements are as follows:
samples analyzed within holding time proper chain of custody maintained calibration verification standard within limits (85%-115%) method blank within acceptable limits
All Method laboratory QC requirements were successfully fulfilled.
Horizon Air Measurement Services, Inc. C33-026-FR (2018)
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6.2.5 SCAQMD Method 307.91
The SCAQMD Method 307.91 analytical QC requirements are as follows:
. samples analyzed within holding time
. proper chain of custody maintained
. duplicate analyses within limits (< 10%)
. calibration verification standard withing limits (95-105%)
. method blank within acceptable limits • matrix spike within acceptable limits (90-110%)
All Method analytical QC requirements were successfully fulfilled.
Horizon Air Measurement Services, Inc. C33-026-FR (2018)
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APPENDIX A - Methods Description
Horizon Air Measurement Services, Inc. C33-026-FR (2018)
Method: Sample Velocity Traverses for Stationary Sources
Principle: To aid in the representative measurements of pollutant emissions and/or total volumetric flow rate from a stationary source, a measurement site where the effluent stream is flowing in a known direction is selected, and the cross section of the stack is divided into a number of equal areas. A traverse point is then located within these equal areas. The method cannot be used when, 1) flow is cyclonic or swirling, 2) stack is small than about 0.30 meter (12 inches) in diameter or 3) the measurement of the site is less than two stack or duct diameters downstream or less than a half diameter upstream from the flow disturbance.
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Method: Stack Gas Velocity and Volumetric Flow Rate
Applicable for Methods:
EPA Method 2, CARS 2, SCAQMD Method 2.1
Principle: The average gas velocity in a stack gas is determined from the gas density and from measurement of the average velocity head with a type S or standard pitot tube.
Sampling Procedure: Set up the apparatus as shown in the figure. Measure the velocity head and
(temperature at the traverse points specified by EPA Method 2, CARB Method 2 or SCAQMD Method 2.1. Measure the static pressure in the stack and determine the atmospheric pressure. The stack gas molecular weight is determined from independent measurements of 02, CO, and H20 concentrations.
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Sample Recovery: and Analyses:
Where,
The stack gas velocity is determined from the measured average velocity head, the measured dry concentrations of 02 and CO, and the measured concentration of H2O. The velocity is determined from the following set of equations:
AP = velocity head, inches in H20 Ts = gas/temperature, degrees R Ps = absolute static pressure
Principle: A gas sample is extracted at a constant rate from the source; moisture is removed from the stream and determined either volumetrically or gravimetrically.
Sampling Procedure: Set up train as shown in the following figure. Sample is drawn at a constant rate through a sufficiently heated probe. The probe is connected to the impinger train by Teflon or glass tubing. The train consists of two greenburg smith impinger (SCAQMD 4.1) or one modified and 1 greenburg smith impinger (CARB & EPA) each containing 100 ml of water, an empty impinger as a knock-out and an impinger containing silica gel to protect the pump from moisture.
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Sample Recovery:
Following testing, moisture content is determined gravimetrically or and Analyses: volumetrically from initial and final impinger contents weights or volume.
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Method:
Reference:
Principle:
Sampling Procedure:
Sample Recovery:
Analytical Procedure:
Determination of Particulate Matter Emissions From Stationary Sources Using a Wet Impingement Train
SCAQMD Method 5.1
Stack gas is withdrawn isokinetically from the source through a sample train. Particulate matter is collected in impingers containing deionized water and on a back-up filter. The impingers are contained in an ice bath to maintain a sampled gas temperature of approximately 15° C (60° F). The filter is not heated.
The sampling train is shown in the figure below. The sample is drawn isokinetically through a glass or quartz probe (hi-temp). The probe is connected to an impinger train by Teflon tubing. The train consists of two Greenburg-Smith impingers which contain 100 ml of DI water; an empty impinger as a knock-out; and an impinger containing silica gel to protect the pump from moisture. Sample is withdrawn isokinetically from each predetermined sample point (determined using SCAQMD Method 1.1) through the sample train, which is followed by a vacuum line, a pump, a dry gas meter and a calibrated orifice.
1. 2. 3.
Temperature Sensor . Nozzle • Glass Lined Stainless Steel Probe
11. 12. 13.
Ice Bath Filter Sealed Pump (Leak Free)
4. S-type Pitdt Tube 14. Filter for Pump 5. Stack Wall 13. Metering Valve 6. Temperature Sensor Meter 16. Vacuum Gauge 7. Pizot.Tube Inclined Manometer 17. By-pass Valve -- • 8. Impinger with 100 ml 1120 18. Temperature Compensated 9. Empty Bubbler. Dry Gas Meter 10. Bubbler with Silica Gel 19. Orifice
20. Orifice Inclined Manometer
The moisture content is determined either gravimetrically or volumetrically from initial and final impinger weights or volume. Then the filter, probe/impinger rinse (including nozzle rinse, liner rinse, impinger contents and rinses) and silica gel are recovered into Containers #1, #2 and #3, respectively.
The aqueous sample is filtered through a tared fiberglass filter. An organic extraction is performed on the resulting solution using methylene chloride. Both the extraction filter and sample train filter are desiccated then measured gravimetrically. The organic extract and aqueous catch are evaporated, desiccated and measured gravimetrically.
If significant levels of sulfur compounds are present in the stack, each sample fraction is analyzed by acid-base titration for acid sulfate content and by barium-thorin titration for sulfate content.
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Method: Speciated VOC's by GC/MS Analyses or GC Analyses
Reference: EPA TO-15 (Canister Method)
Principle: A sample is collected using stainless steel canisters and analyzed using the appropriate GC or GC/MS techniques to quantify speciated volatile organic compounds.
Sampling Procedure: Sample are collected using stainless steel canisters which are evacuated to less than 10 mm Hg absolute. The tanks are pressurized and evacuated three (lines with ultrapure nitrogen and leak checked prior to use. Representative, integrated samples are collected through a heat conditioned stainless steel probe followed by a 1/4" O.D. Teflon sample line. The gas samples are metered into the canisters through the rotometer maintaining a constant flow rate throughout each sampling period.
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Method: Determination of Total Gaseous Non-Methane Organic Emissions as Carbon
Reference: SCAQMD Method 25.3
Principle: A sample of flue gas is drawn through a condensate trap (mini-impinger) and into an evacuated six liter SUMMA canister. Volatile organic compounds (VOC), as total gaseous non-methane organics (TGNMO), are determined by combining results from independent analysis of condensate in the traps and gases in the SUMMA canisters.
Sampling Procedure:
Analytical Procedure:
Duplicate gas samples are withdrawn from a source at a constant rate through condensate traps immersed in an ice bath followed by evacuated six liter (nominal) SUMMA canisters. Heavy organic components condense as liquids and solids in the condensate traps. Lighter components pass as gases through the traps into the canisters. The combined results from canisters and mini-impinger analyses are used to determine a qualitative and quantitative expression of the effluent gas stream. Duplicate sampling is designed into the system to demonstrate precision.
The sampling apparatus is checked for leaks prior to the sampling program by capping the end of the sample probe. The sample flow valve is then opened and then closed to introduce vacuum to the system. The vacuum drop should then cease numerically above 10 in. Hg. A cease in movement of the vacuum gauge for a period of ten minutes indicates an acceptable leak check. When sampling is initiated, the vacuum gauge must indicate a canister vacuum of greater than 28 in. Hg. Immediately after sampling a post-test leak check is performed, followed by a rinse of the PFA line into the condensate trap with 0.5 to 1.0 ml of hydrocarbon free water.
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Condensate traps are analyzed for total organic carbon by liquid injection into an infrared total organic carbon analyzer.
The organic content of the sample fraction collected in each canister is measured by injecting a portion into the FID/TCA analysis system which uses a two phase gas chromatography (GC) column to separate carbon monoxide (CO), methane (CH4) and carbon dioxide (CO2) from each other and from the total gaseous non-methane organics (TGNMO) which are eluted as backflush. All eluted components are first oxidized to CO, by a hopcalite catalyst and then reduced to methane by a nickel catalyst. The resulting methane is detected using the flame ionization detector. A gas standard containing CO, CH,, CO, and propane, traceable to NBS, is used to calibrated the FID/TCA analysis system.
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The continuous emissions monitoring system consists of a Thermo Electron Model 10 chemiluminescence NO/NO analyzer, a Servomex Paramagnetic 0, analyzer, a Thermo Electron Model 48C CO gas filter correlation analyzer and a Horiba PIR 2000 non dispersive infrared CO2 analyzer. All analyzer specifications are provided in Table 1. All concentrations are determined on a dry basis. Concentrations of NOR, CO, 0, and CO, are continuously recorded on a 10-inch strip chart recorder and a Daq View Data Acquisition System (DAS). The extractive monitoring system conforms with the requirements of SCAQMD Method 100.1.
The sampling probe (heated to 250°F), constructed of 1/2 inch-diameter 316 stainless steel, is connected to a condenser with a six foot length of 3/8 inch Teflon line (heated to 250°F). A Nupro stainless steel filter (10 micron) is connected at the tip of the probe and maintained at stack temperature.
The condenser consists of a series of two stainless steel moisture knock-out bottles immersed in an ice water bath. The system is designed to minimize contact between the sample and the condensate. Condensate is continuously removed from the knock-out bottles via a peristaltic pump. The condenser outlet temperature is monitored either manually at 10-minute intervals or on a strip chart recorder/DAS system. The sample exiting the condenser is then transported through a filter, housed in a stainless steel holder, followed by 3/8 inch 0.D. Teflon tubing and a Teflon coated (or stainless steel/viton) diaphragm pump to the sample manifold. The sample manifold is constructed of stainless steel tubing and directs the sample through each of four rotameters to the NO monitor, 02 monitor, CO monitor, CO2 monitor and excess sample exhaust line, respectively. Sample flow through each channel is controlled by a back pressure regulator and by stainless steel needle valves on each rotameter. All components of the sampling system that contact the sample are composed of stainless steel, Teflon or glass.
Immediately upstream of the NO. analyzer(s) is an ammonia scrubber which removes all ammonia from the sample gas stream prior to introduction to the N0. analyzer to avoid interference. The ammonia scrubber consists of a stainless steel or other nonreactive cylindrical housing which contains 135cc of Perma Pure ammonia scrubbing Media A and 65cc of scrubbing Media B.
The calibration system is comprised of two parts: the analyzer calibration and the system bias check. The calibration gases are, at a minimum, certified to ± 1% by the manufacturer. Where necessary to comply with the reference method requirements, EPA Protocol 1 gases are used. The cylinders are equipped with pressure regulators which supply the calibration gas to the analyzers at the same pressure and flow rate as the sample. The selection of zero, span or sample gas directed to each analyzer is accomplished by operation of the zero, calibration or sample selector knobs located on the main flow control panel.
For SCAQMD Method 100.1 testing, the following procedures are conducted before and after each series of test runs:
Leak Check:
The leak check is performed by plugging the end of the sampling probe, evacuating the system to at least 20 inches of Hg. The leak check is deemed satisfactory if the system holds 20 inches of Hg vacuum for five minutes with less than one inch Hg loss.
Linearity Check:
The NOx, CO, CO2 and 02 analyzers linearity check is performed by introducing, at a minimum, zero gas, mid range calibration gas (40-60% scale) and high range calibration gas (80-100% scale). Instrument span value is set on each instrument with the mid range gas. The high range calibration gas (80-100% scale) is then introduced into each instrument without any calibration adjustments. Linearity is confirmed, if all values agree with the calibration gas value to within 1% of the range.
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Stratification Check:
A stack stratificatiolicheck is performed (pre-test only) by traversing the stack with the appropriate number of traverse alternately with the reference point (center). If the gas composition is homogenous, <10% variation between any traverse points in the gas stream and the normalized average point, single point gas sampling is performed at the reference point. If stratification exceeds the 10% criteria, then the stack cross section is traversed during sampling.
System Bias Check:
The system bias check is accomplished by transporting the same gases used to zero and span the analyzers to the sample system as close as practical to the probe inlet. This is accomplished by opening a valve located on the probe, allowing the gas to flow to the probe and back through the moisture knockout and sample line to the analyzers. During this check the system is operated at the normal sampling rate with no adjustments. The system bias check is considered valid if the difference between the gas concentration exhibited by the measurement system which a known concentration gas is introduced at the sampling probe tip and when the sample gas is introduced directly to the analyzer, does not exceed ± 5% of the analyzer range.
Response Time:
Response time (upscale and downscale) for each analyzer is recorded during the system bias check. Upscale response time is defined as the time it takes the subject analyzer gas to reach 95% of the calibration gas value after introducing the upscale gas to the sample bias calibration system. Downscale response time is defined as the time it takes the subject analyzer to return to zero after the zero gas is introduced into the sample system bias calibration system.
NO Conversion Efficiency
The NO, analyzer NO2 conversion efficiency is determined by injecting a NO2 gas standard directly into the NO, analyzer (after initial calibration). The analyzer response must be a least 90% of the NO2 standard gas value.
In between each sampling run the following procedures are conducted:
Zero and Calibration Drift Check:
. Upon the completion of each test run, the zero and calibration drift check is performed by introducing zero and mid range
. calibration gases to the instruments, with no adjustments (with the exception of flow to instruments) after each test run. The analyzer response must be within ± 3% of the actual calibration gas value.
Analyzer Calibration:
Upon completion of the drift test, the analyzer calibration is performed by introducing the zero and mid range gases to each analyzer prior to the upcoming test run and adjusting the instrument calibration as necessary.
System Bias Check
(same as above)
A schematic of the sample system and specific information of the analytical equipment is provided in the following pages.
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CO GAS FILTER CORRELATION -- THERMO ELECTRON MODEL 48C
Response Time (0-95%) Zero Drift Span Drift Linearity Accuracy Operating Ranges (ppm) Output
1 minute + 0.2 ppm CO Less than 1% full scale in 24 hours + 1% full scale, all ranges + 0.1 ppm CO 10, 100, 200, 500, 1,000, 2,000, 5,000, 10,000 0-1 volt
CO2 INFRARED GAS ANALYZER -- HORIBA- PIR 2000
Response Time (0-90%)
5 seconds Zero Drift
+ 1% of full scale in 24 hours Span Drift
+ 1% of full scale in 24 hours Linearity + 2% of full scale Resolution
Less than 1% of full scale Operating Ranges (%)
0-5, 0-20 Output
0-1 volt
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TABLE 1 (Cont.)
YOKOGAWA MODEL LR8100 SIX PEN STRIP CHART RECORDER
Pen Speed up to 120 cm/min Measuring Response 0-20 volts Linearity Error 0.25% Accuracy 0.3% Zero Suppression Manual (from 1 to 10X full scale)
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Interferences: Compounds containing nitrogen (other than ammonia) may cause interference.
Response Time: 90%, 1.5 seconds (NO mode) and 1.7 seconds (NO x mode)
Sampling Procedure:
Analytical Procedure:
A representative flue gas sample is collected and conditioned using the CEM system described previously. If EPA Method 20 is used, that method's specific procedures for selecting sample points are used.
The oxides of nitrogen monitoring instrument is a chemiluminescent nitric oxide analyzer. the operational basis of the instrument is the chemiluminescent reaction of NO and ozone (03) to form NO2 inan excited state. Light emission results chemiluminescence is monitored through an optical filter by a high sensitivity photomultiplier tube, the output of which is electronically processed so it is linearly proportional to the NO concentration. The output of the instrument is in ppmV.
When NO2 is expected to be present in the flue gas, a supercooled water dropout flask will be placed in the sample line to avoid loss of NO2. Since NO2 is highly soluble in water, "freezing out" the water will allow the NO2 to reach the analyzers for analysis. The analyzer measures NO only. In the NO mode, the gas is passed through a moly converter which converts NO2 to NO and a total NOx measurement is obtained. NO2 is determined as the difference between NO and NOR. Use of a moly converter instead of a stainless steel converter eliminates NH3 interference; NH3 is converted to NO with a stainless converter, but not with a moly converter.
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Principle: A sample is continuously withdrawn from the flue gas stream, conditioned and conveyed to the instrument for direct readout of 02 concentration.
Analyzer: Servo Mex
Measurement Principle: Paramagnetic
Ranges: 0-25% 0-100%
Accuracy: 1% of full scale
Output: 0-1 V
Interferences: Halogens and halogenated compounds will cause a positive interference. Acid gases will consume the fuel cell and cause a slow calibration drift.
Response Time: 90% <60 seconds
Sampling Procedure:
Analytical Procedure:
A representative flue gas sample is collected and conditioned using the CEM system described previously. If Method 20 is used, that method's specific procedures for selecting sample points are used. Otherwise, stratification checks are performed at the start of a test program to select single or multiple-point sample locations.
An electrochemical cell is used to measure 02 concentration. Oxygen in the flue gas diffuses through a Teflon membrane and is reduced on the surface of the cathode. A corresponding oxidation occurs at the anode internally and an electric current is produced that is proportional to the concentration of oxygen. This current is measured and conditioned by the instrument's electronic circuitry to give an output in percent 02 by volume.
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Method:
Applicable Reference
Principle:
Analyzer:
Measurement Principle:
Accuracy:
Ranges:
Output:
Interferences:
Analytical Procedure:
Carbon Dioxide (CO2) by Continuous Analyzer
EPA 3A, CARB 100, BAAQMD ST-5, SCAQMD 100.1
A sample is continuously drawn from the flue gas stream, conditioned and conveyed to the instrument for direct readout of CO2 concentration.
Horiba PIR 2000
Non-dispersive infrared (NDIR)
1% of full scale
0-5%, 0-15%, 0-25%
0-1 V
A possible interference includes water. Since the instrument receives dried sample gas, this interference is not significant.
5 seconds
A representative flue gas sample is collected and conditioned using the CEM system described previously.
Carbon dioxide concentrations are measured by short path length non-dispersive infrared analyzers. These instruments measure the differential in infrared energy absorbed from energy beams passed through a reference cell (containing a gas selected to have minimal absorption of infrared energy in the wavelength absorbed by the gas component of interest) and a sample cell through which the sample gas flows continuously. The differential absorption appears as a reading on a scale of 0-100%.
Response Time:
Sampling Procedure:
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Carbon Monoxide (CO) by NDIR/Gas FilterCorrelation
EPA 10; CARB 1-100; BAAQMD ST-6, SCAQMD 100.1
A sample is continuously drawn from the flue gas stream, conditioned and conveyed to the instrument for direct readout of CO concentration.
A representative flue gas sample is collected and conditioned using the CEM system described previously. Sample point selection has been described previously.
Radiation from an infrared source is chopped and then passed through a gas filter which alternates between CO and N2 due to rotation of a filter wheel. The radiation then passes through a narrow band-pass filter and a multiple optical pass sample cell where absorption by the sample gas occurs. The IR radiation exits the sample cell and falls on a solid state IR detector.
Method:
Applicable Reference Methods:
Principle:
Analyzer:
Measurement Principle:
Precision:
Ranges:
Output:
Interferences:
Rise/Fall times (0-95%)
Sampling Procedure:
Analytical Procedure:
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Method: Sulfur Dioxide (SO2) by Pulsed Fluorescent
Principle: A sample is continuously drawn from the flue gas stream, conditioned and conveyed to the instrument for direct readout of SO2 concentration.
Interferences: Less than lower detectable limit except for the following: NO <3 ppb, m-xylene <2 ppm, H20 <2% of reading.
Response Time: 80 seconds
Sampling Procedure:
Analytical Procedure:
A representative flue gas sample is collected and conditioned using the CEM system described previously. Sample point selection has been described previously.
The sample flows into the fluorescent chamber, where pulsating UV light excites the SO2 molecules. The condensing lens focuses the pulsating UV light into the mirror assembly. The mirror assembly contains four selecting mirrors that reflect only the wavelengths which excite SO2 molecules. As excited SO2 molecules decay to lower energy states they emit UV light that is proportional to the SO2 concentration. The PMT (photomultiplier tube) detects UV light emission from decaying SO2 molecules. The PMT continuously monitors pulsating UV light source and is connected to a circuit that compensates for fluctuating in the light.
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Selected Speciated Sulfur Component Measurement by GC/MS & ELCD
This method measures selected reduced sulfur species, including carbonyl sulfide, methyl mercaptan, ethyl mercaptan, dimethyl sulfide, carbon disulfide, isopropyl mercaptan, n-propyl mercaptan, and dimethyl disulfide in gaseous sample matrix using gas chromatographic component separation and a mass spectrometer as detector. A non-polar methyl silicon capillary gas chromatographic column is used for component separation and selected ion monitoring technique is used for component detection and quantification. Sample component quantification is obtained by the external standard - method of detector calibration using multi-component gaseous standards as prepared by Scott Specialty. The lower detection limit varies by component but is at least 0.1 ppmv ethyl mercaptan (component of lowest sensitivity) for a 0.40 ml sample volume injection. The upper quantitation limit has not been tested beyond 80 ppmv dimethyl disulfide, for which response remained linear.
Hydrogen sulfide is measured by a Hall electrolytic conductivity detector operated in the oxidative sulfur mode. A Chromosil 310 column (5' x 1/8" Telfon tubing) is operated isothermally at 60°C. to separate H2S from other components in a typical sample. A separate Teflon fixed volume loop injection on a 6-port Kell-F non-metal valve is made to analyze for H2S.
Expected Lower Detection Limits: (assume 0.65 ml injection volume for H2S by Hall detector and 0.40 ml injection volume for all GC/MS measured sulfur components)
A Hewlett-Packard 5890 series II gas chromatograph (GC), Hewlett-Packard 5971A Mass Selective Detector, Pentium MS/DOS computer and HP operating software are used for all sulfur species except H2S. The GC is fitted with a heated 6-port Valco 1/16" line, sample injection valve. All gas transfer lines to the sample loop are fused silica lined Restek tubing. The fixed volume (0.40 ml) sample loop is Teflon. The transfer line from the valve to the GC column is cleaned and treated blank 0.32 mm OD fused silica line with polyimide coating.
H2S is measured using a Varian 1400 GC with the Hall oxidative quartz tube furnace and electrolytic cell attached. Nitrogen is used as carrier and air is used as the combustion gas.
Gaseous standards are prepared by Scott Specialty and are contained in two separate aluminum cylinders and a Scotty IV canister as follows:
Clean glass volumetric syringes, volumes 10, 20, & 50 ml, with smooth glass barrel (not sintered glass) are used to make volumetric dilutions of either sample or standard as necessary.
GC/MS SIM parameters: Dwell per ion start time Ions
Group 1: 75 msec. 7.0 min. 60, 34
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Group 1: Group 2: Group 3:
Group 4:
Component
Group 2: 75 msec. 10.0 min. 47,48,64
Group 3: 75 msec. 14.5 min. 47,62,76,78,43,61 88,84
Group 4: 75 msec. 19.5 min. 79,94,122,108
Group 5: 75 msec. 21.0 min. 79,80,94,108,122 126,136,140,150 154,64,66
Sulfur dioxide can included in Group chromatograph well detection limit.
Calibration:
be analyzed by monitoring mass 64 which is 2 ions, however this component does not and peak shape may result in inadequate
Gaseous standards may be analyzed prior to or after a set of samples. Response factors are determined from a single point standard calibration. Periodically multi-point calibrations are performed to verify linearity. Consistency of standard response with continuing calibrations is observed to indicate performance of multi-point calibration.
Low concentration samples may be analyzed (the lower detection limit may be extended past that using direct, whole air injection) by cryogenically focusing a measured volume of gaseous sample onto a glass bead filled Teflon loop immersed in liquid argon. The
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sample is thermally transferred upon injection by immersing the sample loop in near boiling temperature water.
Procedure:
A volumetric sample of landfill or source collected gas is transferred from a Tedlar bag sample container to the 6-port -valve injection line using a glass syringe. A Teflon loop of known volume is used to inject whole sample of expected concentration range from 0.1 to approximately 20 ppmv sulfur component. If sample concentrations exceed that of the standard, appropriate volumetric sample dilutions are made using the glass syringes with dry nitrogen diluent. Immediately after sample injection, the GC/MS is started. Standards are analyzed in the same manner as samples. Appropriate component peaks are monitored and integrated after sample analysis data set has been obtained.
Hydrogen sulfide is measured using the Hall detector by a separate direct fixed loop valve injection using Teflon loop, transfer lines, and Teflon Chromosil 310 GC column.
A response factor for a standard component is calculated as:
.rf = std. amt. / std. area
Sample concentration is calculated using the response factor:
conc. = rf x sample area
At least 10% of samples in a sample set, or minimum of one sample per set are analyzed twice to determine precision. A separate report showing repeat analyses results is included with an analytical report of sulfur component concentrations per each sample set. Repeat analyses usually agree within +/- 10% depending on component concentration level. Agreement may not be as good near the lower limit of detection. A nitrogen blank is analyzed between standards and samples to determine that there is no component carry-over. The injection loop and transfer lines are heated with clean nitrogen flush between each successive sample injection. Samples are analyzed as soon after they are received as possible, preferably same day. Samples are usually analyzed before standards to prevent carry-over, since most sulfur components measured in landfill gas samples are lower in concentration than those in the standards.
GC/MS Analysis Conditions:
GC conditions: a 30 Mx 0.2 mm, 0.50 um film methyl silicon PONA column from Hewlett-Packard is temperature programmed as follows:
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-60 degrees C, hold 3 min. 15 degrees C min. to 220 degrees C, hold 5 min.
Valve oven Temp. 98 degrees C GC/MS transfer line 180 degrees C Carrier gas is helium, pressure regulated at 21 psi.
MS Conditions:
MS calibration is performed periodically prior to performing analyses using PFTBA (perfluoro-tributylamine) as supplied by
. Hewlett-Packard and as controlled by HP software under the mid-range auto tune program. Solvent delay = 7.5 min.
Hall Detector/GC Analysis Conditions:
6 x 1/8" Teflon, Chromosil 310 analytical column 60 degrees C, isothermal Valve oven & transfer line @ room Temp. Carrier gas is nitrogen, flow rate 18 cc/min. Air oxidation gas, flow rate 18 cc/min. Quartz tube oxidation oven Temp. 630 degrees C.
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Designation: D 3588 — 98 (Reapproved 2003)
111,1 1 INTERNATIONAL
Standard Practice for Calculating Heat Value, Compressibility Factor, and Relative Density of Gaseous Fuels'
This standard is issued under the fixed designation 0 3583; the number immediately following the designation indicates the year of original adoption or in the case of revision, the year of last revision. A number in parentheses indicates the year of last rcapproval. A superscript epsilon (c) indicates an editorial change since the last revision or rcapproval.
I. Scope
1.1 This practice covers procedures for calculating heating value, relative density, and compressibility factor at base conditions (14.696 psia and 60°F (15.6°C)) for natural gas mixtures from compositional analysis.' It applies to all com-mon types of utility gaseous fuels, for example, dry natural gas, reformed gas, oil gas (both high and low Btu), propane-air, carbureted water gas, coke oven gas, and retort coal gas, for which suitable methods of analysis as described in Section 6 are available. Calculation procedures for other base conditions are given.
1.2 The values stated in inch-pound units are to be regarded as the standard. The SI units given in parentheses are for information only.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appro-priate scrfiety and health practices and determine the applica-bility of regulatory limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards: D 1717 Method for Analysis of Commercial Butane-Butene
. Mixtures and Isobutylene by Gas Chromatography' D 1945 Test Method for Analysis of Natural Gas by Gas
Chromatography' D 1946 Practice for Analysis of Reformed Gas by Gas
Chromatography" D 2163 Test Method for Analysis of Liquefied Petroleum
(LP) Gases and Propane Concentrates by Gas Chromatog- raphy' .
Thispractice is under the jurisdiction of ASTM Committee D03 on Gaseous Fuels.and is the direct responsibility of Subcommittee 1)03.03 on Determination of Heating Value and Relative Density of Gaseous Fuels.
Current edition approved May 10, 2003. Published May 2003. Originally approycd in 199S. Last previous edition approved in 1998 as 03583-98.
A more rigorous calculation of Z(T,P) at both base conditions and higher pressures can be made using the calculation procedures in "Compressibility and Super Compressibility for Natural Gas and Other Hydrocarbon Gases," American Gas Association Transmission Measurement Committee Report 8. AGA Cat. No. XQ1235, 1935, AGA, 1515 Wilson Blvd., Arlington, VA 22209.
Discontinued. Sec 1981 Annual Book grAS7'M Sun:dank, Vol 6:91. Annual Bank gr45TA1 Sun:dank, Vol 05.06.
s Annual Book grASTA1 Stantharly, Vol 05.01.
D 2650 Test Method for Chemical Composition of Gases by Mass Spectrometry'
2.2 GPA Standards: GPA 2145 Physical Constants for the Paraffin Hydrocarbons
and Other Components in Natural Gas6 GPA Standard 2166 Methods of Obtaining Natural Gas
Samples for Analysis by Gas Chromatography(' GPA 2172 Calculation of Gross Heating Value, Relative
Density, and Compressibility Factor for Natural Gas Mixtures fibril Compositional Analysis6.7
GPA Standard 2261 Method of Analysis for Natural Gas and Similar Gaseous Mixtures by Gas Chromatography6
GPA Technical Publication TP-17 Table of Physical Prop-erties of Hydrocarbons for Extended Analysis of Natural Gases'
GPSA Data Book, Fig. 23-2, Physical Constanis6 2.3 TRC Document: TRC Thermodynamic Tables—Hydrocarbons8 2.4 ANSI Standard: ANSI Z 132.1-1969: Base Conditions of Pressure and
Temperature for the Volumetric Measurement of Natural Gas9't°
3. Terminology
3.1 Definitions: 3.1.1 British thermal unit—the defined International Tables
British thermal unit (Btu). 3.1.1.1 Discussion—The defining relationships are:
'Available from Gas Processors Association, 6526 E. 69th, Tulsa, OK 74145. 'The sole source of supply or the program its either BASIC or FORTRAN
suitable for running on computers known to the committee at this time is the Gas Processors Association. If you are aware of alternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting orate responsible technical committee which you may attend.
Available from Thermodynamics Research Center, The Texas MN! University, College Station. Tx 77343-3111.
" Available from the American National Standards Institute. 25 W. 43rd St., 4th Floor, New York, NY 10036.
m Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR: D03-1007.
Copyright @ABTA/ International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United Slates.
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• D 3588
By these relationships, 1 Btu = 1 055.055 852 62 J (exact). For most putposes, the value (rounded) 1 Btu = 1055.056 .1 is adequate.
3.1.2 compressibility factor (z)—the ratio of the actual volume of a given mass of gas at a specified temperature and pressure to its volume calculated from the ideal gas law under the same conditions.
3.1.3 gross heating vahte—the amount of energy transferred as heat from the complete, ideal combustion of the gas with air, at standard temperature, in which all the water formed by the reaction condenses to liquid. The values for the pure gases appear in GM Standard 2145, which is revised annually. If the gross heating value has a volumetric rather than a mass or molar basis, a base pressure must also be specified.
3.1.4 net heating vahte—the amount of energy transferred as heat from the total, ideal combustion of the gas at standard temperature in which all the water formed by the reaction remains in the vapor state. Condensation of any "spectator" water does not contribute to the net heating value. If the net heating value has a volumetric rather than a mass or molar basis, a base pressure must also be specified.
3.1.5 relative density—the ratio of the density of the gas-eous fuel, under observed conditions of temperature and pressure, to the density of dry air (of normal carbon dioxide content) at the same temperature and pressure.
3.1.6 standard cubic jbot of gas—the amount of gas that occupies 1 ft3 (0.028 m3) at a temperature of 60°F (15.6°C) under a given base pressure and either saturated with water vapor (wet) or free of water vapor (dry) as specified (see ANSI Z 132.1). In this practice, calculations have been made at 14.696 psia and 60°F (15.6°C), because the yearly update of GPA 2145 by the Thermodynamics Research Center, on which these calculations are based, are given for this base pressure. Conversions to other base conditions should be made at the end of the calculation to reduce roundoff errors.
3.1.7 standard temperature (USA)-60°F (15.6°C). 3.2 Symbols: 3.2.1 Nomenclature: 3.2.1.1 B—second virial coefficient for gas mixture 3.2.1.2 V137 —summation factor for calculating real gas
correction (alternate method) 3.2.1.3 (cor)—corrected for water content 3.2.1.4 (dry)—value on water-free basis 3.2.1.5 e/density for gas relative to the density of air. ' 3.2.1.6 did—ideal relative density or relative molar mass,
that is, molar mass of gas relative to molar mass of air 3.2.1.7 Gid—molar mass ratio 3.2.1.8 id —gross heating value per unit mass 3.2.1.9 fr,-(1 —gross heating value per unit volume 3.2.1.10 F1 —gross heating value per unit mole 3.2.1.11 /2,1,`,/ —net heating value per unit mass 3.2.1.12 hi,f1 —net heating value per unit volume 3.2.1.13 h,i,d —net heating value per unit mole 3.2.1.14 a, b, c—in Eq 1, integers required to balance the
equation: C, carbon; H, hydrogen; S, sulfur; 0, oxygen 3.2.1.15 (id)—ideal gas state 3.2.1.16 (0—liquid phase 3.2.1.17 M—molar mass
— 98(2003)
3.2.1.18 m—mass flow rate 3.2.1.19 n—number of components 3.2.1.20 P—pressure in absolute units (psia) 3.2.1.21 Old—ideal energy per unit time released as heat
upon combustion 3.2.1.22 R—gas constant, 10.7316 psia.113/(lb mol•R) in this
practice (based upon R = 8.314 48 J/(mol-K)) 3.2.1.23 (sat)—denotes saturation value 3.2.1.24 T—absolute temperature, °R = °F + 459.67 or K=
°C + 273.15 3.2.1.25 (T, P)—value dependent upon temperature and
erty 3.2.1.29 6—repeatability of property 3.2.1.30 p—density in mass per unit volume 3.2.1.31 Ey._, —property summed for Components 1
through n, where n represents the total number of components in the mixture
3.2.2 Superscripts: 3.2.2.1 id—ideal gas value 3.2.2.2 /—liquid 3.2.2.3 a—value at saturation (vapor pressure) 3.2.2.4 '—reproducibility 3.2.3 Subscripts: 3.2.3.1 a—value for air 3.2.3.2 a—relative number of atoms of carbon in Eq 1 3.2.3.3 h—relative number of atoms of hydrogen in Eq 3.2.3.4 c—relative number of atoms of sulfur in Eq 1 3.2.3.5 j—property for component j 3.2.3.6 li—non-ideal gas property for component i 3.2.3.7 ij—non-ideal gas property for mixture of i and j 3.2.3.8 if—non-ideal gas property for component] 3.2.3.9 iv—value for water 3.2.3.10 1—property for Component 1 3.2.3.11 2—property for Component 2
4. Summary of Practice
4.1 The ideal gas heating value and ideal gas relative density at base conditions (14.696 psia and 60°F (5.6°C)) are calculated from the molar composition and the respective ideal gas values for the components; these values are then adjusted by means of a calculated compressibility factor.
5. Significance and Use
5.1 The heating value is a measure of the suitability of a pure gas or a gas mixture for use as a fuel; it indicates the amount of energy that can be obtained as heat by burning a unit of gas. For use as heating agents, the relative merits of gases from different sources and having different compositions can be compared readily on the basis of their heating values. Therefore, the heating value is used as a parameter for determining the price of gas in custody transfer. It is also an essential factor in calculating the efficiencies of energy con-version devices such as gas-fired turbines. The heating values of a gas depend not only upon the temperature and pressure, but also upon the degree of saturation with water vapor.
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0) ID 3588 - 98 (2003)
However, some calorimetric methods for measuring heating values are based upon the gas being saturated with water at the specified conditions.
5.2 The relative density (specific gravity) of a gas quantifies the density of the gas as compared with that of air under the same conditions.
6. Methods of Analysis
6.1 Determine the molar composition of the gas in accor-dance with any ASTM or GPA method that yields the complete composition, exclusive of water, but including all other com-ponents present in amounts of 0.1 % or more, in terms of components or groups of components listed in Table I. At least 98 % of the sample must be reported as individual components (that is, not more than a total of 2 % reported as groups of components such as butanes, pentanes, hexanes, butenes, and
so forth). Any group used must be one of those listed in Table 1 for which average values appear. The following test methods are applicable to this practice when appropriate for the sample under test: Test Methods D 1717, D- 1945, D 2163, and D 2650.
7. Calculation-Ideal Gas Values; Ideal Heating Value
7.1 An ideal combustion reaction in general terms for fuel and air in the ideal gas state is:
C„ft,,sc (id) + + 1114 + c)0,(id) = aCO3(id) + (1,12)1{20 (id or I)
+ 60,(irl) (I)
where id denotes the ideal gas state and / denotes liquid phase. The ideal net heating value results when all the water remains in the ideal gas state. The ideal gross heating value results when all the water formed by the reaction condenses to liquid. For water, the reduction from II,O(id) to H20(/) is fif,d.
TABLE 1 Properties of Natural Gas Components at 60°F and 14.696 psia^
Compound Formula Molar Mass, lb-lbmol-1°
Molar Mass, Ratio, Gid°
Ideal Gross Heating Value° Ideal Net Healing Value Summation Factor, b1,
A This table is consistent with GPA 2145-89, but it is necessary to use the values from the most recent edition of GPA 2145 for custody transfer calculations. o 1984 Atomic Weights: C = 12.011, H = 1.00794, 0 = 15.9994, N = 14.0067, S = 32.06. °Molar mass ratio is (he ratio of the molar mass of the gas to that of air. o Based upon ideal reaction; the entry for water represents the total enthalpy of vaporization. E Composition from: F. E. Jones, J. Res. Nat. Bur. Stand., Vol. 83, 419, 1978.
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40' D 3588 — 98 (2003)
- B. , the ideal cnthalpy of vaporization, which is somewhat larger than the enthalpy of vaporization H. - •
7.1.1 Because the gross heating value results from an ideal combustion reaction, ideal gas relationships apply. The ideal gross heating value per unit mass for a mixture, Ft', is:
H,4„1 = x .1=1 = I j
wj I j141- ±
(2)
where: xi is the mole fraction of Component/ Mi is the molar mass of Component j jkom Table I, and n is the total mtmber of components.
7.1.2 is the pure component, ideal gross heating value per unit mas for Component ] (at 60°F (15.6°C) in Table I). Values of flint,' are independent of pressure, but they vary with temperature.
7.2 Ideal Gas Density 7.2.1 The ideal gas density, pid, is:
phi = (PIR7) E
(3) J=1
where: M is the molar mass of the mixture,
(4)
P is the base pressure in absolute units (psia), R is the gas constant, 10.7316 psialt3/(lb mol•°R) in this practice, based upon R = 8.31448 .1/(mol-K), T is the base temperature in absolute units (°R = °F + 459.67). Values of the ideal gas density at 60°F (15.6°C) and 14.696 psia are in GPA Standard 2145.
7.3 Ideal Relative Density: 7.3.1 The ideal relative density did is:
= = = /14/A‘„ (5 ) J=I
where: M, is the molar mass of air. The ideal relative density is the molar mass ratio.
7.4 Gross Heating Value per Unit Vu/nine: 7.4.1 Multiplication of the gross heating value per unit mass
by the ideal gas density provides the gross heating value per unit volume, fiff / :
= rid tqiid (6)
11`,..` is the pure component gross heating value per unit volume for Component] at specified temperature and pressure (60°F (15.6°C) and 14.696 psia in Table 1, ideal gas values).
7.4.2 Conversion of values in Table 1 to different pressure bases results from multiplying by the pressure ratio:
(P) = (P = 14.696) x P/14.696 (7)
7.5 Real Gas Values—Compressibility Factor: 7.5.1 The compressibility factor is:
Z (7-,P) = plp= (MPIR7)Ip (8)
where p is the real gas density in mass per unit volume. At conditions near ambient, the truncated virial equation of state satisfactorily represents the volumetric behavior of natural gas:
Z (T.P)--= I BPIR7' (9)
where B is the second virial coefficient for the gas mixture. The second virial coefficient for a mixture is:
B = B +x ß,, + ••• + x B„„ + "I"
= E E may (10)
where Bs is the second virial coefficient for Component./ and is the second cross virial coefficient for Components i and].
The second virial coefficients are functions of temperature. Eq 9 can be used with Eq 10 for calculation of the compressibility factor for the various pressure bases, but it is not accurate at pressures greater than two atmospheres. Special treatment is not required for H, and He at mole fractions up to 0.01. Calculations can be made with Bii = 0 for hydrogen and helium.
7.5.2 Eq 9 and Eq 10 for calculation of Z(T,P) for a gas mixture are rigorous but require considerable calculations and information that is not always available. An alternative, ap-proximate expression for Z(7P) that is more convenient for hand calculations is:
z(T,P)= P{E \ 492 i= I
where 131; = BAT and Vi37. is the summation factor for 11 Component]. Values of -\/Ç at 60°F (15.6°C) appear in Table 2. The method based upon Eq II has been adopted for this practice.
7.6 Real Gas Density: 7.6.1 The real gas density p at a specific temperature and
pressure is:
P = Pid/Z, (12)
where: pid and Z are evaluated at the same temperature and pressure.
7.7 Real Relative Density: 7.7.1 The real relative density d is:
d -= pip„ = ATZ„hl,/„Z (13)
7.8 Real Heating Value—The real heating value is not given by division of the ideal heating value by the compressibility factor. Real gas heating values differ from the ideal gas values by less than one part in l04 at 14.696 psia, which is of the order of the accuracy of the heating values.
7.9 Gross Heating Value of Water Wet Gas: 7.9.1 If the gas contains water as a component but the
compositional analysis is on a dry basis, it is necessary to adjust the mole fractions to reflect the presence of water. The corrected mole fractions are:
xi(cor) = (I -x„.) (14)
The mole fraction of water can range from zero up to the saturated value. The saturated value For x„, is, assuming Raoult's Law:
x„.(sat) = P://' (15)
where: P. is the vapor pressure of water (0.256 36 psia at 60°F (15.6°C)).
7.9.2 Technically, water has a gross heating value, the ideal enthalpy of condensation. If only the water that is formed
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(0 D 3588.-98 (2003)
TABLE 2 Example Calculations of Gas Properties at 60°F and 14.696 psia (Gas Analysis on Dry Basis)I
Nora-Division (WHIP by Z does not give a real gas heating value butt rather an ideal gas heating value per real cubic feet. Ally digits carried beyond 1 part in 1000 are not significant but only allieviate roundoff error. Although CO, has a carbon atom, its a = 0 because it is not part of the Net formula
Ax,„= (0.256 36)/14.696 = 0.0174 dd (dry gas) = 0.6991 Z (dry gas) = 1 - (0.014 8112(14.696) = 0.9968 Z (dry air) = 1 - (0.005012(14.696) = 0.9996 G (dry gas, dry air) = 0.6991(0.9996)/0.9968 = 0.7011 G (dry gas, sat air) = 0.6991(0.9995)10.9968 a 0.7010 Mid (dry gas, dry air) = 1179.7 13tutr3 Htid (sat gas, dry air) = 1179.7(0.9826) = 1159.1 Eitu-fra I - 0.9826 Gid (sat gas) = 0.6991(0.9826) + 0.0174(0.622 02) = 0.6978 Z (sat gas) = 1 - (0.9826(0.014 81) + 0.0174(0.0623)12(14.696) -a 0.9964 Z (sat air) = I - (0.9826(0.0050) + 0.0174(0.0623)12(14.696) = 0.9995 G (sat gas, dry air) = 0.6978(0.9996)/0.9964 = 0.7001 G (sat gas, sat air) = 0.6978(0.9995)/0.9964 = 0.7000 (1-1012)(dry gas, dry air) = 1179.7/0.9968 = 1183.5 Eltuira (Hvid/Z) (sat gas, dry air) = 1159.11(0.9964)" 1163.3 atu-11-3
during the combustion condenses, then the heat released upon combustion of a wet gas with dry air becomes:
fir (wet gas) = (I -x„.)H 1(dry gas) (16)
For water-saturated gas, x„. at 60° F (15.6° C) is 0.256 361P1, where P1, is the base pressure. Eq 16 is adequate for custody transfer applications as a matter of definition. However, this equation does not accurately describe the effect of water upon the heating value. Appendix XI contains a rigorous examina-tion of the effect of water.
7.10 Calculation qf the Ideal Energy Released as Heal: 7.10.1 When multiplied by the gas flow rate, the ideal gross
heating value provides the ideal energy released as heat upon combustion, Oki , an ideal gas property:
= (17)
where this the mass flow rate. For an ideal gas, the mass flow tate is related to the volumetric flow rate, (Ad , by:
di = pid phi (18)
and
Old = 1.'4114/. (19)
7.10.2 The ideal gas flow rate is related to the real gas flow rate by:
= 1.117, (20)
where J' is the real gas volumetric flow rate and Z(7P) is the real gas compressibility factor at the same T and P. Hence, combining Eq 19 and Eq 20 gives:
= 1.11Z (T,P) (21)
NOTE I -Th e ideal energy released per unit time as heat upon com-bustion, ofei , can be calculated using the mass flow rate (Eq 17), the ideal gas flow rate (Eq 19), or the real gas flow rate (Eq 21), bulls always an ideal gas property. Division of ti,h./ by the gas compressibility factor ZMP) does not produce a real gas healing value but only allows calculation of (5" using the real gas flow rate rather than the ideal gas flow rate.
8. Precision
8.1 The properties reported in this practice derive from experimental enthalpy of combustion measurements which, in general, are accurate to 1 part in 1000. The extra digits that appear in the accompanying tables alleviate problems associ-ated with roundoff errors and internal consistency, but they are not significant.Table 3
8.2 The values of properties in this practice are those that appear in GPA Standard 2172-97, Fig. 23-2 of the GPSA Engineering Data Book, CPA TP-17, and the TRCThermody-namic Tables-Hydrocarbons. CPA Standard 2145 is updated annually and the values in that standard should be used in all calculations.
NOTE 2-Three sources of error must be considered: errors in heating values of the components, errors in the calculated compressibility factor, and errors in the composition. The uncertainty (twice the standard deviation) of the ideal gas heating values for components should be 0.03 %. Such errors affect the bias and the agreement between calculated and measured heating values, but they do not affect the precision. Error in the calculated compressibility factor varies with the composition of the gas, but for natural gas, this error should be less than 0.03 % and
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• D 3588 - 98 (2003)
TABLE 3 Example Calculations of Gas Properties at 60°F and 14.696 psia (Gas Analysis on Wet Basis)"
Nora-Division of fivid by Z does not give a real gas heating value but rather an ideal gas heating value per real cubic feet. Any digits carried beyond 1 part in 1000 arc not significant but only allieviate roundoff error. Although CO, has a carbon atom, its c = 0 because it is not part of the fuel formula C„11051„.
negligible compared to errors arising from uncertainty in composition. In this practice, the errors in the heating values of the components and the calculated compressibility factor, Z, are neglected. The precision of the method is related to the repeatability and reproducibility of the analysis. An example appears in .
Nora 3-It is essential to include all components in the gas sample that appear with mole fractions greater than or equal to 0.001 in the analysis. Some routine analyses do not determine compounds such as He and H,S, but these compounds arc important to the calculations.
8.3 Repeatability: 8.3.1 [fall the components are analyzed and the results are
normalized, then the repeatability of the heating value, 8/1 is:
r/ 11 = E Ulf - )8.cir (22) 11` (11' )2 J=1
8.3.2 If the results of the analysis are made to sum to 1.0 by calculating the methane mole fraction as the difference be-tween 1.0 and the sum of the mole fractions of the other components, then
SH I 1 " . - = - 2 ueatA2 Hid (23)
where 8x1 is the repeatability of the method of analysis for Component j. The differences between heating values calcu-lated from successive pairs of analysis performed by the same operator using the same sample of gas and the same instrument should exceed 28H in only 5 % of the tests when 811 is taken as one standard deviation.
8.4 Reproducibility-The reproducibility SHI is calculated from Eq 22 and Eq 23 using 8x5, the reproducibility of the method of analysis for Compound j. The diffèrence between heating values calculated from analysis obtained in different laboratories is expected to exceed 811' for only 5% of the analyses.
APPENDIXES
(Nonmandatory Information)
XI. EFFECT OF WATER UPON THE HEATING VALUE
X1.1 Custody transfer of natural gas uses a simple pricing equation that states that the cost of gas is the rate of energy released upon combustion multiplied by the price of gas per energy unit multiplied by the time or accounting period. The rate of energy released upon combustion is the product of the heating value of the gas and the flow rate of the gas. The flow rate of the gas requires knowledge of the compressibility factor and the relative density of the gas. All three custody transfer properties (heating value, compressibility factor, and relative
density) can be calculated from the composition given pure component property tables. The equations for calculating the properties of dry natural gas arc well known, but this appendix also presents an account of the effects of water contained in the gas and in the air used to burn the gas.
X I .2 The heating value of a natural gas is the absolute value of its enthalpy of combustion in an ideal combustion reaction. The heating value is, therefore, an ideal gas property
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(.0 D 3588
that can be calculated unambiguously from tables of pure component values and it has no pressure dependence.
X1.3 An ideal combustion reaction with fuel and air in the ideal gas state and the possibility of water in the fuel and air is:
where: a, p, and 1, are stoichiometric coefficients, E is the fraction excess air, the composition of air is assumed to be that of Table X1.1, n, and the moles of water contained in the gas, n. are the moles of water contained in the air, n, are the moles of water contained in the product gas mixture, n;,, are the moles of gas that actually condense, .1.'c is the mole fraction of CO, in the gas, and xN is the mole fraction of N, in the gas. If air has been injected into the gas, it is assumed that the effect is accounted for in the excess fraction E. Fuel gas mixtures would have non-integer values of a, 13 and
X1.4 It is customary to define hypothetical reference states for the water formed by the reaction denoted by Eq 1 (as opposed to "spectator" water that enters the reaction carried by the gas or air). If we assume that the water formed in the reaction remains in the ideal gas state, the heating value is termed "net." If we assume that the water formed in the reactien condenses totally to the liquid state, the heating value is termed "gross." The gross heating value is greater than the net heating value by the ideal enthalpy of vaporization for water:
-98 (2003)
where: H = enthalpy, / = liquid state, and II' = water.
The quantity H,,, (id) - fi,,.(1) is the ideal enthalpy of vaporization for water.
X1.5 It is possible to calculate a mat gas heating value rather than using a hypothetical state, but the calculations are tedious, the numerical values are negligibly different, and the mathematical simplicity of the defining equation is lost. It is customary in the gas industry to use gross heating value for most calculations, so for the remainder of this appendix, the term "heating value" refers to the gross value.
X1.6 Eq 7 in Section 7 provides the recipe to convert the heating value from one base pressure to another. Note that when using Eq 7, 11id should be calculated using the values from Table I before converting the pressure; the individual values in Table I should not be converted. Conversion to another temperature is more complicated. Heating value data exist at 25°C based upon the reaction:
X1.7 The experiments use pure oxygen and arc corrected to stoichiometric proportions. It is necessary to correct the sen-sible heat effects to arrive at a different temperature:
thrld(T) = Hnid (25) + erd_.E cirldr (X1.4)
where:
(Xi.5)
+ (a + f3/4 +1')Co, (X1.6)
heating value (gross) - healing value (net) = H„.(id)- H„.(1) and: Cil,d is the ideal specific heat at constant pressure,- /- (X1.2) denotes reactants and r' denotes products.
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= A'wd iftlid-X„.111%1 1=1
(X2.5)
D 3588 - 98 (2003)
X2. ACCOUNTING FOR WATER
X2.I If the gas contains water (or must be assumed to be saturated) but the compositional analysis is on a dry basis, it is necessary to adjust the mole fractions to account for the fact that water. has displaced some gas, thus lowering the heating value. The mole fraction of water in the gas results from the definition of relative humidity:
x„. = P„`.1 P = n„. 1(1 + n„) (X2.1)
(Based upon one mole of the fuel cHoS,i) where hv is the relative humidity of the gas, P,"„ is the vapor pressure of water, and n„. denotes moles of water: For saturated gas /7-1' is unity. Rearranging Eq X2.1 gives the moles of water:
n„. = 41(1 -xi ) (X2.2)
The corrected mole fractions then become:
Xi(cor)=x,[1 „ - = -x„Jx; (X2.3)
and the heating value becomes:
Ho' = (I -x 4, thr (X2.4) - r=t
where water is not included in the N components of the summation. If the compositional analysis determines x,„ and water is included in the N components of the summation:
X2.2 It is necessary to remove the effect of water because, although water has a heating value, it is only a condensation effect. Water carried by wet gas (spectator water) does not actually condense, and only water formed in the reaction contributes to heating value. .
X2.3 Accounting for water in the above manner is sufficient for defined custody transfer conditions, but when trying to model actual situations, the question becomes much more complicated. It is obvious that all of the reaction water actually cannot condense because in a situation in which both gas and air are thy some of the reaction water saturates the product gases and the remainder condenses. It is possible to account for these effects in a general manner. To do so, it is necessary to calculate , „ 14. , and n;„ .
n./ {a + y + (xx +.vc)/(1 + (Et + (3/4 + -y)0.00162(1 + a) (X2.8)
+3.728 73(1 + a) + 0.043 83(1 + a) + a] +
n. = + -y + (.vm + sc)1(1- xi/ - xc) + (a + 13/4 + -y)[0.001 62(1 + a)
+3.728 73(1 + a) + 0.043 83(1 + a) -I- q)(P,VP)/(1-1VP)
ni„.= 13/2 + + (X2.9)
where: h „ is the relative humidity of the air. Eq X2.6 and Eq X2.7 are reformulations of Eq X2.I to reflect inlet conditions. Eq X2.8 reflects Eq X2.1 for the saturated product gas (it must be saturated before any water can condense). Eq X2.9 is a water balance: f3/2 are the moles of water formed by the reaction, 4+ n„ are the moles of water that enter with the gas and air, /4, are the moles of water that saturate the product gas, and 14, are the moles of water that condense. Therefore, the complete correction for the effect of water on heating value is:
(I -.;,-x.) + (a + 13/4 + -y)(3.774 18 + 4.774 18 E)] X (PVP)/( I - P,)11-41.]
X2.4 Depending upon the relative humidities of the gas and air, the observed heating value can be greater or smaller than that calculated using Eq X2.4 or Eq X2.5. A humidity of air exists for each gas above which Hpid is greater than that calculated by Eq X2.4 or Eq X2.5. That critical value depends upon the gas composition, the humidity of the gas, and the amount of excess air. For pure, dry methane with no excess air, h„= 0.793 45.
X3. REAL GAS PROPERTIES
X3.1 In principal, we have enough information to convert the heating value to a real gas property (it is not necessary to do so for relative density because the molar mass ratio, Gm, is
the desired property). This is simply a matter of evaluating the integral:
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0) D 3588 — 98 (2003)
fic,{1(;) 1
I (X3.1)
where:
(,0/1) v_ T(p_V) = 8_ r_d11 = ., (LB „. _ rd./. dv P
where V is the molar volume. The temperature dependence of 1) must be defined, but in the custody transfer region it is easy to do so. The products and reactants again correspond to Eq X1.3.
X3.2 While it is obviously possible to make the required calculations to convert the heating value into a real gas
property, it serves no custody transfer purpose to do so. As we have seen, the cost equation is unchanged; the calculations while obvious are tedious. Hi' is slightly different from Hvid because the base pressure is low; the likelihood of having all the information required to use Eq X3.1 is remote, The heating value is defined in a hypothetical state. It is not possible, at base conditions, to have all the water formed in the reaction be either all gas or all liquid; some of the water formed is in each state. Thus, if the definition is of a hypothetical state, using a hypothetical real gas rather than an ideal gas state adds nothing but complexity.
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TABLE I Natural Gas Components and Range of Composition Covered
0.01 to 10 0.01 to 10 0.01 to 20 0.01 to 100 0.01 to 20 0.01 to 100 0.01 to 100 0.3 to 30 0.01 to 100 0.01 to 10 0.01 to 10 0.01 to 2 0.01 to 2 0.01 to 2 0.01 to '2 0.01 to
composition of the sample is calculated by comparing either the peak heights, or the peak areas, or both, with the corre-sponding values obtained with the reference standard.
4. Significance and Use • 4.1 This test method is of significance for providing data for
calculating physical properties of the sample, such as heating value and relative density, or for monitoring the concentrations of one or more of the components in a mixture.
5. Apparatus
5.1 Detector-The detector shall be a thenital-conductivity type, or its equivalent in sensitivity and stability. The thermal conductivity detector must be sufficiently sensitive to produce a signal of at least 0.5 mV for I mol % n-butane in a 0.25-mL sample.
5.2 Recording Instruments-Either strip-chart recorders or electronic integrators, or both, are used to display the separated components. Although a strip-chart recorder is not required when using electronic integration, it is highly desirable for evaluation of instrument performance.
5.2.1 The recorder shall be a strip-chart recorder with a full-range scale of 5 mV or less (1 mV preferred), The width of the chart shall be .not less than 150 mm. A maximum pen response time of 2s (1 s preferred) and a minimum chart speed of 10 rrunimin shall be required. Faster speeds up to 100 mm/min are desirable if the chromatogram is to be interpreted using manual methods to obtain areas.
Designation: D 1945 - 03 _251110 iivrontanormt.
Standard Test Method for Analysis of Natural Gas by Gas Chromatographyl
This standard is issued under the fixed designation D 1945; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval.A superscript epsilon (c) indicates an editorial change since the last revision or reapproval.
1. Scope*
1.1 This test method covers the determination of the chemi-cal composition of natural gases and similar gaseous mixtures within the range of composition shown in Table I. This test method may be abbreviated for the analysis of lean natural gases' containing negligible amounts of hexanes and higher hydrocarbons, or for the determination of one or more compo-nents, as required.
1.2 The values stated in sr units are to be regarded as the standard. The values given in parentheses are for information only.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.
2. Referenced Documents 2.1 ASTM Standards: D 2597 Test Method for Analysis of Demethanized Hydro-
carbon Liquid Mixtures Containing Nitrogen and Carbon Dioxide by Gas Chromatography2
D 3588 Practice for Calculating Heat Value, Compressibil-ity Factor, and Relative Density (Specific Gravity) of Gaseous Fuels3
E 260 Practice for Packed Column Gas Chromatography4
3. Summary of Test Method
3.1 Components in a representative sample are physically separated by gas chromatography (GC) and compared to calibration data obtained under identical operating conditions from a reference standard mixture of known composition. The numerous heavy-end components of a sample can be grouped into irregular peaks by reversing the direction of the carrier gas through the'column at such time as to group the heavy ends either as Cs and heavier, C6 and heavier, or C. and heavier. The
I This test method is under the jurisdiction ofASTM Committee 003 on Gaseous Fuels and is the direct responsibility of Subcommittee 003.07 on Analysis of Chemical Composition of Gaseous Fuels.
Current edition approved May 10, 2003. Published July 2003, Originally approved in 1962. Last previous edition approved in 2001 as D1945-96(2001).
2 Annual Book of ASTM Standard; Vol 05.02. 3 Annual Book of ASTM Standards, Vol 05.05. 4 Annual Book of ASTM Standards, Vol 14.02.
*A Summary of Changes section appears at the end of this standard.
4,4hi ASTM Into ma Waal Lad by INS undor (Ica nso with ASTM
... _ . . Sold to:HORIZON AR MEASUREMENT. C116703013
CARRIER TO • GAS COLUMI■T
GAS CHRO TOGRAPH SAMPLE VALVE
SAMPLE MANOMETER
CYLINDER
NEEDLE VALVE
TO VACUUM
UMP
VENT
!I
D 1945 — 03
if
5.2.2 Electronic or Computing Integrators—Proof of sepa-ration and response equivalent to that for a recorder is required for displays other than by chart recorder. Baseline tracking with tangent skim peak detection is recommended.
5.3 Attenuator—If the chromatogram is to be interpreted using manual methods, an attenuator must be used with the detector output signal to maintain maximum peaks within the recorder chart range. The attenuator must be accurate to within 0.5 % between the attenuator range steps.
5.4 Sample Inlet System: The sample inlet system shall be constructed of
materi4s that are inert and nonadsorptive with respect to the compofients in the sample. The preferred material of construc-tion is htainless steel. Copper, brass, and other copper-bearing alloys"p.re unacceptable. The sample inlet system from the cylindef valve to the GC column inlet must be maintained at a temperature constant to ±1°C.
5.4.2 Provision must be made to introduce into the carrier gas ahead of the analyzing column a gas-phaie sample that has been entrapped in a fixed volume loop or tubular section. The fixed loop or section shall be so constructed that the total volume, including dead space, shall not normally exceed 0.5 InL at 1 atm. If increased accuracy of the hexanes and heavier portions of the analysis is required, a larger sample size may be used (see Test Method D 2597). The sample volume must be reproducible such that successive runs agree within 1 % on each component. A flowing sample inlet system is acceptable as long as viscosity effects are accounted for.
Nora 1—The sample size limitation of 0.5 rnL or smaller is selected relative to linearity of detector response, and efficiency of column separation. Larger samples may be used to determine low-quantity components to increase measurement accuracy.
5.4.3 An optional manifold arrangement for entering vacuum samples is shown in Fig. 1.
5.5 Column Temperature Control: 5.5.1 Isothermal—When isothermal operation is used,
maintain the analyzer columns at a temperature constant to 0.3°C during the course of the sample run and corresponding reference run.
5.5.2 Temperature Programming—Temperature program-ming may be used, as feasible. The oven temperature shall not exceed the recommended temperature limit for the materials in the column.
5.6 Detector Temperature Control—Maintain the detector temperature at a temperature constant to 03°C during the course of the sample run and the corresponding reference run. The detector temperature shall be equal to or greater than the maximum column temperature.
5.7 Carrier Gas Controls—The instrument shall be equipped with suitable facilities to provide a flowof carrier gas through the analyzer and detector at a flow rate that is constant to 1 % throughout the analysis of the sample and the reference standard. The purity of the carrier gas may be improved by flowing the carrier gas through selective filters prior to its entry into the chromatograph.
5.8 Columns: 5.8.1 The columns shall be constructed of materials that are
inert and nonadsorptive with respect.to the components in the sample. The preferred material of construction is stainless steel. Copper and copper-bearing alloys are unacceptable.
5.8.2 An adsorption-type column. and a partition-type col-umn may be used to make the analysis.
Nom 2—See Practice E 260.
• 5.8.2.1 Adsorption Column—This column must completely separate oxygen, nitrogen, and methane. A 13K molecular sieve 80/100 mesh is recommended for direct injection. A 5A column can be used if a pre-cut column is present to remove interfering hydrocarbons. If a recorder is used, the recorder pen must return to the baseline between each successive peak. The resolution (R) must be 1.5 or greater as calculated in the following equation:
x2 — R(1,2) — + X 2, (I)
Y2
where ,c1, x2 are the retention times and yfi y2 are the peak widths. Fig. 2 illustrates the calculation for resolution. Fig. 3 is a chromatogram obtained with an adsorption column.
TO (-->- MERCURY
TRAP
FIG. I Suggested Manifold Arrangement for Entering Vacuum Samples
-33. lOhI ASTM Inlamattonal 2
lad by IHS UndOr lica n a with ASTM
Sold (o:HOR I ZO N AIR MEASUREMENL 0 I 670300 .....rfssettrvl m neAc•emirtnn rvstrn;tio4U.1■ 1,,trt (rrtrn IttS
2i017/11m) n.ocvni ((Ur
D 1945 — 03
CD
RETENTION FIG. 2 Calculation for Resolution
COLUMN: 2 meter Type 13X molecular sieve, 80-100 mesh
SAMPLE SIZE: 0.25 mL,
CARRIER GAS: Helium @ 30 .mL • imin •
4 Minutes
FIG. 3 Separation Column for Oxygen, Nitrogen, and Methane (See Annex A2)
5.8.2.2 Partition Column—This column must separate ethane through pentanes, and carbon dioxide. If a recorder is used, the recorder pen must return to the base line between each peak for propane and succeeding peaks, and to base line within 2 % of full-scale deflection for components eluted ahead of propane, with measurements being at the attenuation of the peak. Separation of carbon dioxide must be sufficient so that a 0.25-mL sample containing 0.I-mol % carbon dioxide will produce a clearly measurable response. The resolution (R) must be 1.5 or greater as calculated in the above equation. The separation should be completed within 40 min, including reversal of'flow after n-pentane to yield a group response for hexanes and heavier components. Figs. 4-6 are examples of chromatograms obtained on some of the suitable partition columns.
5.8.3 General—Other column packing materials that pro-vide satisfactory separation of components of interest may he used (see Fig. 7). In multicolumn applications, his preferred to use front-end backflush of the heavy ends.
NOTE 3—The chromatograms in Figs. 3-8 are only illustrations of typical separations. The operating conditions, including columns, are also typical and are subject to optimization by competent personnel.
5.9 Drier—Unless water is known not to interfere in the analysis, a drier must be provided in the sample entering system, ahead of the sample valve. The drier must remove moisture without removing selective components to be deter-mined in the analysis.
NOTE 4—See A2.2 for preparation of a suitable drier. -34- 3 Jot ASTM Intomationtl
tad by IHS undar liconin with Acru
D 1945 — 03
C0LUMN-25% MEE on Chromosorb P, 7 meters @ 25°C CARRIER GAS: Helium @ 40 mL./min. SAMPLE SIZE: 0.25 mt.
18 16 14 12
Minutes FIG. 4 Chromatogram of Natural Gas (MEE Column) (See Annex A2)
* COLUMN: Chromemorb PAW, 20.0/500, lom
CARRIER GAS: Helium @ 40 mL./min.
SAMPLE SIZE: 0.25 /a,.
30 25 20
15 10 5
0
Minutes FIG. 5 Chromatogram of Natural Gas (Silicone 200/500 Column) (See Annex A2)
5.10 Valves—Valves or sample splitters, or both, are re-quired to permit switching, backflushing, or for simultaneous analysis.
5.11 Manometer—May be either U-tube type or well type equipped with an accurately graduated and easily read scale covering the range 0 to 900 mm (36 in.) of mercury or larger. The U-tube type is useful, since it permits filling the sample loop with up to two atmospheres of sample pressure, thus
extending the range of all components. The well type inher-ently offers better precision and is preferred when calibrating with pure components. Samples with up to one atmosphere of pressure can be entered. With either type manometer the mm scale can be read more accurately than the inch scale. Caution should be used handling mercury because of its toxic nature. Avoid contact with the skin as much as possible. Wash thoroughly after contact. 35-
Tight ASTM Intomattonet 4
'clod by IHS todor Ilcatuo with ASTM
Sold to:HORIZON AIR MEASUREMENT. 01670300
111„ D 1 9 4 5 — 03
COLUMN:
DIDP-3me ter +DMS -6me ter @ 35°C.
CARRIER GAS: Helium @ 75 mL. /min.
SAMPLE SIZE: 0.5
N r. 1 r 4 P4 P-r 0 i va Z H
, I 20 18 16 14 12
Minutes FIG. 6 Chromatogram of Natural Gas (See Annex A2)
FIG. 7 Chromatogram of Natural Gas (Muiti-Column Application) (See Annex A2)
5.12 Vacuum Pump—Must have the capability of producing a vacuum of 1 mm of mercury absolute or less.
6. Preparation of Apparatus 6.1 Linearity Check—To establish linearity of response for
the thermal conductivity detector, it is necessary to complete the following procedure:
6.1.1 The major component of interest (methane for natural gas) is charged to the chromatograph by way of the fixed-size sample loop at partial pressure increments of 13 kPa (100 mm Hg) from 13 to 100 kPa (100 to 760 mm Hg) or the prevailing atmospheric pressure.
- 3 6 -
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5 rd bYIHS undarkanso with ASPA
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• D 1945 — 03
2 meter x 3mm mol. sieve 13x @ 50 C Argon carrier @ 40 ml,./min. Detector @ 100mA.
5 4 3
2 1
Minutes FIG. 8 Separation of Helium and Hydrogen
6.1.2 The integrated peak responses for the area generated at each cif the pressure increments are plotted versus their partial pressttre (see Fig. 9).
6.1:3 The plotted results should yield a straight line. A perfe4ly linear response would display a straight line at a 450 angle using the logarithmic values.
6.1.4 Any curved line indicates the fixed volume sample loop is too large. A smaller loop size should replace the fixed volume loop and 6.1.1 through 6.1.4 should be repeated (see Fig. 9).
6.1.5 The linearity over the range of interest must be known for each component. It is useful to construct a table noting the response factor deviation in changing concentration. (See Table 2 and Table 3).
6.1.6 It should be noted that nitrogen, methane, and ethane exhibit less than 1 % compressibility at atmospheric pressure. Other natural gas components do exhibit a significant com-pressibility at pressures less than atmospheric.
6.1.7 Most components that have vapor pressures of less than 100 kPa (15 psia) cannot be used as a pure gas for a linearity study because they will not exhibit sufficient vapor pressure for a manometer reading to 100 kPa (760 mm Hg). For these components, a mixture with nitrogen or methane can be used to establish a partial pressure that can extend the total pressure to 100 kPas (760 mm Hg). Using Table 4 for vapor pressures at 38°C (100°F), calculate the maximum pressure to which a given component can be blended with nitrogen as follows:
B --= (100 X V)Ii
P = (i x A4)1100
ASTM tod by MS undo( ken] a whh AST!. I...4ml L-4,1 ne natwn4Inn nemn:thui 2MOt 1LInn n fenm IRS
where: B = blend pressure, max, kPa (mm Hg); V = vapor pressure, kPa (mm Hg);
= mol %; P = partial pressure, kPa (mm Hg); and M = manometer pressure, kPa (mm Hg).
6.2 . Procedure for Linearity Check: 6.2.1 Connect the pure-component source to the sample-
entry system. Evacuate the sample-entry system and observe the manometer for leaks. (See Fig. 1 for a suggested manifold arrangement.) The sample-entry system must be vacuum tight.
6.2.2 Carefully open the needle valve to admit the pure component up to 13 kPa (100 mm Hg) of partial pressure.
6.2.3 Record the exact partial pressure and actuate the sample valve to place the sample onto the column, Record the peak area of the pure component.
6.2.4 Repeat 6.2.3 for 26, 39, 52, 65, 78, and 91 kPa (200, 300, 400, 500, 600, and 700 mm Hg) on the manometer, recording the peak area obtained for sample analysis at each of these pressures.
6.2.5 Plot the area data (x axis) versus the partial pressures (y axis) on a linear graph as shown in Fig. 9.
6.2.6 An alternative method is to obtain a blend of all the components and charge the sample loop at partial pressure over the range of interest. If a gas blender is available, the mixture can be diluted with methane thereby giving response curves for all the components. (Warning—If it is not possible to obtain information on the linearity of the available gas chrernatograph detector for all of the test gas components, then as a minimum requirement the linearity data must be obtained for any gas
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(2)
(3)
6
D 1945 - 03
* 1111111111111111111111111111111111111 I i Illi
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7
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00 II
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component that exceeds a concentration of 5 mol%. Chromato-graphs are not truly linear over wide concentration ranges and linearity should be established over the range of interest.)
7. Reference Standards
7.1 Moisture-free gas mixtures of known composition are required for comparison with the test sample. They must contain known percents of the components, except oxygen (Note 5), that are to be determined in the unknown sample. All components in.the reference standard must be homogenous in the vapor state at the time of use. The concentration of a component in the reference standard gas should not be less than
one half nor more than twice the concentration of the corre-sponding component in the test gas.
Nora 5-Unless the reference standard is stored in a container that has been tested and proved for inertness to oxygen, it is preferable to calibrate for oxygen by an alternative method.
7.2 Preparation-A reference standard may he prepared by blending pure components. Diluted dry air is a suitable standard for oxygen and nitrogen (see 8.5.1 ).5.6
5 A suitable reference standard is available from Scott Specialty Gases Inc., Plumsteadville, PA.
AThe most recant data for the vapor pressures listed are available from the Thermodynamics Research Center, Texas A&M University System, College Sta-tion, TX 77843.
8. Procedure 8.1 Instrument Preparation—Place the proper column(s) in
operation as needed for the desired run (as described in either 8.4, 8.5, or 8.6). Adjust the operating conditions and allow the chromatograph to stabilize.
8.1.1 For hexanes and higher, heat the sample loop.
Nors 6—Most modern chromatographs have valve ovens that can be temperature controlled. It is strongly recommended in the absence of valve ovens to mount the gas sampling valve in the chromatograph oven and operate at the column temperature.
8.1.2 After the instrument has apparently stabilized, make check runs on the reference standard to establish instrument repeatability. Two consecutive checks must agree within the repeatability limits for the mol % amount present of each component. Either the average of the two consecutive checks, or the latest check agreeing within the repeatability limits of the previous check on each component may be used as the reference standard for all subsequent runs until there is a change in instrument operating conditions. Daily calibrations are recommended.
8.2 Sample Preparation—If desired, hydrogen sulfide may be removed by at least two methods (see Annex A2.3A2.3).
8.2.1 Preparation and Introduction of Sample—Samples must be equilibrated in the laboratory at 20 to 50°F above the source temperhture of the field sampling. The higher the temperature the shorter the equilibration time (approximately 2 h for small sample containers of 300 mLor less). This analysis method assumes field sampling methods have removed en-trained liquids. If the hydrocarbon dewpoint of the sample is known to be lower than the lowest temperature to which the sample has been exposed, it is not necessary to heat the sample.
8.2.2 Connections from the sample container to the sample inlet of the instrument should be made with stainless steel or with short pieces of 'llih,-fluorocarbon. Copper, vinyl, or rubber connections are not acceptable. Heated lines may be necessary for high hydrocarbon content samples.
8.3 Sample Intmduction—The size of the sample introduced to the chromatographic columns shall not exceed 0.5 mL. (This
6 A ten-component reference standard traceable to the National Institute of Standards and Technology (141ST) is available from Institute of Gas Technology (IGT), 3424 S. State Sc.. Chicago, IL 60616.
••••••...
(gay D 1945 — 03
small sample size is necessary to obtain a linear detector response for methane.) Sufficient accuracy can be obtained for the determination of all but the minor constituents by the use of this sample size. When increased response is required for the determination of components present in concentrations not exceeding 5 mol %, it is permissible to use sample and reference standard volumes not exceeding 5 mL. (Avoid introduction of liquids into the sample system.)
8.3.1 Purging Method—Open the outlet valve of the sample cylinder and purge the sample through the inlet system and sample loop or tube. The amount of purging required must be established and verified for each instrument. The sample loop pressure should be near atmospheric. Close the cylinder valve and allow the pressure of the sample in the loop or tube to stabilize. Then immediately inject the contents of the loop or tube into the chromatographic column to avoid infiltration of contaminants.
8.3.2 Water Displacement—If the sample was obtained by water displacement, then water displacement may be used to purge and filI the sample loop or tube. (Warning—Some components, such as carbon dioxide, hydrogen sulfide, and hexanes and higher hydrocarbons, may be partially or com-pletely removed by the water.) •
8.3.3 Evacuation Method—Evacuate the charging system, including the sample loop, and the sample line back to the valve on the sample cylinder, to less than 0.1 kPa (1 rum fig) absolute pressure. Close the valve to the vacuum source and .carefully meter the fuel-gas sample from the sample cylinder until the sample loop is filled to the desired pressure, as indicated on the manometer (see Fig. 1). Inject thesample into the chromatograph.
8.4 Partition Column Run for Ethane and Heavier Hydro-carbons and Carbon Dioxide —This run is made using either helium or hydrogen as the carrier gas; if other than a .thermal conductivity detector is used, select a suitable carrier gas for that detector. Select a sample size in accordance with 8.1. Enter the sample, and backflush heavy components when appropri-ate. Obtain a corresponding response on the reference standard.
8.4.1 Methane may also be determined on this column if the column will separate the methane from nitrogen and oxygen (such as with silicone 200/500 as shown in Fig. 5), and the sample size does not exceed 0.5 mL.
8.5 Adsorption Column Run for Oxygen, Nitrogen, and Methane—Make this run using helium or hydrogen as the carrier gas. The sample size must not exceed 0,5 mr... for the determination of methane. Enter the sample and obtain .a response through methane (Note 5). Likewise, obtain a re-sponse on the reference standard for nitrogen and methane. Obtain a response on dry air for nitrogen and oxygen, if desired. The air must be either entered at an accurately measured reduced pressure, or from a helium-diluted mixture.
8.5.1 A mixture containing approximately 1 % of oxygen can be prepared by pressurizing a container of dry air at atmospheric pressure to 2 MPa (20 atm) with pure helium. This pressure need not be measured precisely, as the concentration of nitrogen in the mixture thus prepared must be determined by comparison to nitrogen in the reference standard. The percent nitrogen is multiplied by 0.268 to obtain the mole percent of
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oxygen or by 0.280 to obtain the mole percent total of oxygen and argon. Do not rely on oxygen standards that have been prepared for more than a few days. It is permissible to use a response factor for oxygen that is relative to a stable constitu-ent.
8.6 Adsorption Column Run for Helium and Hydrogen-Make this run using either nitrogen or argon as the carrier gas. Enter a 1- to 5-mL sample and record the response for helium, followed by hydrogen, which will be just ahead of oxygen (Note 5). Obtain a corresponding response on a reference standard containing suitable concentrations of helium and hydrogen (see Fig. 8).
9. Calculation
9.1 The number of significant digits retained for the quan-titative value of each component shall be such that accuracy is neither sacrificed or exaggerated. The expressed numerical value of any component in the sample should not be presumed to be more accurate than the corresponding certified value of that component in the calibration standard.
9.2 External Standard Method: 9.2.1 Pentanes and Lighter Components-Measure the
height of each component peak for pentanes and lighter, convert to the same attenuation for corresponding components in the sample and reference standard, and calculate the con-centration of each component ih the sample as follows:
c = s x (NB) (4)
whOre: C 5= component concentration in the sample, mol %; A 3:= peak height of component in the sample, mm; B f:= peak height of component in the standard, mm; and S component concentration in the reference standard,
mol %. 9.2.1.1 If air has been run at reduced pressure for oxygen or
nitrogen calibration, or both, correct the equation for pressure as follows:
C = S X (AIB) X (Pall3b) (5)
where:.
•
= pressure at which air is run and Ph = true barometric pressure during the run, with both
pressures being expressed in the same units. 9.2.1.2 Use composition values of 78.1 % nitrogen and
21.9 % oxygen for dry air, because argon elutes with oxygen on a molecular sieves column under the normal conditions of this test method.
9.2.2 Hexanes and Heavier Components-Measure the ar-eas of the hexanes portion and the heptanes and heavier portion of the reverse-flow peak (see Annex Al, Fig. AI.1, and X3.6). Also measure the areas of both pentane peaks on the sample chromatogram, and adjust all measured areas to the same attenuation basis.
9.2.3 Calculate corrected areas of the reverse flow peaks as follows:
where A = average molecular weight of the C7 and heavier fraction.
Nam 7-The value of 98 is usually sufficiently accurate for use as the C 7 and heavier fraction average molecular weight; thesmall amount of CH and heavier present is usually offset by the lighter methyl cyclopentane and cyclohexane that occur in this fraction. A more accurate value for the molecular weight of C7 and heavier can be obtained as described in Annex A1.3.
9.2.4 Calculate the concentration of the two fractions in the sample as follows: Mol % C6 = (corrected C6 area) X (mol % aC5)/(iC5 -1- itC5 area). (8)
9.2.4.1 If the mole percent of iC5 +nC5 has been deter-mined by a separate run with a smaller sized sample, this value need not be redetermined.
9.2.5 The entire reverse flow area may be calculated in this manner as C6 and heavier, or as C5 and heavier should the carrier gas reversal be made after n-butane. The measured area should be corrected by using the average molecular weights of the entire reverse-flow components for the value of A. The - mole percent and area of the iCs and nC5 reverse flow peak of an identically sized sample of reference standard (free of C6 and heavier) shall then be used for calculating the final mole percent value.
9.2.6 Normalize the mole percent values by multiplying each value by 100 and dividing by the sum of the original values. The sum of the original values should not differ from 100.0 % by more than LO %.
9.2.7 See sample calculations in Appendix X2.
10. Precision 10.1 Precision-The precision of this test method, as deter-
mined by the statistical examination of the interlab oratory test results, for gas samples of pipeline quality 38 WIT/m3 (1000 Iitu/SCF) is as follows:
10.1.1 Repeatability-The difference between two succes-sive results obtained by the same operator with the same apparatus under constant operating conditions on identical test materials should be considered suspect if they differ by more than the following amounts:
Component, mol % Repealebility
0 to 0.09 001 0.1 to 0.9 0.04 1.010 4.9 0.07 5.0 to 10 0.00 Over 10 0.10
10.1.2 Reproducibility-The difference between two results obtained by different operators in different laboratories on identical test materials should be considered suspect if they differ by more than the following amounts:
Component, mot % Reproducibility
Corrected C6 area = 72/86 X measured C6 area (6)
Corrected C7 and heavier area = 72/A X measured C7 and heavier area (7)
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0 to 0.09
0.02 0.1 to 0.9
0.07 1.0 10 4.9
0.10 5.0 to 10
0.12 Over to
0.15
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440 D 1945 — 03
11. Keywords 11.1 gas analysis; gas chromatography; natural gas compo-
sition !'
3 ANNEXES
(Mandatory Information)
AL SUPPLEMENTARY PROCEDURF.S
A1.1 Analysis for Only Propane and Heavier Components
A1.1.1 This determination can be made in 10- to I5-min run time by using column conditions to separate propane, isobu-tane, n-butane, isopentarie, n-pentane, hexanes, and heptanes, and heavier, but disregarding separation on ethane and lighter.
AI.1.2 Use a 5-m bis-(2(2-methoxyethoxy) ethyl)ether (B1VIEE) column at about 30°C, or a suitable Length of another partition column that will separate propane through n-pentane in about 5 min. Enter a 1- to 5-mL sample into the column and reverse the carrier gas flow after n-pentane is separated. Obtain a corresponding chromatogram on the reference standard, which can be accomplished in about 5-min run time, as there is no need to reverse the flow on the reference standard. Make calculations in the same manner as for the complete analysis method.
A1.1.3 A determination of propane, isobutane, n-butane, and pentanes and heavier can be made in about 5-min run time by reversing the carrier-gas flow after n-butane. However, it is necessary to know the average molecular weight of the pentanes and heavier components.
A1.2 Single-Run Analysis for Ethane and Heavier Components
A1.2.1 In many cases, a single partition run using a sample size in the order of 1 to 5 mL will be adequate for determining all components except methane, which cannot be determined accurately using this size sample with peak height measure-ments, because of its high concentration.
A1.2.2 Enter a 1- to 5-mL sample into the partition column and reverse the carrier gas flow after n-pentane is separated. Obtain a corresponding chromatogram of the reference stan-dard. Measure the peak heights of ethane through n-pentane and the areas of the pentane peaks of the standard. Make calculations on ethane and heavier components in the same manner as for the compléte analysis method. Methane and lighter may be expressed as the difference between100 and the sum of the determined components.
A1.3 Special Analysis to Determine Hexanes and Heavier Components
A1.3.1 A short partition column can be used advantageously to separate heavy-end components and obtain a more detailed breakdown on composition of the reverse-flow fractions. This information provides quality data and a basis for calculating physical properties such as molecular weight on these frac-tions.
A1.3.2 Fig. Al .1 is a chromatogram that shows components that are separated by a 2-m BMEE column in 20 min. To make this determination, enter a 5-mL sample into the short column and reverse the carrier gas after the separation of n-heptane. Measure areas of all peaks eluted after n-pentane. Correct each peak area to the mol basis by dividing each peak area by the molecular weight of the component. A value of 120 may be used for the molecular weight of the octanes and heavier reverse-flow peak. Calculate the mole percent of the hexanes and heavier components by adding the corrected areas and dividing to make the total 100 %.
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NE
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FIG. A1.1 Composition of Hexanes and Heavier Fraction
A2. PREPARATION OF COLUMNS AND DRIER
A2.1 Preparation of Columns—See Practice E 260.
A2.2 Preparation of Drier—Fill a 10-mm diameter by 100-mm length glass tube with granular phosphorus pentoxide or magnesium perchlorate, observing all proper safety precau-tions. Mount as required to dry the sample. Replace the drying agent after about one half of the material has become spent.
A2.3 Removal of Hydrogen Sulfide: A2.3.1 For samples containing more than about 300 ppm by
mass hydrogen sulfide, remove the hydrogen sulfide by con-necting a tube of sodium hydrate absorbent (Ascarite) ahead of the sample container during sampling, or ahead of the drying tube when entering the sample into the chromatograph. This procedure also removes carbon dioxide, and the results ob-tained will be on the acid-gas free basis.
A2.3.2 Hydrogen sulfide may also be removed by connect-ing a tube of pumice that has been impregnated with cupric
sulfate in the line upstream of both the chromatograph and drying tube. This procedure will remove small amounts of hydrogen sulfide while having but minimal effect on the carbon dioxide in the sample.
A2.4 Column Arrangement—For analyses in which hex-anes and heavier components are to be determined, Fig. A2.1shows an arrangement whereby columns can be quickly and easily changed by the turn of a selector valve. Two columns are necessary to determine all of the components covered in this. test method. However, short and long partition columns provide the flexibility of three partition column lengths, by using them either singly or in series. The connec-tion between 1/1 and V2 in Fig. A2.1 should be as short as possible (20 mm is practical) to minimize dead space between the columns when used in series. If all columns are chosen to operate at the same temperature, then stabilization time be-tween changing columns will be minimized.
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LONG PARTITION COLUMN
SHORT PARTITION COLUMN
(For Spplementary Use Only)
ABSORPTION COLUMN
CARRIER GAS FROM SAMPLING VALVE TO COLUMN
V
Y/4
CARRIER GAS FROM COLUMN TO DETECTOR
FIG. A2.1 Column Arrangement
APPENDIXES
(Nonmandatory Information)
XI. REFERENCE STANDARD MIXTURE
X1.1 Preparation X1.1.1 Gas mixtures of the following typical compositions
will suffice for use as reference standards for most analytical requirements (Note XI. I):
NOTE XI. l—If the mixture is stored under pressure, take care to ensure that the partial pressure of any component does not exceed its vapor pressure at the temperature and pressure at which the sample is stored and used. The lean mixture has a cricondentherm at 60°F and the rich mixture has a cricondentherrn at 100°F.
XI.1.2 A useful method for preparation of a reference standard by weight is as follows:5
XI .1.2.1 Obtain the following equipment and material: Cylinder, 20 L Pressure Cylinders, two 100 mL (A and B) Balance, 2000-g capacity, sensitivity of 10 mg. Pure Components, methane through n-pentane, and carbon
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dioxide. The pure components should be 99+ % pure. Methane should be in a I-L cylinder at 10-MPa (100-atm) pressure. Run a chromatogram of each component to check on its given composition.
X1.1.2.2 Evacuate the 20-L cylinder for several hours. Evacuate 100-mL Cylinder A, and obtain its true weight. Connect Cylinder A to a cylinder of pure n-penlane with a metal connection of calculated length to contain approximately the amount of n-pentane to be added. Flush the connection with the n-pentane by loosening the fitting at the valve on Cylinder A. Tighten the fitting. Close the n-pentane cylinder valve and open Cylinder A valve to admit the n-pentane from the connection and then close the valve on Cylinder A. Disconnect and weigh Cylinder A to obtain the weight of n-pentane added.
X1.1.2.3 Similarly, add isopentane, n-butane, isobutane, propane, ethane, and carbon dioxide, in that order, as desired, in the reference standard. Weigh Cylinder A after each addition to obtain the weight of the component added. Connect Cylinder A to the evacuated 20-L cylinder with as short a clean, small-diameter connector as possible. Open the valve on the 20-L cylinder, then open the valve on Cylinder A. This will result in the transfer of nearly all of the contents of Cyl inder A into the 20-L cylinder. Close the cylinder valves, disconnect, and weigh Cylinder A to determine the weight of mixture that was not transferred to the 20-L cylinder.
X1.1.2.4 Evacuate and weigh 100-mL Cylinder B. Then fill Cylinder B with helium and hydrogen respectively to the pressures required to provide the desired concentrations of these components in the final blend. (Helium and hydrogen are
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prepared and measured separately from the other components to prevent their pressures, while in the I 00-mL cylinder, from causing condensation of the higher hydrocarbons.) Weigh Cylinder B after each addition to obtain the weight of the component added. Connect Cylinder B to the 20-L cylinder with as short a clean, small-diameter connector as possible. Open the valve on the 20-L cylinder, then open the valve on Cylinder B, which will result in the transfer of nearly all of the contents of Cylinder B into the 20-L cylinder. Close the cylinder valves, disconnect, and weigh Cylinder B to obtain the weight of the mixture that was not transferred to the 20-L cylinder.
X1.1.2.5 Weigh a 1-L cylinder containing pure methane at about 10-MPa (100-atm) pressure. Transfer the methane to the 20-L cylinder until the pressure equalizes. Weigh the I-L cylinder to determine the weight of methane transferred.
X1.1.2.6 Thoroughly mix the contents of the 20-L cylinder by heating at the bottom by a convenient means such as hot water or a heat lamp, and leaving the cylinder in a vertical position for at least 6 h.
X1.1.2.7 Use the weights and purities of all components added to calculate the weight composition of the mixture. Convert the weight percent to mole percent.
XI.2 Calibration with Pure Components
X1.2.1 Use helium carrier gas to admit a sample volume of 0.25 to 0.5 mL into the adsorption column, providing methane at 50-kPa (375-mm Hg) and nitrogen at 10-kPa (75-mm Hg) absolute pressure. Run a sample of the standard mixture at 70-kPa (525-mm Hg) pressure and obtain peaks for methane and .nitrogen.
Nore XI.2—Each run made throughout this procedure should be repeated to ensure that peak heights are reproducible after correction for pressure differences to within I mm or I % of the mean value. All peaks should be recorded at an instrument attenuation that gives the maximum measurable peak height.
X1.2.2 Change the carrier gas to argon or nitrogen and, after the base line has stabilized, enter a sample of pure helium at 7-kPa (50-mm Hg) absolute pressure, recording the peak at an attenuation that allows maximum peak height. Run a sample of the mixture at 70-kPa (525-mm Hg) absolute pressure and obtain the helium peak.
X1.2.3 Switch to the partition column with helium carrier gas, and run the gas mixture at 70-kPa (525-mm Hg) absolute pressure. Then admit samples of pure ethane and propane at 10-kPa (75-mm Hg) absolute pressure, and butanes, pentanes, and carbon dioxide at 5-kPa (38-mm Hg) absolute pressure.
X1.2.4 Run the gas mixture at 70-kPa (525-mm Hg) abso-lute pressure.
X1.2.5 Calculate the composition of the prepared gas mix-ture as follows:
X1.2.5.1 Correct peak heights of all pure components and the respective components in the blend to the same attenuation (Note X1.2).
X1.2.5.2 Calculate the concentration of each component as follows:
C = (1001VAIB)(P00 ) (X1.1) .
where: C . = component concentration, mol; A = peak height of component in blend; B = peak height of pure component;
= pressure at which blend is run, kPa (mm Hg); Ph = pressure at which component is run, kPa (mm Hg);
and V. = volume fraction of pure component.
NOTE XI.3-1/1 = 1.000 if the calibration component is free of impu-rities.
X1.2.5.3 Normalize values to 100.0 %.
XI.3 Calibration using Relative Molar Response Values
X1.3.1 Relative response ratios can be derived from linear-ity data and used for calculating response factors. This elimi-nates the need for a multicomponent standard for daily calibration. The test method can be used on any gas chromato-graph using a thermal conductivity or therrnistor detector.
X1.3.2 Obtain a blend that brackets the expected concen-tration the instrument will be analyzing. The major component (methane) is used as the balance gas and may fall below the expected concentration. This component is present in the daily calibration standard and linearity is assured from previous tests.
XI.3.3 Inject the sample at reduced pressures using the apparatus in Fig. 1 or using a mechanical gas blender. Obtain repeatable peak areas or height at 90, 75, 60,45,30, and 15 % of absolute pressure. For 100 kPa (760 mm Hg), the pressures used are 90 kPa (684 mm Hg), 75 kPa (570 mm n rig), 60 kPa (456 mm Hg), 45 Kpa (342 mm rig), 30 kPa (228 mm Hg), 15 kPa (114 mm Hg).
X1.3.4 Plot the area or height (attenuated at the same height as the reference component) versus concentration and calculate the slope of the line by the least squares method. Given the equation of the line as l' = cro al X where Y represents the area or height points and X the concentration poihts. The line is assumed to intersect through the origin and (to= 0. The slope al can be calculated by:
2XY al =
(2112 (X1.2)
X1.3.5 Ratio the slopes of the referenced components (i) to the slopes of the reference components (r) present in the daily calibration standard. This gives the Relative Molar Response factor (RAM) for component (i). The reference component must be present in the same instrumental sequence (except Hexanes+) as the referenced components. For instance, pro-pane can be the reference component for the butanes and pentanes if propane is separated on the same column in the same sequence as the butanes and pentanes. Ethane can be the reference component for carbon dioxide if it elutes in the same sequence as carbon dioxide. The hexanes + peak can be refer-enced to propane or calculated as mentioned in the body of the standard.
X1.3.6 For daily calibration, a four-component standard is used containing nitrogen, methane, ethane, and propane. The fewer components eliminates dew point problems, reactivity, is more accurate and can be blended at a higher pressure. The referenced components' response factors are calculated from
44.
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TABLE X1.1 Least Square Calculation for Slope of Iso-Butane (Table X1.2).
XI.3.7 Periodic checks of the RMR relationship is recom-
slope = 2XY/ZY2 9.9594e.07 mended. The relationship is independent of temperature, sample size, and carrier gas flow rate. If changes occur in these operating conditions, all of the components will be affected equally and the calculated response factors will shift accord-ingly. See Table X1.1 and Fig. XI.! and Table XI.2.
• the current reference factor and the Relative Molar Response factor. Following is a description of the basic calculations, an example of deriving a Relative Molar Response factor (Fig. X1.1), and a table showing how response factors are calculated
0.150 0.300
0.450 61.602 0.750 0.900 1.000
Mole% FIG. X1.1 Example of Deriving a Relative Molar Response Factor
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TABLE X1.2 Calculation of Response Factors Using Relative Molar Response Values
Component
Mole % In Reference .Standard
Response of Reference Standard
Response Factor From Reference
Standard S/B,K
Relative MolarA Response from
Stapeffq RMRI
Response Factor of Referenced Components (RMR1)x(K1)
AThe Relative Molar Response Is a constant that Is calculated by dividing the slope of (he referenced component by the component that Is present in the reference standard. For example:
X3. PRECAUTIONS FOR AVOIDING COMMON CAUSES 01? ERRORS
X3.1 fitexane and Heavier Content Change X3. I:. I The amounts of heavy-end compounds in natural gas
are eas:ily changed during handling and entering of samples to give seliously erroneous low or high values. Concentration of these 6mponents has been observed to occur in a number of cases because of collection of heavier components in the sample loop during purging of the system. The surface effect of small diameter tubing acts as a separating column and must not be used in the sampling and entering system when components heavier than pentanes are to be determined. An accumulation of oily film in the sampling system greatly aggravates this
problem. Also, the richer the gas, the worse the problem. Periodically, check C6 and heavier repeatability of the appara-tus by making several check runs on the same sample. It is helpful to retain a sample containing some hexanes and heavier for periodic checking. When enlargement of the heavy end peaks is noted, thoroughly clean the sampling valve and loop with acetone. This trouble has been experienced with some inlet systems even when clean and with the specified sample loop size. This contamination can be minimized by such techniques as purging with inert gas, heating the sample loop, using a vacuum system, or other such effective means.
^The response for a constituent in the sample has been corrected to the same attenuation as for that constituent In the reference standard. °Average molecular weight of Co + =92. cCorrected Co response = (original response of 92.1) x (72/92) = 72.1. °Mal % Co + = (0.218 + 0.203) X (72.1)496.0 + 86.8) = 0.166.
% iCs % nCs Areas 1C+ nC 5 46 -
601 ASTM fnlamatiocial 15
to„ D 1945 - 03
X3.2 Acid Gas Content Change
X3.2.1 The carbon dioxide and hydrogen sulfide contents of gas are easily altered during sampling and handling. If samples containing carbon dioxide or hydrogen sulfide, or both, are to be taken, use completely dry sample cylinders, connections, and lines, as moisture will selectively absorb appreciable amounts of the acid gases. If hydrogen is present, use alumi-num, stainless steel, or other materials inert to hydrogen sulfide for the cylinder, valves, lines, and connections.
X3.3 Sample Dew Point
X3.3.1 Nonrepresentative samples frequently occur because of condensation of liquid. Maintain all samples above the hydrocarbon dew point. If cooled below this, heat 10°C or more above the dew point for several hours before using. If the dew point is unknown, heat above the sampling temperature.
X3.4 Sample Inlet System
X3.4.I Do not use rubber or plastic that may preferentially adsorb sample components. Keep the system short and the drier small to minimize the purging required.
X3.5 Sample Size Repeatability X3.5.I Varying back pressures on the sample loop may
impair sample size repeatability. X3.5.2 Make it a practice to make all reverse flów determi-
nations in the same carrier gas flow direction. All single-peak determinations and corresponding reference runs will then be made in the same carrier gas flow direction.
X3.5.3 Be sure that the inlet drier is in good condition. Moisture on the column will enlarge the reverse flow peak.
X3.5.4 Be sure the column is clean by occasionally giving it several hours sweep of carrier gas in reverse flow direction. A level baseline should be quickly attained in either flow direc-tion if the column is clean.
X3.5.5 When the reverse flow valve is turned, there is a reversal of pressure conditions at the column ends that upsets the carrier gas flow. This flow should quickly return to the same flow rate and the baseline level out. If it does not, the cause
may be a leakin the carrier gas system, faulty flow regulator, or an unbalanced condition of the column or plumbing.
X3.6 Reference Standard X3.6.I Maintain the reference standard at +15°C or a tem-
perature that is above the hydrocarbon dew point. If the reference standard should be exposed to lower temperatures, heat at the bottom for several hours before removing a sample. If in doubt about the composition, check the n-pentane and isopentane values with pure components by the procedure prescribed in Annex A2.
X3.7 Measurements X3.7.1 The baseline and tops of peaks should be plainly
visible for making peak height measurements. Do not use a fixed zero line as the baseline, but use the actual observed baseline. On high sensitivity, this baseline may drift slightly without harm and it need not frequently be moved back to zero. A strip-chart recorder with an offset zero is desirable. The area of reverse flow peak may be measured by planimeter or geometric construction. The reverse flow area, and the pen-tanes peaks used for comparison, should be measured by the same method. That is, use either geometric construction or planimeter, but do not intermix. When a planimeter is used, carefully make several tracings and use the average. Check this average by a second group of tracings.
X3.8 Miscellaneous X3.8.1 Moisture in the carrier gas that would cause trouble
on the reverse flow may be safeguarded against by installing a cartridge of molecular sieves ahead of the instrument. Usually 1 m of 6-mm tubing packed with 30- to 60-mesh molecular sieves is adequate, if changed with each cylinderof carrier gas.
X3.8.2 Check the carrier gas flow system periodically for leaks with soap or leak detector solution.
X3.8.3 Use electrical contact cleaner on the attenuator if noisy contacts are indicated.
X3.8.4 Peaks with square tops with omission of small peaks can be caused by a sluggish recorder. If this condition cannot be remedied by adjustment of the gain, check the electronics in the recorder.
SUMMARY OF CHANGES
Committee D03 as identified the location of selected changes to this standard since the last issue ( D 1945-96 (Reapproved 2001)) that may impact the use of this standard.
(/)Updated Section 8.1.2 to replace the criteria of two con- concentrations > 0.1%, which resulted in labs performing secutive checks agreeing within 1 % of the amount present of
multiple analyses to try and meet the tighter requirements to be
each component, since this requirement was much tighter to
in compliance with the method. meet than the method 'Y' limits for all components with % mole .(2) Sections 10.1.1 and 10.1.2 were revised.
.47 -
'QM ASTM Inlamallonal ad by IRS undar 'icons° with ASTM
16 Said tollORIZON AIR MEASUREMENT. 01670300 _
(CV D 1945 -03
ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such patent tights, and (ho risk of infringement of such tights, are entirely their own responsibility.
This standard is subject to revision at any time by the responsible technical committee and must be reviewed every live years end linol revised, either reapproved orwithdrawn.Yourcomments are invited either for mvislon of this standard or for additional standards and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, at the address shown below.
This standard Is copyrighted by ASTM international, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, Linked Slates. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at 610-832-9585 (phone), 610-832-9555 ((ax), or service @astm.org (e-mae or through the ASTM Waite (www.astm.arg).
ighl ASTM Inhnnallonal
17 tod by IHR tinrint
APPENDIX B - Computer Printout of Results
Horizon Air Measurement Services, Inc. C33-026-FR (2018) -49-
AVG. STACK TEMPERATURE AVG. SQUARE DELTA P NOZZLE DIAMETER BAROMETRIC PRESSURE SAMPLING TIME SAMPLE VOLUME AVG. METER TEMP. AVG. DELTA H DGM CALIB. FACTOR [Y] WATER COLLECTED CO2 02 CO CH4 N2 STACK AREA STATIC PRESSURE PITOT COEFFICIENT SAMPLE VOLUME DRY WATER AT STD. MOISTURE MOLE FRACTION DRY GAS MOLECULAR WT.DRY EXCESS AIR MOLECULAR WT. WET STACK GAS PRESSURE STACK VELOCITY VOLUMETRIC FLOWRATE, DRY STD. VOLUMETRIC FLOWRATE, ACTUAL ISOKINETIC RATIO
CALCULATIONS FOR GRAIN LOADING AND EMISSION RATES
TOTAL PARTICULATE
mg
13.4 PARTICULATE CONCENTRATION
gr/dscf
0.00376 PARTICULATE EMISSION RATE
lb/hr
0.989
HORIZON AIR MEASUREMENT SERVICES, INC. -51- C33026.SCAQMD.Rule.1150.1.FlareVV.CH4.F2
Note: All values preceded by "<" are below the detection limit. The reported values are the detection limit. NA - Not Applicale: Destruction efficiency can not be calculated since both inlet and outlet values are below the detection limit.
HORIZON AIR MEASUREMENT SERVICES, INC.-
C33026.SCAQMD.Rule.1150.1.FlareW.CH4.F2 - 67
Trace Organic Species - Destruction Efficiency Results
Note: All values preceded by "<" are below the detection limit. The reported values are the detection limit. NA - Not Applicale: Destruction efficiency can not be calculated since both inlet and outlet values are below the detection limit.
Species
Hydrogen Sulfide
HORIZON AIR MEASUREMENT SERVICES, INC. C33026.SCAQMD.Rule.1150.1.FlareW.CH4.F2 - 68-
Trace Organic Species - Destruction Efficiency Results
Note: All values preceded by "<" are below the detection limit. The reported values are the detection limit. NA - Not Applicale: Destruction efficiency can not be calculated since both inlet and outlet values are below the detection limit.
HORIZON AIR MEASUREMENT SERVICES, INC. -69- C33026.SCAQMD.Rule.1150.1.FlareW.CH4.F2
APPENDIX C - Field Data
Horizon Air Measurement Services, Inc. C33-026-FR (2018) -70-
VELOCITY DATA SHEET - METHOD 2
Baro. Press:
Static Press:
Source Equipment Identification
Facility:
Source:
Job #:
Run #:
Date:
Operator:
Chiquita Canyon LF Pitot Tube #:
Pitot Tube Type:
Magnehelic
Thermocouple
Temp. Meter
A11 -4 --1L
I ■4 _v
Flare No. 2 n 5 b C33-026 #: p wy CL— 4 - i ' n, 6 11/1. It-)r,11 #:
l9- (2oll"3- #: TA4 - ti —
/14 L4 , 513 Point
# Position
in. Velocity Head
in. H20 Stack
Temp °F Delta P @ 0 Deg. JAW=
Cyclonic Flow Angle
A6 48.4 3:0 3d IS2.._ 2- 5 34.0 ',;/' ‘ 0 3 3 ISq- .2- 4 24.1 .03--2... (5' I I 0 3 16.0 0,03/ 15- c. 0
2 9.1
1 2.9 D.0 I 5 (L-t-9 0
B6 0, 0 Lt.? 1 -.3 3 5 o s D 5-7.. 0-31 0
4 0 °Ç3 (5-2.- -- 0
3 Q. OL-f-,2, (5"25 2.
2 O • 39 I '5-2_2— -, .,_.
C6 0, -0 (Vo / L1 IS3 0
5 0. DS-3 I 1r 75 0
4 0' 13 ( I+ 2—' 0
3 Ds D Li' 2_ ( 5-• 7 2- 0
2
1 0 .0'3 S- P-f -scr( 2 D6
5 0. 51 I 'I tl D
4 D• 011" I 0 0
3 0 • °L-r7-- i 5-0 cr 0
2 0 'i) 3 'I i 6- 2° 0 1 D., .) 2S,/ 15M-7). 0
Average JAP= T5= /AP = L.
Sample Location
D, upstream: 0.4
D, downstream: 4.0
Stack Diameter: 136"
Side View
..........i.-
a
IL 5-ci II
I 5LN"
Top View
1\ I 6
0
QA/QC Checks
Lea15 Check
Initial: V V Final: fr IV
Thermocouple Check
Thermocouple Temp: Li 2-- Ambient Temp:
(Must be within 2°F)
Continuity Check:
Rising T:
Falling T:
Pitot Tube Inspections
Pitot Opening Undamaged: t/
Pitot Head Untwisted:
Pitot Face Parallel: V
CADocurnents and Settings\trailer\My Docurrients\Data Sheets\Chiquita Cyn\MITcl 2 Velocity-Flare2.wpd Revised January 27, 2015
JOB NO. C33-026 PLANT Chiquita Canyon Landfill DATE 12./7_0 fi LOCATION Castaic, CA OPERATOR- Pc-T - SOURCE Flare No. 2 RUN NO. I SAMPLE BOX NO.
TIME START
PARTICULATE FIELD DATA
METER BOXNO. METER AH @ I • '6 "5 7-
PROBE I.D. NO. 0; ^ 1" Y=
NOZZLE DIAMETER, in. 0 • -3-6-(z( STACK DIAMETER, in. 136" PROBE HEATER SETTING NA HEATER BOX SETTING NA A Cp FACTOR 0.84 FILTERNO. e- 062_ CPM FILTER NO. NA
ASSUMED MOISTURE, % 12- AMBIENTTEMPERATURE BARO. PRESS. 29.t .r STATIC PRESS. U • Ck)e NOMAGRAPH INDEX E50
PRE TEST LEAK CHECKS METER 0 • cpC @ I r in. Hg PITOTS / @ n in. H20
P# TIME T °F.'
AP in H10
JAP Au in H20
veer ft3
T., IN F
T., OUT F
OVEN °F.
CPM °F
IMP. OUT °F
VAC. (in Hg)
A6 0 ¡Ç) s 0.036 š'o 2Sí J93 193 by 1 b 1 NA NA 3&.) il 5 2'5 1 4-116 0 .032- 2p -7,9 I . 5.- -7 2_ (Jail 3B 35- 4 5 I 5-o 1) 0.0321 2--1 213i '7 ,-i C9s- 110 3 7.5 I LIS35 0.030 2....9 -Lei Lo . (1, -1 c" l.iec Liz "3 2 10 p_17r. 0 , 0 2„15 2-7_ '2-1 '2, .1 -7 s-- Gil WI 3 I 12.5 (rir 0 ,b1 E., )i ti 3 0et I 7 5-' bo '1(' z. r
B6 15 I s-oz, o.0q7 3.0 30 t .--7 2-2.- 7 -4 Cici qta s" 5 17.5 I 51'5 0.053 ii.2.- .30 4.5 1 CA 4 20 tr-LLe D05-'3 L1,2,- '307 ,, 1 -lc, (09 3 22.5 !(Z6 õ . Oils- 31lP 'Sip ci.°) -Pi 70 S-C) 2 25 i 5-"ii9 L)û1, 3.3 3 1 2. - 5-- -16 lb 5-' I I-1 I 27.5 ¡593 (5.033 2..L, 3 ic, o i tp lb ,6"
C6 30 * /Li 5-3 0 .ogi 31 311.1ip-rg -72.. -11 q9 9 5 32.5 11-1 G1 0 . 'Vc I 4 .1 319 ‘ 1 13 -71 LILA 5" 4 35 (t4 Gi t .0,-11--- 1.k-0 -i2-7---- - s" --Pi -ii 11G, 41- r 3 37.5 / rot, 0 r 0 3 1 34 --5z-r. 0 79 i I LO 5 L-1 2 40 ) LI -7 1 0 .039 3 , 1 3 2;1 . c" 71 1/ 5--o 2-1 I 42.5 /44 G I) t) .0310 -2-9 3-i.1' 79 -7 7 SI I
POST TEST LEAK CHECKS Meter @ /2_ in. Hg Pitots NA in. H20
Nozzle Cal DI D2 D, Average
I
JOB NO. C33-026 PLANT Chiquita Canyon Landfill DATE 1247,0 / LOCATION_Castaic,CA OPERATOR A-I SOURCE Landfill Gas RUN NO. SAMPLE BOX NO.
TIME START
PARTICULATE FIELD DATA
METER BOXNO. METER AH @ Y= PROBE I.D. NO. NA NOZZLE DIAMETER, in. NA STACK DIAMETER, in. NA PROBE HEATER SETTING NA HEATER BOX SETTING NA A Cp FACTOR NA FILTER NO. NA CPM FILTER NO
NA
ASSUMED MOISTURE,% NA AMBIENT TEMPERATURE 5 BARO. PRESS. 2_7. 0 3*- STATIC PRESS. NA NOMAGRAPH INDEX NA
PRE TEST LEAK CHECKS METER Q. CO 5- in. Hg PITOTS NA @ in. H2O
PH TIME Ts "F
A P in 1120
,/ A P A H in 1120
Vrn fl?
T IN ,,
To, OUT "F
OVEN "F
CPM "F
IMP. OUT °F
VAC. (in Hg)
Single 0 NA NA NA a .0 3 i , -7 US Ç8 Li (.0 NA NA i-jo --z_ 10 2,o 3.e' 6-7 5-1 1-1 1:0 -z- 20 '7,0 tir.1 30 '2-0 SS . 0 -1 o Ss" ¿1c3 7.- 40 7.-- 0 6 17 • I 7 zi q--e '-I1 •-z._ 50 `7---..0 (.01 . 1 7 3 Leo /4 6 Z
Specific volume, BTU, and F factor are calculated using labortatory analysis results for methane, carbon dioxide, nitrogen, oxygen, TGNMO, and sulfur compounds in equations that include assumed values for the specific volume of gases (CH4, CO2, N2, 02, Ar, and (CH2)n). The specific volume of gases were taken from the Scott Speciality Gases catalogue, 2001, and represents "as is" ideal gas at 60° F and 1 atm. The F factor is calculated according to the equation in ASTM D-3588.B89
January 2, 2018 Horizon Air Measurement Services, Inc. C33 - 026 Chiquita Canyon Landfill Flare No,2 Exhuast
Date Received: December 20, 2017 Date Analyzed: December 20, - 29, 2017
Methane, ethane and total gaseous non-methane organics were measured by flame ionizatior detection/total combustion analysis (FID/TCA). Organic carbon in water vial samples were measured by Dohrman total organic carbon analyzer, water FID/TCA.
I Lab No. I I ID Canister Canister Canister Impinger Impinger
I I Methane I Ethane I TGNMO I Carbon I Volume P1 P2
TGNMO is total gaseous non-methane organics (excluding ethane), reported as ppmvC. Ethane is reported as ppmvC. * Note - Impinger sample results are not field blank corrected. The field blank (impinger H7) contained 0.26ug carbon, corresponding to 0.12 ppm carbon for a 4.63 liter sample. P 1 and P2 are initial and final pressures measured in mm Hg.
page 1 of 2 -86-
QUALITY ASSURANCE SUMMARY (Repeat Analysis)
Source Location: Date Received: Date Analyzed:
Components
Chiquita Canyon Landfill December 20, 2017 December 20, - 29, 2017
A set of 2 SUMMA canister/impinger samples, laboratory numbers 13547-(9 - 10), was analyzed for methane, ethane, total gaseous non-methane organics (TGNMO), TOC. Agreement between repeat analysis is a measure of precision and is shown in the column
"% Difference from Mean". The average % Difference from Mean for 4 repeat measurements from the sample set of 2 SUMMA canister/impinger samples is 3.7%.
* total amount containing meta, para, and ortho isomers
Laboratory Director
PaT81. of 2
Page 2 of 2 -89 -
QUALITY ASSURANCE SUMMARY (Repeat Analyses)
Project No.: Date Received: Date Analyzed:
Components
C33-026 December 20, 2017 December 21, 2017
Sample ID
Repeat Analysis Mean Conc.
% Diff. From Mean Run #1 Run #2
(Concentration in ppbv)
Benzene 026-LFG 3220 3180 3200 0.62
Benzyl chloride 026-LFG <40 <40
Chlorobenzene 026-LFG <40 <40
Dichlorobenzenes 026-LFG <60 <60
1,1-dichloroethane 026-LFG <40 <40
1,2-dichloroethane 026-LFG 641 680 660 3.0
1,1-dichloroethylene 026-LFG <40 <40
Dichloromethane 026-LFG 919 838 878 4.6
1,2-dibromoethane 026-LFG <40 <40
Perchloroethylene 026-LFG 236 254 245 3.7
Carbon tetrachloride 026-LFG <30 <30
Toluene 026-LFG 11800 12600 12200 3.3
1,1,1-trichloroethane 026-LFG <30 <30
Trichloroethene 026-LFG 195 211 203 3.9
Chloroform 026-LFG <30 <30
Vinyl chloride 026-LFG 88.1 87.0 87.6 0.63
m+p-xylenes 026-LFG 1620 1800 1710 5.3
o-xylene 026-LFG 455 504 480 5.1
Four SUMMA canister samples, laboratory numbers 13547-(12-14), were analyzed for SCAQMD Rule 1150.1 components. Agreement between repeat analyses is a measure of precision and is shown above in the column "% Difference from Mean". The average % difference from mean for 14 repeat measurement from four SUMMA canister samples is 3.4%.
2E% Inc. 23917 Craftsman Rd., Calabasas, CA 91302 • (818) 223-3277 • FAX (818) 223-8250
environmental consultants laboratory services
LABORATORY ANALYSIS REPORT
atmaa.com
7?-?
Hydrogen Sulfide Analysis in Tedlar Bag Samples by Method SCAQMD 307.91
Report Date: Client:
Project Location: Project No.:
Date Received: Date Analyzed:
January 5, 2018 Horizon Air Measurement Services Chiquita Cyn LF C33-026 December 20, 2017 December 20 & 21, 2017
ANALYSIS DESCRIPTION
Hydrogen sulfide analysis measured by gas chromatography with sulfur chemfluminescence detector (SCD), SCAQMD 307.91
Four Tedlar bag samples, laboratory numbers 13547-(11-14), were analyzed for hydrogen sulfide. Agreement between repeat analyses is a measure of precision and is shown above in the column "% Difference from Mean". The % difference from mean for 1 repeat measurement from four Tedlar. bag samples is 3.5%.
One Tedlar bag sample, laboratory number 13547-14, was analyzed for total reduced sulfur compounds. Agreement between repeat analyses is a measure of precision and is shown above in the column "% Difference from Mean". The average % difference from mean for 4 repeat measurements from one Tedlar bag sample is 6.6%.
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APPENDIX E - Operating Data
Horizon Air Measurement Services, Inc. C33-026-FR (2018)
INOMMINEII -MOMPAMMOMMI NOWNOMMI MOM NOMMOMMII MENEM M NOMMON al IMIMIM:21 EMOMEMOOMII 111110 MI •IONIUMMANOMMIN MONOMMOMMIN MOOMMION • • MI! • MAINNOMMINNON NOMMONNOMM IMMUNE • MMUS Mil -40AMMIRMANONNON NONNOMMOMMO OMMOMMON MIME NMI .NAMMOMMINNOMON NOMMONONIMON MUM OMEN Mil Lampuol000moomo OMMONNOMMON ai II NONNI NMI .MHISSERNMENUM SOMMENNEMEN MINEINE NU NN NU --MININENNIONMENE NOMMINEMEN MENEM
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niniallg-ann=1_1==MIM 11111111111111MMIIIIISNMOMIIIIIIIMMI111111111111M=11111111111111111111111=1111111111 1111111=10111111111111111111111111111•111/1111111111 IIMMIL-MOMMIMMIMIIIIIIMEMirionemummimmE11•11111•1111111111111111111111111111 IIIIOMMIINIMM. MMMINIMOIIIIM MEW OMMIIIIIIMIMIM1111 II INAIMOIMIIIIInoMMINIIIIIMI OINI■111•1111111 1111111i1MEOMMEMMIMIMIIIMIIIII MIMIIIIIIIIIIIIIIIIIIMIIIIIIIIIIIII 0 11111111111111111111rNIIMMIIMMII111111111111111111111•111111111/1111111111 O1111rm•Nal•IMENIMMIIIIIIIIII 1111111111111MMIIIIIIIIMMIIMIII II 1111111111MOMIIMIlizA IIMIIIIIIMMI MIMIIIIIII■ OM III1,01NMV'AMMIM■MIMIIIIIIIMN IIMMIIIIIIIIIIIIMMOMMIIIIIIMI II ______________________Ill IMIIMMI111111111Q111111111111111111111VOIMMIMIMMOOMI Ilniiill1111EMIIIMMEMMEMIIIIM 4.:L - 0 11111111111=111=11111111111111•1111011=111111111 • 4.IMIN NM 1111111112=1111111111•111M111 -0 - -0 11111111111•111M111111111111111111011111111111t11 0 111•111111111111111111111R I MII E710011•111111111111110111111111111111 1111•11111111111111111111111111111111111= MIIIIIIIIIMIOMIIIIIIIIIIIMMIIIIIIIMIMIMMMEMMIMMOO Mfill VOMIIMIMIMMOIIIIIIIII 111111111■111111111111111111MMILIMMIIMIIIIIIIIIM /1111111101111115111111."1111111 MO ONOWIIIIMMI1111■MIMIO 1111111111MMIIM111111111111111111=1111•111111111111MIIIIIIIIIIIIIIIIMIIIIMM11111111111111111111111111111B IMM11111■20110IMUMMIIIMIIIIIIIIIIII 1111=111110111M1111111111111111111MION1111111MMIIIIIIIMMIMMIIIIIII WIIIMIMITZIMMISI IMIIII=IMIONIMIIMIMOMMOMIIMI 11=1111111111M111=1111=111M1111111111111IONOMOMMMIIIMMIMIIIIMMIIIMMIIIIIIIIMEMOMM - IIIIMIMIIIIMMOMMIIIIIIIIIIIIIIIIIIIIIMI 11111111M111111111111111111=11111111101M111111111111111=1111111111111•11111111111111111•1111101■1111O •111111=MIIIIIMOMO1111111111111111111=11 11•1101111111111111•111111111111111111111 11111111111111•1111111111111111111111111111111111111MMIIIIMIIIIMMIIMMIMIM IIIIIIIMMIIIIIIIIIIIIIIMIIIMMIIMME IIIIMOMMIIIII111111111111=1111111 II IIIMMIIIIIIIIIIIIIIIIIIIIMIIIIIIMMI IIMIIIIIIIMIIIIIIIIIMMEMMIMO ffilIMIIIIIIMMOMIMIIIIIIIIIIIIIMMIIII (4. 7,1 11111•111111111M11111111•111111111•11111111111 - co ----q - - IMIMMIIIIIIIMOMIMMI 1111011111111MOIMMIIMOMMIMMIMII • IIIMIIIIIIIIIIIMIMIIIIIIIIIIIIIIIIIIMIN - o o 111■11111111111111•1 MIMIIIIIIIIMMO11111111•111MIIMMI MIMMIIIIIIIIIIIMMM11111111111111111111111111MM11111111•111111111111111111111•1111111111 11.11111•11111111111111111111111111MMIMMIIIO IIMIIIIIMIMMIIIIMIIIIIIIIMIIIIIIIIIIIMMI11111111111111111MMIIIIIMMIIIIIIMMIMMIMMIIIIIIIIIIIIIIIII IIIMIIIMIIMMIIIIIIIIIMMIIIMMI 11111111■1111111111111MIIIIMM111111•111111111111111111111111 M1111111111111111111/1111111111MIIIMOIM OBOMMOMINIMIIIIIMMIIIIIIIIMMIIIIIIII 11111111111MOMMOMMIIIMIMIIIIIIIIIIIIIIIIMMIIIIIIMIMM■IIMMIIIIIIIMIIMMIMOOMMIll IIIMMIIIIMOIMMIIM=MMOMO IIIMIII■MMIIIIMMMIM1111111111111111111111111111M11111111111111111111MIM11111111111111111111111MIMMIMMI MOMMIIMIM111111111111111111MOOMME 111111111111111=111MMI II 011111•1111111111111=1 IM=111111111■MIIIIIIII 111111111M1111111M111111111111MIIIIIIIIIMI MMIMIIIIMMIMIMM111111111111111111110111111111111M11111111111111111=11111111111111111111111MIMIIIIIIIIIIMMI MOMMONIMIIIIIMIIIIMIIIMMIONO IIIIIIIIMOMIMIMIOMMIIMIMIIIMIIIIIIIIMIIIIIIIIIIIMM•IMOO1lMI■MIIIII MIMOMMIIIIIIIIIIMMIMMI111111111 iv co 111=111111111•111•111111111111111111=11111111 Tv co • ••110111111111111•111111115111 MIMIEMIMMINIIIIIII MIMI= 0- -0 IIIIIMMOM11111111111,1MIIMIIIIMINIMMI 0 -0 . - - 1111■111111111IIII OM 1110111111111=11111 11111111111111011111M1 IMMMIIIIIIIIMMIMMINIIIIIIMIMMIll1.1.10111111 • 11.2.4.1211111.111111.1111111=1111111111111.11.1 MIMI IIIMONIMMMIOMOIMIIMI 1111111■1111111MMIMIIMM 11OM= MIMMIIIMIIIIII M11111111111■1111111111111 IIMOMIIMMIIIMIMMILEmismtmill ..'"•""'""m"":11.11111111111111111111111111111111 IIIIIIIMIIIIIIMMIIIIM IIMIIIIOIMMIIOIIMIMOMIMIMO IMIIIIIMMIIMIIIMIIMIIMIIIIIIMIMIIIIMIIIIIIMIIIIIIIIIMMIIIIMMIIIIIIIIIIIIIIIIIIMIMIIIIIIIIMI OMIIIMIIIIIIIIIIIIM■IMMIll MI M1111011111111MIMOMIMMIIIIMIIIIIMIIIIIIIIMOMIMIIIIIIIIIIMINIMOMMOMIll IIIIIIIMMIMOIMIMIIMIMIMMIMII 11■1111M■OMIMIMO11011111111MIIIMMMMIMIIMMILIMOIMMIIIIIIIIMMIIIIIMIIIIIIIIII 111111111111111111111DOIM■MIIIIIIIIIIN 111010=1111111111111111111111111111111111111111MMIMO1111111111■11MOM 11111111MMIOW111111111111111111111111=111111 MMMIIIIIMMIIIIIIIIIIIIIIIIIIMMIMIIIIIIIIIIIIIIMHIIMIMIIIMIIIMMII•MMIIMI 111111111=1111111111•11111MIMINIMI 1=11111111111=11•11111111111111111111M111111111 ,-2..._co - - IMMIIIIMIIIIIIIIMIN MN MIIIIIIIIIMIIIIIIIIMMMII IMMIIIMMIIIIIM1111111111111111MMII 0 0 - - - . • IIIIIIMMOMMIIIIII
• IIII
MIMI 11=01111MMIMIIIMMIOINIO 1111111111111111111111111111111111111111111111111111111111111111111■11111111111111111111 TO 111/111M111111111111111111110111MO I NIIIIIIMIMIIIIIIMIIIIIIIIIIIIIIIHMIMIIIIMI■1IIIIMIOMIMMIIIIIIIIMIIIIIIIIIMIIMIOMIMI
Certification performed in accordance with "EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards (May 2012)" document EPA 600/R-12/531, using the assay procedures listed. Analytical Methodology does not require correction for analytical interference. This cylinder has a total analytical
uncertainty as stated below with a confidence level of 95%. There are no significant impurities which affect the use of this calibration mixture. Al! concentrations are on a volume/volume basis unless otherwise noted.
Do Not Use This Cylinder below 100 psig, i.e. 0.7 megapascals.
ANALYTICAL RESULTS Component Requested
Concentration Actual Protocol Total Relative Concentration Method Uncertainty
48-124621363-1 144.3 CF 2015 PSIG 660 Jun 08, 2017
Certification performed in accordance with "EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards (May 2012)" document EPA 600/R-12/531, using the assay procedures listed. Analytical Methodology does not require correction for analytical interference. This cylinder has a total analytical
uncertainty as stated below with a confidence level of 95%. There are no significant impurities which affect the use of this calibration mixture. All concentrations are on a volume/volume basis unless otherwise noted.
Do Not Use This Cylinder below 100 psiçj. i.e. 0.7 me a ascals.
ANALYTICAL RESULTS Component Requested Actual Protocol Total Relative Assay
ANALYTICAL EQUIPMENT Instrument/Make/Model Analytical Principle Last Multipoint Calibration
Thermo 42-iLS 1115848421 NO Chemiluminescence Jun 05, 2017 Thermo 42-iLS 1115848421 NOx Chemiluminescence Jun 05,2017
Triad Data Available Upon Request
Ap • oved for Release - 121 - Page 1 of 48-1 24621 363-1
mum an Air Liquide company
Airgas Specialty Gases Airgas USA, LLC 11711 S. Alameda Street Los Angeles, CA 90059 Airgas.com
CERTIFICATE OF ANALYSIS Grade of Product: EPA Protocol
Part Number: E021\1199E15A0529 Reference Number: 48-124628314-1 Cylinder Number: CC347181 Cylinder Volume: 144.3 CF Laboratory: 124 - Los Angeles - CA Cylinder Pressure: 2015 PSIG PGVP Number: B32017 Valve Outlet: 660 Gas Code: NO,NOX,BALN Certification Date: Jul 17, 2017
Expiration Date: Jull7 2020 "A Certification performed in accordance with "EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards (May 2012)" document EPA
600/R-12/531, using the assay procedures listed. Analytical Methodology does not require correction for analytical interference. This cylinder has a total analytical uncertainty as stated below with a confidence level of 95%. There are no significant impurities which affect the use of this calibration mixture. All concentrations are on a
volume/volume basis unless otherwise noted. Do Not Use This Cylinder below 100 psig, i.e. 0.7 megapascals.
ANALYTICAL RESULTS Component Requested Actual Protocol Total Relative Assay
Thermo 42-iLS 1115848421 NO Thermo 42-iLS 1115848421 NOx
ANALYTICAL EQUIPMENT Analytical Principle
Chemiluminescence Chemiluminescence
Last Multipoint Calibration
Jul 06, 2017 Jul 06, 2017
Triad Data Available Upon Request
Approved for Release -122- Page 1 of 48-124628314-1
an Ai Liquide company
Airgas Specialty Gases Airgas USA, LLC 11711 S. Alameda Street Los Angeles, CA 90059 Airgas.com
CERTIFICATE OF ANALYSIS Grade of Product: EPA Protocol
Part Number: E03N199E15A1471 Reference Number: 48-124594486-1 Cylinder Number: EB0063875 Cylinder Volume: 144.3 CF Laboratory: 124 - Los Angeles - CA Cylinder Pressure: 2015 PSIG PGVP Number: B32017 Valve Outlet: 660 Gas Code: CO,NO,NOX,BALN Certification Date: Jan 11, 2017
Expiration Date: Jan 11, 2020 Certification performed in accordance with "EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards (May 2012)" document EPA
600/R-12/531, using the assay procedures listed. Analytical Methodology does not require correction for analytical interference. This cylinder has a total analytical uncertainty as stated below with a confidence level of 95%. There are no significant impurities which affect the use of this calibration mixture. All concentrations are on a
volume/volume basis unless otherwise noted. Do Not Use This Cylinder below 100 psig, i.e. 0.7 me a ascals.
• Component Requested Concentration
ANALYTICAL RESULTS Actual Protocol Total Relative Assay Concentration Method Uncertainty Dates
Feb 22, 2020 Jun 02, 2017 Nov 19, 2019 Feb 24. 2019
Cylinder No
CC434404 APEX1099237 CC403933 CC500997
Nicolet 6700 AHR0801551 CO Nicolet 6700 AHR0801551 NO Nicolet 6700 AHR0801551 NO2
FTIR FTIR FTIR
Mar 09, 2017 Mar 14, 2017 Mar 20, 2017
VOII=Ii1011111111•111111121MA,
CERTIFICATE OF ANALYSIS Grade of Product: EPA Protocol
Airgas Specialty Gases 11711 S. Alameda Street Los Angeles , CA 90059 323-568-2208 Fax: 323-567-3686 Airgas.com
Part Number: E03N199E15A0259 Reference Number: 48-124611646-1 Cylinder Number: CC10405 Cylinder Volume: 144.3 CF Laboratory: 124 - Los Angeles - CA Cylinder Pressure: 2015 PSIG PGVP Number: B32017 Valve Outlet: 660 Gas Code: CO,NO,NOX,BALN Certification Date: Apr 07, 2017
Expiration Date: Apr 07, 2020 • Certification performed in accordance with TPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards (May 2012) document EPA
600/R-12/531, using the assay procedures listed. Analytical Methodology does not require correction for analytical interference. This cylinder has a total analytical uncertainty as stated below with a confidence level of 95%. There are no significant impurities which affect the use of this calibration mixture. All concentrations are on a
volume/volume basis unless otherwise noted. Do Not Use This Cylinder below 100 psig, i.e. 0.7 me a ascals.
ANALYTICAL RESULTS Actual Protocol Total Relative Concentration Method Uncertainty
45.52 PPM
G1
+/- 0.9% NIST Traceable 45.49 PPM
G1
+/- 0.7% NIST Traceable 45.13 PPM
G1
+/- 0.8% NIST Traceable
Assay Dates
03/31/2017, 04/07/2017 03/31/2017
03/31/2017, 04/07/2017
The SRM, PRM or RGM noted above is only in reference to the GMIS used in the assay and not part of the analysis.
ANALYTICAL EQUIPMENT Instrument/Make/Model
Analytical Principle Last Multipoint Calibration
Triad Data Available Upon Request
Approved for Release - 124- Page 1 of 48-124611646-1
Certification performed in accordance with TPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards (May 2012) document EPA 600/R-12/531, using the assay procedures listed. Analytical Methodology does not require correction for analytical interference. This cylinder has a total analytical
uncertainty as slated below with a confidence level of 95%. There are no significant impurities which affect the use of this calibration mixture. All concentrations are on a volume/volume basis unless otherwise noted.
Do Not Use This Cylinder below 100 psig, i.e. 0.7 megapascals.
ANALYTICAL RESULTS Component Requested Actual Protocol Total Relative Assay
CALIBRATION STANDARDS Type Lot ID Cylinder No Concentration Uncertainty Expiration Date NTRM 12062227 CC365470 97.56 PPM CARBON MONOXIDE/NITROGEN +/- 0.6% May 25, 2018 PRM 12328 680179 10.01 PPM NITROGEN DIOXIDE/NITROGEN +/- 2.0% Ocl15, 2014 NTRM 13061027 CC423321 99.86 PPM NITRIC OXIDE/NITROGEN +/- 0.8% Nov19, 2019 GMIS 1211201301 CC501041 4.950 PPM NITROGEN DIOXIDE/NITROGEN +/-2.0% Dec11, 2016 The SRM, PRM or RGM noted above is only in reference to the GMIS used in the assay and not part of the analysis.
Instrument/Make/Model ANALYTICAL EQUIPMENT Analytical Principle Last Multipoint Calibration
Nicolet 6700 AHR0801551 CO FTIR Jul 18, 2016 Nicolet 6700 AHR0801551 NO FTIR Jul 29, 2016 Nicolet 6700 AHR0801551 NO2 FTIR - Aug 02, 2016
an Air L guide company
Airgas Specialty Gases Airgas USA, LLC 11711 S. Alameda Street Los Angeles, CA 90059 Airgas.com
CERTIFICATE OF ANALYSIS Grade of Product: EPA Protocol
Part Number: E03N199E15A0260 Reference Number: 48-124570416-1 Cylinder Number: CC26660 Cylinder Volume: 144.3 CF Laboratory: 124 - Los Angeles - CA Cylinder Pressure: 2015 PSIG PGVP Number: B32016 Valve Outlet: 660 Gas Code: CO,NO,NOX,BALN Certification Date: Aug 19, 2016
Expiration Date: Aug 19, 2024
Triad Data Available Upon Request
Signature on file -125 -
Approved for Release Page 1 of 48-1 2457041 6-1
Approvecifor Release 126-
Aims CERTIFICATE OF ANALYSIS Grade of Product: EPA Protocol
Airgas Specialty Gases 11711 S. Alameda Street Los Angeles , CA 90059
Part Number: E02N199E15A0552 Reference Number:
323-568-2208 Fax: 323-567-3686 IA
48-12445Mlas.cm Cylinder. Number: CC85517 Cylinder Volume: 144.3 CF Laboratory: ASG - Los Angeles - CA Cylinder Pressure: 2015 PSIG PGVP Number: B32014 Valve Outlet: 350 Gas Code: CO,BALN Certification Date: Oct 13, 2014
Expiration Date: Oct 13, 2022 Certification performed in accordance with 'EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards (May 2012)" document EPA
600/R-12/531, using the assay procedures listed. Analytical Methodology does not require correction for analytical interference. This cylinder has a total analytical uncertainty as stated below with a confidence level of 95%. There are no significant impurities which affect the use of this calibration mixture. All concentrations are on a
volume/volume basis unless otherwise noted. Do Not Use This Cylinder below 100 psig, i.e. 0.7 me a ascals.
Component Requested Concentration
ANALYTICAL RESULTS Actual Protocol Concentration Method
Airgas Specialty Gases Airgas USA, LLC 11711 S. Alameda Street Los Angeles, CA 90059 Airgas.com
CERTIFICATE OF ANALYSIS Grade of Product: EPA Protocol
Part Number: E03N181E1 5A0006 Reference Number: 48-401048828-1 Cylinder Number: CC175551 Cylinder Volume: 149.3 CF Laboratory: 124 - Los Angeles (SAP) - CA Cylinder Pressure: 2015 PSIG PGVP Number: B32017 Valve Outlet: 590 Gas Code: CO2,02,BALN Certification Date: Nov 10, 2017 41\
Expiration Date: Nov 10, 2026
. Certification performed in accordance with TPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards (May 2012)" document EPA 600/R-12/531, using the assay procedures listed. Analytical Methodology does not require correction for analytical interference. This cylinder has a total analytical
uncertainty as stated below with a confidence level of 95%. There are no significant impurities which affect the use of this calibration mixture. All concentrations are on a volume/volume basis unless otherwise noted.
Do Not Use This Cylinder below 100 psig, i.e. 0.7 me a ascals.
Component Requested Concentration
ANALYTICAL RESULTS Actual Protocol Total Relative Assay Concentration Method Uncertainty Dates
11.002 % CARBON DIOXIDE/NITROGEN +/- 0.6% Jan 11, 2018
16.04% OXYGEN/NITROGEN +/- 0.6% Oct 06, 2021
Instrument/Make/Model
ANALYTICAL EQUIPMENT Analytical Principle Last Multipoint Calibration
SIEMENS 6E CO2 SIEMENS OXYMAT 6
NDIR Oct 23, 2017 PARAMAGNETIC Oct 23,2017
Triad Data Available Upon Request
Approved for Release Page 1 048-401048828-1
-127-
Airgas CERTIFICATE OF ANALYSIS
Grade of Product: EPA Protocol
Airgas Specialty Gases 11711 South Alameda Street Los Angeles, CA 90059 (323) 568-2203 Fax: (323) 567-3686 www.alrgas.com
Part Number: E03N164E15A0001 Reference Number: 48-124348198-1 Cylinder Number: CC302347 Cylinder Volume: - 154.8 CF Laboratory: ASG - Los Angeles - CA Cylinder Pressure: 2015 PSIG PGVP Number: B32012 Valve Outlet: 590
Analysis Date: Dec 06, 2012
Expiration Date: Dec 06, 2020
Certification performed in accordance with "EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards (May 2012)" document EPA 600/R-12/531, using the assay procedures listed. Analytical Methodology does not require correction for analytical interference. This cylinder has a total analytical uncertainty as stated below
with a confidence level of 95%. There are no significant impurities which affect the use of this calibration mixture. All concentrations are on a volume/volume basis unless otherwise noted.
Do Not Use This Cylinder below 100 psig, i.e. 0.7 megapascals.
Component -
ANALYTICAL RESULTS
Requested Actual Protocol Concentration Concentration• Method
Total Relative Uncertainty
CARBON DIOXIDE
OXYGEN
NITROGEN
13.50 % 13.60% G1
22.50% 22.02% G1
Balance . .
+1- 1% NIST Traceable
+1- 1% NIST Traceable
Type Lot ID Cylinder No CALIBRATION STANDARDS Concentration Expiration Date .
NTRM 120613
NTRM 090614
Instrument/Make/Model
CC360804 .
CC273756
11.002% CARBON DIOXIDE/NITROGEN
22.53 % OXYGEN/NITROGEN
ANALYTICAL EQUIPMENT Analytical Principle ‘.
Jan 11,2018
Aug 01, 2013
Last Multipoint Calibration
Nicolet 6700 AMP0900118 CO2
SIEMENS OXYMAT 6
FTIR
PARAMAGNETIC
Nov 15, 2012
Dec 03, 2012
Triad Data Available Upon Request
Notes:
Approved for Release
Page 1 of 48-124348198-1
-128-
APPENDIX H - Correspondences
Horizon Air Measurement Services, Inc. C33-026-FR (2018) -129-
Test Notification/Test Plan Chiquita Canyon Landfill (C33-026-TP) https://apps.rackspace.com/versions/webmail/12.9.9-RC/popup.php...
Test Notification/Test Plan Chiquita Canyon Landfill (C33-026-TP) From: [email protected]
Sent: Wed, Nov 8, 2017 at 3:49 pm
To: Charlie Tupac, Mike Dean, Steve Cassulo, Aliassar, Salar
Cc: Joe Bennett, Rich Vacherot, Deborah Vacherot
C33_026_1P_FINAL.pdf (17.5 KB)
Hello Charlie,
Please find attached a pdf copy of the Test Notification/Test Plan for Chiquita Canyon Landfill Flare No. 2 Permit AN 491442 (Facility ID No. 119219) for your review and approval.
Please note that testing is currently scheduled for December 20, 2017.
Should you have any questions or concerns, please feel free to contact the office.
Thank you,
Mandy Jones Horizon Air Measurement Services, Inc. 310 Cortez Circle Camarillo CA 93012 Phone: 805.482.8753 Fax: 805.482.8754 Email: [email protected] Website: www.horizonairmeasurement.com
-130-
1 of! 11/10/2017, 7:39 AM
Joseph M. Bennett Tecmical Operations Manager
NI IN /Mk II•1 411111111■ Mill IN 11116.111•1 INK VS ELM 11111 /WWI VIM" IN is! 1110•1•11G, AMR/ IIIIII
./MMII/11■1 VENII NAINL.---7•1•11.. -WNW MI K 1 E AIR MEASUREMENT SERVICES, INC.
Horizon No.: C33-026-TP
November 8, 2017
Mr. Charles Tupac AQAC Supervisor South Coast Air Quality Management District 21865 East Copley Drive Diamond Bar, California 91765
RE: TEST NOTIFICATION/TEST PLAN CIHQUITA CANYON LANDFILL FLARE NO. 2 PERMIT AN 491442 (FACILITY ID NO. 119219)
Dear Mr. Tupac:
Please let this letter serve as notification that Horizon Air Measurement Services, Inc. (Horizon) will be conducting a source testing program on Landfill Flare No. 2 at the Chiquita Canyon Landfill on December 20, 2017. All testing will be conducted in accordance with the previously approved source test protocol submitted by Horizon Air Measurement Services in 2009 (C33-020-TP) and the subsequent SCAQMD protocol evaluation. Please note that referenced test protocol was for an initial flare test which included supplemental compounds (PAH's and aldehydes), however these compounds will not be included in this test program.
If you have any questions or concerns regarding this notification, please call me at (805) 482-8753.
Sincerely,
HO IR MEA UREMENT SERVICES, INC.
ec: Mike Dean, S CS Engineers Steve Cassulo, Chiquita Canyon Landfill Salar Aliassar, SCS Engineers
Horizon Air Measurement Services, Inc. C33-026-FR (2018)
-132-
KWIA
South Coat Air Quality Management District 21865 Copley Drive, Diamond Bar, CA 91765-4178
-__ • • • Section: D Page 9 Facility 1.D. 119219 Revision ti: 3 Date: January 9,20 N
PERMIT TO OPERATE
Permit No. G23473 A/N 491442
Equipment Description:
LANDFILL GAS FLARE SYSTEM CONSISTING OF:
1. THREE BLOWERS (STAND-BY), LAMSON, MODEL NO. 853, EACH 2000 CFM, WITH A 60 HP MOTOR VENTING LANDFILL GAS FROM COLLECTION WELLS AND TRENCHES.
2. CONDENSATE KNOCK-OUT/FILTER, 5'- 0" DIA. X 10' — 6" H., SERVING BOTH FLARES.
3. FLARE, NO. 1, JOHN ZINK, MODEL ZTOF, 11 '-4" DIA. X 50'-0" H., RATED AT 4000 SCFM CAPACITY, 120 MMBTU PER HOUR WITH A FLAME ARRESTOR, UV SCANNER, FOUR AUTOMATIC COMBUSTION AIR DAMPERS AND FLARE ALARM SYSTEM.
4. AUTOMATED IGNITION SYSTEM WITH PROPANE GAS PILOT ASSEMBLY, IGNITION TRANSFORMER, AND TWO 5-GALLON CAPACITY PROPANE TANKS.
5. CONDENSATE INJECTION SYSTEM WITH TWO PUMPS, COMPRESSOR, INJECTORS, VALVES AND CONTROLS.
6. TWO MULTI-STAGE CENTRIFUGAL BLOWERS, EACH GARDNER DENVER/LAMSON 150 HP MOTOR, 4000 SCFM, VENTING LANDFILL GAS FROM COLLECTION WELLS AND TRENCHES.
7. ENCLOSED FLARE, NO. 2, JOHN ZINK, ZINK ULTRA LOW EMISSION (ZULE)„ I2'- 0" DIA. X 50'41" H., MAXIMUM BEAT INPUT OF 120 MMBTU PER HOUR OF LANDFILL GAS, WITH A COMBUSTION AIR BLOWER, COMBUSTION AIR/LFG MIXING CHAMBER, A FLAME ARRESTOR, UV SCANNER, ELECTRIC IGNITER, PROPANE GAS PILOT, LOUVERS, AUTOMATIC LANDFILL GAS FLOW AND FLARE TEMPERATURE CONTROL SYSTEM, AND AN AUTOMATIC FLARE SHUTDOWN AND ALARM SYSTEM.
8. CONDENSATE INJECTION SYSTEM WITH ASSOCIATED PUMP(S), COMPRESSOR(S), INJECTORS, VALVES AND CONTROLS.
Conditions:
OPERATION OF THIS EQUIPMENT SHALL BE CONDUCTED IN COMPLIANCE WITH ALL DATA AND SPECIFICATIONS SUBMITTED WITH THE APPLICATION UNDER WHICH THIS PERMIT IS ISSUED UNLESS OTHERWISE NOTED BELOW. [RULE 204]
2. THIS EQUIPMENT SHALL BE PROPERLY MAINTAINED AND KEPT IN GOOD OPERATING CONDITION AT ALL TIMES. [RULE 204]
3. THIS EQUIPMENT SHALL BE OPERATED AND MAINTAINED BY PERSONNEL PROPERLY TRAINED IN ITS OPERATION.
-133-
South Coast Air Quality Management District 21865 Copley Drive, Diamond Bar, CA 91765-4178
4. EACH FLARE SHALL BE EQUIPPED WITH A TEMPERATURE INDICATOR AND RECORDER WHICH MEASURES AND RECORDS THE EXHAUST GAS TEMPERATURE IN EACH FLARE STACK. THE TEMPERATURE INDICATOR AND RECORDER SHALL OPERATE WHENEVER THE FLARE IS IN OPERATION. THE TEMPERATURE SHALL BE MEASURED AT A LOCATION ABOVE THE FLAME ZONE, AT LEAST 0.6 SECOND DOWNSTREAM OF THE BURNER, AND NOT LESS THAN THREE (3) FEET BELOW THE TOP OF EACH STACK. [RULE I303(a) (I)-BACT, 3004 (a) (4)]
5. WHENEVER THE FLARE(S) IS (ARE) IN OPERATION, A TEMPERATURE OF NOT LESS THAN 1400 DEGREES F, 15 MINUTE AVERAGE, AS MEASURED BY THE TEMPERATURE INDICATOR AND RECORDER SHALL BE MAINTAINED EXCEPT DURING PERIODS OF STARTUP AND SHUTDOWN. STARTUP IS DEFINED AS THE PERIOD FROM FLARE IGNITION TO THE TIME WHEN 1400 DEGREES F IS ACHIEVED, NOT TO EXCEED 30 MINUTES. SHUTDOWN IS THE PERIOD FROM WHEN THE GAS VALVE BEGINS TO BE SHUT AND COMPLETELY SHUTS OFF, NOT TO EXCEED 30 MINUTES. [RULE 1303(a) (1)-BACT]
6. A FLOW INDICATOR AND RECORDING DEVICE SHALL BE MAINTAINED IN THE LANDFILL GAS SUPPLY LINE TO EACH FLARE TO MEASURE AND RECORD THE QUANTITY OF LANDFILL GAS (IN SCFM) BEING BURNED IN EACH FLARE. [RULE 1303(b) (2)-OFFSET, 3004 (a) (4)]
7. ALL RECORDING DEVICES SHALL BE SYNCHRONIZED WITH RESPECT TO TIME OF THE DAY. [RULE 204]
8. THE TOTAL VOLUME OF LANDFILL GAS BURNED IN EACH FLARE SHALL NOT EXCEED 4,000 STANDARD CUBIC FEET PER MINUTE (SUM). [RULE 1303(b) (1) AND (b) (2)-M0DELING AND OFFSET, 14011
9. THE MAXIMUM HEAT INPUT RATE TO EACH FLARE SHALL NOT EXCEED 120 MMBTU PER HOUR. A LOG SHALL BE KEPT INDICATING THE TOTAL HEATING VALUE OF LANDFILL GAS BURNED IN EACH FLARE BASED ON THE RECORDED FLOW RATE (SCFM) AND THE LATEST WEEKLY BTU CONTENT (BTU/SCF) READING. [RULE 1303(b) (1) AND (b) (2)-MODELING AND OFFSET, 1401]
10. THE AUTOMATIC SHUTDOWN SAFETY SYSTEM SHALL BE TESTED MONTHLY FOR PROPER OPERATION OF EACH FLARE AND THE RESULTS RECORDED. [RULE 1303(a) (1)-BACT]
11. CONDENSATE INJECTION TOTAL FLOW RATE AND HEAT INPUT RATE (BTU/FIR), FOR ALL OF THE NOZZLES, SHALL BE RECORDED AND RECORDS SHALL BE MAINTAINED ON FILE. CALCULATED INJECTION RATE FOR EACH NOZZLE SHALL NOT EXCEED 0.077 GPM/BTU/HR.
12. THE OPERATOR SHALL CONDUCT ANNUAL PERFORMANCE SOURCE TEST FOR EACHDF THE FLARES (WITHIN 12 MONTHS OF THE PRIOR SOURCE TEST), AT MAXIMUM HEAT INPUT RATE, IN ACCORDANCE WITH SCAQMD APPROVED SOURCE TEST PROTOCOL. WRITTEN NOTIFICATION OF THE SCHEDULED TEST DATE SHALL BE PROVIDED TO THE SCAQMD AT LEAST SEVEN 0) DAYS PRIOR TO THE DATE SO THAT THE TESTING MAY BE OBSERVED BY
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South Coast Air Quality Management District • Section: D Page II
21865 Copley Drive, Diamond Bar, CA 91765-4178 Facility Mil: 119219 Revision if: 3 Date: January 9,2014
SCAQMD PERSONNEL. THE TESTING SHALL BE CONDUCTED WHEN THE EQUIPMENT IS IN FULL OPERATION, AND SHALL INCLUDE, BUT NOT LIMITED TO, A TEST OF THE INLET TO THE FLARE AND THE FLARE EXHAUST FOR:
A. METHANE B. TOTAL NON-METHANE ORGANIC COMPOUNDS (TNMOC) C. CARCINOGENIC AND TOXIC AIR CONTAMINANTS (INLET AND EXHAUST) INCLUDING,
BUT NOT LIMITED TO, COMPOUNDS LISTED UNDER RULE 1150.1, TABLE-1 (CORE GROUP).
D. NOX, AS NO2 (EXHAUST ONLY) E. SOX, AS SO2 (EXHAUST ONLY) F. CO (EXHAUST ONLY) G. PMIO REPORTED AS TOTAL PM (EXHAUST ONLY) H. OXYGEN I. MOISTURE CONTENT J. TEMPERATURE K. FLOW RATE . [RULE 1303(b) (1) AND (b) (2)--MODELING AND OFFSET, 1401, 3004 (a) (4)]
13. THE SOURCE TEST REPORT, FOR EACH FLARE SHALL INCLUDE;
A. EMISSIONS OF CO, NOx, TNMOCs, PM10 (TOTAL PM) AND S0x, IN UNITS OF LBS/HR AND PPMV (EXCEPT PM10), OVERALL METHANE AND TNMOC DESTRUCTION EFFICIENCY (WT %) AND TNMOC EMISSIONS (PPMV), ON A DRY BASIS, AS HEXANE AT 3% OXYGEN.
B. THE TEST SHALL BE PERFORMED BY A TESTING LABORATORY CERTIFIED TO MEET THE CRITERIA IN SCAQMD RULE 304(1) (CONFLICT OF INTEREST).
C. SAMPLING FACILITIES SHALL COMPLY WITH SCAQMD "GUIDELINES FOR CONSTRUCTION OF SAMPLING AND TESTING FACILITIES" PURSUANT TO RULE 217.
[RULE 204, 217, RULE 1150.1, 40CFR60 SUBPART WWW]
14. THE MAXIMUM FLARE SKIN TEMPERATURE AT ANY LOCATION SHALL NOT EXCEED 250 DEGREES FAHRENHEIT. [RULE 217]
15. ALL LANDFILL GAS COLLECTED SHALL BE DIRECTED TO A PROCESSING FACILITY, WHICH CAN ADEQUATELY PROCESS THE VOLUME OF LFG COLLECTED, OR TO THE COMBUSTION EQUIPMENT THAT HAS BEEN ISSUED A VALID PERMIT TO CONSTRUCT OR OPERATE BY THE SCAQMD. [RULE 1150.1, 1303(a) (1)-BACT, 40CFR60 SUBPART WWW]
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South Coast Air Quality Management District 21865 Copley Drive, Diamond Bar, CA 91765-4178 ■
Section: D Page 12 Facility 1.D.1: 119219 Revision /I: 3 Datc: January 9.2014
FACILITY PERMIT TO OPERATE CHIQUITA CANYON, LLC
16 EMISSIONS FROM FLARE NO. I SHALL NOT EXCEED THE FOLLOWING:
POLLUTANT LBS/HR
CO 5.6 NOX AS NO2 3.9 PM10 1.4 RUG 0.92 SOX AS SO2 2.5 [RULE 1303(a) (I) -BACT, RULE 1303(b) (1) AND (b) (2)-MODELING AND OFFSET, 1401]
17 EMISSIONS FROM FLARE NO. 2 SHALL NOT EXCEED THE FOLLOWING:
POLLUTANT LBS/HR
CO 7.2 NOX AS NO2 2.4 PMIO 1.4 ROG 133 SOX AS SO2 2.5 [RULE 1303(a) (1) -BACT, RULE 1303(b) (1) AND (b) (2)-MODELING AND OFFSET, 1401]
18. THE OPERATOR SHALL OPERATE AND MAINTAIN THIS EQUIPMENT ACCORDING TO THE FOLLOWING REQUIREMENTS:
THE EXHAUST TEMPERATURE SHALL BE MAINTAINED AT A MINIMUM OF 1,400 DEGREES FAHRENHEIT (FOR F-1 & F-2) WHENEVER THE EQUIPMENT IT SERVES IS IN OPERATION.
CONTINUOUS EXHAUST TEMPERATURE MONITORING AND RECORDING SYSTEM SHALL BE PURSUANT TO THE OPERATION AND MAINTENANCE REQUIREMENTS SPECIFIED IN 40 CFR PART 64.7. SUCH A SYSTEM SHALL HAVE AN ACCURACY OF WITHIN ±1% OF THE TEMPERATURE BEING MONITORED AND SHALL BE INSPECTED, MAINTAINED, AND CALIBRATED ON AN ANNUAL BASIS IN ACCORDANCE WITH THE MANUFACTURER'S SPECIFICATIONS USING AN APPLICABLE SCAQMD OR EPA APPROVED METHOD.
FOR THE PURPOSE OF THIS CONDITION, A DEVIATION SHALL BE DEFINED AS WHEN A TEMPERATURE OF LESS THAN 1,400 DEGREES FAHRENHEIT (FOR F-I & F-2) OCCURS DURTNG NORMAL OPERATION EXCEPT DURING STARTUPS OR SHUTDOWNS, NOT TO EXCEED 30 MINUTES. THE EXHAUST TEMPERATURE SHALL BE AVERAGED OVER A 15-MINUTE PERIOD,
AND HOURLY AVERAGE SHALL BE COMPUTED FROM SUCH DATA POINTS. THE OPERATOR SHALL REVIEW THE RECORDS OF TEMPERATURE ON A DAILY BASIS TO DETERMINE IF A DEVIATION OCCURS OR SHALL INSTALL AN ALARM SYSTEM TO ALERT THE OPERATOR WHEN A DEVIATION OCCURS.
SEMI-ANNUAL REPORTING SPECIFIED IN CONDITION NO. 23 IN SECTION K, WHENEVER A DEVIATION OCCURS IN WHICH THE TEMPERATURE OF THE FLARE FALLS BELOW 1,400 DEGREES FAHRENHEIT, THE OPERATOR SHALL TAKE NECESSARY CORRECTIVE ACTIONS AS EXPEDITIOUSLY AS PRACTICABLE IN ACCORDANCE WITH GOOD AIR POLLUTION CONTROL
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South Coast Air Quality Management District 21865 Copley Drive, Diamond Bar, CA 91765-4178
Section: D Page 13 Facility I.D.II: 119219 Revision II: 3 Date: January 9,2014
PRACTICES FOR MINIMIZING EMISSIONS. RECORDS OF THE DURATION AND CAUSE (INCLUDING UNKNOWN CAUSE, IF APPLICABLE) OF THE DEVIATION AND THE CORRECTIVE ACTIONS TAKEN SHALL BE INCLUDED IN THE SEMI-ANNUAL REPORTING.
ALL DEVIATIONS SHALL BE REPORTED TO THE SCAQMD ON A SEMI-ANNUAL BASIS PURSUANT TO THE REQUIREMENTS SPECIFIED IN 40 CFR PART 64.9 AND CONDITION NOS. 22 AND 23 IN SECTION K OF THIS PERMIT.
THE OPERATOR SHALL SUBMIT AN APPLICATION WITH A QUALITY IMPROVEMENT PLAN (QIP) IN ACCORDANCE WITH 40 CFR PART 64.8 TO THE SCAQMD IF AN ACCUMULATION OF DEVIATIONS EXCEEDS 5 PERCENT DURATION OF THIS EQUIPMENT'S TOTAL OPERATING TIME FOR ANY SEMI-ANNUAL REPORTING PERIOD SPECIFIED IN CONDITION NO. 23 IN SECTION K OF THIS PERMIT. THE REQUIRED QIP SHALL BE SUBMITTED TO THE SCAQMD WITHIN 90 CALENDAR DAYS AFTER THE DUE DATE FOR THE SEMI-ANNUAL MONITORING REPORT.
THE OPERATOR SHALL KEEP ADEQUATE RECORDS IN A FORMAT THAT IS ACCEPTABLE TO THE SCAQMD TO DEMONSTRATE COMPLIANCE WITH ALL APPLICABLE REQUIREMENTS SPECIFIED IN THIS CONDITION AND 40 CFR PART 64.9 FOR A MINIMUM OF FIVE YEARS. [40CFR PART 64]
19. OPERATION OF THIS EQUIPMENT SHALL NOT RESULT IN THE RELEASE OF RAW LANDFILL GAS INTO THE ATMOSPHERE. ANY BREAKDOWN OR MALFUNCTION OF THIS EQUIPMENT RESULTING IN THE EMISSION OF RAW LANDFILL GAS SHALL BE REPORTED TO THE SCAQMD WITHIN TWENTY FOUR HOURS AFTER OCCURRENCE AND IMMEDIATE REMEDIAL MEASURES SHALL BE UNDERTAKEN TO CORRECT THE PROBLEM AND PREVENT FURTHER EMISSIONS INTO THE ATMOSPHERE. [RULE 430]
20. THE APPLICANT SHALL CONDUCT A GAS LEAK DETECTION PROGRAM WITH A COMBUSTIBLE DETECTOR CALIBRATED FOR METHANE BY INSPECTING THE BLOWERS AND ALL EQUIPMENT DOWNSTREAM OF THE BLOWERS. THIS INSPECTION PROGRAM SHALL BE CONDUCTED ONCE A WEEK. ALL LEAKS DETECTED ABOVE 500 PPM SHALL BE REPORTED TO THE SCAQMD WITHIN
21 HOURS OF DETECTION AND REPAIRED WITHIN 3 WORKING DAYS OF DETECTION. A LOG SHOWING THE RESULTS OF EACH INSPECTION SHALL BE MAINTAINED AND SHALL BE AVAILABLE TO SCAQMD PERSONNEL UPON REQUEST. [RULE I303(a) (I)-BACT, RULE 402]
22. ALL RECORDS SHALL BE KEPT AND MAINTAINED FOR AT LEAST FIVE YEARS AND SHALL BE MADE AVAILABLE TO SCAQMD PERSONNEL UPON REQUEST. [RULE3004 (a) (4)]
Emissions and Requirements:
23. THIS EQUIPMENT IS SUBJECT TO THE APPLICABLE REQUIREMENTS OF THE FOLLOWING RULES AND REGULATIONS:
Horizon Air Measurement Services, Inc. C33-026-FR (2018)
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South Coast Air Quality Management District
MOP-a15A LA-11-Mbi
21865 Copley Drive, Diamond Bar, CA 91765-4178 (909) 396-2000 • www.aqmd.gov
March 15,2017
Mr. Richard Vacherot Horizon Air Measurement Services, Inc. 310 Cortez Circle Camarillo, CA 93012
Subject: LAP Approval Notice Reference # 94LA0211
Dear Mr. Vacherot:
We completed our review of the renewal application you submitted for approval under the South Coast Air Quality Management District's Laboratory Approval Program (SCAQMD LAP). We are pleased to inform you that your firm is approved for the period beginning May 31, 2017, and ending May 31, 2018 for the following methods:
Thank you for participating in the SCAQMD LAP. Your cooperation helps us to achieve the goal of the LAP: to maintain high standards of quality in the sampling and analysis of source emissions. You may direct any questions or information to LAP Coordinator, Glenn Kasai. He may be reached by telephone at (909) 396-2271, or via e-mail at [email protected].
Sincerely,
Dipankar Sarkar Program Supervisor Source Test Engineering
DS:G1(./gk
170315 LapRenewal.doc
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APPENDIX K - No Conflict of Interest Form
Horizon Air Measurement Services, Inc. C33-026-FR (2018)
STATEMENT OF No CONFLICT OF INTEREST AS AN INDEPENDENT TESTING LABORATORY
(To be completed by authorized source testing firm representative and included in source test report)
The following facility and equipment were tested by my source testing firm, and are the subjects of this Statement:
Facility ID: 119219
Facility Name: Chiquita Canyon Landfill
Equipment Address: 29201 Henry Mayo Drive
Castaic, California 91384
Equipment Tested: Flare No. 2
Device ID, A/N, P/N: A/N 491442
Date(s) Tested: 12/20/17
I state, as its legally authorized representative, that the source testing firm of:
Source Test Firm: Business Address:
Horizon Air Measurement Serivces, Inc. 310 Cortez Circle Camarillo, CA 93012
is an "Independent Testing Laboratory" as defined in District Rule 304(k):
For the purposes of this Rule, when an independent testing laboratory is used for the purposes of establishing compliance with District rules or to obtain a District permit to operate, it must meet all of the following criteria: (1) The testing laboratory shall have no financial interest in the company or facility being
tested, or in the parent company or any subsidiary thereof (2) The company or facility being tested, or parent company or any subsidiary thereof shall
have no financial interest in the testing laboratory; (3) Any company or facility responsible for the emission of significant quantities of
pollutants to the atmosphere, or parent company or any subsidiary thereof shall have no financial interest in the testing laboratory; and
(4) The testing laboratory shall not be in partnership with, own or be owned by, in part or in full, the contractor who has provided or installed equipment (basic or control), or monitoring systems, or is providing maintenance for installed equipment or monitoring systems, for the company being tested.
Furthermore, I state that any contracts or agreements entered into by my source testing firm and the facility referenced above, or its designated contractor(s), either verbal or written, are not contingent upon the outcome of the source testing, or the source testing information provided to the SCAQMD.
Form ST-110 : No Conflict of Interest.wpd (Revised 10/07/04)
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Horizon Air Measurement Services, Inc. C33-026-FR (2018)