1、Designation: D7599 16Standard 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 designation D7599; th
2、e 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 or reapproval.1.
3、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 with tandemmass spect
4、rometry (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 US EPARegion5 Chicago Regional Laboratory (CRL).1.3 The values stated in SI unit
5、s 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 Reporting Limit (RL) and
6、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,triethanolamine, and N-ethyld
7、iethanolamine 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 reporting limit (chromatogra
8、ms 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, N-methyldiethanolami
9、ne 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-bility of regulatory limi
10、tations 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 Management Systems in LaboratoriesEngaged
11、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 Monitoring the Uncer-tainty of Test Results of a
12、Test Method Using ControlChart Techniques2.2 Other Documents:EPA publication SW-846 Test Methods for Evaluating SolidWaste, Physical/Chemical Methods33. Terminology3.1 Definitions:1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommitt
13、ee D19.06 on Methods forAnalysis forOrganic Substances in Water.Current edition approved Feb. 1, 2016. Published May 2016. Originallyapproved in 2009. Last previous edition approved in 2009 as D7599 092. DOI:10.1520/D7599-16.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcon
14、tact ASTM Customer 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, 2216
15、1 or at http:/www.epa.gov/epawaste/hazard/testmethods/index.htm.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States13.1.1 For definitions of terms used in this standard, refer toTerminology D1129.3.2 Definitions of Terms Specific to This
16、Standard:3.2.1 detection verification level, DVL, na concentrationthat has a signal/noise ratio greater than 3:1 and is at least 3times below the reporting limit (RL).3.2.2 ethanolamines, nin this test method,diethanolamine, triethanolamine, N-methyldiethanolamine andN-ethyldiethanolamine collective
17、ly.3.2.3 independent reference material, IRM, na material ofknown purity and concentration obtained either from theNational Institute of 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.
18、1 CCC, nContinuing Calibration Check3.3.2 IC, nInitial Calibration3.3.3 LC, nLiquid Chromatography3.3.4 LCS/LCSD, nLaboratory Control Sample/Laboratory Control Sample Duplicate3.3.5 MDL, nMethod Detection Limit3.3.6 MeOH, nMethanol3.3.7 mM, nmillimolar,110-3moles/L3.3.8 MRM, nMultiple Reaction Monit
19、oring3.3.9 MS/MSD, nMatrix Spike/Matrix Spike Duplicate3.3.10 NA, adjNot Available3.3.11 ND, nnon-detect3.3.12 P (Diethanolamine-D8),where 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 app
20、lies to this method. Ana-lysts should wear safety glasses, gloves, and lab coats whenworking in the lab. Analysts should review the Safety 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 T
21、eflon-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. Refer to Guide D3856 and PracticesD3694.10.2 PreservationStore samples between 0C and 6Cfrom the time of collection until analys
22、is. 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 sample analyzed after thecalibration curve is a blank to ensure there is no carry-over.Thegrad
23、ient 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 WashSolvent: 50 % Acetonitrile/50 % Wa-ter; Normal wash, approximately 13 second wash time.11.1.
24、5 Autosampler PurgeThree loop volumes.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
25、 this test method may be used.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., a
26、nd the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.TABLE 3 Multi-Laboratory Recovery Data in Reagent WaterAnalyte SpikeConc.(ppb)# Results # Labs Bias PrecisionMeanRecovery(%)MinRecovery(%)MaxRecovery(%)Overall SD(%)Pooledwithin-labSD (%
27、)OverallRSD (%)Pooledwithin-labRSD (%)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 5.70Tr
28、iethanolamine 25 24 6 87.70 35.96 157.20 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.
29、00 132.00 39.42 7.47 43.51 10.42N-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
30、.24 13.29 28.55 16.70N-Methyldiethanolamine 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
31、 9.40 20.51 9.25D7599 16411.1.6 Specific instrument manufacturer wash/purge speci-fications should be followed in order to eliminate samplecarry-over in the analysis of ethanolamines.11.2 Mass Spectrometer Parameters:811.2.1 In order to acquire the maximum number of datapoints per SRM channel while
32、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 onesurrogate and four target compounds which are located in thesame multiple reaction monitoring (MRM
33、) 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 setting.Capillary Voltage: 0.5 kVCone: Variable depending on analyte (Table 5)Extractor: 2 VoltsRF Lens: 0.2
34、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 (Table 5)Exit Energy: 2Low Mass Resolution 2: 15High
35、 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 spectrometer must be calibrated per manu-facturer specific
36、ations 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 theinstrument, analy
37、ze seven calibration standards containing theseven concentration levels of the ethanolamines anddiethanolamine-D8surrogate prior to analysis as shown inTable 2. A calibration stock standard solution is prepared fromstandard materials or purchased as certified solutions. Stockstandard solution A (Lev
38、el 7) containing diethanolamine,triethanolamine, N-methyldiethanolamine andN-ethyldiethanolamine and diethanolamine-D8is prepared atLevel 7 concentration and aliquots of that solution are dilutedto prepare Levels 1 through 6.The following steps will producestandards with the concentration values sho
39、wn in Table 2. Theanalyst is responsible for recording initial component weightscarefully when working with pure materials and correctlycarrying the weights through the dilution calculations.12.2.1 Prepare stock standard solution A (Level 7) byadding, to a 100 mL volumetric flask, individual methano
40、lsolutions 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 preparation ofthe Level 7 standard can be accomplished using differentvolumes and concentrations of stoc
41、k solutions as is accustomedin 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 then diluted with water toprepare the desired calibration levels in 2-mL amber glass LCvials. The calib
42、ration 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. Calibration standards are not filtered.12.2.3 Inject each standard and obtain a chromatogram foreach one. A
43、n 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 analyte is used for quantitation andconfirmation. This gives confirmation by isolating the parention
44、, 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 asTABLE 4 Gradient Conditions for Liquid ChromatographyTime(min)Flow(L/mi
45、n)PercentCH3CNPercentWaterPercent200 mmolarAmmoniumAcetate0 400 95 0 51 400 95 0 52 400 90 0 104 300 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 5TABLE 5 Retention Times, SRM Ions, and Analyte-Specific Mass Spectrometer ParametersAnalyte
46、 SRM MassTransition(Parent Product)Retention Time(min)Cone Voltage(Volts)Collision Energy(eV)Diethanolamine 106 87.8 13.0 25 11Triethanolamine 150.2 132.1 12.3 25 14N-Ethyldiethanolamine 134.2 116 12.4 25 13N-Methyldiethanolamine 120.1 101.9 12.8 25 13Diethanolamine-D8(Surrogate) 114 95.8 13.0 25 12
47、D7599 165an 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 is not recommended.1
48、2.2.5 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 cause
49、sthe 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 high or low, causes thecurve to be 0.99. In thisevent, the reporting range must be modified to reflect thischange. Each calibration point used to generate the curve musthave a calculated percent deviation less than 25 % from thegenerated curve.12.2.7 The retention time window of the SRM transitionsmust be within 5 %
