1、Designation: D7599 16 (Reapproved 2017)Standard Test Method forDetermination of Diethanolamine, Triethanolamine,N-Methyldiethanolamine and N-Ethyldiethanolamine in Waterby Single Reaction Monitoring Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS)1This standard is issued under the fixed des
2、ignation D7599; the number immediately following the designation 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
3、 or reapproval.1. Scope1.1 This procedure covers the determination ofdiethanolamine, triethanolamine, N-methyldiethanolamine andN-ethyldiethanolamine (referred to collectively as ethano-lamines in this test method) in surface water by direct injectionusing liquid chromatography (LC) and detected wit
4、h tandemmass spectrometry (MS/MS). These analytes are qualitativelyand quantitatively determined by this test method. This testmethod adheres to single reaction monitoring (SRM) massspectrometry.1.2 This test method has been developed by U.S. EPARegion 5 Chicago Regional Laboratory (CRL).1.3 The val
5、ues 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 the ethanolamines are listed in Table 1.1.4.1 The DVL is required to be at a concentration at least3 times below the Repo
6、rting Limit (RL) and have a signal/noise ratio greater than 3:1. Fig. 1 displays the signal/noiseratios at the DVLs and at higher concentrations forN-methyldiethanolamine.1.4.2 The reporting limit is the concentration of the Level 1calibration standard as shown in Table 2 for diethanolamine,triethan
7、olamine, and N-ethyldiethanolamine and Level 2 forN-methyldiethanolamine. The reporting limit forN-methyldiethanolamine is set at 50 g/L due to poor sensi-tivity at a 5 g/L concentration which did not meet the DVLcriteria. The DVL for N-methyldiethanolamine is at 10 g/L,which forces a raised reporti
8、ng limit (chromatograms areshown in Fig. 1). However, the multi-laboratory validationrequired a spike of all target analytes at 25 g/L. The meanrecovery for N-methyldiethanolamine at this level was 88 % asshown in Table 3. If your instruments sensitivity can meet therequirements in this test method,
9、 N-methyldiethanolamine mayhave a 25 g/L reporting limit.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-bili
10、ty of regulatory limitations prior to use.1.6 This international standard was developed in accor-dance with internationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the Wor
11、ld Trade Organization TechnicalBarriers to Trade (TBT) Committee.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 fo
12、r 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 AnalysisE2554 Practice for Estimating and Monit
13、oring the Uncer-tainty of Test Results of a Test Method Using ControlChart Techniques1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved June 1
14、5, 2017. Published July 2017. Originallyapproved in 2009. Last previous edition approved in 2016 as D7599 16. DOI:10.1520/D7599-16R17.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume info
15、rmation, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardizat
16、ion established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.12.2 Other Documents:EPA publication SW-846 Test Methods for Evaluating SolidWaste, Physical/Chem
17、ical Methods33. Terminology3.1 Definitions:3.1.1 For definitions of terms used in this standard, refer toTerminology D1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 detection verification level, DVL, na concentrationthat has a signal/noise ratio greater than 3:1 and is at least 3times
18、 below the reporting limit (RL).3.2.2 ethanolamines, nin this test method,diethanolamine, triethanolamine, N-methyldiethanolamine andN-ethyldiethanolamine collectively.3.2.3 independent reference material, IRM, na material ofknown purity and concentration obtained either from theNational Institute o
19、f Standards andTechnology (NIST) or otherreputable supplier. The IRM shall be obtained from a differentlot of material than is used for calibration.3.3 Acronyms:3.3.1 CCC, nContinuing Calibration Check3.3.2 IC, nInitial Calibration3.3.3 LC, nLiquid Chromatography3.3.4 LCS/LCSD, nLaboratory Control S
20、ample/Laboratory Control Sample Duplicate3.3.5 MDL, nMethod Detection Limit3.3.6 MeOH, nMethanol3.3.7 mM, nmillimolar,1103moles/L3.3.8 MRM, nMultiple Reaction Monitoring3.3.9 MS/MSD, nMatrix Spike/Matrix Spike Duplicate3.3.10 NA, adjNot Available3.3.11 ND, nnon-detect3.3.12 P (Diethanolamine-D8),whe
21、re the ethylene moieties contain all2H (CAS # 103691-51-6).8.12.1 Diethanolamine-D8is used as a surrogate in thisstandard.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 Safe
22、ty DataSheets (SDS) for all reagents used in this test 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 samp
23、ling prac-tices should be followed. Refer to Guide D3856 and PracticesD3694.8AWaters Quattro (a trademark of the Waters Corporation, Milford, MA) microAPI mass spectrometer, or equivalent, was found suitable for use The multi-laboratory study included Applied Biosystems, Varian and Waters mass spect
24、rom-eters.9A Millex HV Syringe-Driven Filter Unit PVDF 0.45 m (MilliporeCorporation, Catalog # SLHV033NS; Millex is a trademark of Merck KGAA,Darmstadt, Germany) has been found suitable for use for this test method, any filterunit may be used that meets the performance of this test method may be use
25、d.10Reagent Chemicals, American Chemical 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 Pharmac
26、opeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.TABLE 3 Multi-Laboratory Recovery Data in Reagent WaterAnalyteSpike Conc.(ppb)# Results # LabsBias PrecisionMeanRecovery(%)MinRecovery(%)MaxRecovery(%)Overall SD(%)Pooledwithin-labSD (%)OverallRSD (%)Pooledwithin-l
27、abRSD (%)Diethanolamine 25 24 6 96.34 51.00 156.96 31.31 10.96 32.50 9.49Diethanolamine 50 24 6 101.41 54.00 154.80 29.54 7.97 29.13 7.91Diethanolamine 200 24 6 101.57 61.00 138.00 20.98 10.50 20.66 10.85Diethanolamine 425 24 6 102.06 70.00 138.82 17.98 5.90 17.61 5.70Triethanolamine 25 24 6 87.70 3
28、5.96 157.20 27.00 25.18 30.79 27.48Triethanolamine 50 24 6 94.95 67.00 121.66 16.39 9.57 17.26 9.66Triethanolamine 200 22 6 105.00 79.50 132.00 14.06 11.81 13.39 11.52Triethanolamine 425 24 6 96.94 40.00 144.94 27.56 4.41 28.43 5.76N-Ethyldiethanolamine 25 24 6 90.61 31.00 132.00 39.42 7.47 43.51 10
29、.42N-Ethyldiethanolamine 50 23 6 111.88 49.00 146.00 28.71 7.19 25.66 7.56N-Ethyldiethanolamine 200 24 6 106.20 60.00 134.00 23.09 11.96 21.74 12.23N-Ethyldiethanolamine 425 24 6 99.67 51.00 130.00 23.07 4.68 23.15 6.01N-Methyldiethanolamine 25 24 6 88.43 41.72 133.60 25.24 13.29 28.55 16.70N-Methyl
30、diethanolamine 50 24 6 102.28 56.00 153.80 25.85 8.73 25.27 8.22N-Methyldiethanolamine 200 24 6 101.02 59.00 136.50 20.07 9.51 19.87 9.54N-Methyldiethanolamine 425 24 6 94.75 63.00 115.76 15.02 3.34 15.85 3.72Diethanolamine-D8(Surrogate)200 96 6 103.02 60.00 151.95 21.13 9.40 20.51 9.25D7599 16 (201
31、7)410.2 PreservationStore samples between 0C and 6Cfrom the time of collection until analysis. Analyze the samplewithin 7 days of collection.11. Preparation of LC/MS/MS11.1 LC Chromatograph Operating Conditions:611.1.1 Injection volumes of all calibration standards andsamples are 25 L. The first sam
32、ple analyzed after thecalibration curve is a blank to ensure there is no carry-over.Thegradient conditions for the liquid chromatograph are shown inTable 4.11.1.2 TemperaturesColumn, 30C; Samplecompartment, 15C.11.1.3 Seal WashSolvent: 50 % Acetonitrile/50 % Water;Time: 5 minutes.11.1.4 Needle WashS
33、olvent: 50 % 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 ethanolamines.11.2 Mass Spe
34、ctrometer Parameters:811.2.1 In order to acquire the maximum number 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 on
35、ly onesurrogate and four target compounds which are located in thesame multiple reaction monitoring (MRM) experiment win-dow. Variable parameters regarding retention times, SRMTransitions and cone and collision energies are shown in Table5.The instrument is set in the Electrospray (+) positive setti
36、ng.Capillary Voltage: 0.5 kVCone: Variable depending on analyte (Table 5)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 Energ
37、y: 1Collision Energy: Variable depending on analyte (Table 5)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.
38、 Calibration and Standardization12.1 The mass spectrometer 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 follow
39、ed when performing the test method.12.2 Calibration and StandardizationTo calibrate theinstrument, analyze seven calibration standards containing theseven concentration levels of the ethanolamines anddiethanolamine-D8surrogate prior to analysis as shown inTable 2. A calibration stock standard soluti
40、on is prepared fromstandard materials or purchased as certified solutions. Stockstandard solution A (Level 7) containing diethanolamine,triethanolamine, N-methyldiethanolamine andN-ethyldiethanolamine and diethanolamine-D8is prepared atLevel 7 concentration and aliquots of that solution are dilutedt
41、o prepare Levels 1 through 6.The following steps will producestandards with the concentration values shown in Table 2. Theanalyst is responsible for recording initial component weightscarefully when working with pure materials and correctlycarrying the weights through the dilution calculations.12.2.
42、1 Prepare stock standard solution A (Level 7) byadding, to a 100 mL volumetric flask, individual methanolsolutions of the following: 50 L of diethanolamine,triethanolamine, N-methyldiethanolamine,N-ethyldiethanolamine and diethanolamine-D8each at 1 g/Lconcentration, dilute to 100 mL with water. The
43、preparation ofthe Level 7 standard can be accomplished using differentvolumes and concentrations of stock solutions as is accustomedTABLE 4 Gradient Conditions for Liquid ChromatographyTime(min)Flow(L/min)PercentCH3CNPercentWaterPercent200 mmolarAmmoniumAcetate0 400 95 0 51 400 95 0 52 400 90 0 104
44、300 90 0 1010 300 60 30 1013 300 60 30 1015 300 40 50 1018 300 30 60 1020 300 30 60 1025 300 95 0 527 300 95 0 5D7599 16 (2017)5in the individual laboratory. Depending on stock concentra-tions prepared, the solubility at that concentration will have tobe ensured.12.2.2 Aliquots of Solution A are the
45、n 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 control failure. Calibra
46、tion 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 transition of each
47、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
48、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 or quadratic calibration curves. Forcing the calibra-tion through the origin
49、is not recommended.12.2.5 Linear calibration may be used if the coefficient ofdetermination, r2, is 0.98 for the analyte. The point of originis 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 in order togive more emphasis to the lower concentrations. If one of thecalibration standards, other than the
