1、Designation: D7598 09Standard 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 ado
2、ption 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 covers the determination of thiodiglycol(TDG) in surface
3、 water by direct injection using liquidchromatography (LC) and detected with tandem mass spec-trometry (MS/MS). TDG is qualitatively and quantitativelydetermined by this method. This method adheres to singlereaction monitoring (SRM) mass spectrometry.1.2 This test method has been developed in suppor
4、t of theNational Homeland Security Research Center, US EPA byRegion 5 Chicago Regional Laboratory.1.3 The values stated in SI units are to be regarded asstandard. No other units of measurement are included in thisstandard.1.4 The Detection Verification Level (DVL) and ReportingRange for TDG are list
5、ed 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 RL is the concentration of the level 1 calibrationstandard as shown in Table 2. Th
6、e 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 appro-priate safety and health practices and determine the applica-bility of regulat
7、ory 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 Methods of Committee D19 on WaterD3856 Guide for Good Laboratory Practices in Labor
8、ato-ries Engaged in Sampling and 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 AnalysisE2554 Practice for Estimating and Monitoring the Unce
9、r-tainty of Test Results of a Test Method in a SingleLaboratory Using a Control Sample Program2.2 Other Documents:EPApublication SW-846 Test Methods for Evaluating SolidWaste, Physical/Chemical Methods33. Terminology3.1 Definitions:3.1.1 detection verification level (DVL), na concentrationthat has a
10、 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.3.2 Abbreviations:3.2.1 NDnon-detect4. Summary of Test Methods4.1 This is a performance based meth
11、od and modificationsare allowed to improve 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 analyzeddire
12、ctly by LC/MS/MS.4.3 Thiodiglycol and 3,3-thiodipropanol (surrogate) areidentified by retention time and one SRM transition. The target1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic S
13、ubstances in Water.Current edition approved Dec. 1, 2009. Published January 2010.2For 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 Summary page
14、 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:/www.epa.gov/epawaste/hazard/testmethods/index.htm.TABLE 1 Detection Verification Level and Reporting RangeAnalyte DVL (g/L) Report
15、ing Range (g/L)Thiodiglycol 20 10010 0001Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.analyte and surrogate are quantitated using the SRM transitionsutilizing an external calibration. The final report issued foreach sample lists th
16、e concentration of TDG and the 3,3-thiodipropanol surrogate 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 ot
17、her commercialuses. They are used as ingredients to produce 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 wa
18、ter-based inks,ballpoint pen inks, dyes and some pesticides.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
19、baselines. All of these materialsare demonstrated to be 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 i
20、n an oven at 250C for 15 to 30minutes. All glassware is 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 sam
21、ple. The extent of matrixinterferences can vary considerably from sample source de-pending on variations of the sample matrix.7. Apparatus7.1 LC/MS/MS System7.1.1 Liquid Chromatography (LC) SystemA completeLC system is needed in order to analyze samples.5A system4Additional information about CWC and
22、 thiodiglycol is available on the Internetat http:/www.opcw.org (2009)5A Waters Alliance High Performance Liquid Chromatography (HPLC) Systemwas used to develop this test method. The multi-laboratory study included Agilentand Waters LC systems.FIG. 1 Example SRM Chromatograms Signal/Noise at Detecti
23、on Verification LevelTABLE 2 Concentrations of Calibration Standards (PPB)Analyte/Surrogate LV 1 LV 2 LV 3 LV 4 LV 5 LV 6 LV 7Thiodiglycol 100 250 500 1000 2500 5000 10 0003,3-Thiodipropanol 100 250 500 1000 2500 5000 10 000D7598 092that is capable of performing at the flows, pressures, controlledte
24、mperatures, sample volumes and requirements of the stan-dard may be used.7.1.2 Analytical Column-SIELCPrimesep SB 5 m, 100 particle, 150 mm 3 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 requirem
25、ents in this standard maybe used.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 A 25-mL lock tip glass syringe size is recommendedsince
26、 a 25-mL sample size is used in 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
27、 spectropho-tometry grade chemicals 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 sufficientl
28、yhigh purity to permit their use 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 contamina
29、nts at concentrationssufficient to interfere with the analysis.8.3 GasesUltrapure nitrogen and argon.8.4 Acetonitrile (CAS # 75-05-8).8.5 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).8.9 Thiodiglycol (CAS # 111-48-8).8.10 3,3-Th
30、iodipropanol (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 reagents used in this method.10. Sampling10.1 Sampli
31、ngGrab samples must be collected in$25-mL pre-cleaned amber glass bottles with Teflon-linedcaps demonstrated to be free of interferences. This test methodrequires a 25-mL sample size per analysis. Conventionalsampling practices should be followed. Refer to Guide D3856and Practices D3694.10.2 Preserv
32、ationStore 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 andsamples are 50 L. The first sample analyzed aft
33、er 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; Sample compart-ment, 15C.11.1.3 Seal WashSolvent: 50 % Acetonitrile/50 % Water;Time: 5 minutes.11.1.4 Needle WashSolvent: 50 %
34、Acetonitrile/50 % Wa-ter; Normal Wash, approximately 13 second wash time.11.1.5 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 Parameters6:1
35、1.2.1 In order to acquire the maximum number of datapoints per SRM channel while maintaining adequate sensitiv-ity, the tune parameters may be optimized according to yourinstrument. Each peak requires at least 10 scans per peak foradequate quantitation. This standard contains only one targetcompound
36、 and one surrogate which are in different SRM6A 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 Chemical Society Specifications, AmericanC
37、hemical 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. Pharmacopeial Convention, Inc. (USPC), R
38、ockville,MD.TABLE 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 95 516 300 0 95 5D7598 093experiment windows in order to optimize the number of scans
39、and 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 on analyte (Table 4)Extractor: 2 VoltsRF Lens: 0.2 Volts
40、Source 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 (Table 4)Exit Energy: 2Low Mass Resolution 2: 15High Mass
41、 resolution 2: 15Ion Energy 2: 0.5Multiplier: 650Gas Cell Pirani Gauge: 3.3 3 103TorrInter-Channel Delay: 0.02 secondsInter-Scan Delay: 0.1 secondsRepeats: 1Span: 0 DaltonsDwell: 0.1 Seconds12. Calibration and Standardization12.1 The mass spectrometer must be calibrated per manu-facturer specificati
42、ons 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 and StandardizationTo calibrate the in-strument, analyz
43、e 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. Stock standard solution A(Level 7) containing TDG an
44、d 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 for recording initialcomponent weights carefully when w
45、orking 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 and 3,3-thiodipropanol each at 4 g/L, dilute to 100 mL
46、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 concentrationwill have to be ensured.12.2.2 Aliquots of
47、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 months if not previously discarded forquality contro
48、l 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 quantitation of the target analyte and surrogate.The SRM t
49、ransition 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 becalculated using the data system software to generate linearregression
