Contents. Purpose. 1.Measurement Condition. 2.Sample. 3.Standard Requirement. 4.Contents of evaluation. 5.Result. 6.Conclusion. 7.Notices.

Similar documents
ElvaX Sulfur in Oil analyzer

1) Analysis of Ultra Low Sulfur in Automotive Fuels According to ASTM D by Sulfur Analyzer Micro-Z ULS (Rigaku Application Note XRF1053)

Article: Sulfur Testing VPS Quality Approach By Dr Sunil Kumar Laboratory Manager Fujairah, UAE

SPECTRO XRF Report. SPECTRO iq II

Low cost EDXRF elemental analyzer

Sulfur in Oil Analyzer

EDXRF APPLICATION NOTE SULFUR IN BUNKER FUEL # 1230

Are You Prepared For Tier 3 Gasoline Standards? Presented by: Shaun Spiro and Leslie Johnson

Elemental Analysis Advanced

ASTM D7039. Sulfur analysis plus a further 21 elements by MWDXRF. Model SS1000-S Sulfur in oil, petrol, diesel All liquids The new S1000 series MWDXRF

ISO 8754 INTERNATIONAL STANDARD. Petroleum products Determination of sulfur content Energy-dispersive X-ray fluorescence spectrometry

MESA-7220 Multi-Element Analyzer Using EDXRF Technology

MESA-7220 Measurement of Sulfur, Chlorine and other elements in Petroleum Products Using Mono-chromatic, Polarized EDXRF Analysis

ISO INTERNATIONAL STANDARD

University Of Oregon Additional Specifications

better analysis counts

ISO 8754 INTERNATIONAL STANDARD. Petroleum products Determination of sulfur content Energy-dispersive X-ray fluorescence spectrometry

TIER 3 MOTOR VEHICLE FUEL STANDARDS FOR DENATURED FUEL ETHANOL

Detection of Sulfur Compounds in Natural Gas According to ASTM D5504 with an Agilent Dual Plasma Sulfur Chemiluminescence Detector

Monitor Chlorine in Crude at Sub-ppm Levels

a) Solution of 53.5 g L -1 of Triton TM X-100. Solution without Triton TM X-100

Determination of Phenolic Antioxidant DBPC and DBP Levels in Electrical Insulating Oil

INTERNATIONAL MARITIME ORGANIZATION (IMO) Technical File and Copy of United States Environmental Protection Agency (EPA) Statement of Compliance

CHAPTER 4 : RESISTANCE TO PROGRESS OF A VEHICLE - MEASUREMENT METHOD ON THE ROAD - SIMULATION ON A CHASSIS DYNAMOMETER

The Analysis of Biodiesel for Inorganic Contaminants, including Sulfur, by ICP-OES

Analysis of Petroleum Samples Using the Teledyne Leeman Labs

Determination of chlorine/chlorides using MWD- XRF

Testing Instrumentation Gasboard 5020 for exhaust gases from petrol or LPG engines

High Temperature Simulated Distillation Performance Using the Agilent 8890 Gas Chromatograph

Voting Draft Standard

GC/MS Analysis of Trace Fatty Acid Methyl Esters (FAME) in Jet Fuel Using Energy Institute Method IP585

Technical File Engine Model: MD706MX (4.2L 230) - MD706MS (4.2L 200)

Photograph 1, Current feed to connector test loop

Technical Offer. Antek Model 6200 Analyzer Determine Total Sulfur and Total Nitrogen in a single analyzer

WEBINAR: WDXRF for Petrochemical Analysis More Than a One-Trick Pony. October 31,

X-ray Essentials from XOS Proven Performance

This is a new permit condition titled, "2D.1111 Subpart ZZZZ, Part 63 (Existing Non-Emergency nonblack start CI > 500 brake HP)"

Dispersed Water in Jet Turbine Fuels: Negating the Effect on Particle Counting

Determining the Ethanol Content of Denatured Fuel Ethanol Using Near Infrared. Gulf Coast Conference Patrick Ritz PAC LP

Detection of Volatile Organic Compounds in Gasoline and Diesel Using the znose Edward J. Staples, Electronic Sensor Technology

Methanol in Biodiesel by EN14110 with the HT3 and Versa Automated Headspace Analyzers. Versa HT3. Application Note. Abstract.

breakthrough versatility

Standard Operating Procedure for Detecting MEA Triazine in a Crude Oil Matrix using LONESTAR TM

Sulfur Detection at ppb Levels in Light Hydrocarbon Streams

REPORT NUMBER: MID-001 ORIGINAL ISSUE DATE: Sept 27, 2013 REVISED DATE: NA

DEVELOPMENT OF DRAFT AMENDMENTS TO MARPOL ANNEX VI. Verification issues and control mechanism and actions

COMPREHENSIVE EVALUATION OF AVL S 1065 COMPLIANT GASEOUS PEMS

Measurement Testing Plan and nvpm LTO Mass and Number Metric Development

SOUTH AFRICAN NATIONAL STANDARD

PRODUCT CONFORMITY CERTIFICATE

ULTRASONIC EXAMINATION

FEATURES AND BENEFITS

ISBN SANS 342:2006 Edition 4 SOUTH AFRICAN NATIONAL STANDARD Automotive diesel fuel Published by Standards South Africa 1 dr lategan roa

ASTM D Test to Low ppb. Contact us today for a copy of the Southwest Research Institute D-5453 Fitness for Use Report.

Analysis of Sulfur and Trace Element Content in FAME

Analysis of biodiesel oil (as per ASTM D6751 & EN 14214) using the Agilent 5100 SVDV ICP-OES

Technical Procedure for Gas Chromatography (GC-FID)

TSHR 6000 series TN/TS/TX analyzer

RRI PERFORMANCE ASSESSMENT OF AFTERMARKET PERFORMANCE MODIFICATION 1 (12)

SCOPE OF ACCREDITATION TO ISO/IEC 17025:2005

224 Sulfur Standards 224 Biodiesel 225 Crude Oil 225 Diesel 225 Isooctane 226 Mineral Oil 226 Residual Oil SCP SCIENCE

SCOPE OF ACCREDITATION TO ISO/IEC 17025:2005

QUALITY ASSURANCE & LAB ACCREDITATION

Process Analyzer. Cold Filter Plugging Point Process Analyzer CFPP-4. Credible Solutions for the Oil and Gas Industry

Closed Cup Flash Point Tester

CLASSIFICATION NOTES. Type Testing Procedure for. Crankcase Explosion Relief Valves

ASTM Consensus Standards The Latest in Packaging Testing. Presented by: Dhuanne Dodrill President Rollprint Packaging Products, Inc.

Elcometer 506 Pull- Off Adhesion Gauge. elcometer.com 1

SOUTH AFRICAN NATIONAL STANDARD

ASTM B117 Testing Quality Control

973 Dew Point Mirror. Portable Industrial Chilled Mirror Hygrometer. Typical applications: REFLECTING YOUR STANDARDS

Gas Chromatographic Analysis of Diesel Fuel Dilution for In-Service Motor Oil Using ASTM Method D7593

Stability, Linearity and Repeatability of Nitrogen Determination by Flash Combustion using Argon as Carrier Gas

High Throughput Mineral Oil Analysis (Hydrocarbon Oil Index) by GC-FID Using the Agilent Low Thermal Mass (LTM) System

Prodigy ICP Application Note: # 1039

DNVGL-CP-0110 Edition March 2016

SKN_N0106AnnexJ_R2. Annex J - Specific requirements for PVT collector Certification. 1. Introduction and definition

Proposal to establish a laboratory for combustion studies

DaimlerChrysler Alternative Particulate Measurement page 1/8

The FMM force tester can be controlled using L1 software for limit, cycling, hold and coefficient of friction testing.

Agilent 7693A Automated Liquid Sampler

Monitoring Quick Guide 5

Application Note. Abstract. Authors. Environmental Analysis

High-Pressure Differential Scanning Calorimetry

TÜV RHEINLAND ENERGIE UND UMWELT GMBH

Triple offset butterfly valve meets the stringent requirements of TA-Luft and ISO Advanced environmental protection the ZETRIX way!

Product Loss During Retail Motor Fuel Dispenser Inspection

Elcometer 506 Pull- Off Adhesion Gauge. Product Brochure/Flyer. 506 PAT Adhesion Tester

SSP-Series Portable Balances Operation Manual

A Comparison of Boat Introduction and Direct Injection using the Thermo Scientific ipro 5000 Series Combustion Analyzer

FULL AUTOMATIC ASPHALTENE ANALYZER APD-500A USER S GUIDE

X-ray Analysis in Petrochemical and Polymer Industries: Challenges and Solutions

Test Procedure for Measuring Fuel Economy and Emissions of Trucks Equipped with Aftermarket Devices

TSHR 7000 series TN-TS-TX analyzer

ANALYTICAL STUDY ON THE UNCERTAINTY OF LOAD CELLS CALIBRATED WITH DEADWEIGHT-FORCE-STANDARD MACHINE AND FORCE-COMPARATOR MACHINE

Alberta Innovates - Technology Futures ~ Fuels & Lubricants

Incubators. Incubators

Optidew Vision Optical Dew-Point Meter

Pursuing high precision, speed, and ease of use

Solid biofuels Determination of total content of sulfur and chlorine

Transcription:

ASTM D4294 :Standard Test Method for Sulfur in Petroleum and Petroleum Products by Energy Dispersive X-ray Fluorescence Spectrometry ISO8754 :Petroleum products Determination of sulfur content Energy-dispersive X-ray fluorescence spectrometry Compliance check by EDX-7000 SHIMADZU Corp.

Contents Purpose 1.Measurement Condition 2.Sample 3.Standard Requirement 4.Contents of evaluation 5.Result 6.Conclusion 7.Notices Appendix

Purpose Verify and confirm that the EDX-7000 meets the requirements of ASTM D4294-10 Verify and confirm that the EDX-7000 meets the requirements of ISO8754

1.Measurement Condition Instrument: EDX-7000 Factor Required Standard Requirement (ASTM D4249 ISO8754) Actual Condition Temperature Not specified. Room Temperature (25 ) Humidity Not specified. Normal ambient condition (50%) Changing Air Presser Warming-up Time Film Atmosphere Counting Time Not specified. ASTM: Not specified. ISO: Shall be continuously switched on. 6µm Polyester, Polypropylene, Polycarbonate, Polyimide ASTM: Air and Helium ISO: Not specified ASTM: 1 to 5minute ISO: Not specified Normal ambient condition. 15 minutes or more 5µm Polypropylene film ASTM: Air and Helium ISO: Air ASTM: 200sec and 100sec ISO: Same as ASTM D 4294

2.Sample Calibration Sample Contents of Sulfur Catalog Number Analytical Service 0, 20, 50, 100, 200, 400, 500, 600, 800, 1000ppm SMO Analytical Service 0, 0.1, 0.2, 0.5, 0.75, 1, 2, 3, 4, 5wt% SMO(HL) Measurement Sample Contents of Sulfur Catalog Number Japan Petroleum Institute(JPI) 0.00wt% S0316 JPI 0.2wt% S0245 JPI 0.5wt% S0225 JPI 1.0wt% S0226 JPI 4.0wt% S0317 SPEX 50ppm DSS8-AY SPEX 100ppm DSS8-1Y SPEX 300ppm DSS8-CY SPEX 500ppm DSS8-1AY SPEX(Diesel) 100ppm SDSF-100-Y

3.Standard Requirement S:Sulfur standard value Standard Number Request items Request content Standard criterion Repeatability The difference between results obtained by the same operator with the same apparatus under constant operating conditions on identical test material would, in the long run, in the normal and correct operation of the test method, exceed the value in only one case in twenty Base oil: r=0.4347 S 0.6446 ppm Diesel: r=1.6658 S 0.3300 ppm ASTM D4294 Reproducibility The difference two single and independent test results obtained by different operators working in different laboratories on identical test material would, in the long run, in the normal and correct operation of the test method, exceed the value in only one case in twenty. Base oil: R=1.9182 S 0.6446 ppm Diesel: R=8.9798 S 0.3300 ppm Blank Be performed before the measurement is preferably blank calibration, the value is less than 2.0ppm. 2.0ppm or less ISO8754 Repeatability Reproducibility The difference between two test results obtained by the same operator with the same apparatus under constant operating conditions on identical test material would, in the long run, in the normal and correct operation of the test method, exceed the value in only one case in twenty. The difference two single and independent test results obtained by different operators working in different laboratories on identical test material would in the long run, in the normal and correct operation of the test method, exceed the value in only one case in twenty. Concentration range (0.03<S<0.05)wt% r=0.045(s+0.05) wt% Concentration range (S>0.05)wt% r=0.0215(s+0.15) wt% Concentration range (0.03<S<0.05)wt% R=0.1781(S+0.05)wt% Concentration range (S>0.05)wt% R=0.0812(S+0.15)wt%

4. Contents of evaluation S:Sulfur standard value Standard number Test contents Contents of evaluation Standard criterion Repeatability Compare the standard criterion and the range of the measurement value through the performance of 20 times measurement with the same operator, apparatus and sample in the same laboratory. Base oil r=0.4347 S 0.6446 ppm Diesel r=1.6658 S 0.3300 ppm ASTM D4294 Reproducibility Compare the standard criterion and the range of the measurement value through the performance of 20 times measurement with the different operator, apparatus and same sample in the different laboratory. Base oil R=1.9182 S 0.6446 ppm Diesel R=8.9798 S 0.3300 ppm Blank Performs 20 measurements of sample sulfur content 0.0ppm, to obtain an maximum value. 2.0ppm or less ISO8754 Repeatability Reproducibility Compare the standard criterion and the range of the measurement value through the performance of 2 sets of 20 times measurement with the same operator, apparatus and sample in the same laboratory. Prepare the new sample and cell each set of measurement. Compare the standard criterion and the range of the measurement value through the performance of 20 times measurement with the different operator, apparatus and same sample in the different laboratory. Concentration range (0.03<S<0.05)wt% r=0.045(s+0.05) wt% Concentration range (S>0.05)wt% r=0.0215(s+0.15) wt% Concentration range (0.03<S<0.05)wt% R=0.1781(S+0.05)wt% Concentration range (S>0.05)wt% R=0.0812(S+0.15)wt%

4. Contents of evaluation Verification other items Contents of evaluation Accuracy of Calibration Curve Lower limit of detection (LLD) The content of the evaluation Evaluate the accuracy of the calibration curve. Calculate Lower limit detection from the obtained calibration curve. Lower limit of detection calculation equation L. L. D. = 3 C NET BG T A NET:Fluorescent X-ray intensity of S [cps/µa] BG:Background intensity of S[cps/µA] C:Sulfur concentration in oil[ppm] T:Integration time[sec] A:Current value[µa]

4. Contents of evaluation Standard Requirement for Criterion Standard Number Test contents Standard value Standard Criterion [ppm] ASTM D4294 ISO 8754 Standard criterion and sulfur content of the sample used in this testing. Repeatability Reproducibility 50ppm 100ppm 500ppm 0.5wt% 4.0wt% 50ppm 500ppm 4.0wt% 5.4 8.5 24 106 405 23 105 1776 Repeatability (Diesel) 100ppm 7.8 Reproducibility (Diesel) 100ppm 41 Blank 0.0ppm 2.0ppm or less Repeatability Reproducibility 300ppm 500ppm 0.2wt 1.0wt 4.0wt% 500ppm 4.0wt% 36 43 72 247 677 162 3370

5.Result 5.1 Measurement result(astm D 4294) (Judgment)<(Standard criterion) Note)Standard scope range is in colored cell, otherwise is stricter than scope range Test content Measurement time (sec) Standard criterion (ppm) Air [ppm] Judgment Result He [ppm] Judgment Repeatability Base oil 50ppm 300 5.4 5.0 OK Repeatability Base oil 100ppm 200 8.5 7.1 OK Repeatability Base oil 500ppm 200 24 16 OK 12 OK Repeatability Base oil 0.5wt% 100 102 64 OK 44 OK Repeatability Base oil 4.0wt% 100 405 257 OK 159 OK Repeatability diesel 100ppm 200 7.8 5.2 OK Repeatability Base oil 500ppm 100 24 23 OK 14 OK Repeatability Base oil 0.5wt% 50 102 80 OK 41 OK Repeatability Base oil 4.0wt% 50 405 220 OK 91 OK Reproducibility Base oil 50ppm 300 23 5.4 OK Reproducibility Base oil 500ppm 200 105 31 OK 12 OK Reproducibility Base oil 4.0wt% 100 1776 388 OK 667 OK Reproducibility Diesel 100ppm 200 41 17 OK Blank 200 2.0 1.9 OK

5.Result 5.2 Measurement result(iso8754) (Judgment)<(Standard criterion) Test content Measurement time [sec] Standard criterion [ppm] Measurement results Air[ppm] Judgment Repeatability 0.03wt% 200 36 19 OK Repeatability 0.05wt% 200 43 23 OK Repeatability 0.2wt% 100 72 35 OK Repeatability 1.0wt% 100 247 100 OK Repeatability 4.0wt% 100 677 315 OK Reproducibility 0.03wt% 200 162 38 OK Reproducibility 4.0wt% 100 3370 464 OK

5.Result 5.3 Verification other results Spectrum at air and He condition Calibration curve at He condition Air He X-ray intensity[cps/µa] Accuracy of calibration curve at 0-1000ppm range and LLD Standard value[ppm] Accuracy LLD(200sec) Air 8.66 [ppm] 5.61 [ppm] He 5.31 [ppm] 2.49 [ppm]

5.Result 5.4 Typical measured results 20 times measurements at ASTM:500ppm Air He 550 550 500ppm_Air 500ppm_He 500 500 450 0 5 10 15 20 450 0 5 10 15 20

6.Conclusion Compliant contents For Repeatability of ASTM D4294 [Base Oil] It was confirmed that EDX-7000 can comply with ASTM D4294 at sulfur concentration of 500ppm or more under the Air condition. In the He condition, EDX-7000 can also comply with ASTM D4294 at low sulfur concentration range of 50ppm. It was confirmed that EDX-7000 can comply with ASTM D4294 even if the measurement time is shorter (50sec) than the required condition. [Diesel Oil] It was confirmed that EDX-7000 can comply with ASTM D4259 at sulfur concentration of 100ppm or more under the He condition. For Reproducibility of ASTM D4294 [Base Oil] It was confirmed that EDX-7000 can comply with ASTM D4294 at sulfur concentration of 500ppm or more under the Air and He conditions. [Diesel Oil] It was confirmed that EDX-7000 can comply with ASTM D4259 at sulfur concentration of 100ppm or more under the He condition. For ISO8754 It was confirmed that EDX-7000 can comply with ISO8754 at all concentration range. ASTM D4294 Air condition ASTM D4294 He condition ISO8754 Air condition Repeatability Base oil 500ppm or more 50ppm or more All concentration range Reproducibility Base oil 500ppm or more 50ppm or more All concentration range Repeatability Diesel 100ppm or more Reproducibility Diesel 100ppm or more

7.Notices Due to the influence of the wrinkles in the film to be used, may affect the measurement result. Please measure to double check the status of the film. In particular, PET film(mylar film) is more stable than polypropylene film in the measurement of the high concentration sample. It is possible that the mylar film was suitable for measurement at long term in same sample. However, mylar film must be careful in the analysis for diffraction line is overlapped with the peak of sulfur. Effect of the film was increased by measurement under using the turret, it is following results, however it is pass the standard criterion. Base oil Stand by time until measurement Without turret With turret Standard criterion 5000ppm 3 hours 44ppm 80ppm 102 4wt% 4 hours 159ppm 314ppm 405

Appendix Certified reference material information No. S0316 S0245 S0225 S0226 Name Concentrate(wt %) Reference Materials of sulfur Reference Materials of sulfur Reference Materials of sulfur 0.5wt% equivalent Reference Materials of sulfur 0.00 0.20 0.47 1.02 Uncertainty 0.01 0.01 0.01 Density(g/cm3) 0.8600 0.8428 0.8496 0.9169 C/H 6.2 6.2 6.3 7.1 No. Name Concentrate(wt %) S0317 Reference Materials of sulfur 4.0wt% equivalent 4.01 Uncertainty 0.03 Density(g/cm3) 0.9693 C/H 8.1

Appendix Certified reference material information No. DSS8-AY DSS8-1Y DSS8-CY DSS8-1AY Description Sulfur Oil Standard Sulfur Oil Standard Sulfur Oil Standard Sulfur Oil Standard Matrix Base Oil 20 Base Oil 20 Base Oil 20 Base Oil 20 Concentrate [ppm] 50 100 300 500 Uncertainty ±1% ±1% ±1% ±1% Density(g/cm3) 0.802g/mL 0.802g/mL 0.802g/mL 0.802g/mL No. Description SDSF-100-Y Sulfur Oil Standard Matrix Concentrate (ppm) #2 Diesel Fuel 100 Uncertainty ±1% Density(g/cm3) 0.822g/mL

Appendix ASTM: Repeatability Base oil Data in air Sample Base oil Base oil Measurement time (sec) 200 100 100 100 50 50 Concentration[ppm] 500 4700 40000.0 500 4700 40000 Number of times 1 508.5 4967.3 40225.7 500.6 4946 41001.8 2 508.5 4981.4 40220.8 503.9 4957.3 41015.4 3 514.2 4972.8 40293.3 517.3 4946 40996.5 4 515.2 4982.5 40264.3 505.6 4967.8 40994 5 502.5 4988.2 40336.1 522.3 4960.2 41011.2 6 511.9 4978.7 40341.2 512.7 4951.7 41001.5 7 513.3 4990.8 40360.4 523.3 4970.4 41007 8 506.9 4991.7 40404.1 508.1 4974.2 41043.8 9 510.8 4978.5 40336.6 519.4 4974.5 41085.9 10 515.6 4984.7 40424.1 517 4950.9 40993.9 11 516.9 4993.5 40425.3 522.1 4963.4 41073.2 12 514.9 4991.7 40301.4 511.6 4946.5 41068.1 13 518.6 4990.2 40372 518.7 4980.1 41110 14 515 4971.6 40380.1 517.5 4987.1 41130 15 512.5 4973.4 40454.3 516.5 4967.4 41133 16 507 5020.4 40360.2 507.9 4945.9 41121.8 17 516.9 4956.9 40390.1 508.2 4938.6 41182.8 18 516.5 4971.3 40398.4 509.6 4958.6 41175.8 19 504.9 5010.7 40370.6 516.9 4945.9 41206.6 20 511.3 4973.8 40477.7 513.2 4907.4 41213.7 Average 512.09 4983.50 40356.83 513.62 4956.99 41078.3 Standard deviation 4.45 14.65 69.52 6.494 17.715 76.56 Maximum 518.6 5020.4 40477.7 523.3 4987.1 41213.7 Minimum 502.5 4956.9 40220.8 500.6 4907.4 40993.9 Range 16.1 63.5 256.9 22.7 79.7 219.8 Criterion 24.02 101.83 404.91 24.02 101.83 404.91 Judgment OK OK OK OK OK OK

Appendix ASTM: Reproducibility Base oil Data in air Sample Base oil A B A B Measurement time[sec] 200 100 Concentration[ppm] 500 40000 1 508.5 489.2 40225.7 40129.5 2 508.5 490.8 40220.8 40205.2 3 514.2 487.4 40293.3 40238.4 4 515.2 490.8 40264.3 40225.4 5 502.5 491.8 40336.1 40296.5 6 511.9 492.1 40341.2 40315.9 7 513.3 489.2 40360.4 40340.3 8 506.9 497.6 40404.1 40337.7 9 510.8 494.3 40336.6 40358.7 10 515.6 494.6 40424.1 40307.1 11 516.9 498.9 40425.3 40380.1 12 514.9 495.7 40301.4 40376.1 13 518.6 503.5 40372 40430.5 14 515 498.4 40380.1 40384.4 15 512.5 501.3 40454.3 40432.6 16 507 500.4 40360.2 40382.6 17 516.9 500.2 40390.1 40455.4 18 516.5 503.8 40398.4 40455.9 19 504.9 499.8 40370.6 40485.5 20 511.3 496.7 40477.7 40517.9 Number of times Average 512.09 495.82 40356.84 40352.79 Standard deviation 4.45 4.98 69.52 99.89 Maximum 518.6 503.8 40477.7 40517.9 Minimum 502.5 487.4 40220.8 40129.5 Range 31.2 388.4 Criterion 105.35 1775.74 Judgment OK OK

Appendix Base oil Diesel Base oil Blank Measurement time[sec] 300 200 200 100 100 200 100 50 50 200 Concentration [ppm] 50 100 500 4700 40000.0 100 500 4700 4.0 0.00 1 51.3 49.1 108.9 101.4 500.6 4722 39895.2 104 522.6 4614.4 39383.5-1.4-0.6 2 52.7 50 109 101.1 499.6 4723.5 39962.4 105.4 519.5 4624.4 39402.4-1.9-3.5 3 49.7 49 109.6 100.4 498.6 4727.2 39997.6 105.4 520.4 4616.1 39403-3.7 1.8 4 51.3 49.6 107.9 100.9 496 4741 40070.3 104.4 517.3 4630 39428.1-2.7-1.4 5 52 50.4 106.3 102.2 496.3 4738.8 40084.5 104.7 523.9 4631.4 39513.7 0.6-0.8 6 51.8 51.9 108.1 100 499.5 4738.7 40117.4 105 525.9 4624.6 39516.5 0.4-3.2 7 51 50.4 110.2 98.2 497.6 4739 40140 106.5 527.5 4638.1 39453.2-1.1-1.3 8 48.9 51.5 109.5 97.3 497 4740 40113.7 105.8 516.9 4614.9 39453.3 1.9-4.2 9 49.2 47.7 109.8 99.6 495.3 4746.3 40143.2 104.3 523.8 4634.1 39437.4-0.5-0.9 Number 10 48.9 50.5 108.7 98 495.4 4756.9 40103.4 105.9 524.2 4642.2 39494-0.9-0.4 of times 11 52.2 49.1 109.7 99 493.9 4751.2 40127.3 105 522.8 4631 39542.9-2.2-4.4 12 51.2 49 110 97.2 493.2 4745.4 40106.5 102.4 530.4 4633.8 39501.9-3.6-1.6 13 47.7 50.4 109.6 95.3 494.1 4754.4 40172.8 104.4 525.4 4647.8 39521.2-3.5 0.4 14 48.7 50.3 108.2 96.9 495 4753.2 40183.2 101.3 525 4639.7 39539.1-1.2-1.1 15 50.2 49.1 111 97.2 490.8 4753.8 40134.2 102.9 527 4633.4 39511.2-3.2 0.4 16 49.9 47.7 110.9 95.1 491.2 4745.8 40163.1 103.7 529.1 4655.1 39505.3-2 -1 17 51.9 47.7 109 97.2 492.4 4756.4 40208.9 105.1 529.4 4625.3 39520.7-1 -0.6 18 50.5 48.6 109.2 96.1 489.8 4765.7 40171.2 103 521 4637.5 39492 1.1-0.4 19 50.4 49.2 106.6 97.2 490.4 4766.4 40204.8 105 524.8 4638 39514-2 -1.7 20 48 49.7 107.6 98.4 488.5 4755.5 40173.2 102.4 527.3 4635.6 39472.8-1.6-1.4 Average 50.37 49.54 108.99 98.43 494.76 4746.06 40113.64 104.33 524.21 4632.37 39480.31-1.42-1.29 Standard deviation 1.46 1.16 1.25 2.05 3.50 12.52 80.83 1.35 3.80 10.42 48.18 1.57 1.54 Maximum 52.7 51.9 111 102.2 500.6 4766.4 40208.9 106.5 530.4 4655.1 39542.9 1.9 1.8 Minimum 47.7 47.7 106.3 95.1 488.5 4722 39895.2 101.3 516.9 4614.4 39383.5-3.7-4.4 Range (Max when Bkank) ASTM: Repeatability Data in He 5 4.2 4.7 7.1 12.1 44.4 313.7 5.2 13.5 40.7 159.4 1.9 1.8 Criterion 5.44 5.44 8.514 8.512 24.02 101.83 404.91 7.81 24.02 101.83 404.91 2.00 2.00 Judgment OK OK OK OK OK OK OK OK OK OK OK OK OK

Appendix ASTM: Reproducibility Data in He Sample Base oil Diesel A B A B A B A B Measurement time[sec] 300 200 100 200 Concentration[ppm] 50 500 40000 100 Number of times 1 51.3 52.6 500.6 492.1 39383.5 39932.3 104 113.3 2 52.7 52.6 499.6 490.7 39402.4 40003.6 105.4 114.5 3 49.7 52.1 498.6 492.2 39403 39909.9 105.4 111.6 4 51.3 53 496 492.8 39428.1 40029.3 104.4 110.4 5 52 51 496.3 492.5 39513.7 39996.7 104.7 112.2 6 51.8 49.7 499.5 493.4 39516.5 40000.1 105 112.6 7 51 49.5 497.6 496.3 39453.2 40018 106.5 111.7 8 48.9 51.4 497 491.6 39453.3 40004.8 105.8 114.7 9 49.2 53.1 495.3 495.1 39437.4 39951.6 104.3 113.8 10 48.9 50.4 495.4 493.4 39494 39974 105.9 114.6 11 52.2 50.4 493.9 490.2 39542.9 39974.5 105 115.4 12 51.2 50.5 493.2 494.2 39501.9 40024.1 102.4 115.6 13 47.7 48.1 494.1 490.6 39521.2 39936.4 104.4 115 14 48.7 49.8 495 494.8 39539.1 40026.2 101.3 115 15 50.2 50.7 490.8 493.3 39511.2 40019.8 102.9 115.6 16 49.9 50.2 491.2 493.6 39505.3 40008.4 103.7 116.8 17 51.9 51.5 492.4 496.6 39520.7 40027.5 105.1 117 18 50.5 50.6 489.8 497.1 39492 40034.2 103 117.9 19 50.4 51.5 490.4 495.6 39514 40016.9 105 118.4 20 48 51.3 488.5 496.7 39472.8 40050.4 102.4 114.7 Average 50.375 51 494.76 493.64 39480.31 39996.94 104.33 114.54 Standard deviation 1.424386 1.247798 3.50 2.11 48.18 38.34 1.35 2.127 Maximum 52.7 53.1 500.6 497.1 39542.9 40050.4 106.5 118.4 Minimum 47.7 48.1 488.5 490.2 39383.5 39909.9 101.3 110.4 Range 5.4 12.1 666.9 17.1 Criterion 23.88 105.35 1775.75 41.04 Judgment OK OK OK OK

Appendix ISO: Repeatability Base oil Data in air Sample Base oil Measurement time[sec] 200 200 100 100 100 Concentration[ppm] 300 500 2000 10000 40000 1 set 2set 1set 2set 1set 2set 1set 2set 1set 2set 1 318.1 312.6 505.9 508.3 2159.9 2150.1 10870.9 10804.4 40430.2 40396.6 2 316.4 313.1 509.2 505.5 2145.2 2140 10844.9 10805.5 40423.3 40391.4 3 321.1 305.3 522.4 511.5 2141.1 2144.1 10856.2 10794.3 40478.4 40467.7 4 315.8 305.5 510.9 508.3 2163.7 2144.1 10817.9 10793.5 40420.4 40437.2 5 322.2 316.9 527.3 505 2139.7 2145.2 10851.1 10789.7 40499.6 40512.8 6 314.8 321.4 517.9 509.1 2142.8 2135.2 10867.6 10795.8 40461.9 40518.2 7 309.5 310.3 528.4 519.7 2159.8 2134.6 10860 10813.1 40379.3 40538.4 8 314.5 310.4 513.3 517.7 2156.4 2140.7 10870 10801.4 40421 40584.4 9 318.1 310.8 524.5 507.2 2141.7 2147.8 10848.8 10803.1 40390.8 40513.3 Number of 10 316.9 324.5 522.1 526.3 2142.7 2150.1 10821.1 10845.1 40372.3 40605.4 times 11 317.8 309.6 527.1 527.8 2155 2147.6 10878.2 10800.4 40392.2 40606.7 12 318.1 310.9 516.8 523.6 2152.5 2146.7 10859.5 10787.5 40409.5 40476.2 13 322.9 306.9 523.8 506.2 2152.3 2141.5 10879.6 10817.9 40352.1 40550.6 14 311 311.3 522.6 526.7 2156.3 2157.5 10861.8 10788.4 40471.5 40559.1 15 314 312 521.6 516.9 2149.1 2147.6 10869.2 10799.1 40384.5 40637.3 16 321.4 309.8 513.1 507.6 2156.9 2148 10865.9 10826.4 40429.2 40538.2 17 316.2 314.4 513.4 524.6 2167.6 2132.2 10876.7 10831.7 40388.4 40569.7 18 313.2 310 514.9 517.6 2157.5 2147.2 10887.2 10835.8 40397.5 40578.4 19 318.9 318.8 522 520.2 2166.7 2149.7 10865.6 10799.9 40346.4 40549.1 20 314.1 312.4 518.4 509.5 2147.5 2142.8 10885.9 10811.5 40427.7 40661.8 Average 316.75 312.34 518.78 514.96 2152.72 2144.63 10861.90 10807.22 40413.81 40534.62 Standard deviation 3.57 4.90 6.40 7.98 8.68 6.05 18.49 16.46 41.104 73.19 Maximum 322.9 324.5 528.4 527.8 2167.6 2157.5 10887.2 10845.1 40499.6 40661.8 Minimum 309.5 305.3 505.9 505 2139.7 2132.2 10817.9 10787.5 40346.4 40391.4 Range 19.2 23.4 35.4 99.7 315.4 Criterion 36.32 43 75.25 247.25 677.25 Judgment OK OK OK OK OK

Appendix ISO: Reproducibility Base oil Data in air Base oil Measurement time[sec] 200 100 Concentration[ppm] 500 40000 A B A B Number of times 1 505.9 492.3 40430.2 40035.5 2 509.2 494 40423.3 40118.9 3 522.4 490.6 40478.4 40142.6 4 510.9 493.9 40420.4 40147 5 527.3 494.9 40499.6 40204 6 517.9 495.3 40461.9 40230.1 7 528.4 492.4 40379.3 40252.4 8 513.3 500.7 40421 40260 9 524.5 497.4 40390.8 40261.6 10 522.1 497.7 40372.3 40216.7 11 527.1 502 40392.2 40294.2 12 516.8 498.8 40409.5 40300.7 13 523.8 506.6 40352.1 40336.4 14 522.6 501.5 40471.5 40295 15 521.6 504.4 40384.5 40357 16 513.1 503.5 40429.2 40285.1 17 513.4 503.3 40388.4 40367.1 18 514.9 506.8 40397.5 40370.7 19 522 502.8 40346.4 40398 20 518.4 499.8 40427.7 40431.6 Average 518.78 498.93 40413.81 40265.23 Standard deviation 6.40 4.94 41.10 101.15 Maximum 528.4 506.8 40499.6 40431.6 Minimum 505.9 490.6 40346.4 40035.5 Range 37.8 464.1 Criterion 162.4 3369.8 Judgment OK OK