Astm d5453

Designation: D5453 − 12Standard Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence1 This standard is issued under the fixed designation D5453; 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 (´) indicates an editorial change since the last revision or reapproval. 1. Scope* 2. Referenced Documents 1.1 This test method covers the determination of total sulfur 2.1 ASTM Standards:2 in liquid hydrocarbons, boiling in the range from approxi- D1298 Test Method for Density, Relative Density, or API mately 25 to 400°C, with viscosities between approximately Gravity of Crude Petroleum and Liquid Petroleum Prod- 0.2 and 20 cSt (mm 2/S) at room temperature. ucts by Hydrometer Method D4052 Test Method for Density, Relative Density, and API 1.2 Three separate interlaboratory studies (ILS) on Gravity of Liquids by Digital Density Meter precision, and three other investigations that resulted in an D4057 Practice for Manual Sampling of Petroleum and ASTM research report, have determined that this test method is Petroleum Products applicable to naphthas, distillates, engine oil, ethanol, Fatty D4177 Practice for Automatic Sampling of Petroleum and Acid Methyl Ester (FAME), and engine fuel such as gasoline, oxygen enriched gasoline (ethanol blends, E-85, M-85, RFG), Petroleum Products diesel, biodiesel, diesel/biodiesel blends, and jet fuel. Samples D6299 Practice for Applying Statistical Quality Assurance containing 1.0 to 8000 mg/kg total sulfur can be analyzed and Control Charting Techniques to Evaluate Analytical (Note 1). Measurement System Performance NOTE 1—Estimates of the pooled limit of quantification (PLOQ) for the 3. Summary of Test Method precision studies were calculated. Values ranged between less than 1.0 and less than 5.0 mg/kg (see Section 8 and 15.1). 3.1 A hydrocarbon sample is either directly injected or placed in a sample boat. The sample or boat, or both, is inserted 1.3 This test method is applicable for total sulfur determi- into a high temperature combustion tube where the sulfur is nation in liquid hydrocarbons containing less than 0.35 % oxidized to sulfur dioxide (SO2) in an oxygen rich atmosphere. (m ⁄m) halogen(s). Water produced during the sample combustion is removed and 1.4 The values stated in SI units are to be regarded as the sample combustion gases are next exposed to ultraviolet standard. No other units of measurement are included in this (UV) light. The SO2 absorbs the energy from the UV light and standard. is converted to excited sulfur dioxide (SO2*). The fluorescence emitted from the excited SO2* as it returns to a stable state, 1.5 This standard does not purport to address all of the SO2, is detected by a photomultiplier tube and the resulting safety concerns, if any, associated with its use. It is the signal is a measure of the sulfur contained in the sample. responsibility of the user of this standard to establish appro- (Warning—Exposure to excessive quantities of ultraviolet priate safety and health practices and determine the applica- (UV) light is injurious to health. The operator must avoid bility of regulatory limitations prior to use. For warning exposing any part of their person, especially their eyes, not statements, see 3.1, 6.3, 6.4, Section 7, and 8.1. only to direct UV light but also to secondary or scattered radiation that is present.) 1 This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of 2 Subcommittee D02.03 on Elemental Analysis. For referenced ASTM standards, visit the ASTM website, www.astm.org, or Current edition approved Nov. 1, 2012. Published February 2013. Originally contact ASTM Customer Service at [email protected]. For Annual Book of ASTM approved in 1993. Last previous edition approved in 2009 as D5453–09. DOI: Standards volume information, refer to the standard’s Document Summary page on 10.1520/D5453-12. the ASTM website. *A Summary of Changes section appears at the end of this standard Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States Copyright by ASTM Int'l (all rights reserved); 1 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. No further reproductions authorized. D5453 − 12 FIG. The oxidation section sample into the oxidation zone at a controlled and repeatable shall be large enough (see Fig.6 Microlitre Syringe—A microlitre syringe capable of (1075 6 25°C) sufficient to pyrolyze all of the sample and accurately delivering 5 to 20-µL quantities.3 Flow Control—The apparatus must be equipped with provides a seal to the inlet of the oxidation area and is swept by flow controllers capable of maintaining a constant supply of a carrier gas. see Fig. 1) to ensure complete combus. and can also be used for purposes of regulatory selective capillary action for water removal.1 Furnace—An electric furnace held at a temperature 5. rate. Apparatus fluorescence of sulfur dioxide by UV light. A syringe drive mechanism which discharges the sample tion of the sample. . or a permeation dryer. The combustion tube must have side arms for the to be analyzed into an inlet carrier stream which directs the introduction of oxygen and carrier gas. degraded.1 Some process catalysts used in petroleum and chemical mechanism for the removal of water vapor. The system provides an area to position the oxygen and carrier gas. Other configurations are acceptable if precision is not required. 2. 2 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement.5 UV Fluorescence Detector—A qualitative and quantita- tive detector capable of measuring light emitted from the 5. 5. Significance and Use 5. Fig. 5.4 Drier Tube—The apparatus must be equipped with a 4. 5. sample carrying mechanism (boat) at a retracted position Copyright by ASTM Int'l (all rights reserved). 5. that utilizes a products. The needle shall be oxidize sulfur to SO2.7. 1 depicts conventional combustion from the microlitre syringe at a rate of approximately 1 µL/s is tubes. This can be accomplished with be used to determine sulfur in process feeds sulfur in finished a membrane drying tube.2 Combustion Tube—A quartz combustion tube con. No further reproductions authorized. The oxidation refining can be poisoned when trace amounts of sulfur bearing reaction produces water vapor which must be eliminated prior materials are contained in the feedstocks. 5. For example. 1 Conventional Combustion Tubes 4.2 Boat Inlet System—An extended combustion tube 5.7. 50 mm (65 mm) long.7 Sample Inlet System—Either of two types of sample structed to allow the direct injection of the sample into the inlet systems can be used. This test method can to measurement by the detector. control.1 Direct Injection—A direct injection inlet system must inlet end of the tube is large enough to accommodate a quartz be capable of allowing the quantitative delivery of the material sample boat. heated oxidation zone of the furnace or constructed so that the 5. 3 Oxygen—High purity (that is. 99. dried over molecular sieves. Pharmacopeial Convention.6 Butyl Sulfide. (optional). American Chemical Society Specifications.K. on Analytical Reagents of the American Chemical Society. A drive mechanism which purity. For 6.1 Purity of Reagents—Reagent grade chemicals shall be correction unnecessary.10 Balance. see Fig. Inc..8 Refrigerated Circulator—An adjustable apparatus ca. chromatography or zero example. 3. moisture 5 ppm w/w maximum. it is intended that all 6. provided it is first ascertained that the reagent is of fully insert the boat into the hottest section of the furnace inlet. U. chromatography or zero grade).) pable of delivering a coolant material at a constant temperature as low as 4°C could be required when using the boat inlet 6. . reagent grade (other sol- injection method (optional). (that is.. (Warning—Flammable solvents. BDH Ltd. FW146. Reagents sulphur content in the sample unknown makes the blank 6.S. use of a solvent with nondetectable level of sulfur contamination relative to the 6. No further reproductions authorized. Rockville.399 % (m/m) S (Note reagents shall conform to the specifications of the Committee 2).7 Thionaphthene (Benzothiophene) . 3 Reagent Chemicals. 17. Correction for sulfur contribution from sol- 5.2 Inert Gas—Argon or helium only.01 mg (optional). FW184. moisture 5 ppm w/w maximum. grade). The boat drive mechanism will used.8 Quartz Wool. Vigorously accelerates combustion. 3 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. DC.90 % (m/m) S (Note 2).4 Toluene. American Chemical Society. see Annual Standards for Laboratory Chemicals.9 Strip Chart Recorder.29. U.3 Other grades may be 6. 6. Copyright by ASTM Int'l (all rights reserved). The combustion tube provides a cooling jacket for the 6. stable and capable of withstanding temperatures inside the MD. advances and withdraws the sample boat into and out of the furnace at a controlled and repeatable rate is required. Washington. Alternatively. with a precision of 60.75 % minimum purity. Xylenes. FW134.20. 99.92 % (m/m) S (Note 2). specimen dilution is required. sufficiently high purity to permit its use without lessening the The sample boats and combustion tube are constructed of accuracy of the determination. D5453 − 12 FIG. (USPC). vents similar to those occurring in samples to be analyzed are also acceptable). quartz. and the United States Pharmacopeia 6. 2 Direct Inject Syringe Drive removed from the furnace. furnace (see Note 3).26. Isooctane . or other suitable absorbent material that is and National Formulary.) used in tests.998 % minimum duction from a microlitre syringe. Poole. high purity grade area in which the retracted boat rests awaiting sample intro. vents (solvent blank) used in standard preparation and sample 5. listed by the American Chemical Society. (Warning— 5. 21. For Suggestions on the testing of reagents not NOTE 2—A correction for chemical impurity can be required.5 Dibenzothiophene. where such specifications are available. 23. Unless otherwise indicated. Dorset. This stock can be further diluted some samples. Samples shall be analyzed as soon as possible after taking from bulk supplies to prevent loss of sulfur or contami- NOTE 4—Working standards that simulate or match the composition or nation due to exposure or contact with sample container.1 Assemble and leak check apparatus according to manu- representative of the samples of interest.2 If the test unit is not used immediately. checked for accuracy and if precision is not degraded. For such samples. care must be exercised when using flammable materials near mendations for further guidance. stock solutions have container.4184 g of 8. sample introduction. (Warning—Samples that are collected at temperatures below NOTE 5—Working standards should be remixed on a regular basis room temperature can undergo expansion and rupture the depending upon frequency of use and age. No further reproductions authorized. to meet conditions described in Table 1. Hazards uniform injection of the sample into the boat by wicking any remaining drops of the sample from the tip of the syringe needle prior to introduction 7. 6. 8. Extra of the sample into the furnace. preferably are portions of one or more liquid petroleum materials that are stable and 9. Sampling solution by accurately weighing approximately 0. matrix of the samples analyzed can reduce test result bias between direct inject and boat sample inlet systems. 3 Boat Inlet System NOTE 3—Materials meeting the requirements in 6. These QC samples facturer’s instructions.1 High temperature is employed in this test method.5748 g of dibenzothiophene or 0. Copyright by ASTM Int'l (all rights reserved). a useful life of about 3 months.10 Quality Control (QC) Samples . 9. can be used to check the validity of the testing process as 9.4562 g of butyl sulfide or 0. leave sufficient air space above the sample to allow room for NOTE 6—Calibration standards can be prepared and diluted on a expansion. Dilute to Practice D4177. depending upon the method of described in Section 14. . then thoroughly NOTE 7—Calibration standards from commercial sources can be used if mix in its container prior to taking a test specimen. do not uncover samples any longer than to desired sulfur concentration (Notes 4-7). Typically. Preparation of Apparatus 6. D5453 − 12 FIG. To preserve volatile components which are in volume with selected solvent. 1000 µg S/mL—Prepare a stock 8. necessary. do not fill the container to the top.8 provide a more 7.2 Adjust the apparatus. 4 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. Consult instrument manufacturer recom.9 Sulfur Stock Solution. the oxidative pyrolysis furnace.1 Obtain a test unit in accordance with Practice D4057 or thionaphthene into a tared 100 mL volumetric flask.) mass/mass basis when result calculations are adjusted to accommodate them. scale mark and record the volume of liquid in the syringe.4–0. The use of a refrigerated circulator to combustion is not compromised and accuracy/precision are not degraded. materials. This procedure can provide greater accuracy checked each day of use.4. Remove syringe once the apparatus has returned calibration bracket the concentrations of the samples being to a stable baseline.00 25. withdrawn from the furnace (Note 12). .2 Fill the syringe as described in 10. 10. Calibration and Standardization techniques available. a curve plotting of the average integrated detector response ( 10.50 5. than the volume delivery method.00 10. Remove the curve can vary. The number of standards used per displace the last drop from the syringe needle.2 Flush the microlitre syringe several times with the and vaporization of the sample begins.00 5.0 µg. For volatile a calibration point equal to 1000 ng or 1. After injection. 5 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. Weigh the y-axis) versus micrograms of sulfur injected (x-axis) (Note 13).00 Inlet oxygen flowmeter setting (0. Allow those indicated may be used.4). Direct injection techniques available. again retract the 10. if equivalent results are obtained. Once the boat has 10. Instrument baseline is sample prior to analysis.00 1000. Once a stable baseline has reestablished.1 For direct injection. Copyright by ASTM Int'l (all rights reserved). can ease sample handling and improve sample combustion characteristics for materials containing very volatile sulfur compounds.1 Perform measurements for the calibration standards plunger so that the lower liquid meniscus falls on the 10 % and blank using one of the procedures described in 10. However. ng/µL Furnace oxygen flowmeter setting (3. Make other volumetric dilutions of the stock tents of the syringe into the boat containing quartz wool or solution to cover the various ranges of operation within these suitable equivalent (see 6.3 A sample injection size recommended for the curve reached its fully retracted position. analyzed.00 Injection Size Injection Size Injection Size 10–20 µL 5–10 µL 5 µL 9.1 The volumetric measurement of the injected material approaching the furnace or an increased time for boat cooling can be obtained by filling the syringe to the selected level.1 Based on anticipated sulfur concentration.3. there are two alternative 10.01 mg is used.5.2 For the boat inlet. promptly start have not been determined.8) at a slow rate being careful to calibration curve guidelines.3. of liquid in the syringe. Narrower ranges than the inlet of the combustion tube and the syringe drive.3. There are two alternative can be necessary to ensure complete sample combustion. See Section 14. quantitatively discharge the con- accordingly. accuracy and precision are not degraded. The Measure the calibration standards and blank three times. D5453 − 12 TABLE 1 Typical Operating Conditions TABLE 2 Typical Sulfur Calibration Ranges and Standard Syringe drive (direct inject) drive rate (700–750) 1 µL/s Concentrations Boat drive (boat inlet) drive rate (700–750) 140–160 mm/min Curve I Curve II Curve III Furnace temperature 1075 ± 25°C Sulfur. flush the syringe and withdraw a new sample. If bubbles are present in the liquid to be reestablished before the boat has been completely column. Construct place of the described manual injection procedure.3 Adjust the instrument sensitivity and baseline stability and perform instrument blanking procedures following manu.4.4 Once the appropriate sample size has been measured facturer’s guidelines. injection into the combustion tube or delivery into the sample NOTE 12—Slowing boat speed or briefly pausing the boat in the furnace boat for analysis (Notes 8-10). the test time for sample residues to be burned from the needle (Needle method precision using narrower ranges than those indicated Blank). Carefully prepare a series of calibration standards 10. Again. The instrument base- line shall remain stable until the boat approaches the furnace 10. can be required.00 100. provided a balance with a NOTE 13—Other calibration curve techniques can be used when precision of 60.8) 10–30 mL/min 1. effective cooling of the sample boat prior to sample NOTE 10—Other injection sizes can be used when complete sample injection is essential.5 Calibrate the instrument using one of the following two meniscus falls on the 10 % scale mark and record the volume techniques. Retract the plunger so that air is aspirated and the lower liquid 10.1.00 100. 10.6) 130–160 mL/min 2. syringe and promptly start the analysis.50 50. difference between the two volume readings is the volume of Subtract the average response of the blank injections from each sample injected (Note 11). minimize the vaporization of the sample until the boat begins 10. carefully insert the syringe into the suggested curves outlined in Table 2. if desired. calibration standard response.1) 450–500 mL/min 0.00 Inlet carrier flowmeter setting (3.00 500.4. NOTE 8—Injection of a constant or similar sample size for all materials analyzed in a selected operating range promotes consistent combustion 10. promptly and quantitatively deliver the sample into the apparatus. select one of 10.8–4. ng/µL Sulfur. sulfur detection following sample injection are directly related NOTE 9—Injection of 10 µL of the 100 ng/µL standard would establish to the volatility of the materials analyzed.3 The level of boat cooling required and the onset of conditions. device before and after injection to determine the amount of This curve shall be linear and system performance must be sample injected. allow at least 1 min for selected from Table 2 shall be quantitatively measured prior to cooling before the next sample injection (Note 12).4–3.2 – 10. Ensure the standards used for the analysis. No further reproductions authorized.4. ng/µL Sulfur. into the microlitre syringe. Then determine the average NOTE 11—An automatic sampling and injection device can be used in integrated response of each concentration (see 6. M/D. and solution three times and calculate the average detector re. Repeat instrument calibration prior to reanalysis of the test V = volume of test specimen solution injected. at 13. if coke or soot is observed on the exit end of the Kg = gravimetric dilution factor. injection). ppm ~ µg/g ! 5 (1) S 3 M 3 Kg grams of sulfur (Note 13). V × D. g/mL. If required.2 – 10.2 Boat Inlet Systems—Increase the residence time for D = density of test specimen solution.6 If analyzer calibration is performed using a different S 3 V 3 Kv calibration curve than listed in Table 2. select an injection size where: based on the curve closest in concentration to the measured D = density of test specimen solution. mg. µL. 6 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. measured directly or calculated from measured mass injected and density. sponses. Kg = gravimetric dilution factor. Report measured using Test Methods D1298. or.3. For results less than 10 Copyright by ASTM Int'l (all rights reserved).4 To obtain one result. The sulfur concentration in the test specimen must volume of test specimen and solvent. mass of test specimen/ in Section 8. V × D. Procedure mass of test specimen and solvent.1 Direct Inject Systems—Reduce the sample size or the G 3 1000 Sulfur. 11. counts. or concentration of solution. with blank correction. and solvent. 11. assemble and leak check the apparatus. 12.4. g/g. µg. mass of the test specimen and the total volume of the test 12. M = mass of test specimen solution injected. If blank late the sulfur content of the test specimen in parts per million correction is required and is not an available instrument option (ppm) as follows: (see 6. ppm ~ µg/g ! 5 (2) 10.3 Cleaning and Recalibration—Clean any coked or M = mass of test specimen solution injected. Section 14).1. either 11. either be less than the concentration of the highest standard and measured directly or calculated from measured greater than the concentration of the lowest standard used in volume injected and density. or both.3. or both. calcu- one of the procedures described in 10. either a weight or volume basis. specimen solution.1 Gravimetric Dilution (mass/mass)— Record the mass measured directly or calculated from measured of the test specimen and the total mass of the test specimen and mass injected and density. the calibration. . injected and density. either specimen. D4052.2 If the apparatus features self calibration routine. calculate the sulfur in the test specimen 11. V = volume of test specimen solution injected. either mea- sooted parts per manufacturer’s instructions. G 3 1000 Sulfur. measure each test specimen G = sulfur found in test specimen. Calculation measure the calibration standards and blank three times using 12.5 Density values needed for calculations are to be 13. Construct the calibration curve to yield values that I = average of integrated detector response for test can be used to report sulfur content on a mass/mass basis.1). 1000 = factor to convert µg/mg to µg/g. report the the temperature at which the sample was tested. 11. g/mL. 11. mg/µL (volu- Decrease the boat drive introduction rate or specimen sample metric dilute injection). No further reproductions authorized. g/g. M/D.1 For analyzers calibrated using a standard curve. solution(s). counts/µg S. sulfur result to the nearest mg/kg. g.2 – 10.1. where: 11. 11. ppm ~ µg/g ! 5 (4) rate of injection.1 For results equal to or greater than 10 mg/kg.5. ppm ~ µg/g ! 5 (3) M 3 Kg 11. ~I 2 Y! Sulfur. µL. D5453 − 12 10. 11. or equivalent. of the specimen into the furnace if V 3D coke or sooting is observed.4 or 10. mass of test specimen/ 11. size.4. mg/µL (neat the boat in the furnace if coke or soot is observed on the boat. a dilution can be performed on S = slope of standard curve.2 For analyzers calibrated using self calibration routine specimen and solvent. mass of test specimen/ combustion tube. Y = y-intercept of standard curve. sured directly or calculated from measured volume ing or adjustment. calibrate the analyzer in accordance with manufacturer’s instructions to yield results expressed as nano.2 Volumetric Dilution (mass/volume)— Record the 1000 = factor to convert µL to mL. After any clean.5. This curve shall be linear and system performance must be checked with each day of use (see or.1 Obtain a test specimen using the procedure described Kv = volumetric dilution factor.3 Inspect the combustion tube and other flow path components to verify complete oxidation of the test specimen.2 Measure the response for the test specimen solution in parts per million (ppm) as follows: using one of the procedures described in 10. ~ I 2 Y ! ~ 1000! Sulfur.3. counts. mass of test specimen and solvent. biodiesel-fuel blends. Quality Control 15.3 sults obtained by the same operator with the same apparatus 400 16.1. SRMs 2298 (4. (3) RR:D02-1465 (1997) gasoline and RFG only.5797 X ~ 0. These samples were gasoline (2) RR:D02-1456 (1999) UVF/X-ray equivalence study.6 6 1. and containing less than 400 mg/kg are shown in Table 3. jet fuel.3 Examples of the above precision estimates for samples (PLOQ) determined in the study.1 Three National Institute of Standards and Technol- reports. 20.1.1 µg/g S). diesel.1 The test method was examined in six separate research 15.1788 X ~ 0. (6) RR:D02-1633 (2008) bio-fuel fitness for use and precision update.2.3 Reproducibility—The difference between two single 14.1 Confirm the performance of the instrument or the test and independent results obtained by different operators work- procedure by analyzing a quality control (QC) sample (6.7 18.4 ogy (NIST) Standard Reference Materials (SRM) were ana- (1) RR:D02-1307 (1992) original with multiple matrices. D5453 − 12 TABLE 3 Repeatability (r) and Reproducibility (R) 15.02902 X (6) 14. etha- 4 Supporting data have been filed at ASTM International Headquarters and may nol. Appendix X1 can be used as the QC/QA 15.3 50 3. sulfur. is as follows (Note 14). No further reproductions authorized. and differences between the ILS determined averages and the ARV biodiesel.1. gasoline.9 15. Precision and Bias in hydrocarbon. See RR:D02-1547 (2000-2001). in after each calibration and at least each day of use thereafter the long run.3 µg/g S) and 2299 (13. ethanol-fuel blends. 7 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. be obtained by requesting the research reports listed in 15. where x = the average of the two test results.4 10. fluorescence. these can be used Less than 400 mg/kg:R 5 0.2 When there is no QC/QA protocol established in the Greater than 400 mg/kg:R 5 0.9 under constant operating conditions on identical test material would.0 6 1. 15. 14. kerosine.10) ing in different laboratories on identical test material would. lyzed to determine the bias.7 6 1.6 1. in the normal and correct operation of the test method.5 µg/g S).6 NOTE 14—Volatile materials can cause a deterioration in precision 5 0. exceed the following values in only 1 case in 20.75! (5) D5453. M-85.1 When QC/Quality Assurance (QA) protocols are where x = the average of the two test results.1. 10 1.9 when not handled with care (see Section 8 and 10.1. .1 analysis.1267 X (8) testing facility. (Accepted Reference Values) of the NIST standards were not (5) RR:D02-1547 (2000-2001) involving 39 labs and 16 statistically significant at the 95% confidence level. Keywords 16. already established in the testing facility. method.4). Greater than 400 mg/kg:r 5 0. as obtained by Concentration r R statistical analysis of test results. in the normal and correct operation of the test (see 10.4 (5– 40 µg ⁄g S) based on practical limits of quantitation 15. in the long run. diesel. 14. State that the results were obtained according to Test Method Less than 400 mg/kg:r 5 0. (mg/kg S) 1 0.0 51. report the sulfur result to the nearest tenth of a mg/kg.75! (7) when they confirm the reliability of the test result. and diesel SRM 2723a (11.2 Bias—The bias of this test method was determined in a system.2 0. biodiesel. E-85.1 The precision of the test method.1. exceed the following values in only 1 case in mg/kg. ultraviolet Copyright by ASTM Int'l (all rights reserved).2 Repeatability—The difference between two test re- 100 5. RFG. 16. See Table samples each of low level gasoline (1–100 µg/g S) and diesel 4. 1992 research report (RR:D02-1307)4 by analysis of standard reference materials (SRMs) containing known levels of sulfur 15.5). The observed (4) RR:D02-1475 (1998) low level gasoline.0 3. the injection of the sample. An ample supply of QC sample material X1. rate of the sample from the syringe.6 (± 1. Control sooting by slowing the injection syringe. of the furnace. larger sample sizes are required for measurement of lower levels of sulfur. or increasing the pyro- mately the 10 % scale mark of the syringe barrel. Generally. While X2.44) 0. X2. prior to the injection of the 5 ppm to 100 mg/kg 5 to 10 µL syringe contents. D5453 − 12 TABLE 4 Comparison of NIST and ASTM Interlaboratory Study (RR) Results NIST SRM Number Sulfur mg/kg NIST Matrix Average Measured mg/kg Observed Statistically Sulfur ASTM ILS Difference Significant mg/kg Sulfur (95% Confidence Level) ? NIST 2298 4. a QC sample is analyzed each testing day with X1.. No further reproductions authorized. After the sample specimen has been measured into the in the sample path.5 It is recommended that. if required.1 No NIST 2299 13. tical control status of the total testing process (see Test Method D6299 and MNL 7). and customer requirements. the QC testing frequency may be reduced. syringe needle into the injection inlet and allow the needle/ Example injection sizes are as follows: septum blank to dissipate.1 Confirm the performance of the instrument or the test criticality of the quality being measured. routinely analyzed.0 (± 1.19) 1. the user routine samples. . the demonstrated procedure by analyzing a quality control (QC) sample. For direct injections it is recom- mended that the needle remain in the furnace until the X2.3 Record the QC results and analyze by control charts or sample precision should be checked against the ASTM test other statistically equivalent techniques to ascertain the statis.8 No APPENDIXES (Nonmandatory Information) X1. 100 mg/kg to % 5 µL Copyright by ASTM Int'l (all rights reserved). Assembly of apparatus to manufacturer’s specification and full insertion of the needle will ensure this.3 Injection Peak/Needle Blank—Avoid integration of determining the best sample size. stability of the testing process. See Test Method D6299 and MNL 7 for further guidance 5 ASTM MNL 7. Manual on Presentation of Data Control Chart Analysis. ASTM International.7 (± 1.52) 2.2 (± 0. W. or a combination thereof. The QC X1.1) Diesel 10. Insert the oxygen or inlet oxygen supply. retract the plunger to form an air gap up to approxi.2 Needle Tip Position during Injection—The needle tip instrument returns to baseline and the analysis of the injected should be presented fully into the hottest part of the inlet area material is complete.6 (± 0.5 Injection Size—As a general rule.5) Gasoline 11. result in instrument re-calibration. QUALITY CONTROL X1. the type of QC investigation for root cause(s). MNL 7). Reset the instrument baseline or Trace to 5 mg/kg 10 to 20 µL enable integration.4 In the absence of explicit requirements given in the should be available for the intended period of use. 8 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. on QC and control charting techniques. but not necessarily. 6th ed. Any out-of-control data should trigger X1. The use of quartz chips in the time of the needle in the furnace must be consistent following combustion zone of the pyrotube is required.3) Gasoline 3. if possible.1 Furnace Temperature—A temperature of 1075 6 X2. IMPORTANT FACTORS IN DIRECT INJECTION ANALYSIS OF HYDROCARBONS USING TEST METHOD D5453 (SULFUR) X2. the frequency of QC testing is dependent on the homogeneous and stable under the anticipated storage condi- tions. frequently check for evi- any baseline upset caused by the needle penetration of the dence of incomplete combustion (sooting) that may be present septum. method precision to ensure data quality.0 No NIST 2723a 11. X2. However.2 Prior to monitoring the measurement process. and must be test method.6 (± 0.4 Residence Time of Needle in Furnace—Residence 25°C is required for sulfur. The QC frequency should be increased if a of the test method needs to determine the average value and control limits of the QC sample (see Test Method D6299 and large number of samples are routinely analyzed.5 when it is demonstrated that the testing is under statistical control. The results of this investigation sample that is regularly tested be representative of the material may. Conshohocken. 7 35-45 mL/min to 300 counts or three times baseline noise. X2. IMPORTANT FACTORS IN BOAT-INLET ANALYSIS OF HYDROCARBONS USING TEST METHOD D5453 (SULFUR) X3.9 Membrane Dryer Purge—Water produced during the force the calibration curve through the 0. rate of injection and needle in furnace stable and noise free. The curve should yield an estimated value that can auxiliary gas flow is used. approximately one accordingly. especially when of injection can vary depending upon sample and syringe analyzing low levels. Control sooting by slowing X3. Additional slowing of boat speed or a brief pause of X3.1 Furnace Temperature—A temperature of 1075 6 levels.3 Boat Entry Rate and Residence Time of Sample in 5 ppm to 100 mg/kg 5 to 10 µL Furnace—Insert the boat into the furnace using a 100 mg/kg to % 5 µL drive rate of 140 to 160 mm/min (Model 735 setting of 700-750).6 Injection Rate and Frequency—Discharge contents of Adjust Gain Factor. below the saturation point of the detector. Mini- Inlet carrier flowmeter settingsA 3. D5453 − 12 TABLE X2. The boat should emerge from the furnace being careful to discharge the last drop. For curve that is linear and that does not exceed the dynamic range an apparatus that utilizes a desiccant scrubber (flow recycle) to of the detector (use a correlation coefficient of 0. The use of quartz chips in the check for evidence of incomplete combustion (sooting) that combustion zone of the pyrotube is required. set membrane dryer purge flow at be used to calculate content in the sample on a mass/mass 200 to 250 mL/min.6 140-160 mL/min mum detector response.0 axis.2 Boat Path —The boat should be presented fully into boat speed into the furnace. Do not X2. basis. . both. combustion of the sample is removed by the membrane dryer.4 Injection Size—As a general rule larger sample sizes 2.10 Sample Homogeneity/Calibration Response—Prior Typical Gas Flows Flowmeter Ball MFC to analysis.8) in the sample boat to aid quanti- times can vary depending on sample volatility and levels of tative delivery of the test specimen.11 Baseline Stability—Prior to analysis. When an guideline). (Model 9000) should be no less than 200 Furnace oxygen flowmeter setting 3. Leak Check. complete combustion of the sample. PMT voltage or sample size.7 Flow Path. µL/s (Model 735 Sample Drive rate of 700 to 750). Assembly of the apparatus to the boat is in the furnace or increasing the pyro-oxygen supply. Example injection sizes are as follows: Trace to 5 mg/kg 10 to 20 µL X3. solvent materials that have minimum or no sulfur contamina- X2. Use quartz wool or soon after detection is complete. replace the drying 2 orders of magnitude—for example. photomultiplier residence time. Model 9000 X2. or both.1 450-500 mL/min Ozone generator flowmeter settingB 1. may be present in the sample path. be certain that the detector baselines are handling techniques.8 Gas Flow Settings—Gas supplies to various points in tion relative to the concentration anticipated in the sample the sample path must be consistently controlled to allow for unknown. for the lowest point A Helium or argon may be used as a carrier gas.5 min between injections.2 Gas Flow Settings—Direct Injection Analysis X2. and cooling capacity of the boat loading area. No further reproductions authorized. and Back Pressure—The users can utilize the baseline evaluate and peak threshold sample flow path must be leak free when pressure tested in functions to reduce baseline noise. furnace residence time. For a given gain factor. While determining the best sample size. use a maximum response of 350 000 to 450 000 counts (Model 7000) as a guideline. level of sulfur being range between 15 to 60 s. Use calibration curves that bracket the expected levels in the sample unknown. on the calibration curve.999 and 1 to provide the membrane dryer purge gas.1. Flow path back pressure during normal operation can Construction—Prepare calibration standards with range from 0. Construct standard concentrations that will yield a calibration This water must then be purged from the membrane dryer.00 psi. the syringe into the furnace at a slow rate. or manufacturer’s specification ensures this. noise-free baseline. may be required for measurement of lower concentration Copyright by ASTM Int'l (all rights reserved). Typical injection frequency allows at least 3. See Table X2. als and impurity of source material. The highest point on the curve is B Flow to ozone generator (optional). Boat in furnace residence suitable equivalent (see 6. mix samples and calibration materials well. X3.12 Calibration Materials/ Standard Curve (2-3 psi).5 Injection Rate and Frequency—Discharge contents of the boat in the furnace may be necessary to ensure complete the syringe into the boat at a slow rate (approximately 1 µL/s) sample combustion. while maintaining a stable. Typical boat in furnace residence times vary depending upon boat speed.5 tube voltage may be adjusted to ensure maximum sensitivity min between injections. frequently 25°C is required for sulfur. Typical injection frequency allows at least X3. determined.4-0. 5 to 100 mg/kg—as a agent when color change (blue to pink) indicates.75 to 2.8-4. accordance with the manufacturers recommended procedure X2. Frequency of injection can element measured. 9 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. Frequency X2. unnecessarily. increasing the length of time the the inlet area of the furnace. Correct for sulfur contribution from solvent materi- smooth.4-3. (Model 7000) should be no less than Inlet oxygen flowmeter setting 0.5-1. The Model 9000 should not have flat-top peaks.6 10-20 mL/min 2000 to 3000 counts. PMT Voltage. for non-atmospheric-vent solvent materials that have minimum or no sulfur contamina- systems. measured. When an auxiliary gas flow is used. Model 9000 users can utilize the baseline evaluate and The sample flow path must be leak free when pressure tested in peak threshold functions to reduce baseline noise. Copyright by ASTM Int'l (all rights reserved).00 psi.75 to 2.5-1. Heat empty boat in the furnace to ensure that boat is may be measured as the sample evaporates when the boat clean.6 Boat Temperature at Time of Sample Introduction— X3. Let boat rest at least 60 s in boat or on the inside areas of the pyrotube near the injection coolant jacket or cooling area between injections. X3. until no sulfur is this evaporation.2 Gas Flow Settings—Boat Inlet Analysis X3. on the calibration curve. See Table X3. SUMMARY OF CHANGES Subcommittee D02. accordingly. (Model 9000) should be no less than 200 Furnace oxygen flowmeter setting 3. or a combination thereof. below the saturation point of the (Model 9000) detector.7 Sample Flow Path: Leak Check and Back Pressure— noise-free baseline. Mini- Inlet carrier flowmeter settingsA 3. Flow path back pressure during normal operation Construction—Prepare calibration standards with can range from 0.11 Boat Blank/Baseline Stability—Prior to analysis. (Model 7000) should be no less than Inlet oxygen flowmeter setting 0.6 130-160 mL/min mum detector response. a calibration curve that is linear and that does not exceed the This water must then be purged. use a maximum response of 350 000 to 450 000 counts (Model 7000) as a guideline. For an apparatus that utilizes dynamic range of the detector (use a correlation coefficient of a desiccant scrubber (flow recycle) to provide the membrane 0. (2) Updated bias statement to correct publication errors and reflect updated bias findings. replace the drying agent when color change mg/kg) as a guideline). (1) Inserted missing parenthesis in numerator in Eq 2. Sub-ambient temperature can reduce baseline upset.7 35-45 mL/min to 300 counts or three times baseline noise. repeat the boat in and out cycle. accordance with the manufacturer’s recommended procedure X3. The highest point on the curve is B Flow to ozone generator (optional). photomultiplier tube voltage.4-0.12 Calibration Materials/ Standard Curve (2 to 3 psi). complete combustion of the sample.10 Sample Homogeneity/Calibration Response—Prior Typical Gas Flows Flowmeter Ball MFC to analysis.03 has identified the location of selected changes to this standard since the last issue (D5453–09) that may impact the use of this standard. can be adjusted to ensure maximum sensitivity while maintaining a stable. X3. . Use calibration smooth.1 450-500 mL/min Ozone generator flowmeter settingB 1. X3. Some sulfur area. The curve should yield an estimated (blue to pink) indicates. Do not force the calibration curve through the 0. 10 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. NOTE X3. Correct for sulfur contribution from solvent materi- the sample path must be consistently controlled to allow for als and impurity of sulfur source material. D5453 − 12 TABLE X3. For a given gain factor. or sample size.0 axis.8 Gas Flow Settings—Gas supplies to various points in unknown. Adjust Gain Factor.1—If the hot boat being returned to the injection area causes approaches the furnace.8-4. es- Sample volatility must be addressed. then rapidly move boat out to injection area.4-3. 5 to 100 dryer purge gas. advance the empty boat has returned to ambient or sub-ambient temperatures prior to into furnace to ensure that no contamination is present in the introduction of sample into boat.6 10-20 mL/min 2000 to 3000 counts. No further reproductions authorized. for the lowest point A Helium or argon may be used as a carrier gas. set value that can be used to calculate content in the sample on a membrane dryer purge flow at 200 to 250 mL/min. ensure boat temperature pecially when analyzing low levels.1. Construct standard concentrations that will yield combustion of the sample is removed by the membrane dryer.999 and 1 to 2 orders of magnitude (for example. tion relative to the concentration anticipated in the sample X3.9 Membrane Dryer Purge—Water produced during the unnecessarily. mass/mass basis. curves that bracket the expected levels in the sample unknown. mix samples and calibration materials well. (3) Inserted new Table 4. 11 Licensed to/printed by Allen Bickel Horiba Scientific pursuant to License Agreement. This standard is copyrighted by ASTM International. D5453 − 12 ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards. or through the ASTM website (www. are entirely their own responsibility. which you may attend. PA 19428-2959. United States. 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