Designation: D 6453 - 08b feeeeerated Standard Test Method for Determination of Total Sulfur in Light Hydrocarbons, Spark Ignition Engine Fuel, Diesel Engine Fuel, and Engine Oil by Ultraviolet Fluorescence’ “Tis! sued der the Sued design D545 the mnt nmin he design ese the yer of ‘Sil aon on te ie of vse, the yea ofa ost A saber n pratense he yar of it eapaealA ‘Spon op (esas a ioe ec th fs esl eyo 1, Scope 2. Referenced Documents LI This test method covers the determination of toal sulfur 2.1 ASTM Standards? in liquid hydrocarbons, boiling in the range from approxi- 1298 Test Method for Density, Relive Density (Specific nutely 25 1 400°C, with viscosities beoween approximately Gravity) or API Gravity of Crude Petroleum and Liguid (02 and 20 81 (nS) at room temperate Patoleum Products by Hydrometer Method 1.2 Thee separate intesaboratry studies (LS) oa prec 4052 Test Method for Density and Relative Density of sion, and thc other investigations that resulted in an ASTM —_‘Liguids by Digital Densiy Meter fesearch report, have determined that this txt method is D087 Practice for Manual Sampling of Petroleum and applicable 10 naphbas, distillates, engine oil, ethanol, Fatty Petroleum Products ‘Acid Methyl Ester (FAME), and engine fuel such a8 gasoline, D417 Practice for Automatie Sampling of Peoleum and ‘oxygen enriched gasoline (ethanol blends, 85, M-BS,RFG), _Peroleum Products ‘ese, biodiesel, Gieseliodieel blends, and je uel. Samples 0.6299 Practice for Applying Statistical Quality Assuran containing 1.0 to 8000 mg/kg tora sulfur ean be analyzed and Control Charting Techniques to Evaluate Analytical (ote 0. Measurement Systems Performance Ne inate oe ni efqaetion 00) eh 3, Summary of Test Method provrion suis were exiled, Vales ranged between les than 1.0 a Fes than 5.0 mg (See Seetion 8 and 15:1). 3.1.4 hydrocarbon sample is either directly injected or 113 ‘Thic tot methind ic applirahle for total sulfir enter. placed in a sample boat. The sample or bos, or both is inserted "Taos min einerre sbuaion be wenn 8 tation gi yrs conaing es tan 035% Suttle de (60) han onan chamospee Je) MB instante ae to be rege ax Wer Foce ding srs comune remove td standard. No other units of messurement are included inthis ie sample combustion gases are next exposed oa vile, pam (OV) light. The $0, absorbs the energy from the UV light and “ is converted to excited sulfur dioxide (SO,*). The fluorescence ert om the excel Oy" tres tos sabe te Sq dete by a phot tube andthe elie Sigal a moss ofthe alr eonaned Ia the sole (WarnlngExposire to excessive guns of lilt {Uy High snus to eh The peaor mit svcd taposing any pac their person, epee Ter ees. nt iy coast UY ight ta also sesorery or seared “ean tats preset) LS This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibilty of the user of this standard 10 establish appro priate safety and health practices and determine the applica: bility of regulatory limitations prior 10 use. For warning statements, see 3.1, 6.3, 6:4 Section 7, and 8.1 This te maha ond the jiclon of ASTM Cannes D2 on —§ ————— Pegs reductase Set respon Saecrstas FO frog ASTM sare, ‘ano en Ble Any onus ASTON sane Serie stv Fr Ave Bak of AST ‘Cem edtonsprove ily 1, 2008, Palsted Aug 2008. Olly ‘Sa volume narra, rte td's Dene Stay Bah pra 195, La pion eon apo 208 sD 859-0, AEASTIO eta *A Summary of Changes section appears tthe end of hondaAlp 0 5453 - 08 Quartz Combustion Tube | Inlet Cariergas id Oxygen Mie Drectined ssrole eo | . o et corns ee — Inlet Corviergas: and Gxygen Mc Beat net ignificance and Use 4.1. Some process catalysts used in petroleum and chemical refining ean be poisoned when trace amour of sulfur bearing ‘materials are contained in the feedstocks. This test method can be used t0 determine sulfur in process feeds sulfur in finished products, and ean also be used for purposes of regulatory conta, 5. Apparatus 5.1 Furnace—An electric furnace held at a temperature (1075 = 25°C) sulficient to pytolyze all of the sample and ‘oxidize sulfur to SO, 2 Combustion Tube—A quar combustion tube con siructed (0 allow the direct injection of the sample into the heated oxidation zone ofthe furnace or constructed so thatthe inet end of the tube is large enough to accommodate a quartz sample boat, The combustion tube must have side arms forthe introduction of oxygen and cartier gas. The oxidation section shall be large enough (see Fig. 1) to ensure complete combus- tion of the sample. Fig. 1 depicts conventional combustion tubes, Other configurations are acceptable if precision is not degraded, 53 Flow Controt—The apparatus rust be equipped with flow comollers capable of mainiining a constant supply of oxygen and carrier gos 5.4 Drier Tube—The apparatus must be equipped with a mechanism for the removal of water vapor. The oxidation reaction produces water vapor which must be eliminated prior to measurement by the detector. This can be accomplished with 1 membrane drying tube, ora permearion dryer, that uilizes & selective capillary action for water removal 55. UV Fluorescence Detecior—A qualitative and quantita- tive detector capable of measuring light emitted from the fluorescence of sulfur dioxide by UV light 56 Microlire Syringe—A micrlite syringe capable of accurately delivering $ 0 20-pL- quantities. The nee shall be ‘50 mm (25 mm) long, 5.7 Sample Inler System—Eiher of two types of sample inlet systems can be used. 5.7.1 Direct Injection—A dicect injection inlet system must be capable of allowing the quantitative delivery ofthe material to be analyzed into an inlet carrier stream which directs the sample info the oxidation zone at a controlled and repeatable rate. A syringe drive mechanism which discharges the sample from the mierolie syringe ata rate of approximately 1 Lis is requited, For example, see Fig. 2 5.72 Boat Inlet Systen—An extended combustion tbe provides a seal tothe inlet of the oxidation area and is swept by A carrier gas. The system provides an ares to position the Sample carrying meebanism (boat) at a retracted! positionAf D 5453 - o8b Inlet Cariergas and Oxygen Mix Directinject Autosampler FIG, 2 Direct inject Syringe Drive removed from the furnace, The boat drive mechanism will fully insert the boat into the hotest section of the furnace inlet. ‘The sample boats and combustion tube are consttucted of {quartz The combustion tube provides @ cooling Jacket or the area in which the rteacted boat rests awaiting sample intro- duction from a microlitre syringe. A drive mechanism which ‘advances and withdraws the sample boat into and eut of the furnace at a contolled and repeatable rate is requised. For ‘example, see Fig. 3 5.8 Refrigerated Cireulator—An adjustable apparatus ca pable of delivering coolant materia at a constant temperature fs low as 4°C could be required when using the boat inlet injection method (optional) 59 Sivip Chart Recorder, (optional). 5.10 Balance, with a precision of +001 mg (optional) 6. Reagents 6.1 Purity of Reagents—Reagent grade chemicals shall be used in tests. Unless otherwise indicated, i is intended that el reagents shall conform to the specifications of the Committee ‘on Analytical Reagents of the American Chemical Society. where such specifications are available.? Other grades may be Used, provided itis first ascertained that the reagent is of vse Chemie, Anerson Chomin)Seciey Speieion, Arsen csi Sec Waingon OC. For Suggestions ethene of reagents nak 1st by We Ameren Chemie Sosey se Anal Saad for Lara Chemis RDM Ls Pon, Dot, Uk nd the Uied Ses Paraacoe (el Natt Panay, US amen Covet, (USPC), eee sufficiently high purity to permit its use without lessening the accuracy of the determination. 6.2 Inert Gas—Argon oF helium only, high purity grade (that is, chromatography or zero grade), 93.988 % minimum purity, moisture $ ppm w/w maximum, 63. Oxyger—High parity (that is, chromatography or zero grade), 99.75 % minimum purty, moisture 5 ppm ww maxi- ‘mur, dried over molecular sieves, (Warning—Vigorously accelerates combustion.) 6.4 Toluene, Xylenes, Iscoctane, reagent grade (other sol vents similar 10 those occurring in samples to be analyzed are ‘also acceptable). Correction for sulfur contribution from sol ‘vens (solvent blank) used in standard preparation and sariple specimen dilution is required. Alternatively, use of a solvent ‘with nonderectable leve! of sulfur contamination relative to the sulphur content in the sample unknown makes the blank correction unnecessary. (Warning--Flammable solvents.) 65 Dibenzothiophene, FW184.26, 17.399 4 (nfm) § (Nowe 2. 66 But Sulfide, FW146.29, 21.92 % (mm) $ (Note 2. 67 Thionaphthene (Benzethiophene), FW134.20, 23.90 5% avin) § (Note 2), [Nore 2—A coretion for chemical impurity canbe require 6.8 Quartz Wool, or other suitable absorbent material tht is stable and capable of withstanding temperatures inside the furmace (see Note 3) Nore 3—Matevias meeting the requitemens in 68 provide = more _niform injction ofthe mpl into the Boa by Wicking any remainingfly 5483 - o8b Boa Drive Rechaniens ly Inlet Camriertias Sha Oxygen Mi FIG, 9 Boat Inlet System rep ore supe tau te pu de aig me roo nrodtion ‘of te spl int the forsee, Consul isrument menofactrer recom ‘mendations for farther guidance 6.9 Sulu Stock Solution, 1000 yg S/mt—Prepare a stock solution by accurately weighing spproximately 0.5748 g of benzothiophene oF 0.4562 g of butyl sulfide oF 0.4184 g of thionaphthene ito a ared 100 ml. yolumetie ask. Dilute to volume wit selected solvent. This stock can be further diluted to desited sulfur concentration (Notes 4-7), Nore 4—Workng standards tha simulate or match the composition or rman of he samples alyzed can rode test sult bias between direst inject an bo sample let syste ‘Nove 5—Working standards should be remixed o separ basis Aepencing upon frequency af use and ag: Typically, stock solution have 4 etal fe of about 3 months ‘Neve 6-—Caliration stnderds can be prepared and dlisted on a inastnass bast when result eaeuiaions a adjusted to aecomniadste then, [Nove 7—Calbation anda rom commercial sores ean be sedi checked for secwraey and precision is net degrede. 6.10 Quality Control (QC) Samples, preferably are portions ‘of one or more liquid petroleum materials that are stable and representative of the samples of interest. These QC samples ‘can be used to check tho validity of the testing, provess as described in Section 14. 7. Mawards 7.1 High temperature is employed inthis test method. Extra cere most be exercised when using flammable materials near the oxidative pyrolysis furnace Sampling 8.1 Obiain a test unit in accordance with Practice D 4057 or Practice D 4177. To preserve volatile components which ate in some samples, do not uncover samples any longer than necessary. Samples shall be analyzed as Soon as possible ater taking from bulk supplies to prevet loss of sulfur or contami ration due to exposure of contact with sample container ‘(Warning—Samples that are collected at temperatures below oom temperature can undergo expansion and rupture the container. For such samples, do no ill the container fo the io leave sufficient ar space above the sample to allow oom for expansion) 82 Ifthe test unit isnot used immediately, then thoroughly tix in its container prior to taking atest specimen. 9. Preparation of Apparatus 9.1. Assemble and leak check apparatus according vo manu factuer’s instructions.Alp 0 sass - ob TABLE 1 Typical Operating Conditions Syma ave reetech ie ae (00-760) ——1 le oat ra bot ava Yate (700-750) 4010 ie Forse onparatee fone a0 Forate angen tonite stig (38-41) ‘5i-s00 mun ‘at cage format 10-00 un ‘ot sara wre 139-168 mia 9.2 Adjust the apparatus, depending upon the method of sample introduction, to meet conditions described in Table 9.3 Aajust the instrument sensitivity and baseline stability and perform instrument blanking procedures following manu- facturer’s guidelines. 10, Calibration and Standardization 10.1 Based on anticipated sulfur concentration, select one of the suggested curves outlined in Table 2. Narrower ranges theo | those indicated may be used, if desired. However, the test ‘method precision using narrower ranges than those indicated hhave not been determined. Ensure the standards used for calibration bracket the concentrations of the samples being analyzed. Carefully prepare a series of calibration standards accontingly. Make other volumetric dilutions of the stock solution to cover the various ranges of operation within these calibration curve guidelines. The namber of standards used per ‘curve can vary, if equivalent results are obtained. 10.2 Flush the microlite syringe several times with the sample prior to analysis. If bubbles are present in the liquid column, flush the syringe and withdraw a new sample. 10.3 A sample size recommended for the curve selected from Table 2 mast be quantitatively measured prio injection imo the combustion tube or delivery into the sample boat for analysis (Note 8 and Note 9), There are two alternative tecliiyecs avaitabte, Nom: $—Injiction a conan snr spl sit for al tei seen opting ngs preter crit eosin ‘Nove 9—Injcion of 10 yl. ofthe 100 gh standard woud esas a.callbraton point egal 1000 1g oF LO 103.1 ‘The volumetric measurement of the injected material can be obtained by filling the syringe to the selected level Rearact the plunger so that air is aspirated and the lower liquid ‘meniscus falls on the 10% scale mark and record the volume fof liquid in the syringe, After injection, again retract the plunger s0 that the lower liquid meniscus falls on the 10°% scale mark and record the volume of liquid inthe syringe. The difference between the to volume readings is the volume of sample injected (Note 10) [Non 1O—An automate sampling and injetion device can Be ase in pce ofthe descibed mana injestion proved. 10.3.2 Fill the syringe as described in 10.3.1, Weigh the device before and after injection to determine the emount of sample injected. This procedure can provide greater accuracy than the volume delivery method, provided a balance with a precision of +0.01 mg is used. 10.4 Once the appropriate sample size has been measured into the microlize syringe, promptly and quantitatively deliver the sample info the apparatus. Again, there are two alfemative techniques available ‘TABLE 2 Typical Sulfur Calforation Ranges and Standard Conconivations ‘cane ‘avait ane surah sutra sie oot 00 a0 scag0 1 Pr Sea 250 ae 60.00 So 10.99 ptm Sie eto se rscton Se TO-20L 10m Suk 10.4.1 For direct injection, esrfully insert the syringe into the inlet of the combustion tube and the syringe drive. Allow time for sample residues co be burned from the needle (Needle Blank). Once a stable baseline has reestablished, promptly start, the analysis. Remove syringe once the apparatus has returned toa stable baseline. 10.4.2 For the boat inlet, quantitatively discharge the con- tents of the syringe into the boat containing quartz wool oF suitable equivalent (see 6.8) at a slow rate being careful to displace the last drop from the syringe needle. Remove the syringe and promptly star the analysis, The instrument base- Tine shall remain stable unl the boat approaches the furnace and. vaporization of the sample begins. Instrument baseline is to be reestablished before the boat has been completely withdrawn from the furnace (Note 11), Once the boat has reached its Fully retracted position, allow at least 1 min for cooling before the next sample injection (Note 11). [Nove L1—Siowing bos sped or bity pug he boat in the race an be nectsary to ensure complete sample combusion. Direct ijeton an ene sample andng and improve sample combustion ebaacerstcs for materials eonsining very Vaal slur compounds. 1.5 The level of boat cooling required ena the onset OF sulfur detection following sample injection are directly related 1 the volatility of the materials analyzed. For volatile materi- ‘als, effective cooling of the sample boat prior 10 sample injection is essential. The use of a refrigerated circulator to ‘minimize the vaporization of the sample until the boat begins Approaching the furnace or an increased time for boat cooling fan be required. 10.5 Calibrate the instrument using one ofthe following two techniques, 10.8.1 Perform measurements for the calibration standards tnd blank using one of the procedures described in 102-10 Measure the calibration standards and blank three times. Subtract the average response ofthe blank injections from each calibration standard response, Then determine the average regrated response of each concentration (see 6.4), Construct fa eurve plotting of the average integrated deteetor response (axis) versus micrograms of sulfur injected (eanis) (Note 12) Tis curve shall be linear snd system performance must be checked each day of use. See Section 14 [Nove 12—Other calibration curv acsigues can be used when oee0- rey end precision me ot degraded. 10.5.2 If the apparatus features self calibration routine, ‘measuse the calibration standaeds and blank three tees using ‘one of the procedures described in 10.2-10.4, If blank corree- ‘ion is required and is not an available instrument option (seeAp 05453 -080 cb of 105.1), ealibeme the analyzer in acconlance with manufacturer's instructions to yield results expressed as nano- rams of sulfur (Note 12). This curve shall be linear and system performance must be checked with cach day of use (see Section Id). 10.6 If analyzer calibration is performed using a dif calibation curve than listed in Table 2, select an injection size based on the curve closest in concentration to the mensured solution(s). Construct the calibration curve to yield values that can De used to report sulfur content on a mass/mass bass, 11, Procedure M11 Obssin 2 west specimen using the procedure described in Section 8, The sulfur concentration in the test specimen must be less than the concentration of the highest standard and greater than the concentration of the lowest standard used in the calibration. If required, a dilution can be performed on either a weight or volume basis. ULL Gravimeric Dilurion (mass/mass)—Record the mass ofthe test specimen and the total mass ofthe test specimen and solvent 11.12 Volumerie Dilution (mass/vatume)—Record the mass of the test specimen and the total volume of the test, specimen and solvent. 11:2 Measure the response for the test specimen sol using one of the procedures described in 1012-10. 11.3 Inspect the combustion tube and other flow path components to verify complete oxidation of the test specimen. 111 Direct Inject Systems-—Reduce the sarople size or the rate of injection, or both, of the specimen into the furnace if coke or sooting is observed. 11.22 Boat Balot Syetome Inoroasa the ratiana time for the boat inthe Furnace if coke or soot is observed on the boat Decrease the boat drive introduction rate or specimen sample size, or both, if eoke or soot is observed on the exit end ofthe combustion tube. 11.33 Cleaning and Recalibvarion—Clean any coked ot sooted pars per manufactures's instructions, After any clean ing or adjustment, assemble and leak check the apparatus Repeat instrument calibration prior to reanalysis of the test specimen, 114 To obtain one result, measure each test specimen solution three cimes and calculate the average detector re- sponses. 1S Density values needed for calculations are to be measured using Test Methods D 1298, D 4052, or equivalent, At the temperature at which the sample was tested, 12, Calealation 12,1 For analyzers calibrated using a standard curve, caleu- late the sulfur content of the test specimen in parts per milion (ppm) as follows: a= Salt. ppm 0) = sqrea o (= ¥0000) Sulfur, po (sad = SSeS @ here: D.= density of test specimen solution, g/m, r faverage of integrated detector response for test specimen solution, counis, Kz = gravimetic dilution factor, mass of test specimen! sass of test specimen and solvent, g/g. K, = volumetric dilution facter, mass of test specimen volume of tes specimen and solvent g/mL, M-—= amass of test specimen solution injected, either measured directly or calculated from measured ‘volume injected and density. ¥ D. & $= slope of standard curve, countsiug S. V = volume of test specimen solution injected, either measused directly or calculated from mensured ‘mass injected and density, M/D.yL, and Y= srimercept of standard curve, counts, 1000 = factor to convert ute ml. 12.2 For analyzers calibrated using self ealbration routine th blank correction, calculate the sulfur inthe est specimen in parts per million (ppm) as follows: Gx 1000 sic too =e . saneom un = 2298 . ste D_ = density of test specimen solution, mg/l. (neat injection}, oF concentration of solution, me/ul. (volumetcic dilate injection), K, = gravimetric dilation factor, mass of est specimen ‘mass of test specimen and solven. B/. AM = inner of toet specimen salution injavtnd. either ‘measured direclly or calculated from measured volume injected and density, V XD, mg, ¥ = volume of test specimen solution injected, either measured directly or calculated from measured ‘mass injected and density, A/D, pl, ulfur Tound in test specimen, yg, and Factor to convert pg/mg to us/B. 13. Report 1.1 For results equal to or greater than 10 mgr, repox the sulfur result to the nearest mg/kg. For resulis less than 10 mgrkg, report the sulfur result to the nearest venth of a mai. State thatthe results were obiained according to Test Method D 5453. 1000 14, Quality Control 14.1 Confirm the performance ofthe instrument or the test, procedure by analyzing a quality control (QC) sample (6.10) fer each calibration and atleast each day of use thereafter (ee 10.5) V4.1 When QCiQuality Assurance (QA) protocols ae already established inthe testing facility, these can be used ‘when they confirm the reliability ofthe test result 14.1.2 When there is no QCIQA protocol established inthe fy, Appendix X1 can be used as the QCIQAAlp 0 5453-085 i 180, S38 15, Precision and Bias 15.1 The test method was examined in six separate research reports (1) RR:D02-1307 (1992) original with multiple matrices, (2) RR:D02-1456 (1999) UVE/X-ray equivalence study, G) RR:DO2-1465 (1997) gasoline and RFG only, (4) RR:DO2-1475 (1998) low level gasoline, diesel, and biodiese!, (5) RR:DO2~1547 (2000-2001) involving 39 labs and 16 samples each of low level gasoline (1-100 g/g $) and diesel (5-40 pple 8) based on practical limits of quantitation (PLOQ) determined in the study, and (6) RR:DO2-1633 (2008) bio-fuel ness for use and precision upaae, 15.1.1 The precision of the vest method, as obtained by satsical analysis of test results, is as follows (Note 13). Nowe 12 Volatile mses can cause » deterioration in pecislon ‘when ot handled wih are Ge Section 8 and 103), 15.1.2 Repearabiliy—The difference between two fest re- sults obiained by the same operator with the same apparatus under constant operating conditions on identical test material “Sapgoting ds hve been lot ASTM ltron Henig and ay be obi by eesti he sear apr set (3 ‘would, in the long run, in the normal and correct operation of the test method, exceed the following values in only 1 case in 20, where x= the average of the two test resus. ‘ess than 400 gh = 0.1788 ss (Greater than 400 mghg: r= 0.02902. 15.1.3 Reproducibility —The difference beween two single and independent results obtained by diferent operators work ing in different laboratories on identical vest material would, io the long run, in the normal and correct operation of the test method, exceed the following values in only 1 ease in 20, where x the average of the to test results ‘Less tan 400 mpg: & = 05797 x o Greater han 400 mfg: = 0.1267 X o 15.2. Bias—The bias of this test method was determined in 41952 research repon (RR:D02-1307)" by analysis of standard reference materials (SRMs) containing knovn levels of sulfur in hydrocarbon. This report indicated that the results obtained nthe SRMs were within the repeatability of the test method. 15.2.1 Three National Institute of Standards and Technol ey (NIST) Standard Reference Materials (SRM) were ani- lyzed to determine the bias. These samples were gesoline SRMs 2298 (4.6 ua/e S) and 2299 (13.6 pg/g S), and diesel ‘SRM 27232 (10 ppig S). There was no significant bias forthe dliescl SRM, but there was a bias of -0.97 and -2.00 for gasoline SRMs 2298 and 2299, respectively. See RR:DU2-1547 (2000- 2001) 15.3. Examples of the above precision estimates for saruples containing less han 400 mg/kg are shown in Table 3 16, Keywords 16.1 aoslyte: biodiesel: biodiesel-fuel blends: B-85: etha- nol ethanol-ful blends; diesel; uorescence; gasoline jet uel kerosine; M-85; REG; sulfur, ultraviolet APPENDIXES (Nonmandatory Information) XL. QUALITY CONTROL Xi.L_ Confirm the performance of the instrument or the test procedure by analyzing a quality contro! (QC) sample. X1.2 Prior to monitoring the measurement process, the user of the test method needs te determine the average value and contol limits of the QC sample (see Test Method D 6299 and MNL 5 X13. Record the QC results and analyze by control charts oF other statistically equivalent techniques to ascertain the statistical contro status of the total testing process (see Test ‘Method D 6299 and MNL 7), Any out-of-control data should “AST AM 7 Mason Psesion of Daa AST Inertial W: Condon ot Cat Ay. he Uwigger investigation for root cause(s). ‘The results of this investigation may, but not necessarily, result in instrument recalibration X14 In the absence of explicit requirements given in the test method, the frequency of QC testing is dependent on the criticality of the quality being measured, the demonsiated stability of the testing process, and customer requirements. Generally, x QC sample is analyzed each testing day with routine samples. The QC frequency should be increased if a large number of samples are routinely analyzed. However, when it is demonstrated that the testing is under statistical control, the QC testing frequency may be reduced, The QC sample precision should be checked against the ASTM test method precision to ensure data qualityAy 0 5453 - 8b X15 Ib is recommended that, if possible, the type of QC sample that is regularly tested be representative of the material outinely analyzed. An ample supply of QC sample material Should be available Fo the intended period of use, and must be X2, IMPORTANT FACTORS IN DIRECT INJECTION ANALYSIS OF HYDROCARBONS USING TEST METHOD 0 5 homogeneous and stable under the anticipated storage cond tions. See Test Method 1 6299 and MNL for further guidance ‘on QC and contol chaning techniques. (SULFUR) X21 Furnace Temperature—A temperature of 1075 25°C is required for sulfur. The use of quarts chips in the ‘combustion zone of the pyratube is required. X22 Needle Tip Position during Injecrion—The needle tip should be presented fully ito the hottest part of the inlet area ff the fumace. Assembly of apparatus to manufacturer's {Specification and full insertion of the needle will ensure this X23 Injection Peak/Needle Blank—Avoid integration of ‘any baseline upset caused by the needle penetration of the Scpium. After the sample specimen has been measured into the Syringe, retract the plunger to form an air gap up tO approxi- futely the 10% scale mark of the syringe barrel. taser the ‘Sringe needle into the injection inlet and allow the necdlef Septum blank to dissipate. Reset the instrument bastline oF fable integration, sf required, prior to the injection of the syringe contents. X24 Residence Time of Needle in Furnace—Residence soe of the needle in the fuenace must be consistent folowing the injection of the sample. For direct injections itis recom iended that the needle remain in the furnace unti) the Tnstrunicit etuns so baacine and the analysis af she injected ‘material is complete X2.5 Injection Size—As a general rule, larger sample sizes are required for messurement of lower levels of sulfur, While determining he best sample size, frequently check for vir {dence of incomplete combustion (sooting) that may be present in the sample path, Control sooting by slowing the injection rate of the sample from the syringe, oF increasing the pyro ‘oxygen or inlet oxygen supply, or « combination thereo. Suggested sample sizes are as follows: Teor § 9a some. Srpmio 00 raha Sito tenga rs 2.6 injection Rete ond Frequency—Discharge contents of the syeinge into the furnace ata slow rate, approximately one Lis (Model 735 Saruple Drive rate of 700 to 750). Frequency Of injection can vary depending upon sample and syringe handling techniques, rae of injection and needle in furnace residence time. Typical injection frequency allows at least 3.5 ‘min between injections. X27 Flow Peth, Leak Check, and Back Pressure—The sample flow path must be leak free when pressure tested in fecordance with the manufacturers recommended procedure {0-3 psil, Flow path back pressure during normal operation can range fiom 0.75 to 2.00 psi. ‘TABLE X2.1 Gas Flow Settings —Direct Injection Anas Typ Ges Fw owns eat UFC {ae cari Bower stras™ 3ea8 woisomuan {te nye ome 8g gaa lozbieumn Fnac exer fone set) Sits —ss0s00 muna (zone ganar wet ato tei? ssisnume 7 rao ign may 3b ued a ar OS. “Fp ane oer ena 2.8 Gas Flow Sertings—Gas supplies 10 various points in the sample path must be consistently controlled to sllow for smooth, complete combustion ofthe sample. See Table X2.1 X29 Membrane Dryer Purge—Water produced doring the combustion of the sample is removed by the membrane dryer. ‘This water must then be purged from the membrane dryer Por fan apparatus that utilizes a desiccant scrubber (flow recycle) ‘0 provide the membrane dryer purge gas. replace the drying gent when color ehange (blue to pink) indicates. When an funifiary gos flow is used, set membrane dryer purge flow at 200 t© 250 mL/min 2.10 Sample Homogenein/Calibration Response —Prior to analysis, mix samples and calibration materials well, Mii Nciector Reponoes (Modal 7000) howl he: no less than 2000 to 3000 counts, (Mode! 9000) should be no less than 200 to 300 counts or three times baseline noise, forthe Lowest pote fon the calibration curve. The highest point on the curve is below the saturation point of the detector, use = avaximurn response of 350 000 to 450.000 counts (Model 7000) as a fuideline. The Mode! 9000 should not have lat-op peaks ‘Adjust Gain Factor, PMT voltage or sample size, or both, accordingly. X21 Baseline Stability Prior to analysis, especially when analyzing low levels, be certain thatthe detecior baselines are stable and noise fre. For a given gain factor, photomultiplier tule voltage may be adjusted to ensure maximum sensitivity ‘while maintaining a stable, noise-free baseline. Mode! 9000 Tusecs can utilize the baseline evaluate and peak threshold functions to reduce baseline noise. X2.12 Calibration Materials! Standard Curve Construetion—Prepare calibration standards with solvent mi ferials that have minimum of no sulfer contamination relative to the concentration aaticipared in the sample unknown Correct for sulfur contribution from solvent materials and impurity of source material, Use calibration curves that bracket the expected levels in the sample unknown, Do not force the ‘calibration curve through the 0:0 axis, unnecessarily, Construct Standard concentrations that will yield a ealbration curve thatily v 5453—o8b is linear and that does not exeeed the dynamic range of the detector (use a correlation coefficient of 0.999 and 1 t0 2 orders ‘of magnitude—for example, 5 0 100 mg/kg—as a guideline). ‘The curve should yield an estimated value that ean be used to caloulate content in the sample on & mass/mass bass X3, IMPORTANT FACTORS IN BOAT-NLET ANALYSIS OF HYDROCARBONS USING TEST METHOD D 5453 (SULFUR) XB Furnace Temperature—A. temperature of 1075. 28°C ig required for sulfur, The use of quar chips in the {combustion zone of the pyrotube is required X32 Boat Path—The boat should be presented fully into the inlet area of the furnace. Assembly of the apparatus to the manufacturer's specification ensures this X33 Boar Bniry Rate and Residence Time of Sample in Furmace—tasen the boat into the furnace using a drive rate of 140 to 160 mvmin (Model 735 setting of 700-750). Addi- ‘ional slowing of boat speed or a brief pause of the boat inthe fornace may be necessary to ensure complete sample combus- tion. The boat should emerge from the furnace soon after detection is complete. Boa in furnace residence times can vary ‘depending on sample volatility and levels of element mes- ‘sured, Typical boat in furnace residence times range between 15 1 60s. X34 Injection Size—As a general rule larger sample sizes may be required for measurement of lower concentration levels. While determining the best sample size, frequently check for evidence of incomplete combustion (sooting) that ‘may be present in the sample path. Control sooting by slowing ‘oat speed into the furnace, inereasing the length of time the haa isin tha farnare ne ineveacing the pyrenrypen supply. both. Suggested sample sizes are as follows: “raze 03 mag orem Spm to 08 hg Seton Scomong ios Suk X35 Injection Rate and Frequency—Discharge contents of| the syringe into the boat ata slow rate (approximately | us) being careful 1o discharge the last drop. Use quartz wool or suitable equivalent (see 6 8) in the sample boat to aid quaati- tative delivery of the test specimen. Frequency of injection can vary depending upon boat speed, level of sulfur being deter- ‘mined, furnace residence time, and cooling capacity of the boat loading area. Typical injection frequency allows at least 2.5, min between injections. X36 Boat Temperature at Time of Sample Introduction — Sample volatility must be addressed; ensure boat vemperature das returned to ambient or sub-ambient temperatures prior to introduction of sample into boat. Let boat rest at least 60 s in| coolant jacket or cooting area between injections. Some sulfur may be measured a8 the sample evaporates when the boat approaches the furnace. Sub-ambient emperature ean reduce this evaporation. X37 Sample Flow Path: Leak Check and Back Pressure— ‘The sample flow path mus be leak free when pressure tested in accordance with the manufuctures’s recommended procedure TABLE X3:1 Gas Flow Settings—Boat inlet Analysis "pial Gas Favs Fewer al MrT Frat carer oer 3458 (96:00 miian bet sagen onmate sting Okoe — ioz0minn Fanace oxygen flowrate eliog Seah Isec00muin (Cane numa awa ele? Hs17__asasnumn 7 Het or argon may be ued am ee aes Eo are gore pina. (210 3 psi). Flow path back pressure during sormal operation ‘can range from 0.75 to 2.00 psi, for non-atmospherie-vent systems. X38 Gas Flow Sertings—Gas supplies to various points in the sample path must be consistently controled to allow for smooth, complete combustion of the sample. See Table X31 X39 Membrane Dryer Purge—Water produced during the combustion ofthe sample is removed by the membrane dryer ‘This water mast then be purged. For an apparatus that uilzes 1 desiccant scrubber (low recycle) to provide the membrane “dryer purge gas, replace the drying agent when color change (blue to pink) indicates. When an cuxiliary gas flow is used, set membrane dryer purge flow at 200 to 250 mimi, X3.10 Sample Homogenelty/Calibration Response—Prior to analysis. mix samples and calibration materials well. Mini ‘mur detector response, (Mode! 7000) should be no less than 2000 to 3000 counts, (Model $000) should be no less than 200 300 counts oF three times baseline noise fr the lowest point ‘on the calibration curve. The highest point on the curve is below the saturation point of the (Model 9000) detector: use | maximum response of 350000 t0 450000 counts (Model 7000) as a guideline. Adjust Gain Factor, PMT Voltage, or sample size, or a combination thereof, accordingly. XB.11 Boar Blank/Baseline Stabilty—Prioe to analysis, es- pecially when analyzing low levels, advance the empty boat imo fuenace to ensure that no contamination is present in the boat or on the inside areas of the pyrotube near the injection sea. Heat empty boat in the furnace to ensute that boat is clean, then rapidly move boat out to injection ea, Note X3.I—f th hot boating retuned to the injection area casey baseline opie, repeat the bost in and ow eyes, wall no solfor is measured, For ven gain fact, phxomulpier re voltage, ean be ‘2djusiod io ensure maximum seesiviy while mainaining a sabe. ‘oie baseline, Model 9000 users en tize he saline evaluate ab ‘pei esha unstns to reduce baseline nose X3.12 Calibration Materials/ Standard Curve Consiruction—Prepare calibration standards with solvent ma~ terials that have minimum or no sulfur contamination relative to the concentration anticipated in the sample unknown, Correct for sulfur contribution from solvent materials andAlly v 545s - 08 impurity of sulfur souree material Use calibration curves that of the detector (use a correlation coefficient of 0.999 and 1 to trroket the expected levels in the sample unknown. Do not 2 orders of magnitude (for example, 5 t0 100 ma/kg) as = force the ealibraton curve through the 0. axis, unnecessarily, guideline), The curve should yield an estimated value that can ‘Constvet standard concentrations that will yield a calibration be used to caleulate content in the sample on & mass/mass ‘save tha is linen and that does not exceed the dynamic range basis SUMMARY OF CHANGES ‘Subcommittee 02.03 has identified the location of selected changes to this stondard since the last issue (0 5453-08) that may impact the use of this standard. (Approved July 1, 2008.) (1) Updated 6.8, 10.4.2, and X3.5, (2) Added Note 3. Suiocommittee 002.03 has identified the location of selected changes to this standard since the Tas ive (0 5433-08) thar may impact the wse of this standard. (Approved Feb, 1, 2008.) (Uy Expanded the Scope (1.2) to include ethanol- and (3) Deleted precision information previously appearing. in biodiesel-fuel blends. 5.11.1 and 15.121 (2) Added keywords. (8) Added new reseatch report ‘Subcommittee 102.03 has identified the location of selected changes to this standard since the last issue (© 5453-06) chat may impact the use of ths standard. (Approved Jan. 15, 2008.) () Updated 69. (2) Added Note 4 regarding the use of working standards, AST iuematona takes 9 postion epacin ne ato any pater igs asanasn conection mi any tr ena eae irs os stand recess arase at cotrtin a the valor Sa? tet a ahd Grnnguman a we igh ar antalya on repost ‘ris sand sj ovo yn bye espana ean red sb revenge ve ae a re econ orvaionh, Your canons oo ive ane lr revs 0 hs sande msl rast TR caguanes vas cemnete nea caeeanaraon at mechrg oe Sra teonen cannon jou nay mony Wl a our commer hae ot es af huang you res cere dns oun Too ASTI Commie Sada, a ees shown aN ‘he and copihed by ASTM inteaona, 100 Ba aor Dv, PO Box C70, West Conhahzcen, A 1420-2559, vine Sere eka sant (eng crate copie) os Sande maybe oad by coactg AST ae wove See i eeigae 0068 ara), SaaS fan), or comeeBusimony (mel oF Meugh the ASTH webate (was