1、Designation: D7598 092Standard Test Method forDetermination of Thiodiglycol in Water by Single ReactionMonitoring Liquid Chromatography/Tandem MassSpectrometry1This standard is issued under the fixed designation D7598; the number immediately following the designation indicates the year oforiginal ad
2、option 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.1NOTEThis test method was changed editorially in February 2012.2NOTEAdded research
3、 report footnote to Section 16 editorially in June 2013.1. Scope1.1 This procedure covers the determination of thiodiglycol(TDG) in surface water by direct injection using liquidchromatography (LC) and detected with tandem mass spec-trometry (MS/MS). TDG is qualitatively and quantitativelydetermined
4、 by this method. This method adheres to singlereaction monitoring (SRM) mass spectrometry.1.2 This test method has been developed by US EPARegion5 Chicago Regional Laboratory (CRL).1.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstan
5、dard.1.4 The Detection Verification Level (DVL) and ReportingRange for TDG are listed in Table 1.1.4.1 The DVL is required to be at a concentration at least3 times below the reporting limit (RL) and have a signal/noiseratio greater than 3:1. Fig. 1 displays the signal/noise ratio atthe DVL.1.4.2 The
6、 RL is the concentration of the level 1 calibrationstandard as shown in Table 2. The reporting limit for thismethod is 100 g/L.1.5 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 a
7、ppro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test
8、Methods of Committee D19 on WaterD3856 Guide for Management Systems in LaboratoriesEngaged in Analysis of WaterD3694 Practices for Preparation of Sample Containers andfor Preservation of Organic ConstituentsD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Water
9、AnalysisE2554 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 Evaluating SolidWaste, Physical/Chemical Methods33. Terminology3.1 Definitions:3.1.1 detection verification
10、level (DVL), na concentrationthat has a signal/noise ratio greater than 3:1 and is at least 3times below the reporting limit (RL).3.1.2 reporting limit (RL), nthe concentration of thelowest-level calibration standard used for quantification.1This test method is under the jurisdiction of ASTM Committ
11、ee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved Dec. 1, 2009. Published January 2010. DOI: 10.1520/D7598-09E02.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Cu
12、stomer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Available from National Technical Information Service (NTIS), U.S. Depart-ment of Commerce, 5285 Port Royal Road, Springfield, VA, 22161 or at http
13、:/www.epa.gov/epawaste/hazard/testmethods/index.htm.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.2 Abbreviations:3.2.1 NDnon-detect4. Summary of Test Methods4.1 This is a performance based method and modificationsare allowed to i
14、mprove performance.4.2 For thiodiglycol analysis, samples are shipped to the labbetween 0C and 6C and analyzed within 7 days of collection.In the lab, the samples are spiked with surrogate, filtered usinga syringe driven Millex HV PVDF filter unit and analyzeddirectly by LC/MS/MS.4.3 Thiodiglycol an
15、d 3,3-thiodipropanol (surrogate) areidentified by retention time and one SRM transition. The targetanalyte and surrogate are quantitated using the SRM transitionsutilizing an external calibration. The final report issued foreach sample lists the concentration of TDG and the 3,3-thiodipropanol surrog
16、ate recovery.5. Significance and Use5.1 Thiodiglycol is a Schedule 2 compound under theChemical Weapons Convention (CWC). Schedule 2 chemicalsinclude those that are precursors to chemical weapons, chemi-cal weapons agents or have a number of other commercialuses. They are used as ingredients to prod
17、uce insecticides,herbicides, lubricants, and some pharmaceutical products.Schedule 2 chemicals can be found in applications unrelated tochemical weapons. Thiodiglycol is both a mustard gas precur-sor and degradant as well as an ingredient in water-based inks,ballpoint pen inks, dyes and some pestici
18、des.45.2 This method has been investigated for use with reagentand surface water.6. Interferences6.1 Method interferences may be caused by contaminants insolvents, reagents, glassware and other apparatus producingdiscrete artifacts or elevated baselines. All of these materialsare demonstrated to be
19、free from interferences by analyzinglaboratory reagent blanks under the same conditions assamples.6.2 All glassware is washed in hot water with a detergent,rinsed in hot water followed by distilled water. The glasswareis then dried and heated in an oven at 250C for 15 to 30minutes. All glassware is
20、subsequently cleaned with acetone,then methanol.6.3 All reagents and solvents should be pesticide residuepurity or higher to minimize interference problems.6.4 Matrix interferences may be caused by contaminantsthat are co-extracted from the sample. The extent of matrixinterferences can vary consider
21、ably from sample source de-pending on variations of the sample matrix.7. Apparatus7.1 LC/MS/MS System7.1.1 Liquid Chromatography (LC) SystemAcomplete LCsystem is needed in order to analyze samples.5Asystem that iscapable of performing at the flows, pressures, controlledtemperatures, sample volumes a
22、nd requirements of the stan-dard may be used.7.1.2 Analytical Column-SIELCPrimesep SB 5 m, 100 particle, 150 mm 2.1 mm or equivalent.7.1.3 Tandem Mass Spectrometer (MS/MS) SystemAMS/MS system capable of MRM analysis.6A system that iscapable of performing at the requirements in this standard maybe us
23、ed.7.2 Filtration Device7.2.1 Hypodermic syringeAlock tip glass syringe capableof holding a Millex HV Syringe Driven Filter Unit PVDF 0.45m (Millipore Corporation, Catalog # SLHV033NS) or similarmay be used.7.2.1.1 A25-mL lock tip glass syringe size is recommendedsince a 25-mL sample size is used in
24、 this test method.7.2.2 FilterMillex HV Syringe Driven Filter Unit PVDF0.45 m (Millipore Corporation, Catalog # SLHV033NS) orsimilar may be used.8. Reagents and Materials8.1 Purity of ReagentsHigh-performance liquid chroma-tography (HPLC) pesticide residue analysis and spectropho-tometry grade chemi
25、cals shall be used in all tests. Unlessindicated otherwise, it is intended that all reagents shallconform to the Committee on Analytical Reagents of theAmerican Chemical Society.7Other reagent grades may beused provided they are first determined they are of sufficientlyhigh purity to permit their us
26、e without affecting the accuracy ofthe measurements.8.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water conformingto Type 1 of Specification D1193. It must be demonstrated thatthis water does not contain contaminants at concentrationssufficient
27、 to interfere with the analysis.8.3 GasesUltrapure nitrogen and argon.8.4 Acetonitrile (CAS # 75-05-8).4Additional information about CWC and thiodiglycol is available on the Internetat http:/www.opcw.org (2009)5A Waters Alliance High Performance Liquid Chromatography (HPLC) Systemwas used to develop
28、 this test method. The multi-laboratory study included Agilentand Waters LC systems.6A Waters Quattro micro API mass spectrometer was used to develop this testmethod. The multi-laboratory study included Agilent, Applied Biosystems, Varianand Waters mass spectrometers.7Reagent Chemicals, American Che
29、mical Society Specifications, AmericanChemical Society, Washington, DC. For Suggestions on the testing of reagents notlisted by the American Chemical Society, see Annual Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. P
30、harmacopeial Convention, Inc. (USPC), Rockville,MD.TABLE 1 Detection Verification Level and Reporting RangeAnalyte DVL (g/L) Reporting Range (g/L)Thiodiglycol 20 10010 000D7598 09228.5 Methanol (CAS # 67-56-1).8.6 Acetone (CAS # 67-64-1).8.7 Ammonium formate (CAS # 540-69-2).8.8 Formic acid (64-18-6
31、).8.9 Thiodiglycol (CAS # 111-48-8).8.10 3,3-Thiodipropanol (CAS # 10595-09-2).9. Hazards9.1 Normal laboratory safety applies to this method. Ana-lysts should wear safety glasses, gloves, and lab coats whenworking in the lab.Analysts should review the Material SafetyData Sheets (MSDS) for all reagen
32、ts used in this method.10. Sampling10.1 SamplingGrab samples must be collected in 25-mLpre-cleaned amber glass bottles with Teflon-lined caps demon-strated to be free of interferences. This test method requires a25-mL sample size per analysis. Conventional sampling prac-tices should be followed. Ref
33、er to Guide D3856 and PracticesD3694.10.2 PreservationStore samples between 0C and 6Cfrom the time of collection until analysis. Analyze the samplewithin 1 day of collection.11. Preparation of LC/MS/MS11.1 LC Chromatograph Operating Conditions5:11.1.1 Injection volumes of all calibration standards a
34、ndsamples are 50 L. The first sample analyzed after thecalibration curve is a blank to ensure there is no carry-over.Thegradient conditions for the liquid chromatograph are shown inTable 3.11.1.2 TemperaturesColumn, 30C; Samplecompartment, 15C.11.1.3 Seal WashSolvent: 50 % Acetonitrile/50 % Water;Ti
35、me: 5 minutes.11.1.4 Needle WashSolvent: 50 % Acetonitrile/50 % Wa-ter; Normal Wash, approximately 13 second wash time.FIG. 1 Example SRM Chromatograms Signal/Noise at Detection Verification LevelTABLE 2 Concentrations of Calibration Standards (PPB)Analyte/Surrogate LV 1 LV 2 LV 3 LV 4 LV 5 LV 6 LV
36、7Thiodiglycol 100 250 500 1000 2500 5000 10 0003,3-Thiodipropanol100 250 500 1000 2500 5000 10 000TABLE 3 Gradient Conditions for Liquid ChromatographyTime(min)Flow(L/min)PercentCH3CNPercentWaterPercent500 mmolarAmmoniumFormate/2%Formic Acid0 300 0 95 52.5 300 0 95 56 300 90 5 510 300 90 5 512 300 0
37、 95 516 300 0 95 5D7598 092311.1.5 Autosampler PurgeThree loop volumes.11.1.6 Specific instrument manufacturer wash/purge speci-fications should be followed in order to eliminate samplecarry-over in the analysis of TDG.11.2 Mass Spectrometer Parameters6:11.2.1 In order to acquire the maximum number
38、of datapoints per SRM channel while maintaining adequatesensitivity, the tune parameters may be optimized according toyour instrument. Each peak requires at least 10 scans per peakfor adequate quantitation. This standard contains only onetarget compound and one surrogate which are in different SRMex
39、periment windows in order to optimize the number of scansand sensitivity. Variable parameters regarding retention times,SRM Transitions and cone and collision energies are shown inTable 4.The instrument is set in the Electrospray (+) positive setting.Capillary Voltage: 3.5 kVCone: Variable depending
40、 on analyte (Table 4)Extractor: 2 VoltsRF Lens: 0.2 VoltsSource Temperature: 120CDesolvation Temperature: 300CDesolvation Gas Flow: 500 L/hrCone Gas Flow: 25 L/hrLow Mass Resolution 1: 14.5High Mass Resolution 1: 14.5Ion Energy 1: 0.5Entrance Energy: 1Collision Energy: Variable depending on analyte
41、(Table 4)Exit Energy: 2Low Mass Resolution 2: 15High Mass resolution 2: 15Ion Energy 2: 0.5Multiplier: 650Gas Cell Pirani Gauge: 3.3 103TorrInter-Channel Delay: 0.02 secondsInter-Scan Delay: 0.1 secondsRepeats: 1Span: 0 DaltonsDwell: 0.1 Seconds12. Calibration and Standardization12.1 The mass spectr
42、ometer must be calibrated per manu-facturer specifications before analysis. In order that analyticalvalues obtained using this test method are valid and accuratewithin the confidence limits of the test method, the followingprocedures must be followed when performing the test method.12.2 Calibration
43、and StandardizationTo calibrate theinstrument, analyze seven calibration standards containing theseven concentration levels of TDG and 3,3-thiodipropanolprior to analysis as shown in Table 2. A calibration stockstandard solution is prepared from standard materials orpurchased as certified solutions.
44、 Stock standard solution A(Level 7) containing TDG and 3,3-thiodipropanol is preparedat Level 7 concentration and aliquots of that solution arediluted to prepare Levels 1 through 6. The following steps willproduce standards with the concentration values shown inTable 2. The analyst is responsible fo
45、r recording initialcomponent weights carefully when working with pure materi-als and correctly carrying the weights through the dilutioncalculations.12.2.1 Prepare stock standard solution A (Level 7) byadding to a 100-mL volumetric flask individual methanolsolutions of the following: 250 L of TDG an
46、d 3,3-thiodipropanol each at 4 g/L, dilute to 100 mL with water. Thepreparation of the Level 7 standard can be accomplished usingdifferent volumes and concentrations of stock solutions as isaccustomed in the individual laboratory. Depending on stockconcentrations prepared, the solubility at that con
47、centrationwill have to be ensured.12.2.2 Aliquots of Solution A are then diluted with water toprepare the desired calibration levels in 2-mL amber glass LCvials. The calibration vials must be used within 24 hours toensure optimum results. Stock calibration standards are rou-tinely replaced every six
48、 months if not previously discarded forquality control failure. Calibration standards are not filtered.12.2.3 Inject each standard and obtain a chromatogram foreach one. An external calibration is used monitoring the SRMtransition of each analyte. Calibration software is utilized toconduct the quant
49、itation of the target analyte and surrogate.The SRM transition of each analyte is used for quantitation andconfirmation. This gives confirmation by isolating the parention, fragmenting it to the product ion, and also relating it to theretention time in the calibration standard.12.2.4 The calibration software manual should be consultedto use the software correctly. The quantitation method is set asan external calibration using the peak areas in ppb or ppm unitsas long as the analyst is consistent. Concentrations may becalcu
