1、Designation: E2838 11 (Reapproved 2016)Standard Test Method forDetermination of Thiodiglycol on Wipes by SolventExtraction Followed by Liquid Chromatography/TandemMass Spectrometry (LC/MS/MS)1This standard is issued under the fixed designation E2838; the number immediately following the designation
2、indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This procedure details the determinati
3、on of thiodiglycol(TDG), also known as 2,2-thiobis-ethanol, on wipes with3,3-thiodipropanol (TDP) as the surrogate. This method isbased upon solvent extraction of wipes by either sonication ora pressurized fluid extraction (PFE) technique as an alternativeoption. The extract is filtered, concentrate
4、d and analyzed byliquid chromatography/tandem mass spectrometry (LC/MS/MS). TDG is qualitatively and quantitatively determined.1.2 UnitsThe values stated in SI units are to be regardedas standard. No other units of measurement are included in thisstandard.1.3 The Method Detection Limit (MDL)2and Rep
5、ortingRange3for TDG are listed in Table 1.1.4 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulator
6、y limitations prior to use.2. Referenced Documents2.1 ASTM Standards:4D653 Terminology Relating to Soil, Rock, and ContainedFluidsD1193 Specification for Reagent WaterD3694 Practices for Preparation of Sample Containers andfor Preservation of Organic ConstituentsD3740 Practice for Minimum Requiremen
7、ts for AgenciesEngaged in Testing and/or Inspection of Soil and Rock asUsed in Engineering Design and ConstructionE2554 Practice for Estimating and Monitoring the Uncer-tainty of Test Results of a Test Method Using ControlChart Techniques2.2 Other Documents:EPA Publication SW-846 Test Methods for Ev
8、aluating SolidWaste, Physical/Chemical Methods5The Code of Federal Regulations, 40 CFR Part 136, Appen-dix B3. Terminology3.1 Abbreviations:3.1.1 mMmillimolar,110-3moles/L3.1.2 NDnon-detect3.1.3 SRMsingle reaction monitoring3.1.4 MRMmultiple reaction monitoring3.1.5 VOAvolatile organic analysis4. Su
9、mmary of Test Method4.1 For TDG wipe analysis, samples are shipped to the labbetween 0C and 6C. The samples are to be extracted,concentrated, and analyzed directly by LC/MS/MS within 7days of collection. The handling, storage, preservation, andLC/MS/MS analysis are consistent between the two extract
10、ionprocedures described in this test method. Only one extractionprocedure is required, documenting which was performed.4.2 TDG and TDP are identified by retention time and oneSRM transition. The target analyte and surrogate are quanti-tated using the SRM transitions utilizing an external calibra-tio
11、n. The final report issued for each sample lists the concen-tration of TDG and the TDP recovery.1This test method is under the jurisdiction of ASTM Committee E54 onHomeland Security Applications and is the direct responsibility of SubcommitteeE54.03 on Decontamination.Current edition approved June 1
12、, 2016. Published July 2016. Originally approvedin 2011. Last previous edition approved in 2011 as E2838 11. DOI: 10.1520/E2838-11R16.2The MDL is determined following the Code of Federal Regulations, 40 CFRPart 136, Appendix B utilizing solvent extraction of wipes by sonication.3Reporting range conc
13、entrations are calculated from Table 4 concentrationsassuming a 10 Linjection of the lowest and highest level calibration standards witha 2 mL final extract volume. Volume variations will change the reporting limit andranges. The reporting limit (RL), lowest concentration of the reporting range, isc
14、alculated from the concentration of the Level 1 calibration standard as shown inTable 4.4For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summa
15、ry page onthe ASTM website.5Available from National Technical Information Service (NTIS), U.S. Depart-ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http:/www.epa.gov/epawaste/hazard/testmethods/index.htmCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Con
16、shohocken, PA 19428-2959. United States15. Significance and Use5.1 This is a performance based method, and modificationsare allowed to improve performance.5.1.1 Due to the rapid development of newer instrumenta-tion and column chemistries changes to the analysis describedin this standard are allowed
17、 as long as better or equivalentperformance data result. Any modifications shall be docu-mented and performance data generated. The user of the datagenerated by this Standard shall be made aware of thesechanges and given the performance data demonstrating betteror equivalent performance.5.2 TDG is a
18、 Schedule 2 compound under the ChemicalWeapons Convention (CWC).6Schedule 2 chemicals includethose that are precursors to chemical weapons, chemicalweapons agents or have a number of other non-militarycommercial uses. Schedule 2 chemicals can also be found inapplications unrelated to chemical weapon
19、s. These chemicalsare used as ingredients to produce insecticides, herbicides,lubricants, and some pharmaceutical products. TDG is amustard gas precursor and a degradant as well as an ingredientin water-based inks, ballpoint pen inks, dyes, and somepesticides.5.3 This method has been investigated fo
20、r use on surfacewipes. TDG is also a human metabolite resulting from sulfurmustard exposure but this method has not been investigated forsuch determinations.6. Interferences6.1 Method interferences may be caused by contaminants insolvents, reagents, glassware, and other apparatus producingdiscrete a
21、rtifacts or elevated baselines. All of these materialsshall be demonstrated to be free from interferences by analyz-ing laboratory reagent blanks under the same conditions assamples.6.2 All reagents and solvents shall be of pesticide residuepurity or higher to minimize interference problems.6.3 Matr
22、ix interferences may be caused by contaminantsthat are co-extracted from the sample. The extent of matrixinterferences can vary considerably from sample source de-pending on variations of the sample matrix.7. Apparatus7.1 LC/MS/MS System:7.1.1 Liquid Chromatography (LC) System7A LC systemis required
23、 in order to analyze samples. A LC system that iscapable of performing at the flows, pressures, controlledtemperatures, sample volumes, and requirements of the stan-dard shall be used.7.1.2 Analytical Column8A column that achieves ad-equate resolution shall be used. The retention times and orderof e
24、lution may change depending on the column used and needto be monitored.Areverse-phase analytical column with strongembedded basic ion-pairing groups was used to develop thistest method.7.1.3 Tandem Mass Spectrometer (MS/MS) System9AMS/MS system capable of multiple reaction monitoring(MRM) analysis o
25、r a system that is capable of performing atthe requirements in this standard shall be used.7.2 Pressurized Fluid Extraction (PFE) Device10(optional)PFE devices with appropriately-sized extractioncells are available that will accommodate the wipe sample sizesused in this test method. Cells shall be m
26、ade of stainless steelor other material capable of withstanding the pressure require-ments (2000 psi) necessary for this procedure. A pressurizedfluid extraction device shall be used that can meet the neces-sary requirements in this test method.7.3 Glass Fiber Filters.117.4 Solvent Blowdown Device,
27、with 24- and 50-vial capacitytrays and a water bath maintained at 50 to 60C for analyte6Additional information about CWC and thiodiglycol is available on the Internetat http:/www.opcw.org (2009).7A Waters Alliance High Performance Liquid Chromatography (HPLC)System was used to develop this test meth
28、od and generate the precision and biasdata presented in Section 17. The sole source of supply of the apparatus known tothe committee at this time is Waters Corporation, Milford, MA 01757. If you areaware of alternative suppliers, please provide this information to ASTM Interna-tional Headquarters. Y
29、our comments will receive careful consideration at a meetingof the responsible technical committee,1which you may attend.8A SIELC- Primesep SB 5 m, 100 particle, 150 by 2.1 mm column wasused to develop this test method and generate the precision and bias data presentedin Section 17. The sole source
30、of supply of the apparatus known to the committeeat this time is SIELC Technologies, Prospect Heights, IL 60070. If you are aware ofalternative suppliers, please provide this information to ASTM InternationalHeadquarters. Your comments will receive careful consideration at a meeting of theresponsibl
31、e technical committee,1which you may attend.9AWaters Quattro microAPI mass spectrometer was used to develop this testmethod and generate the precision and bias data presented in Section 17. The solesource of supply of the apparatus known to the committee at this time is WatersCorporation, Milford, M
32、A 01757. If you are aware of alternative suppliers, pleaseprovide this information to ASTM International Headquarters. Your comments willreceive careful consideration at a meeting of the responsible technical committee,1which you may attend.10A Dionex Accelerated Solvent Extraction (ASE 200) system
33、withappropriately-sized extraction cells was used to develop this test method andgenerate the precision and bias data presented in Section 17. The sole source ofsupply of the apparatus known to the committee at this time is Dionex Corporation,Sunnyvale, CA 94088. If you are aware of alternative supp
34、liers, please provide thisinformation to ASTM International Headquarters. Your comments will receivecareful consideration at a meeting of the responsible technical committee,1whichyou may attend.TABLE 1 Method Detection Limit and Reporting RangeAnalyteCASANumberMDL(g/wipe)Reporting Range(g/wipe)Thio
35、diglycol 111-48-8 0.085 1-803,3-Thiodipropanol(Surrogate)10595-09-2 Not donefor surrogates1-80AChemical Abstract Service (CAS), A division of the American Chemical Society,2540 Olentangy River Road, Columbus, OH, 43202, USA.E2838 11 (2016)2concentration from solvent volumes up to 50 mL or similardev
36、ice shall be used.127.5 Sonication Device, capable of holding 40 mL vials.137.6 Nitrogen Evaporation Device, equipped with a waterbath that can be maintained at 50C for final analyte concen-tration ( Product)RetentionTime(min)ConeVoltage(Volts)CollisionEnergy(eV)Thiodiglycol 123.1 104.9 2.75 18 53,3
37、-Thiodipropanol 151.2 133.1 5.75 19 8E2838 11 (2016)4fragmenting it to the product ion, and relating it to the retentiontime in the calibration standard.12.2.2 The calibration software manual shall be consulted touse the software correctly. The quantitation method is set as anexternal calibration us
38、ing the peak areas in ppb or ppm units aslong as the analyst is consistent. Concentrations may becalculated using the data system software to generate linearregression or quadratic calibration curves. The calibrationcurves may be either linear or quadratic depending on yourinstrument. Forcing the ca
39、libration curve through the origin isnot recommended. Each calibration point used to generate thecurve shall have a calculated percent deviation less than 30%from the generated curve.12.2.3 Linear calibration may be used if the coefficient ofdetermination, r2, is 0.98 for the analyte. The point of o
40、riginis excluded, and a fit weighting of 1/X is used in order to givemore emphasis to the lower concentrations. If one of thecalibration standards other than the high or low point causesthe r2of the curve to be 0.99 for the analyte. The point oforigin is excluded, and a fit weighting of 1/X is used
41、in orderto give more emphasis to the lower concentrations. If one ofthe calibration standards, other than the high or low, causes thecurve to be 0.99. Inthis event, the reporting range shall be modified to reflect thischange.12.2.5 The retention time window of the SRM transitionsshall be within 5% o
42、f the retention time of the analyte in amidpoint calibration standard. If this is not the case, re-analyzethe calibration curve to determine if there was a shift inretention time during the analysis, and re-inject the sample. Ifthe retention time is still incorrect, refer to the analyte as anunknown
43、.12.2.6 A midpoint calibration check standard shall be ana-lyzed at the end of each batch of 20 samples or within 24 hoursafter the initial calibration curve was generated. This endcalibration check shall be the same calibration standard thatwas used to generate the initial curve. The results from t
44、he endcalibration check standard shall have a percent deviation lessthan 30% from the calculated concentration for the targetanalyte and surrogate. If the results are not within these criteria,the problem shall be corrected, and either all samples in thebatch shall be re-analyzed against a new calib
45、ration curve orthe affected results shall be qualified with an indication thatthey do not fall within the performance criteria of the testmethod. If the analyst inspects the vial containing the endcalibration check standard and notices that the sample evapo-rated affecting the concentration, a new e
46、nd calibration checkstandard shall be made and analyzed. If this new end calibra-tion check standard has a percent deviation less than 30% fromthe calculated concentration for the target analyte andsurrogate, the results shall be reported unqualified if all otherquality control parameters are accept
47、able.12.3 If a laboratory has not performed the test before or ifthere has been a major change in the measurement system, forexample, new analyst or new instrument, perform a precisionand bias study to demonstrate laboratory capability and verifythat all technicians are adequately trained and follow
48、 allrelevant safety procedures.12.3.1 Analyze at least four replicates of a wipe samplecontainingTDG andTDPbetween Levels 3-6 of the calibrationrange in the final extract concentration. Each replicate shall betaken through the complete analytical test method.12.3.2 Calculate the mean (average) perce
49、nt recovery andrelative standard deviation (RSD) of the four values andcompare to the ranges of the quality control (QC) acceptancecriteria for the Initial Demonstration of Performance in Table5.12.3.3 This study shall be repeated until the single operatorprecision and mean recovery are within the limits in Table 5.12.3.4 The QC acceptance criteria for the Initial Demon-stration of Performance in Table 5 are preliminary until acollaborative study is conducted. Single lab data is shown inthe Precision and Bias Section. The analyst shall be aware that
